Copyright © Denis Lisson, National Centre for Maritime Engineering and Hydrodynamics, June

2008.

Note the referencing is done per chapter; the cross-referencing of superscripts varies for each
chapter.

The author wishes to acknowledge a debt of gratitude to Mohammadmahdi Ghiji, for his intelligent
and creative contribution towards formatting the recent editions of these lecture notes.

If using these notes as acknowledgement, the reference is:

Lisson, Denis N. Materials Technology Lecture Notes. Australian Maritime College, 2015.

Third printing – 2010

Significant additions of new material were made, together with questions and answers at the end of
each chapter.

Fourth printing – 2011

The author has made significant additions to the chapters on Corrosion and Polymers which reflect
the importance of these topics for students of engineering.

Fifth Printing - 2012

The author has made significant modifications to chapter 10 Polymers. A new chapter has been
prepared on Composites because of their increasing importance in modern engineering practice.

Sixth Printing - 2013

The author has made minor modifications and clarifications in chapters 3,8,9,10,11 and13.

Seventh Printing - 2014

The author has made significant additions to chapter 9, Mechanical Properties, by including an
expanded treatment of bending and torsional forces. Derivations of equations for these topics have
also been appended in the form of a supplement. Elsewhere a number of small changes has been made
to clarify sections of the text and improve the labelling of diagrams.

Eighth Printing – 2015

Significant changes have been made to the order of chapters in order to more closely align their
sequence and relevance to the teaching schedule. A new introduction has been included, emphasizing
the interrelationship between structure, processing and properties of materials. An expansion of the
role of intermolecular bonding on the properties of thermoplastics, has been added to the chapter on
polymers. Modifications have been made to the chapter on Corrosion, with an additional section on
practical monitoring methods.

Ninth Printing – 2016

No significant changes were considered necessary for this printing.

Tenth Printing – 2021

Minor edits to the front matter.

Front cover by Mohammadmahdi Ghiji. 22 June 2015

i
Preface
The purpose of the subject Materials Technology is to introduce students of engineering to the nature
and properties of a range of materials commonly used in engineering structures.

If one were interested only in engineering materials used in quantity, then the study of reinforced
concrete and steel would suffice, since these are the most commonly used materials. However,
adopting the notion that small is beautiful, we should also interest ourselves in the other more exotic
materials currently being developed.

Although reinforced concrete and steel have revolutionised buildings and transport it is the new
materials like polymers, ceramics and composites which have had a great impact in improving our
modern quality of life. Many of the spectacular advances made in electronics, medicine, space travel,
and communications rely upon such materials, and have made possible the knowledge revolution that
we have experienced in our life time.

There are several important aspects of materials which are interdependent. They are processing,
structure, properties and performance/application. A simple example will illustrate this
interconnection. Steel is manufactured from iron ore which is refined and alloyed. During the
processing stages it will undergo various combinations of mechanical and thermal treatments. These
operations will affect its structure and properties, which in turn will determine its application and
performance in practice.

The evolutions of civilizations have been dependent upon the availability of raw materials for
progress. The dictionary definition of materials most apposite in this historic context is, “anything
serving as crude or raw matter for working upon or developing.” Ancient man by a combination of
luck, ingenuity, inspiration and perseverance has fashioned these materials at his disposal into tools,
structures, and works of art. Thus wood, stone, bone, leather and clay gave way to bronze, steel,
precursors to modern concrete, and ultimately to polymers, ceramics and smart composite materials.

Material scientists are now able to design materials, and tailor them to specific requirements. This
technology is only made possible by a detailed understanding of the relationship between structure
and properties, and this knowledge is of very recent origin, roughly the last one hundred years.

Materials Technology is of necessity a multi-discipline, drawing on chemistry, metallurgy and physics

in order to bring together the various strands of knowledge essential to fully understand the true
nature of a material.

The integration of chemistry and materials science in this unit, together with hands-on laboratory
work, is an attempt to present students with a truer understanding of material properties, and thus
prepare them to make informed judgements regarding material selection in the engineering
workplace.

Denis N. Lisson
May 2008

ii
Introduction and Course Structure

This course is designed to introduce students of engineering to concepts relating to the nature,
properties and applications of materials widely used in engineering practice.

The study of Materials Technology requires a multi-disciplinary approach, since a good

background in chemistry, physics, mechanics and mathematics are necessary for successful
mastery of this subject. Although many of the topics are quantitative, and involve problem
solving, a significant number of topics deal also with concepts; these require good language and
communication skills.

The following chapters in this text divide naturally into linked groups as follows:

• Chapters 1 and 2 deal with the structure of crystalline and amorphous materials, and
their mechanical properties.
• Chapters 3 and 4 relate to polymers and composites, including processing and
properties.
• Chapters 5 and 6 discuss the topics under-pinning the modification of the properties of
metals by alloying and heat treatment.
• Chapters 7, 8 and 9 relate to the degradation of materials by environmental factors,
including corrosion.

iii
iv
Table of Contents
The Structure of Metals .................................................................................. 1
1.1 Introduction ........................................................................................................................................................... 2
1.2 The Connection between Structure and Properties .............................................................................. 2
1.2.1 Short and long range order......................................................................................................................... 2
1.3 Atomic Packing Structure – Close Packing of Spheres ......................................................................... 4
1.4 Unit Cells .................................................................................................................................................................. 5
1.4.1 Face Centred Cubic Cells .............................................................................................................................. 7
1.4.2 Body Centred Cubic Cells (BCC Cells)..................................................................................................... 9
1.4.3 Hexagonal Close Packed Cells (HCP Cells) ........................................................................................ 11
1.4.4 Summary of Basic Unit Cell Parameters ............................................................................................. 12
1.5 Volume Density .................................................................................................................................................. 12
1.6 Miller Indices ...................................................................................................................................................... 14
1.6.1 Crystallographic Directions ..................................................................................................................... 14
1.6.2 Crystallographic planes............................................................................................................................. 15
1.7 Slip Planes ............................................................................................................................................................ 17
1.8 Linear and Planar Densities.......................................................................................................................... 18
1.8.1 Linear Density ............................................................................................................................................... 18
1.8.2 Planar Density ............................................................................................................................................... 19
1.9 Crystalline and Non-Crystalline Materials.............................................................................................. 20
1.9.1 Polycrystalline Materials .......................................................................................................................... 20
1.9.2 Anisotropy ...................................................................................................................................................... 21
1.9.3 Amorphous Solids (without structure) .............................................................................................. 21
1.9.4 Polymorphism ............................................................................................................................................... 22
1.10 The Cooling and Solidification of Molten Metal.................................................................................... 22
1.11 Defects in Metals ............................................................................................................................................... 23
1.11.1 Introduction.............................................................................................................................................. 23
1.11.2 Point Defects............................................................................................................................................. 23
1.11.3 Linear Defects – Dislocations ............................................................................................................ 25
1.11.4 Interfacial Defects .................................................................................................................................. 27
1.11.5 Bulk or Volume Defects........................................................................................................................ 29
1.12 Structure – Property – Processing Relationship .................................................................................. 29
1.12.1 Structure .................................................................................................................................................... 30
1.12.2 Properties .................................................................................................................................................. 31
1.12.3 Processing.................................................................................................................................................. 31
1.13 Environmental effects on material behaviour ...................................................................................... 31
1.13.1 Temperature............................................................................................................................................. 31
1.13.2 Corrosion ................................................................................................................................................... 32
1.14 The Structure-Strength Relationship........................................................................................................ 33
1.14.1 Atomic Bonding and Modulus of Elasticity .................................................................................. 33
1.14.2 Ideal Strength ........................................................................................................................................... 35
1.14.3 Imperfections in Crystals .................................................................................................................... 36
1.14.4 Strengthening Mechanisms for Metals .......................................................................................... 39
1.14.5 Plastic Deformation of Polycrystalline materials ...................................................................... 40
1.15 Summary .............................................................................................................................................................. 45
1.16 Question and Answers – The Structure of Metals ............................................................................... 47

Mechanical Properties................................................................................. 52
2.1 Introduction ........................................................................................................................................................ 53
2.2 The Tension Test ............................................................................................................................................... 54
2.2.1 Proportional Test Pieces........................................................................................................................... 56
2.2.2 The Tensile Test – Key Points ................................................................................................................. 57
2.2.3 Definition of Terms ..................................................................................................................................... 57

v
2.3 The Compression Test .................................................................................................................................... 58
2.4 Shear and Torsional Tests ............................................................................................................................. 58
2.5 Elastic Deformation.......................................................................................................................................... 58
2.5.1 Elastic Properties of Materials – Tensile Forces Poisson’s Ratio and Elastic Modulus .. 60
2.5.2 Shear and Torsional forces ...................................................................................................................... 61
2.6 Plastic Deformation.......................................................................................................................................... 65
2.6.1 Plastic Deformation by Slip ..................................................................................................................... 65
2.6.2 Plastic Deformation by Twinning ......................................................................................................... 68
2.6.3 Plastic Deformation of Polycrystalline Metals ................................................................................. 69
2.6.4 Strengthening Mechanisms for Metals ............................................................................................... 71
2.7 Tensile Strength................................................................................................................................................. 74
2.8 Ductility................................................................................................................................................................. 75
2.9 Resilience ............................................................................................................................................................. 76
2.10 Toughness ............................................................................................................................................................ 78
2.11 True Stress and Strain..................................................................................................................................... 78
2.12 Elastic Recovery after Plastic Deformation ............................................................................................ 80
2.13 Impact and Fracture ........................................................................................................................................ 80
2.13.1 Impact Fracture Testing ...................................................................................................................... 83
2.13.2 Ductile to Brittle Transition ............................................................................................................... 86
2.13.3 Assessment of Ductile/Brittle Fracture ........................................................................................ 88
2.13.4 Fracture Mechanics ............................................................................................................................... 89
2.14 Hardness Testing .............................................................................................................................................. 91
2.14.1 Rockwell Hardness ................................................................................................................................ 92
2.14.2 Brinell Hardness (HB) .......................................................................................................................... 93
2.14.3 A Summary of Hardness Measuring Techniques....................................................................... 93
2.14.4 Hardness Inter-Conversion ................................................................................................................ 94
2.14.5 Correlation between Hardness and Tensile Strength ............................................................. 94
2.15 Flexural Strength and the Three-point Bend Test............................................................................... 95
2.15.1 Flexural Stress ......................................................................................................................................... 95
2.15.2 Flexural Strength .................................................................................................................................... 96
2.15.3 Flexural Strain ......................................................................................................................................... 96
2.15.4 Flexural Modulus .................................................................................................................................... 96
2.16 Fatigue and the Fatigue Test ........................................................................................................................ 97
2.16.1 Mechanism of Crack Formation........................................................................................................ 99
2.16.2 Factors affecting Fatigue Life .......................................................................................................... 101
2.17 The Collapse of the Twin Towers ............................................................................................................. 101
2.18 Questions and Answers – Mechanical Properties ............................................................................. 103

Polymers ......................................................................................................... 110

3.1 Introduction ...................................................................................................................................................... 111
3.2 Bonding in Polymers ..................................................................................................................................... 111
3.2.1 The carbon-carbon covalent bond ...................................................................................................... 111
3.2.2 Intermolecular Bonding .......................................................................................................................... 114
3.3 Polymerization and Polymers.................................................................................................................... 117
3.3.1 Introduction ................................................................................................................................................. 117
3.3.2 Classification................................................................................................................................................ 117
3.3.3 Polymer Structure ..................................................................................................................................... 117
3.3.4 Polymer Behaviour ................................................................................................................................... 118
3.3.5 Structure Representation ....................................................................................................................... 118
3.3.6 Polymerization of Ethene to Polyethylene ...................................................................................... 118
3.3.7 Other Important Addition Polymers.................................................................................................. 119
3.3.8 Chain Formation and Functionality ................................................................................................... 120
3.3.9 Chain Formation by Condensation Polymerization .................................................................... 120
3.3.10 Chain Shape and Stereoisomerism................................................................................................ 121

vi
 3.3.11 Degree of polymerization.................................................................................................................. 122
3.3.12 Polymer Classification Scheme ....................................................................................................... 123
3.4 Effect of Heat on Thermoplastics ............................................................................................................. 123
3.4.1 Crystalline Materials ................................................................................................................................ 123
3.4.2 Solidification of noncrystalline thermoplastics ............................................................................ 124
3.4.3 Solidification of a partly crystalline thermoplastic ..................................................................... 125
3.5 The Structure of Thermoplastics .............................................................................................................. 125
3.5.1 The Structure of partly crystalline thermoplastics...................................................................... 125
3.5.2 Stereoisomerism in thermoplastics ................................................................................................... 128
3.6 Commercially important thermoplastics .............................................................................................. 129
3.6.1 Introduction ................................................................................................................................................. 129
3.6.2 Vinyl and vinylidene polymers ............................................................................................................ 129
3.6.3 Polyethylene ................................................................................................................................................ 131
3.6.4 Polyvinylchloride, PVC ............................................................................................................................ 132
3.6.5 Polypropylene ............................................................................................................................................. 132
3.6.6 Polystyrene................................................................................................................................................... 132
3.6.7 Polyacrylonitrile......................................................................................................................................... 132
3.6.8 Polytetrafluoroethylene .......................................................................................................................... 133
3.6.9 Nylon ............................................................................................................................................................... 133
3.7 Deformation Mechanisms for Thermoplastics ................................................................................... 133
3.8 Strengthening mechanisms for thermoplastics ................................................................................. 134
3.8.1 Changing the molecular weight ........................................................................................................... 134
3.8.2 Changing the Proportion of Crystallinity ......................................................................................... 135
3.8.3 Adding Bulky Pendant Groups ............................................................................................................. 135
3.8.4 Adding Polar Pendant Groups .............................................................................................................. 136
3.8.5 Introducing O and N Atoms ................................................................................................................... 137
3.8.6 Adding Phenylene Rings and other Atoms ...................................................................................... 137
3.9 Methods of Forming Polymers .................................................................................................................. 137
3.10 High Strength Fibres ...................................................................................................................................... 139
3.10.1 Carbon Fibre ........................................................................................................................................... 139
3.10.2 Carbon Nanotubes................................................................................................................................ 140
3.10.3 Kevlar ........................................................................................................................................................ 142
3.11 Thermosetting Polymers ............................................................................................................................. 144
3.11.1 Urea Formaldehyde ............................................................................................................................. 144
3.11.2 Epoxy Resin............................................................................................................................................. 145
3.11.3 Properties of Thermosets ................................................................................................................. 147
3.11.4 Additives to Polymers......................................................................................................................... 148
3.12 Polymers Terms and Definitions .............................................................................................................. 149
3.13 Comparative Properties of Metals and Polymers .............................................................................. 149

Composites..................................................................................................... 152
4.1 Introduction ...................................................................................................................................................... 153
4.2 Dispersion Strengthened Composites .................................................................................................... 153
4.3 Fibre Reinforced Composites ..................................................................................................................... 153
4.4 The Rule of Mixture: Predicting the Properties of Composites ................................................... 155
4.4.1 Density ........................................................................................................................................................... 155
4.4.2 Isostrain Conditions for a Lamellar Composite............................................................................. 155
4.4.3 Isostress Conditions for a Lamellar Composite............................................................................. 157
4.4.4 Specific Strength- Strength to Weight Ratio ................................................................................... 159
4.5 Fibre Reinforcing ............................................................................................................................................ 160
4.5.1 Aspect Ratio ................................................................................................................................................. 160
4.5.2 Volume Fraction of Fibres ...................................................................................................................... 161
4.5.3 Orientation of the Fibres......................................................................................................................... 161
4.6 The Matrix .......................................................................................................................................................... 164

vii
4.7 Mechanical Properties of Fibre Reinforced Composites................................................................. 165
4.8 Sandwich Structures ...................................................................................................................................... 168
4.8.1 Introduction ................................................................................................................................................. 168
4.8.2 Core Materials and their Properties .................................................................................................. 169
4.9 Manufacture of Core Panels ........................................................................................................................ 174
4.9.1 Hand Lay up ................................................................................................................................................. 174
4.9.2 Vacuum Bagging ......................................................................................................................................... 175
4.9.3 Prepregs and Their Use ........................................................................................................................... 176
4.10 Use of Sandwich Laminates in Yacht Construction ........................................................................... 182
4.10.1 Questions and Answers – Polymers.............................................................................................. 182

Phase Diagrams............................................................................................ 184

5.1 Introduction ...................................................................................................................................................... 185
5.2 One Component Phase Diagrams ............................................................................................................. 185
5.3 Pure Metals and Alloys ................................................................................................................................. 188
5.3.1 Components in a Solid Alloy.................................................................................................................. 188
5.3.2 Solid Solutions and Compounds in Alloys ....................................................................................... 189
5.4 Thermal Equilibrium Phase Diagrams ................................................................................................... 190
5.4.1 The Construction of a Phase Diagram ............................................................................................... 190
5.4.2 The Construction of a Copper-Nickel Phase Diagram ................................................................ 191
5.4.3 A binary single phase system (Cu-Ni) ............................................................................................... 193
5.5 Mechanical Properties of Isomorphous Alloys ................................................................................... 197
5.6 The Binary Euectic System (Pb-Sn) ......................................................................................................... 198
5.6.1 Key Points for the Lead-Tin System ................................................................................................... 199
5.6.2 Analysis of Phases, Microconstituents for Pb-Sn System .......................................................... 199
5.6.3 40% Sn Alloy 4 ............................................................................................................................................ 204
5.7 The Allotropy of Iron ..................................................................................................................................... 207
5.8 The Iron-Carbon Phase Diagram .............................................................................................................. 208
5.8.1 Introduction ................................................................................................................................................. 208
5.8.2 Microconstituents and Phases in Hypoeutectoid Steels ............................................................ 211
5.8.3 Microstructures and Phases in Hypereutectoid Steels .............................................................. 214
5.8.4 Effects of Non-Equilibrium Cooling.................................................................................................... 217
5.8.5 Effects of Alloying Elements .................................................................................................................. 217
5.9 Plain Carbon Steels ......................................................................................................................................... 219
5.9.1 Some Applications of Plain Carbon Steels ....................................................................................... 219
5.9.2 A Simple Classification of Plain Carbon Steels ............................................................................... 219
5.10 Questions and Answers – Phase Diagrams........................................................................................... 220

Heat Treatment ............................................................................................ 224

6.1 Introduction to Diffusion ............................................................................................................................. 225
6.1.1 Thermodynamics of Diffusion .............................................................................................................. 225
6.1.2 The Mechanisms of Diffusion................................................................................................................ 226
6.1.3 Mathematical Analysis of Diffusion.................................................................................................... 227
6.1.4 Diffusion Coefficient D, and its Temperature Dependence ...................................................... 228
6.2 Recrystallization and Grain Growth ........................................................................................................ 229
6.3 Phase Transformations ................................................................................................................................ 234
6.4 Microstructural Changes.............................................................................................................................. 235
6.4.1 Pearlite (Eutectoid)................................................................................................................................... 235
6.4.2 Bainite ............................................................................................................................................................ 236
6.4.3 Spheroidite ................................................................................................................................................... 237
6.4.4 Martensite ..................................................................................................................................................... 238
6.5 Temperature-Time-Transformation (TTT) Diagrams) ................................................................... 239
6.6 Continuous-Cooling-Transformation (CCT Diagrams).................................................................... 242
6.7 Mechanical Properties of Iron-Carbon Alloys Containing Transformed Phases ................. 244

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 6.7.1 Pearlite ........................................................................................................................................................... 244
6.7.2 Spheroidite ................................................................................................................................................... 245
6.7.3 Martensite ..................................................................................................................................................... 245
6.8 Tempered Martensite.................................................................................................................................... 245
6.8.1 Temper Embrittlement ........................................................................................................................... 249
6.9 Review of Phase Transformations and Mechanical Properties ................................................... 250
6.10 Reasons for Heat Treatment....................................................................................................................... 251
6.11 Heat Treating Process ................................................................................................................................... 251
6.11.1 Hardening ................................................................................................................................................ 251
6.11.2 Quenching ................................................................................................................................................ 252
6.11.3 Tempering ............................................................................................................................................... 253
6.11.4 Processing Heat Treatments for Steel.......................................................................................... 254
6.11.5 Summary of Heat treatments and Properties ........................................................................... 258
6.11.6 Heat treatment of welds .................................................................................................................... 260
6.12 Martensitic Transformation and Hardenability ................................................................................. 263
6.13 Jominy End-Quench Hardenability Test ................................................................................................ 264
6.14 Correlation of Hardenability and Cooling Curve Information ...................................................... 265
6.15 Surface Hardening of Steel .......................................................................................................................... 267
6.15.1 Selective Heating of the Surface ..................................................................................................... 267
6.15.2 Changing the Surface Chemistry .................................................................................................... 268
6.16 Powder Metallurgy ......................................................................................................................................... 269
6.17 Questions and Answers – Heat Treatment ........................................................................................... 272

Electrochemistry ......................................................................................... 280

7.1 Introduction ...................................................................................................................................................... 281
7.2 Oxidation and Reduction ............................................................................................................................. 281
7.3 Oxidation Numbers ........................................................................................................................................ 281
7.3.1 Rules................................................................................................................................................................ 281
7.4 Oxidation of Metals by Acid or Salt .......................................................................................................... 282
7.5 The Activity Series .......................................................................................................................................... 282
7.6 Voltaic or Galvanic Cells ............................................................................................................................... 283
7.7 Cell EMF under Standard Conditions...................................................................................................... 284
7.8 Standard Reduction Half Cell Potentials ............................................................................................... 285
7.8.1 Rules................................................................................................................................................................ 287
7.8.2 Example Problem....................................................................................................................................... 288
7.9 Strengths of Oxidizing and Reducing Agents....................................................................................... 288
7.10 Free Energy (G), and Redox Reactions ................................................................................................... 289
7.10.1 Standard Free Energy ∆G° ................................................................................................................ 290
7.11 EMF and Change in Free Energy ∆G ........................................................................................................ 290
7.12 Cell EMF under Non-standard Conditions ............................................................................................ 291
7.13 Concentration Cells ........................................................................................................................................ 292
7.13.1 Example Problem ................................................................................................................................. 294
7.14 Batteries.............................................................................................................................................................. 296
7.14.1 The Lead-Acid Battery ........................................................................................................................ 296
7.14.2 The Lithium-ion Battery .................................................................................................................... 297
7.14.3 Fuel Cells .................................................................................................................................................. 298
7.15 The Electrolytic Cell ....................................................................................................................................... 301
7.16 Quantitative Aspects of Electrolysis........................................................................................................ 302
7.16.1 Faraday’s Laws ...................................................................................................................................... 303
7.16.2 Electrical Work ...................................................................................................................................... 305
7.17 Aluminium Production ................................................................................................................................. 306
7.17.1 The Ore ..................................................................................................................................................... 307
7.17.2 The Hydrometallurgy of Refining .................................................................................................. 307
7.17.3 Calcining the Alumina ......................................................................................................................... 307

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 7.17.4 Electrolytic Reduction ........................................................................................................................ 307
7.17.5 Energy Requirements ......................................................................................................................... 308
7.17.6 Recycling .................................................................................................................................................. 309
7.18 Questions and Answers – Electrochemistry and Cells..................................................................... 309

Corrosion ........................................................................................................ 313

8.1 Introduction ...................................................................................................................................................... 314
8.2 The Galvantic Series....................................................................................................................................... 314
8.3 Rusting of Steel ................................................................................................................................................ 314
8.4 Passivity .............................................................................................................................................................. 317
8.5 Factors Increasing the Rate of Corrosion.............................................................................................. 317
8.6 Types of Corrosion ......................................................................................................................................... 317
8.6.1 Uniform Corrosion .................................................................................................................................... 317
8.6.2 Galvanic or Bimetallic Corrosion......................................................................................................... 318
8.6.3 Differential Aeration, and Crevice Corrosion ................................................................................. 322
8.6.4 Pitting Corrosion ........................................................................................................................................ 325
8.6.5 Intergranular Corrosion.......................................................................................................................... 325
8.6.6 Selective Leaching ..................................................................................................................................... 327
8.6.7 Impingement and Erosion Corrosion ................................................................................................ 328
8.6.8 Cavitation Corrosion ................................................................................................................................ 330
8.6.9 Stress Corrosion ......................................................................................................................................... 333
8.6.10 Stray Current Corrosion .................................................................................................................... 334
8.6.11 Bacterial Corrosion .............................................................................................................................. 336
8.7 Hydrogen Embrittlement............................................................................................................................. 337
8.8 Corrosive Environments .............................................................................................................................. 338
8.9 Types of Surface Oxides on Metals .......................................................................................................... 338
8.10 Anodic Corrosion Sites.................................................................................................................................. 339
8.11 Methods of Preventing Corrosion ............................................................................................................ 340
8.11.1 Choice of Material................................................................................................................................. 340
8.11.2 Change the Nature of the Environment....................................................................................... 341
8.11.3 Design ........................................................................................................................................................ 342
8.11.4 Inhibition and Environmental Control ........................................................................................ 344
8.11.5 Protective Coatings .............................................................................................................................. 344
8.11.6 Cathodic Protection ............................................................................................................................. 344
8.11.7 Anodic Protection................................................................................................................................. 352
8.11.8 Electropolishing Stainless Steel...................................................................................................... 353
8.12 Corrosion Monitoring.................................................................................................................................... 356
8.12.1 Corrosion Rates ..................................................................................................................................... 356
8.12.2 Corrosion Potential.............................................................................................................................. 357
8.12.3 Weight loss and Corrosion Penetration Rate, CPR ................................................................. 359
8.12.4 Thickness Measurement.................................................................................................................... 360
8.12.5 Other monitoring Methods ............................................................................................................... 360
8.13 Corrosion Case Histories.............................................................................................................................. 360
8.13.1 Introduction............................................................................................................................................ 360
8.14 Question and Answers – Corrosion ......................................................................................................... 361

Concrete .......................................................................................................... 364

9.1 Introduction ...................................................................................................................................................... 365
9.2 Cement................................................................................................................................................................. 365
9.3 Concrete .............................................................................................................................................................. 367
9.3.1 The Strength of Concrete ........................................................................................................................ 367
9.3.2 Reinforced Concrete ................................................................................................................................. 368
9.3.3 Compression Testing of Concrete ....................................................................................................... 370
9.4 Corrosion of Reinforced Concrete............................................................................................................ 371

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 9.4.1 Introduction ................................................................................................................................................. 371
9.4.2 Concrete as an Environment for Steel............................................................................................... 371
9.4.3 Loss of Alkalinity by Carbonation ....................................................................................................... 374
9.4.4 Attack by Chloride Ions ........................................................................................................................... 375
9.4.5 Protecting the Passive Film on Steel Reinforcing ......................................................................... 375
9.5 The Corrosion of Non-Ferrous Metals in Concrete ........................................................................... 378
9.5.1 Introduction ................................................................................................................................................. 378
9.5.2 Aluminium .................................................................................................................................................... 378
9.5.3 Lead ................................................................................................................................................................. 379
9.5.4 Zinc .................................................................................................................................................................. 379
9.6 Corrosion of Concrete in Aggressive Environments ........................................................................ 379
9.6.1 Introduction ................................................................................................................................................. 379
9.6.2 Acidic and Softwaters and Aggressive Soils ................................................................................... 379
9.6.3 Sulphate Attack on Concrete ................................................................................................................. 379
9.6.4 Sewage Attack ............................................................................................................................................. 380
9.6.5 Seawater Attack on Concrete ................................................................................................................ 380
9.7 Ceramics ............................................................................................................................................................. 381
9.7.1 Atomic structures ...................................................................................................................................... 381
9.7.2 Silicate ceramics ......................................................................................................................................... 382
9.7.3 The ceramic bond ...................................................................................................................................... 382
9.7.4 Simple Silicates ........................................................................................................................................... 383
9.7.5 Layered silicates......................................................................................................................................... 383
9.7.6 Properties of Ceramics ............................................................................................................................ 385

Appendices:

Appendix A Decimal Fractions and Multiples1……………………………………..…………………….383

Appendix B Greek Alphabet1…………………………………………………………………………………….384
Appendix C Fundamental Constants2………………………………………………………………………..385
Appendix D List of Elements2……………………………………………………………………………………386
Appendix E Periodic Table2………………………………………………………………………….…………..387
Appendix F Common Ions2……………………………………………………………………….………………388
Appendix G Standard Reduction Potentials at 25°C2…………………………………...……………..389
Appendix H Aqueous Equilibrium Constants2…………………………………………………………....392
Appendix I Thermodynamic Quantities for Selected Substances at 298.15 K (250C) . .393

xi
Introduction To Materials Technology

Introduction To Materials Technology

Materials Technology Page xii

Introduction To Materials Technology

Before embarking on a study of this unit, it will be beneficial to look briefly at the definitions relating
to the discipline of materials engineering and the various components that make it up.

1.1 Material: This is the substance or substances of which a thing is made or composed. The term
engineering materials is sometimes used to refer specifically to materials used to produce engineering
components. However, there is no clear line of demarcation between the two terms, and they are used
interchangeably. Figure 1-1 illustrates the development of materials over time from prehistoric times
up to the present day.

Figure 1-11: The development of materials over time

It can be seen that the earliest materials, gold, skin, stone and straw were all naturally occurring. Later
on, techniques had to be devised to extract and shape materials into useful objects. Stone, bronze and
iron were of such importance that the era of their dominance is named after them. Note the non-linear
time scale used, and the fact that almost all of the materials in use today have been developed in the
last 100 years or so. Figure 1-2 illustrates the main classes of contemporary engineering materials
currently in use.

Figure 1-21: Available engineering materials

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Introduction To Materials Technology

The five families of materials illustrated above may be combined in various geometries to create
hybrids or composites. Composites are the newest materials in an ever expanding inventory now
available to engineers.

1.2 Materials science: This is a scientific discipline that is primarily concerned with the search for
basic knowledge about the structure and properties of materials. The factors that make up the
structure and hence its properties are its constituent chemical elements, and the way it has been
processed. These characteristics taken together and related through the laws of thermodynamics and
kinetics, govern the material’s microstructure and hence its properties. Materials science relies upon
other basic disciplines, namely chemistry, physics, mathematics and mechanics as illustrated in
Figure 1-3.The discovery and design of new materials is the province of the materials scientist, often
working in collaboration with engineers.

Figure 1-32: Disciplines underpinning materials science

1.3 Materials engineering: This is an engineering discipline that is primarily concerned with
applying knowledge of a material to a particular engineering application, needed or desired by
society.

1.4 Structure, processing and properties: This is the three-part relationship between the internal
structure of the material, the type and number of processes involved in its manufacture, and the final
property of the material. It is illustrated in Figure 1-4.

Figure 1-43 :The materials paradigm

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Introduction To Materials Technology

This schematic diagram in the form of a tetrahedron is known as the materials paradigm. If the
engineer changes any one of the variables in the relationship, changes will result in one or more of
the others. This practice allows a potent control to be exercised over the material’s properties and
applications.

1.5 Example: The interrelation between structure, processing and properties may be demonstrated
for cast iron in order to further illuminate this important paradigm.

(i) Structure: The structure referred to is the internal structure and is illustrated in Figure 1-5.

Figure 1-54: The various levels of internal structure for cast iron.

The four levels of internal structure for cast iron are as follows:

(a) The atomic structure.

(b) The crystal structure, representing the aggregates of atoms.

(c) The grain structure, representing the aggregates of crystals.

(d) The microstructure, representing the phases present, namely pearlite in a matrix of
ferrite.

The structures represented by (c) and (d) are the result of several variables during
manufacture, specifically the composition, the cooling rate of the molten casting, and heat
treatments performed after casting such as annealing.

(ii) Processing: The casting, (primary shaping), and heat treatments, (secondary processes),
referred to below, are part of a heirarchy of possible processes performed during production
of the material. They are illustrated in Figure 1-6.

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Introduction To Materials Technology

Figure 1-61: The classes of processes for engineering materials.

Properties: These may be expressed in tables, bar charts or bubble charts. The three modes of
presentation are illustrated below for cast iron.

Figure 1-7 represents a table listing the principal mechanical properties of the various grades
of cast iron.

Figure 1-75: A table of engineering properties for cast irons.

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Figure 1-8 illustrates a bar chart listing the modulus of elasticity values for all major
engineering materials.

Figure 1-81: A bar chart of modulus of elasticity.

Figure 1-8 reveals the difference in stiffness, measured as the modulus of elasticity E between
the families of materials. Although cast iron is not specifically labelled, it occupies the region
in the top left hand corner, together with the steels. Note the logarithmic scale for the modulus
E, measured in GPa. It will be observed that polymers have a wide spread of values, and these
are generally much lower than those for metals and alloys. Note also that E differs between
the largest and smallest value by a factor of more than 10 million! The bar chart clearly
differentiates between the specified property for families of materials in terms of their spatial
distribution. In this respect it is vastly superior to the representation by table as illustrated in
Figure 1-7.

Figure 1-9 illustrates a bubble chart, plotting two variables, namely the modulus of elasticity
against density.

Figure 1-91: A bubble chart of modulus and density.

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Introduction To Materials Technology

The bubble chart delineates the differences across families of materials even more clearly than
the bar chart. The bubble chart is particularly useful when an overview of properties is
required, and enables the correct choice of material type to be made in order to optimise the
required outcome.

1.6 The first cast iron structure: This was the bridge built in Shropshire UK in 1709 by Abraham
Darby using cast iron members bolted together. It is illustrated in Figure 1-10. The bridge was over-
designed, and ruined the builder financially. As materials technology advanced, steel became the
preferred material over cast iron for the manufacture of civil engineering structures. This was only
made possible after the process for manufacturing steel became available in the mid 1800’s.

Figure 1-106: The cast iron bridge in Shropshire UK.

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1.7 A graphic illustration of mechanical properties:

Figure 1-111: Mechanical properties relevant to performance.

Figure 1-11 illustrates the mechanical property directly linked to performance, namely :

(i) Modulus of elasticity E, a measure of stiffness, or the capacity of a material to sustain a load
without plastic deformation.

(ii) Yield strength σy, the stress required to produce a very small plastic strain, usually 0.002.

(iii)Fracture toughness K1c, the measure of a material’s resistance to fracture when a crack is
present.

References
1 Ashby, M., Shercliff, H., Cebon, D., Materials, Engineering, Processing and Design,
Elsevier, Butterworth-Heinemann, 2007.
2 Smith, W.F., Hashemi, J., Foundations of Materials Science and Engineering, 5th Ed.,
McGraw Hill, 2010.
3 www.ece.cmu.edu/news/calender/2014.
4 Askeland, D.R., The Science and Engineering of Materials, 2nd Ed., PWS-Kent, 1989.
5 Schlenker, B.R., Introduction to Materials Science, SI Ed., The Jacaranda Press, 1986.
6 Bronowski, J., The Ascent of Man, BBC, 1973.

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Chapter 1: The Structure of Metals

The Structure of Metals

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Chapter 1: The Structure of Metals

1.1 Introduction
The use of the term "material" generally means a substance or mixture of substances that are held
together by strong chemical bonds throughout the whole sample. Materials are held together by
different chemical bonds, for example, covalent network, ionic, and metallic. In addition to these
chemical bonds, are the molecular bonds. These bonds are known as London dispersion forces,
dipole-dipole forces, ion-dipole forces and hydrogen bonds. In all cases these molecular bonds are
weaker than the chemical bonds.

1.2 The Connection between Structure and Properties

The relationship between certain properties of metals such as lustre, high electrical and thermal
conductivity and high levels of ductility and malleability can be successfully accounted for by the
"electron-sea" model of metallic bonding.

However, this theory does not account, for example, for the variation in strength manifested in the
melting points of metals across a period in the periodic table. The electron sea model would
incorrectly predict a uniform increase in melting point as a function of the increase in the number of
electrons across a period. It can be seen therefore that a new more sophisticated bonding model is
needed to explain this phenomenon. This model is known as the molecular orbital bonding model,
which is not discussed here. Details may be found in reference 1.

1.2.1 Short and long range order

The term “order”refers to the degree of interaction between atoms, but more commonly molecules in
materials. The higher the order, the greater, and the more long term is the symmetry. The degree of
order of a material has profound implications for its properties.

1.2.1.1 No Order

Inert gases such as argon have no order. Their atoms randomly fill up the space in which the gas is
confined, and there is no mutual attraction between the atoms.

1.2.1.2 Short range Order

A material displays short range order if its molecules exerts some degree of attraction to its
immediate neighbours only.

Examples are water molecules as a result of hydrogen bonding, and SiO44- units in silica ceramic
glasses. Polymers also display short range order, and may be partly crystalline, (long range order),
and amorphous, (short term order) all together in the same bulk sample.

1.2.1.3 Long ranger Order

Metals almost always show long term order, manifest in their crystalline structure. Semiconductors,
ceramics, and polymers possess a combination of short and long term orders.

Figure 1-1 illustrates crystalline and amorphous zones in a thermoplastic polymer.

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Chapter 1: The Structure of Metals

Figure 1-1

The diagram below illustrates (a) no order, (b), (c), short term order, and (d) long term order.

Figure 1-2

1.2.1.4 Bonding Energy

When any combination of atoms come together, for example atoms of iron in steel, there will be an
optimal bond distance between atoms associated with a condition of minimum energy. This bond
length is characteristic of the type of atoms involved, and the temperature. The characteristic bond
length is a position of equilibrium, resulting when the attractive forces are balanced exactly by the
repulsive forces. When this point of equilibrium is reached and the net force is zero, the energy
released is a maximum, and the system is stable. Figure 1-3 illustrates how force and energy vary with
interatomic distance.

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Chapter 1: The Structure of Metals

Figure 1-34

The interatomic spacing oa’ occurs when force F = 0, and is also associated with the lowest potential
energy for the system. The shaded area in (a) is equivalent to the depth of the energy trough in (b).
The equilibrium spacing oa’ represents a very stable state, and it takes considerable force per unit
area to stretch or compress beyond this point. For steel, the modulus of elasticity is 2000 MPa, and
this quantity is a measure of bond strength. For metals and alloys the individual atoms will pack
closely together in cubic or hexagonal crystal lattices to minimize energy. These arrangements can be
reproduced as a good model by using hard spheres as detailed in section 1.3.

1.3 Atomic Packing Structure – Close Packing of Spheres

When considering the structure of metals, their 'packing' and properties may be studied by looking
at the way uniform spheres (atoms of a pure metal) may be arranged. The most efficient or closest
packing is illustrated in Figure 1-4.

Figure 1-41 Close packing of equal sized spheres. (a) Close packing of a single layer of equal-sized spheres. (b)
In the hexagonal close-packed structure the atoms in the third layer lie directly over those in the first layer.
The order of layers is ABAB. (c) In the cubic close packed structure the atoms in the third layer are not over
those in the first layer. Instead, they are offset a bit, and it’s the fourth layer that lies directly over the first.
Thus, the order of layers is ABCA.

This form of packing leads to structures known as close packed hexagonal and close packed cubic,
CPH and CPC respectively.

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Chapter 1: The Structure of Metals

1.4 Unit Cells

The repeating unit of a solid, the 'crystalline brick' is known as the unit cell. This unit cell is the
smallest entity that shows clearly the symmetry characteristic of the entire pattern or array. The
crystal lattice can be represented by a 3D array of points. Each point in the crystal lattice represents
an atom or an ion. Figure 1-5 shows a crystal lattice and its unit cell. In general unit cells are
parallepipeds, that is, six sided figures with parallel faces.

Figure 1-51 Part of a simple crystal lattice and its associated unit cell. A lattice is an array of points that define
the positions of particles in a crystalline solid. Each lattice point represents an identical environment in the
solid. The points here are shown connected by lines to help convey the three-dimensional character of the
lattice and to help us see the unit cell.

The lattices of all crystalline solids, in particular salts, and metals can be described by seven types if
unit cells. However metals and alloys exist in one of three basic forms, namely hexagonal close packed
(HCP), body centred cubic (BCC) and face centred cubic (FCC). The seven unit cells are illustrated in
Figure 1-6.

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Chapter 1: The Structure of Metals

Figure 1-62 Lattice parameter relationships and figures showing unit cell geometries for the seven crystal
systems.

The three common types of cubic cells are shown below in Figure 1-7.

Figure 1-71 Space-filling view of cubic unit cells. Only the portion of each atom that belongs to the unit cell is
shown.

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Chapter 1: The Structure of Metals

1.4.1 Face Centred Cubic Cells

Metals which have a FCC structure are copper, aluminium, silver, gold and lead. Note that these metals
are extremely malleable and ductile. The face centred cubic structure may be illustrated in several
ways, namely:

i. A hard sphere unit cell which shows only that portion of each atom that belongs to the unit
cell. Figure 1-8(a)
ii. A reduced sphere unit cell which shows clearly the geometry of the cell. Figure 1-8(b)
iii. An aggregate of many atoms shows the unit cell as part of the structure of a large number of
close packed spheres. Figure 1-8(c)

Figure 1-82 For the face-centred cubic crystal structure.

1.4.1.1 Relationship between the Cube Edge Length a, and the Atomic Radius R

Figure 1-92 Illustration of the face-centred unit cell.

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Chapter 1: The Structure of Metals

From Figure 1-9, using Pythagoras theorem 1:

( 4R )
a2 + a2 =
2

2a 2 = 16 R 2
a = 8R 2
a = 2 2R (1-1)

1.4.1.2 Coordination Number

Because the structure of a metal may be modelled on the various ways in which spheres may be close
packed, it follows that each atom in the structure will always be surrounded by the same number of
nearest neighbours or touching atoms, and that number will be dependent upon the nature of the
packing. For the FCC unit cell, the coordination number equals 12. This number may be obtained by
counting the atoms in Figure 1-8(a).

1.4.1.3 Atomic Packing Factor

This is the total volume of the spheres in the hard-sphere model divided by the volume of the unit cell.
VS
APF = (1-2)
VC
Where
VS is the volume of atoms in a unit cell.
VC is the total unit cell volume.

To find the volume of atoms in a unit cell:

 
 1
VS =  6 × + 8 ×  × π R
1  4 3
  2  8   3 
 face atoms corner atoms  Vsphere
4
= ( 3 + 1) × π R 3
3
16
VS = π R 3
3
To find the total unit cell volume, cube edge length:
VC = a 3

( )
3
= 2 2R
3
= 23 × 2 × R 3 = 8 × 2 2 × R 3
VC = 16 2 R 3

Hence to find the atomic packing factor for FCC:

1 Pythagoras Theorem states that for a right angle triangle a2 + b2 = h2.

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Chapter 1: The Structure of Metals

16
π R3
APF = 3
16 2 R 3
π
=
3 2
≈ 0.74

This value of 0.74 is the highest theoretical packing possible for close packed spheres of the same
diameter.

1.4.2 Body Centred Cubic Cells (BCC Cells)

1.4.2.1 Relationship between the Cube Edge Length a, and the Atomic Radius R

Metals which have BCC structure are chromium, iron, molybdenum and tungsten. The models for the
BCC crystal structure are illustrated in Figure 1-10.

Figure 1-102 The body-centred cubic crystal structure.

Figure 1-11(a), (b), (c), below represents the diagonal plane ABED as a reduced sphere BCC cell. The
diagonal, BD, equals 4R since all the atoms are touching.

Figure 1-11 Face view of body-centred cubic

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Chapter 1: The Structure of Metals

Figure 8-11 (c) Face view of body-centred cubic.

Consider the diagonal plane ABCD, considering the right angled triangle BAD, and by Pythagoras
Theorem.

( ) ( 4R )
2
a2 + =
2
2a
a 2 + 2a 2 =
16 R 2
3a 2 = 16 R 2
16 2
a2 = R
3
4R
a= (1-3)
3

1.4.2.2 Coordination Number

Coordination number for BCC is 8. Refer to Figure 1-10(a)

1.4.2.3 Atomic Packing Factor

To find the volume of atoms in a unit cell:

 

VS =  8 × + 1
1
×1  × π R 3
4
  8 centre atom  
3
 corner atoms  Vsphere
4
= (1 + 1) × π R 3
3
8
VS = π R 3
3
To find the total unit cell volume, cube edge length:

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Chapter 1: The Structure of Metals

VC = a 3
3
 4R  43 R 3
= =  3
 3 3
64 R 3
VC =
3 3
Hence to find the atomic packing factor for BCC using Equation (1-2):
8 3
πR 8π R 3 3 3
APF 3 =
= ×
64 R 3 3 64 R 3
3 3

π 3
=
8
≈ 0.68

Since the coordination number is 8, which is less than for the FCC it would be logical for the APF also
to be less than for the FCC system.

1.4.3 Hexagonal Close Packed Cells (HCP Cells)

Figure 1-122 Hexagonal close-packed structure.

Metals which have HCP structure are cadmium, cobalt, titanium and zinc. The models for the HCP
crystal structure are illustrated in Figure 1-12.

To find the atoms/cell:

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Chapter 1: The Structure of Metals

1 1
N= 12 × + 2× + 3
×1
 6  2 central atoms
top&bottom face atoms centre face atoms

= 2 +1+ 3
N =6

Coordination number = 12
Atomic packing factor = 0.74

1.4.4 Summary of Basic Unit Cell Parameters

Crystal Cube edge Coordination Atomic packing Equivalent number

system length, a number factor, APF of atoms/cell
FCC 2 2R 12 0.74 4
4R
BCC 8 0.68 2
3
HCP — 12 0.74 6
Table 1-12 Summary of basic unit cell parameters.

1.5 Volume Density

A Knowledge of the crystal structure permits a computation of the theoretical density of a metal as
follows.
nA
ρ= (1-4)
VC N A
Where
ρ = density in g/cm3
n = number of atoms/unit cell
A = atomic weight of the metal in g/mole
VC = volume of the unit cell in cm3
NA = Avogadro’s number = 6.023×1023 atoms/mol

The dimensional consistency of Equation (1-4) can be verified as follows:

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Chapter 1: The Structure of Metals

g
LHS=
cm 3

no.atoms g
×
cell mole
RHS=
cm 3 N
×
cell mole

no. atoms g
= ×
N cm 3

g no. atoms constant

= 3
= = constant
cm N constant

= LHS

Hence Equation (1-4) is dimensionally consistent.

Example 8.1 Calculate the density of copper which is a FCC crystal. The atomic radius of Cu is
0.128nm.

Solution
For a FCC crystal:
a = 2 2R
= 2 2 ( 0.128 ×10−7 )
=2.56 2 ×10−8cm
VCCu = a 3

( 2.56 )
3
= 2 ×10−8 cm3
Using Equation (1-4):
n × ACu
ρCu =
VCCu × N A
atoms g
4 × 63.5
= cell mol
( 2.56 ×10 ) × ( 6.023 ×1023 )
3 cm 3 atoms
−8
2
cell mol
= 8.89g/cm3

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Chapter 1: The Structure of Metals

1.6 Miller Indices

Miller indices are a set of integers that designate directions and planes in crystal systems. For cubic
crystals there are 3 integers, and for the hexagonal system there are 4 integers. Figure 1-13(a), and
(b) illustrates a unit cubic cell with respect to a set of coordinate axes, x, y, and z, showing axial lengths
(a, b, and c), and interaxial angles (α, β and γ). Distance is measured by the number of lattice
parameters that must be moved in each of the x, y, z coordinates to get from the origin to the point in
question. The equivalent Miller indices are represented by the general coordinates (hkl).

Figure 1-13 (a), (b)

Certain directions in the unit cell are of particular importance, because metals deform in directions
along which the atoms are in closest contact, that is in directions and planes with the highest packing
density. It is useful to be able to designate these directions, and Miller indices are the system used:

1.6.1 Crystallographic Directions

A crystallographic direction is defined as a line or vector between two points. The following steps are
required to assign a set of coordinates:

1. The vector is drawn through the origin of a set of coordinate axes as illustrated in Figure 1-14.
2. The length of the vector as projected onto the x, y and z axes is determined. These intercepts
are marked a, b and c.
3. These three numbers are multiplied by a common factor to reduce them to the smallest
integers u, v and w.
4. The crystallographic coordinates are written in square brackets without commas as [uvw] as
the direction vector.
The following example is given:

Determine the indices for the direction shown in the figure below.

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Chapter 1: The Structure of Metals

Figure 1-14

The vector passes through the origin, so no translation is necessary.

The projections of the vector onto the x, y and z axes are: a = ½, b = 1 and c = 0 respectively. Reducing
these numbers to the lowest common multiple is achieved by multiplying by 2 to give 1, 2 and 0.

Hence the coordinates are [120].

1.6.2 Crystallographic planes

Crystallographic planes are represented by Miller Indices, which are defined as: the reciprocals of the
fractional intercepts that the plane makes with the crystallographic x, y, and z axes of the unit cell.
Parallel planes have the same Miller Indices.

The following steps are required to assign a set of Miller Indices to a plane:

1. If the plane passes through the origin, a new origin must be established at the corner of
another unit cell.
2. The plane will either intersect or be parallel to the three axes. The length of the planar
intercept for each axis is determined in terms of the lattice parameters a, b, and c.
3. The reciprocals of these numbers are taken. Note that a parallel plane will intercept at infinity
and its reciprocal will therefore be zero.
4. Convert the set of numbers to their lowest common multiples, h, k, and l.
5. The Miller Indices are inserted inside parentheses without commas as (hkl).

1.6.2.1 Crystallographic Planes – Illustrative examples

1. Determine the Miller indices for the planes shown in the figure below.

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Chapter 1: The Structure of Metals

Figure 1-15

Since the plane passes through the selected origin 0, a new origin must be drawn at 0’ as
illustrated in (b).

The plane is parallel to the x axis, and its intercept is ∞a. The intercepts on the y and z axes
with respect to the new origin 0’ are –b and c/2 respectively. The following steps to convert
these integers to Miller indices are illustrated in the table below.

x y z
Intercepts ∞a -b c/2
Lattice parameter ∞ -1 1/2
Reciprocal 0 -1 2
Reductions h k l 0 -1 2
Table 1-2

Miller indices are (0ī2). Note that a negative number is shown with a bar over the index.

2. Determine the Miller indices of the crystallographic polar illustrated in Figure 1-16.

Figure 1-165

Create a new origin in accordance with the rules. This can be done by moving the plane parallel to the
z axis ¼ unit to the right along the y axis as shown in (b). The new intercepts of the transposed plane
5 12
are now (+1, - , ∞). Taking reciprocals of these intercepts gives, (1, - , 0). Converting to lowest
12 5
common multiples gives (5 12 ���� 0), the Miller indices for the plane.

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Chapter 1: The Structure of Metals

1.7 Slip Planes

A slip system is a combination of a crystallographic plane, and within that plane, a crystallographic
direction, along which slip by the movement of dislocations occurs. (See also section 2.7). These slip
planes are the planes of highest atomic packing, since they will most easily transmit applied forces.
The direction of the slip planes will depend upon the crystal structure of the metal. For the cubic
system the common slip planes are:

BCC (110), (112), (123)

FCC (111)
The following example will illustrate how to construct a (112) slip plane. The Miller indices (hkl) are
(112). The reciprocals of these indices will give the coordinates of the intercepts (xyz), namely (1 1
0.5). These intercepts are now marked on the x, y and z axes respectively, and joined to give the
required slip plane as illustrated in Figure 1-17.

Figure 1-17

An important relationship for the cubic system only is that the perpendicular distance between two
adjacent parallel slip planes is the same as the Miller indices of that plane. For example the [100]
direction is perpendicular to the (100) crystal plane.

In cubic crystal systems the interplanar spacing between two parallel planes is designated dhkl, where
h, k and l are the Miller indices of the planes. It can be shown by geometry that:
𝑎𝑎
dhkl = , where a = cube edge length, (lattice constant).
√ℎ 2 +𝑘𝑘 2 +𝑙𝑙 2

For example the interplanar spacing for the (112) slip planes illustrated in figure 8.16 for copper
where a = 0.362 nm is:
0.362 0.362
dhkl = 2 2 2 = 6 = 0.148 nm
√1 +1 +2 √

The figures below illustrates three of the more common slip planes for metals with a cubic crystal
structure, namely (100), (110) and (111).

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Chapter 1: The Structure of Metals

Figure 1-18

1.8 Linear and Planar Densities

In a crystalline substance linear and planar densities are important considerations relative to the
process of slip. Slip is the mechanism by which metals plastically deform. Slip occurs on the most
densely packed crystallographic planes, that is, planes with the highest atomic packing. The directions
of these planes will vary depending upon the crystal system of the metal. It is useful to be able to
designate planes in unit cells along which slip occurs.

1.8.1 Linear Density

Number of atoms centred on the direction vector

Linear Density =
Length of the direction vector

1
=
Units = nm -1
Length

Consider the (110) plane for a FCC crystal

Figure 1-192 Representation of a (110) crystallographic planes.

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Chapter 1: The Structure of Metals

Consider the 6 atoms in the (110) plane of the FCC unit cell as shown in Figure 1-19. These 6 atoms
are further illustrated in Figure 1-20.

4R

Figure 1-202 (a) reduced sphere FCC unit cell with (110) plane. (b) Atomic packing of an FCC (110) plane.
Corresponding positions from (a) are indicted.

1
In the (110) direction there is an equivalence of two atoms, that is, of an atom at ACDF corners
2
plus 1 atom in the centre of each of the sides ABC and DEF.
number of atoms
LD =
length of AC
2
LD110 =
4R
1
= nm -1
2R

1.8.2 Planar Density

Number of atoms centred on a plane

Planar Density =
Area of the plane
Referring again to Figure 1-20:
Number of atoms centred on a plane
PD =
Area of the plane
2
PD110 =
Area ACDF
2
=
4 Ra
But for a FCC crystal, a = 2 2 R

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Chapter 1: The Structure of Metals

2
PD110 =
4 Ra
2 1 2
= = =
(
4R 2 2R ) 4 2R 2
8R 2

0.1768 -2
= nm
R2

Similar calculations may be made for LD110 and PD110 for the BCC system using Figure 1-11(a) – (c). It
should be noted that linear density and planar density values represent equivalent directions and
planes respectively in crystalline materials.

1.9 Crystalline and Non-Crystalline Materials

In a single crystal there is a perfect and repeated arrangement of atoms throughout the entire
specimen. All unit cells interlock, and have the same orientation. For example, in gem stones, the
atomic structure is reflected in the macroscopic form of the macrocrystal.

1.9.1 Polycrystalline Materials

Most solids are polycrystalline, and are composed of a collection of small randomly orientated
crystals. During solidification, grains grow by the accretion of other atoms to the random surfaces
presented, as illustrated in Figure 1-21.

Figure 1-212 Schematic diagrams of the various stages in the solidification of a polycrystalline material; the
square grids depict unit cells. (a) Small crystallite nuclei. (b) Growth of the crystallites; the obstruction of
some grains that are adjacent to one another is also shown. (c) Upon completion of solidification, grains
having irregular shapes have formed. (d) The grain structure as it would appear under the microscope; dark
lines are the grain boundaries.

The planes between grains of random orientation are grain boundaries, that is, regions of lowest
atomic density. Impurities often concentrate at grain boundaries. Boundaries represent regions of
highest surface energy, and are more prone to chemical attack than the body of the crystal, for
example, etching in metallography.

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1.9.2 Anisotropy

Anisotropic behaviour results in a change in value of a property like Young’s modulus, electrical
conductivity or refractive index in different directions in a material. This is due to variation in atomic
spacing in the material. The following table shows the variation in the E, Young’s modulus with
direction. Note that the units are in GPa.
Plane
Material Crystal structure (100) (110) (111)
Al FCC 63.7 72.6 76.1
Cu FCC 66.7 130.3 191.1
α Fe BCC 125.0 210.5 272.7
W BCC 384.6 384.6 384.6
Table 1-32 Variation in Young’s modulus, E, in GPa.

If the measured property is independent of direction, the substance is isotropic.

1.9.3 Amorphous Solids (without structure)

Amorphous materials may be characterized as follows:

i. They lack systematic arrangements of atoms over relatively large atomic distances.
ii. They form from the liquid state when there is insufficient time for an orderly transformation
into the solid state, for example, the rapid cooling of viscous high molecular weight polymers
or glasses.
iii. Amorphous structures are more complex and random than crystalline structures.
iv. Most metals, alloys, and some ceramics are usually crystalline.
v. Polymers may be completely non-crystalline or semi-crystalline, depending upon their
chemistry.
The structures of crystalline and amorphous silica are illustrated in Figure 1-22.

Figure 1-221 Schematic comparisons of crystalline SiO2 (quartz) and amorphous SiO2 (quartz glass). The
structures are actually three-dimensional and not planar as drawn. The two-dimensional unit shown as the
basic building block of the structure (silicon and three oxygen’s) actually has four oxygen’s, the fours coming
out of the plane of the paper and capable of bonding to other silicon atoms. The actual three-dimensional
building block is shown.

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1.9.4 Polymorphism

Some elements have more than one crystal structure. This is known as polymorphism or allotropy.
The crystal structure depends upon temperature and pressure. Common examples are carbon,
(graphite and diamond), and iron, BCC at room temperature, FCC at 912°C.

1.10 The Cooling and Solidification of Molten Metal

The solidification of molten metal is a process of crystallisation, and results in the formation of a
polycrystalline mass having as its principal unit the metallic grain. Metallic grains are true crystals in
that they possess normal crystal lattices; however, they are bounded by irregular three-dimensional
surfaces known as grain boundaries rather than by the plane faces so characteristic of minerals. The
crystallisation of a pure metal has four stages.

i. As the metal reaches its freezing point, the latent heat of fusion begins to be given out, and
small groups of atoms form stable configurations known as nuclei, these being unit cells of the
appropriate crystal lattice or other three-dimensional atom aggregates which are sufficiently
stable. Copper, for instance, forms face-centred cubic unit cells as nucleation begins.
ii. The growth now begins from these nuclei as more and more atoms attach themselves to the
ever-growing lattice. Growth is directional and crystal skeletons known as dendrites begin to
form.
iii. The dendrites continue to grow until their arms almost meet, this being the initial stage in the
formation of grain boundaries.
iv. The remaining liquid metal solidifies between the main arms of the dendrites by a process
known as secondary growth, and the formation of the grains and grain boundaries is now
complete.

Figure 1-233 (A), (B) and (C) show three stages in the dendritic solidification of a pure metal. Note that no
traces of the original dendrites remain when solidification is complete. (D) is a three-dimensional
representation of a dendrite growing from a melt.

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1.11 Defects in Metals

1.11.1 Introduction

It has been assumed in the earlier sections of this chapter that perfect order exists in metals. The
concept of the close packing of spheres as a true representation of perfect order with respect to the
packing of atoms is a useful model which accounts for the various crystal structures that exists in
metals and alloys. However, within this model allowance must be made for 'packing imperfections'
that result from a variety of factors such as impurity atoms present, and non-equilibrium effects due
to mechanical and thermal treatments during the casting and mechanical working of the metal.

*Thelatent heat of fusion is the amount of thermal energy released as the metal undergoes the phase
change from liquid to solid.

1.11.2 Point Defects

1.11.2.1 Vacancies

Vacancies are the most common point defect and result when an atom is missing from its lattice point.
See Figure 1-24.

1.11.2.2 Self Interstitials

Self interstitials result from an atom occupying an interstitial space. Such abnormalities introduce
large distortion and hence stress surrounding the defect. Such defects are much less probable than
vacancies. The point defects are illustrated in Figure 1-24.

Figure 1-242 Two-dimensional representations of a vacancy and a self-interstitial.

1.11.2.3 Impurities in solids

100% pure metals are technically impossible to manufacture. Most alloys of commercial importance
consist of the solvent metal to which is added one or more solute atoms. It is a general rule that the
mechanical properties of pure metals are greatly improved by alloying. Some examples can be seen
in Table 1-4.

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Alloyed metal Elements used

Steel Iron + carbon, manganese etc
Brass Copper + zinc and lead
Bronze Copper + tin
Duralumin Aluminium + copper
Diecast alloy Zinc + copper and aluminium

Table 1-42 Elements used in creation on alloys.

A solid solution forms when solute atoms of a metal or non-metal are added to a host atom without a
change of crystal structure and without any new phase(s) being formed. Solid solutions may be
substitutional or interstitial, and are illustrated in Figure 1-25.

Figure 1-252 Two-dimensional schematic representation of substitutional and interstitial impurity atoms.

For substitutional solid solutions to form, several criteria must be met. They are:

i. Total solid solution is only possible when the difference in atomic radii of the two atoms is
less than 15%.
ii. Crystal structures of both metals must be the same.
iii. The electronegativities of both metals must be the same or very similar.
iv. A host metal will more easily dissolve an alloying metal if the latter has a higher valency to the
host metal, all other things being equal.

A classic example of a substitutional solid solution is the alloy of copper-nickel which shows complete
solid solubility across the complete range of composition.

Note the individual similarities between copper and nickel:

i. Atomic radii: Cu = 0.128nm and Ni = 0.125nm.
ii. Crystal structure: both FCC.
iii. Electronegativity: Cu = 1.9 and Ni = 1.8 (Pauling scale)
iv. Valency: Cu = +1 and Ni = +2.
Interstitial solid solutions occur when the alloying atom is small enough to fit within the interstices
of the host metal. Most interstitial atoms are larger than the interstices and hence this causes local
strain and distortion of the host lattice. Consequently interstitial solid solutions are usually less than
10% of the alloying element.

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A common example is steel in which iron holds carbon in interstitial solid solution. The atomic radius
of iron and carbon is 0.124nm and 0.071nm respectively.

It is of interest to note that iron exists in two allotropic forms:

i. BCC Fe shows low C solubility being a maximum at 727°C.

ii. FCC Fe shows an increased solubility for C, being a maximum of 2.14% at 1147°C.
Most combinations of metals do not form continuous solid solutions, and as a result two or more
different phases result. These multiphase alloys represent the majority of commercially important
alloys.

1.11.3 Linear Defects – Dislocations

Linear defects are associated primarily with mechanical deformation. Linear defects are known as
dislocations. A typical example of one type of dislocation is the edge dislocation illustrated in Figure
1-26.

Figure 1-26

The edge dislocation can be represented by slicing half way through a perfect crystal, spreading the
crystal apart, and inserting an extra half plane of atoms in the gap produced as shown above.

Figure 1-27

The dislocation is designated by the inverted T symbol where the shaft of the T points towards the
extra plane of atoms as shown in Figure 1-27. This configuration lends itself to a simple quantitative
designation by using the Burgers vector, b. This parameter is the displacement vector necessary to
close a stepwise loop around the defect. This vector is illustrated below, where (a) represents a
perfect crystal, and (b) a dislocation, and where the closure vector b represents the magnitude of the

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defect. For an edge dislocation the Burgers vector is perpendicular to the dislocation line as shown in
the figure below.

Figure 1-28

A second type of dislocation is the screw dislocation illustrated below.

Figure 1-29

The screw dislocation derives its name from the spiral stacking of crystal planes around the
dislocation line. For the screw dislocation the Burgers vector is parallel to the dislocation line. This is
illustrated in the figure above which shows the step on the surface of a crystal by the motion of an
edge and a screw dislocation respectively.

It should be noted that the edge and the screw dislocations represent the “pure extremes “of linear
defects, and that most linear defects are in fact a “mixture “or combination of the two extremes. To
illustrate the extent to which these defects occur in metals, and other types of materials, the term
linear density is defined as the total number of dislocations per unit volume or unit area. Dislocation
densities as low as 103 mm-2 are typically found in carefully solidified metal crystals. For heavily
deformed metals, the densities may run as high as 109 to 1010 mm-2. For heat treated metals the
density can diminish to between 105 and 106 mm-2.

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1.11.4 Interfacial Defects

Interfacial defects are boundaries that have two dimensions, separating different crystal structures
of phases. Examples of this type of defect are grain boundaries and twin boundaries discussed below.

1.11.4.1 Grain Boundaries

A grain boundary is the boundary separating two or more crystals having different crystallographic
orientations, in polycrystalline materials.

Figure 1-302 Schematic diagram showing small and high-angle grain boundaries and the adjacent atom
positions.

Figure 1-30 illustrates, from an atomic perspective, the appearance of small and high angle grain
boundaries. These boundaries can also be illustrated as resulting from an alignment of dislocations
illustrated in Figure 1-31.

Figure 1-312 Demonstration of how a tilt boundary having an angle of misorientation, θ, results from an
alignment of edge dislocations.

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Several points can be made about grain boundaries:

i. The atoms are bonded less regularly along grain boundaries

ii. Atomic packing in grain boundaries is lower than within the body of the crystal.
iii. Energy levels in grain boundaries are elevated, being greater for high angle than for low angle
boundaries.
iv. Grain boundaries are more chemically active than the grains themselves as a consequence of
their high interfacial energy.
v. Impurity atoms tend to segregate at grain boundaries.
vi. The interfacial energy of small grained materials is higher than for coarse grained materials
as a consequence of their higher surface area.
vii. Grains grow at elevated temperatures to reduce the total boundary energy. Larger grains have
lower surface area and facilitate the tendency of a system to move towards a state of minimum
energy.
It should be noted that the bonding along grain boundaries of polycrystalline materials is very strong
due to strong cohesive forces within and across the boundary. The phenomenon of grain growth is
important in the heat treatment of alloys, and will be covered in more depth in 12.0 Heat Treatment
of Alloys.

1.11.4.2 Twin Boundaries

A twin boundary is a specific type of grain boundary across which there is mirror image symmetry as
illustrated in Figure 1-32.

Figure 1-322 Schematic diagram showing a twin plane or boundary and the adjacent atom positions (coloured
circles).

Twins result from atomic displacements that result from applied mechanical shear forces in BCC and
HCP metals. FCC metals commonly show annealing twins associated with heat treatment. The
orientation of twinned grain boundaries depends upon the crystal structure. Figure 1-33 illustrates a
photomicrograph of a polished and etched specimen of brass showing twinning.

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Figure 1-332 Photomicrograph of a polycrystalline brass specimen. 60x.

1.11.5 Bulk or Volume Defects

These are macroscopic defects such as cracks, porosity and foreign inclusions, usually introduced
during processing and fabrication operations such as casting, rolling or extrusion and forging et
cetera.

1.12 Structure – Property – Processing Relationship

When an engineer designs a component for a particular application he must be aware of the three-
part relationship between structure, properties, and processing, as the three are intimately inter-
related. This relationship is shown in the figure below, which illustrates aluminium being rolled into
foil. The rolling process changes the metal’s structure, and increases its strength.

Figure 1-34

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1.12.1 Structure

ATOMIC STRUCTURE
The structure of a material may be considered on several levels, all of which influence the final
behaviour of the product. At the finest level is the atomic structure. At this level it is the electronic
arrangement that profoundly determines electrical, magnetic, thermal, optical, and chemical
properties such as resistance to corrosion, and effects on the environment.

CRYSTAL STRUCTURE
At the next level is the crystal structure of the material. The arrangement of the atoms in space affects
the mechanical properties of metals such as resistance to deformation, and ductility. Some materials
like ceramics and polymers are not always crystalline, and exist in the amorphous state, partly or
wholly. Amorphous materials behave very differently than crystalline materials, for example with
respect to melting and boiling points, and also whether they are transparent or translucent.

GRAIN STRUCTURE
The next level is the grain structure, that is the aggregate of crystals together. A polycrystalline form
of a material will behave quite differently than a single crystal of the same material, for example
silicon chips for integrated circuits are single crystals, and have quite different properties to bulk
silicon produced by the reduction of silica quartz.

The final level to be considered is the phase structure, where the phase is a physically distinct atomic
arrangement within the bulk structure, like pearlite and ferrite in cast iron. The amount and
distribution of phases in an alloy significantly affects many properties, and often dictates the type of
processing applicable.

The diagram below illustrates these four levels of structure commonly encountered in materials,
namely, (a) atomic structure, (b) crystal structure,(c) grain structure of iron (x100), (d) multiple
phase structure in white cast iron (x200).

Figure 1-35

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1.12.2 Properties

A table of common mechanical and physical properties are reproduced below. Suffice to say at this
point is that the design engineer must specify the nature of the required property, and how this may
be achieved and sustained in manufacture. In many cases the properties of the material will dictate
the type of processing that is appropriate for its production.

Table 1-5

1.12.3 Processing

Materials processing produces the desired shape of a component from the bulk shape of the formless
material. It will be obvious that the method of processing will be chosen to suit the specific properties
of the material.

1.13 Environmental effects on material behaviour

There are many physical, chemical, and mechanical factors in the environment that can affect the
properties of a material in service, and these must be taken into account at the design stage. Two of
the most common factors are temperature, and corrosion.

1.13.1 Temperature

Changes in temperature can dramatically alter the properties of a material, high temperatures
generally weakening most materials. This is illustrated in the Figure 1-13.

Metals are strengthened by heat treatment, but if heated to high temperatures, suddenly lose their
strength, as illustrated in the premature collapse of the Twin Towers building in 9/11. In addition
very low temperatures may cause a normally ductile metal to experience brittle fracture. Ceramics
can degrade at high temperatures, an example being concrete, which will become powdery, and
totally disintegrate. Polymers are generally intolerant of high temperatures, and may melt or char.

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Figure 1-36

1.13.2 Corrosion

Most metals and polymers react with air/oxygen, and other corrosive gases, particularly at elevated
temperatures. A variety of corrosive liquids also readily attack materials, for example acids and bases
corrode metals, while organic solvents will attack polymers. Bacteria are also a source of corrosive
attack on certain metals, and acidic ceramics such as silica will corrode basic oxide ceramic
refractories. See chapter 8 for Corrosion in detail.

The diagram below illustrates what happens when hydrogen dissolves in copper, producing steam at
the grain boundaries. The build up of gas will ultimately lead to fracture at the grain boundaries.

Figure 1-37

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1.14 The Structure-Strength Relationship

Introduction
Engineers, no matter what their speciality, are primarily concerned with the strength of materials
employed in their structures. In this context, load bearing structures require materials of
reproducible mechanical properties. When elastic design principles are employed for design
purposes, stresses in a material shall not exceed the yield strength σy.

When applied stress changes from elastic to plastic, ductility ε and tensile strength σTS are of crucial
importance, and become vitally relevant in design.

For plastic deformation, the dislocation and their movement play a key role in the plastic flow of
crystalline materials, and metals in particular. Practical treatments and processes have been
developed to modify properties affecting strength and ductility, and thus ensure that metals are more
suitable for engineering applications.

The section following will develop the key relationships between structure and strength.

1.14.1 Atomic Bonding and Modulus of Elasticity

In its simplest form, bonding between atoms, although electrical in nature, can also be viewed as
analogous to a stretched spring. This model is valid, particularly when considering engineering
materials and their load bearing characteristics. Electrostatic attraction between atoms is short range
acting, but permits atoms to move with respect to one another within the limits of the repulsive and
attractive forces impressed upon them. Springs, likewise, are limited in their capacity to react to
compressive and tensile forces. In this respect the stiffness of the spring may be compared to the bond
strength of the material.

Figure 1-386: Force-displacement graph for simple atomic bonding

Figure 1-38 illustrates the atomic bond-spring model, where the atom has a diameter a, and is
assumed to occupy one side of a unit cube of area a2 . The displacement upon the application of a force
F is δ, and the spring stiffness S is the slope of the F-δ graph, namely F/δ. Thus,

F
S= (1-5)
δ

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Table 1-6 lists the values for bond stiffness S and modulus of elasticity E, corresponding to the five
types of bonding associated with engineering materials. The correlation between bond stiffness and
elastic modulus will be obvious upon inspection of the data.

Bond stiffness, S, Elastic modulus, E,

Bond type Example
(N/m) (GPa)
Covalent Carbon fibre 50-180 200-1000
Metallic Metals, alloys 15-75 60-300
Ionic ceramics 8-24 32-96
Hydrogen Many polymers 3-6 2-12
Van der Waals polymers 0.5-1 1-4

Table 1-6

The exact relationship between bond stiffness and elastic modulus may now be developed in order to
fully substantiate our model.

When a force F is applied to a pair of atoms, the stress

F
σ= (1-6)
a0

δ
The strain ε= (1-7)
a0
Substituting (1-6) and (1-7) into (1-5) gives
Sε
σ= (1-8)
a0
𝑆𝑆𝑆𝑆
Given σ = E ε, and substituting (1-8), = 𝐸𝐸 ɛ, thus
𝑎𝑎0

S
E= (1-9)
a0
To determine the lowest range for E, consider the largest atom where a0 = 4 × 10-10 m and the weakest
bond with S = 0.5 N/m. Thus from (1-9)

0.5
𝐸𝐸 = 4×10−10 = 1.25 𝐺𝐺 𝑃𝑃𝑃𝑃 (1-10)

Thus E ≈ 1.25 GPa represents the lower value of the elastic limit for solids as determined by the
modelling employed, and verified for the weakest form of bonding, namely van der Waals, as inTable
1-6.

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1.14.2 Ideal Strength

Figure 1-38 illustrates the stretching of a bond within the elastic range, where the force-extension
relationship is linear, and therefore within the elastic limit of the spring.

In engineering practice however, materials are often exposed to plastic deformation and breakage.
Figure 1-39 illustrates this situation as a stress-strain curve, (identical in shape to a load-extension
curve), for a single atomic bond.

The force stretches the bond, and ultimately the atoms loose contact with each other. Breakage then
occurs. It should be noted that inter-atomic bonding acts over a distance no greater than about 10%
of the diameter of the atom. Thus the force required to break the bond is

a 
F ≈S 0  (1-11)
 10 

Figure 1-396: Stress-strain curve for a single atomic bond

Equation (1-11) represents the ideal or theoretical force required to break a single atomic bond. Thus
the ideal strength
𝐹𝐹𝑚𝑚𝑚𝑚𝑚𝑚. 𝑆𝑆 𝐸𝐸
σideal ≈ ≈ ≈ (1-12)
𝑎𝑎02 10𝑎𝑎0 10
𝜎𝜎𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 1
In actual fact a broad examination of engineering materials indicates that 𝐸𝐸
≈ is more often the
15
case as illustrated in Figure 1-40.

Figure 1-406 : Ideal strength of engineering materials

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Most materials fall short of achieving the ideal strength as predicted from bonding theory. This is due
to the presence of large numbers of imperfections in the lattice of the material. Defects are found in
all materials, including metals, polymers, composites and ceramics. Empirical testing over the years
has verified that all materials are consistently weaker in practice than bonding theory predicts.

1.14.3 Imperfections in Crystals

These arise because of the vast numbers of atoms present in materials. Even a volume as small as
1 cm3 contains about 1023 atoms. It is impossible for such large numbers of atoms to take up their
equilibrium positions in a crystal network during the solidification process, and thus the presence of
irregularities is inevitable. The four common types of crystalline defects are illustrated in Figure 1-41.

Figure 1-416: The four types of defects in crystals; (a) Illustrates the presence of vacancies or missing atoms.
(b) Illustrates the presence of substitutional and interstitial impurities. (c) Illustrates a dislocation.
(d) Illustrates grain boundaries.

It was discovered that the very low measured strength, and the higher than predicted ductility of
crystalline materials could be accounted for by the presence of dislocations. The movement of
dislocations under an applied stress was found to play a profound role in determining the mechanical
properties of materials. This discovery led logically to the development of modern strengthening
techniques, now universally employed in materials processing. Before discussing the other types of
defects we will first examine the nature of the dislocation.

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1.14.3.1 Dislocations

The main characteristics of dislocations are listed below in point form.

i. This defect arises when an extra half plane of atoms are inserted into the crystal lattice as
illustrated in Figure 1-42.

Figure 1-426 An edge dislocation in a metal

ii. The atoms immediately adjacent to the inserted half plane of atoms at the top will be under
compression, and those at the bottom will be in tension. These atoms will experience a higher
level of potential energy than their immediate neighbours.

iii. When a shearing force is applied to the top half of the system, the dislocation line denoted by
the inverted T’s separate the slipped top from the bottom.

iv. It is much easier to move a dislocation through a crystal by breaking single bonds, than to
break all the bonds in the plane, before moving on. The very existence of the extra row of
atoms makes this mechanism possible. Thus the presence of dislocations will lower the shear
stress needed to plastically deform the material. Ironically, material without such defects is
more difficult to deform.

v. The net displacement of a dislocation will be in increments of one atomic spacing, and
equivalent to b, the Burgers vector.

vi. The result of the slip moving a distance b is a shear strain γ illustrated in Figure 1-43.

Figure 1-436: Transmission of a dislocation by shear force

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vii. The transmission of a dislocation is easier in some planes within the lattice than others. These
preferred planes are known as slip planes, and are regions with highest atomic packing. Shear
forces transmit more easily through close packed arrays of atoms, in comparison to less dense
packing. This is illustrated in Figure 1-44, where the larger slopes of the tangents between
adjacent spheres indicates a greater resistance to shear stress, and hence larger applied
stresses are required to achieve plastic deformation. This is the case for planes with non-close
packing.

Figure 1-447: Close and non-close packing of spheres

This explains why the close packed FCC metals such as copper and nickel are more ductile
than iron and chromium. The latter belong to the BCC system, which is not close packed.

The slip planes for the three crystal types associated with metals are illustrated in Figure 1-45,
as shaded areas.

Figure 1-456: Slip planes in unit cells

viii. At the atomic level, individual slip displacements are tiny, in the order of 10-10 m. However
when the material is deformed, the bulk displacement is visible as a series of slips along
preferred slip planes, illustrated in Figure 1-46.

Figure 1-466: Bulk shear in a metal under tension

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1.14.3.2 Grain Boundaries

Grain boundaries are surface imperfections present in polycrystalline materials, and illustrated in
Figure 1-41(d). They separate crystals with different orientations. The grain boundary is a narrow
region between grains of about 2-5 atomic diameters in width. The atomic packing is lower than in
the body of the crystal, and it is this property that restricts the movement of dislocations. The surface
energy of grain boundaries are higher than the internal grain itself, and they are therefore regions
where nucleation and subsequent grain growth occur.

1.14.4 Strengthening Mechanisms for Metals

When a metal is plastically deformed, the applied force must overcome the internal frictional forces f
within the material. Since metals deform by shear, these shearing forces must exceed the natural
resistance to the movement of dislocations through the lattice. It can be shown that for deformation,
the shearing force must be greater than the frictional force per unit of dislocation movement. That is,
f
τ> (1-13)
b
where τ = the shearing force required for deformation, f = the lattice resistance to plastic shear, and
b = the unit movement of the dislocation by one lattice unit, equivalent to the Burgers vector b.

As a general rule, metals have low values of lattice resistance f, and may require strengthening to meet
the wide range of engineering applications. The four common strengthening processes are solid
solution, precipitation hardening, work hardening and grain size reduction. The one characteristic
that all these processes have in common is that they operate on the principle of restricting the motion
of dislocations. Figure 1-47 illustrates the methods employed to increase the resistance to the
movement of dislocations.

Figure 1-476: A dislocation worms-eye view of a slip plane

1.14.4.1 Perfect lattice

A perfect lattice has no defects, and exhibits a regular array of atoms as in Figure 1-47(a). It offers
minimal resistance to the movement of dislocations.

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1.14.4.2 Solid solution hardening

In solution hardening, foreign substitutional atoms are introduced to impede dislocation movement
as in Figure 1-47(b). These substituted atoms are usually alloying elements, eg zinc or tin in copper
producing brass or bronze. Alloys are thus always stronger than their pure base metal. See also section
2.6.4.

1.14.4.3 Precipitation hardening

Precipitation hardening involves the formation of large bulky precipitates in-situ, as a result of the
ageing of certain aluminium alloys containing copper, as in Figure 1-47(c).

1.14.4.4 Work hardening

Work hardening a metal involves cold working the metal by mechanical deformation processes such
as rolling, extrusion or forging. These processes serve to greatly increase the numbers of dislocations,
causing the formation of “forests” of intersecting dislocations, as illustrated in Figure 1-47(d)
andFigure 1-48. Consequently the movement of dislocations becomes more and more restricted as
cold working continues. The metal thus continues to harden and become more brittle as a result of
plastic deformation.

Figure 1-486: Forest dislocations due to work hardening

Cold working significantly increases the number of dislocations from dislocation densities of
1010 m/m3 in the annealed state to 1017 m/m3 in the work hardened state. Heat treatment by
annealing, allows the lattice to “relax” and soften, and the number of dislocations are significantly
reduced. See also section 2.6.4.

1.14.4.5 Grain refining

Grain boundaries act as barriers to the movement of dislocations. Any process that reduces the size
of the grains will increase the length of the grain boundaries and therefore strengthen the metal.

1.14.5 Plastic Deformation of Polycrystalline materials

In practice all metals industrially manufactured, are polycrystalline in nature; that is they consist of
many crystals, each with different orientations. In the following discussion we will examine the
structural factors that under-pin plastic deformation. This discussion will focus upon single crystals
and then extend to polycrystalline materials, in which form they constitute the corner- stone for use
in engineering structures.

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1.14.5.1 Conditions required to maximize shear stress

The optimal angle to maximize slip by shear is when the angle 𝜃𝜃 between the applied stress and the
normal to the slip plane is 450. The proof of this statement is developed using Figure 1-49. In this
diagram, the tensile force F, resolved parallel to the slip plane, is F sin 𝜃𝜃. The area of the slip plane is
𝐴𝐴
and the shear stress is therefore:
cos 𝜃𝜃

F sin θ
=τ = σ sinθ cosθ (1-14)
A / cos θ
𝐹𝐹
where σ = .
𝐴𝐴

When the value of τ is plotted against 𝜃𝜃 in Figure 1-49, this data confirms that the resolved shear
stress τ, is a maximum when the slip plane normal is at 450 to the applied stress, under which
conditions τ = σ/2.

Figure 1-496: Resolution of shear stress during the application of a tensile stress to a metal specimen

1.14.5.2 Schmid’s law

This law gives the relationship between uniaxial stress and the resulting resolved shear stress, during
the process of slip. For a single crystal,
Τr = σ cosλ cosϕ (1-15)
where τr = the resolved shear stress parallel to the slip plane, σ = the uniaxial stress, 𝛌𝛌 = the angle
between the slip plane and the direction of applied stress, and ∅ = the angle between the normal to
the slip plane and the direction of the applied stress, illustrated in Figure 1-50

Figure 1-507: Slip in a single crystal

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The derivation of Schmid’s law is simplified by reference to Figure 1-51.

Figure 1-51: Schmid’s law constructions

From Figure 1-51(a) From Figure 1-51(b)

𝐹𝐹𝑟𝑟 𝐴𝐴0
= cos 𝛌𝛌 = cos ∅
𝐹𝐹 𝐴𝐴1

A0
Fr =F cosλ (1-16) A1 = (1-17)
cos φ
𝐹𝐹𝑟𝑟
Since τr = , substituting equations (1-16) and (1-17) give,
𝐴𝐴1

F cos λ F
=
     cosλ cosφ = σ cosλ cosφ ( Schmid ' s Law)
A0 A0 (1-18)
cos φ
Slip occurs, when the shear stress τ acting on the slip plane reaches some critical value τc. This
corresponds to the stress required to move dislocations across the slip plane, and begin the process
of plastic deformation. The tensile stress corresponding to the critical shear stress is the yield stress
σy. At this point

τ c   
=σ y cosλ cosφ (1-19)

For a polycrystalline material, as the tensile stress σ is increased, the resolved shear stress τr
increases on each slip system until the critical shear stress on the primary slip system is reached. Slip
then begins on this system, with the tensile stress equivalent to the yield stress σy. Upon continued
loading, the next highest value of critical shear stress reached will cause slip on the secondary system.
The secondary slip system has a less favourable orientation than the primary slip system, and so on.
Thus plastic deformation will proceed step wise in this fashion, until the metal ultimately fails.

From equation (1-19), the term cos𝛌𝛌cos∅ is known as the Schmid factor M. At the critical shear stress
for the primary slip system,
τc τ
σ c   
= = c (1-20)
cosλ cosφ M

where in this instance σc = σy . It can be shown that as 𝛌𝛌 and ∅ deviate from 450, the Schmid factor M
decreases, and thus the applied tensile stress σc from equation (1-20) will increase as illustrated in
Figure 1-52. This is a result of the uniaxial stress having to overcome successively less favourably
oriented slip systems in the polycrystalline metal.

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Chapter 1: The Structure of Metals

Figure 1-52: The Schmid factor vs yield stress

The σy plot against M in Figure 1-52 is for a 1020 plain carbon steel with a nominal yield stress of 300
MPa. Inspection of the plot will indicate that the critical, and hence the lowest shear stress τc for slip
on the primary slip system, occurs when 𝛌𝛌 = ∅ = 450, and corresponds to half the yield stress.

At 𝛌𝛌 = 900 = ∅, the Schmid factor M is zero, and hence from (1-20), σ = ∞. This indicates that there is
no active shear stress component acting on the slip system. Figure 1-53 illustrates the favoured
orientations for slip to occur.

Figure 1-538: Ease of plastic deformation as a function of slip plane orientation

1.14.5.3 Shear stress on polycrystalline materials

When a shear stress acts upon an aggregate of crystals, some crystals will have more favourable
orientations for shear than others. The random orientation of the grains will represent an increase in
strength over a single crystal. It has been shown that as a consequence, the tensile stress to cause
yielding of a material with many grains, will be about three times the shear strength of a single crystal.
Thus,

σ y ≈ 3τ y (1-21)
where σy = yield stress

τy = shear stress at the yield point

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Chapter 1: The Structure of Metals

1.14.5.4 Strength and ductility, (a case history)

The extent to which the properties of metals can be modified by combinations of strengthening
mechanisms, often combined with heat treatment processes, are illustrated inFigure 1-54. By a
combination of these processes, the yield strength of copper based alloys can be changed by a factor
of 20 times, and the elongation by a factor of 50 times . This dramatic transformation applies equally
to all classes of alloys. For further details see also section 2.6 under Plastic Deformation.

Figure 1-546: Modification of the mechanical properties of copper alloys

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Chapter 1: The Structure of Metals

1.15 Summary
Important Definitions

1. Amorphous: Without structure; lacking in long range atomic order.

𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑜𝑜𝑜𝑜 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑖𝑖𝑖𝑖 𝑡𝑡ℎ𝑒𝑒 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
2. Atomic Packing Factor: APF =
𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉 𝑜𝑜𝑜𝑜 𝑡𝑡ℎ𝑒𝑒 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐

3. Coordination number: The number of atoms surrounding any other atom in a close
packed crystal system.
4. Crystal, Crystalline: A regular three-dimensional pattern of atoms, ions or molecules; the
state of a solid material characterized by a periodic and repeating three-dimensional
array of atoms, ions or molecules.
5. Grain: An individual crystal in a polycrystalline metal.
6. Interplanar Distance: The distance dhkl between adjacent parallel planes in a crystalline
material; they may be slip planes.
𝑎𝑎
dhkl = .
√ℎ 2+ 𝑘𝑘 2 + 𝑙𝑙 2

7. Lattice Parameter: This is the edge length a of the unit cell, usually measured in
nanometers, nm.
8. Linear Defect, (Dislocation): A linear crystalline defect around which there is atomic
misalignment. Dislocations promote the process of plastic deformation by their ready
motion under applied shear forces. See also section 2.7.
9. Linear Density: LD
𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝑜𝑜𝑜𝑜 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑜𝑜𝑜𝑜 𝑡𝑡ℎ𝑒𝑒 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣
LD =
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿ℎ 𝑜𝑜𝑜𝑜 𝑡𝑡ℎ𝑒𝑒 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣

10. Miller Indices: A set of three integers, h, k, l, that designate crystallographic planes, as
determined from the reciprocals of the fractional axial intercepts, x, y, z. Miller indices
are represented as (hkl).
𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝑜𝑜𝑜𝑜 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑜𝑜𝑜𝑜 𝑎𝑎 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝
11. Planar Density: PD =
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑜𝑜𝑜𝑜 𝑡𝑡ℎ𝑒𝑒 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝

12. Polycrystalline: Refers to crystalline materials that are composed of more than one
crystal or grain.
𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀 𝑝𝑝𝑝𝑝𝑝𝑝 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
13. Volume Density: ρv is the mass per unit volume = . This property can be
𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉 𝑝𝑝𝑝𝑝𝑝𝑝 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
𝑛𝑛𝑛𝑛
calculated from the formula: ρv = 𝑁𝑁
𝑉𝑉𝑐𝑐 𝐴𝐴

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Chapter 1: The Structure of Metals

Summary of Crystal Systems

1. Body Centred Cubic, (BCC)5

𝟒𝟒𝟒𝟒
Figure 1-55 BCC unit cell showing relationship between a and R. (a = )
√𝟑𝟑

2. Face Centred Cubic, (FCC)5

𝟒𝟒𝟒𝟒
Figure 1-56 FCC unit cell showing relationship between a and R, (a = )
√𝟐𝟐

Note: In the above diagrams, (a) is the reduced sphere unit cell, and (b, c) are the hard sphere
representations.

Parameters for selected unit cells are tabled in section 1.16.

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Chapter 1: The Structure of Metals

1.16 Question and Answers – The Structure of Metals

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Chapter 1: The Structure of Metals

PROBLEMS

Q8.1 Determine the theoretical density for BCC iron, and compare the value obtained with the actual
value.

Q8.2 Determine the Miller indices of the directions A, B, and C in the figure below.

Q8.3 Calculate the planar density and packing fraction for the (010) and (020) planes in simple cubic
polonium, given that:
a0 = 3.34 x 10-8 cm

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Chapter 1: The Structure of Metals

A8.1
For Fe, a0 = 0.2866 nm, and n the number of atoms/cell for a BCC crystal = 2.

Atomic weight A of Fe = 55.85 g/mol

Vc ,volume of unit cell = a03 = (0.2866 nm)3 = (0.2855 x 10-7 cm)3

= 23.54 x 10-24 cm3

Using the formula, ρ = nA/Vc NA, where NA = Avogadros number,

= 6.023 x 1023 atoms/mol

2 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑝𝑝𝑝𝑝𝑝𝑝 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑥𝑥 55.85 𝑔𝑔 𝑝𝑝𝑝𝑝𝑝𝑝 𝑚𝑚𝑚𝑚𝑚𝑚

ρ =
23.54 𝑥𝑥 10−24 𝑐𝑐𝑐𝑐3 𝑥𝑥 6.023 𝑥𝑥 1023

= 7.88 g/cm3
Actual density = 7.87 g/cm3.

A8.2

Direction A
(a) The two points are 0,0,0, and 1,0,0
(b) 1,0,0 – 0,0,0 = 1,0,0
(c) No fractions to clear, or integers to reduce
(d) [100]

Direction B
(a) The two points are 0,0,0, and 1,1,1
(b) 1,1,1 – 0,0,0 = 1,1,1
(c) No fractions to clear or integers to reduce
(d) [111]

Direction C
(a) The two points are ½,1,0, and 0,0,1
(b) 0,0,1 – ½,1,0 = -1/2,-1,1
(c) 2(-1/2,-1,1) = -1,-2,2
�2
(d) [1 � 2]

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Chapter 1: The Structure of Metals

A8.3
The simple cubic system for polonium is illustrated below:

Figure 1-57

a0 for polonium = 3.34 x 10-8cm.

The (010) plane may be represented by the diagram below, deduced by reference to Figure 1-57.

𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑝𝑝𝑝𝑝𝑝𝑝 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓

PD = = 1 atom/(3.34 x 10-8)2 cm2
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑜𝑜𝑜𝑜 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
= 8.96 x 1014 atoms/cm2

𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑜𝑜𝑜𝑜 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑝𝑝𝑝𝑝𝑝𝑝 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 1 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑥𝑥 𝜋𝜋𝑟𝑟 2 𝜋𝜋𝑟𝑟 2 𝜋𝜋

PF = = = = = 0.785
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑜𝑜𝑜𝑜 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 (2𝑟𝑟)2 4𝑟𝑟 2 4

Further examination of figure 1 will indicate that no atoms are centred on the (020) plane, and
therefore the planar density and packing factor are zero for this plane.

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Chapter 1: The Structure of Metals

References

1 Brown, Theodore L., H E. Lemay, Jr, and Bruce E. Bursten. Chemistry the Central
Science. 10th ed. Upper Saddle River, NJ: Pearson, Prentice Hall, 2006.
2 Callister, Jr., William D. Materials Science and Engineering an Introduction. 7th ed.
York, PA: Techbooks, 2007.
3 Schlenker, B R. Introduction to Materials Science. SI ed. Sydney, Australia: John Wiley
& Sons, 1974.
4 van Vlack, L. H, Elements of Materials Science and Engineering, 3rd ed., Addison-
Wesley, 1975.
5 Smith, W. F, Hashimi, J, Foundations of Materials Science and Engineering, 5th ed.,
McGraw-Hill, 2010.
6 Ashby, M., Shercliff, H., Cebon, D., Materials, Engineering, Science, Processing and
Design, Elsevier, Butterworth-Heinemann, 2007.
7 http://www.mse.ncsu.edu/zhu
8 academic.uprm.edu/pcarceres/Courses/Mech/Met-3A.pdf

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Chapter 2: Mechanical Properties

Mechanical Properties

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Chapter 2: Mechanical Properties

2.1 Introduction
Engineers need to be familiar with the mechanical properties and test methods for materials of
construction in order to design safe and functional structures. The predicted behaviour of a metal
structure under load may be determined by mechanical testing. Loads may be tensile, compressive,
shear or torsional as depicted in Figure 2-1.

Figure 2-13 (a) Schematic illustration of how a tensile load produces an elongation and positive linear strain.
Dashed lines represent the shape before deformation; solid lines, after deformation. (b) Schematic illustration
of how a compressive load produces contraction and a negative linear strain. (c) Schematic representation of
shear strain γ , where γ = tan θ . (d) Schematic representation of Torsional deformation (i.e., angle of twist ϕ )
produced by an applied torque.

Load bearing structures require materials with reliable and reproducible strength properties. Elastic
design requires that no part of the structure shall deform plastically. For this to occur, stresses present
shall not exceed the yield strength σy at any point in the structure.

The common forces present in engineering structures are tensile, compressive, shear and torsional.
Each of these will be dealt with in the following sections, but it will be useful to consider here the
fundamental atomic forces underpinning these bulk properties, together with their inter-
relationships.

Figure 2-2 illustrates the electrostatic bonding forces between two atoms as a function of their inter-
atomic spacing. At large spacings the attractive and repulsive forces are very small, in accord with the

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Chapter 2: Mechanical Properties

inverse square law. As the atoms approach each other each force increases. At the point a’ the sum of
the opposing forces is zero, and this represents the equilibrium spacing or the bond length for the two
atoms. Note that this equilibrium also corresponds to the most stable thermodynamic state, and is
therefore associated with minimum potential energy as illustrated in figure (b). These force and
energy diagrams have direct implications to engineering materials, in particular to their behaviour
when subjected to tensile and shearing forces.

Figure 2-25 Electrostatic bonding force and energy curves for two atoms

2.2 The Tension Test

This test together with other mechanical tests such as impact, hardness and compression must be
carried out under carefully controlled conditions. This is essential if reproducibility is to be achieved
and if conformance to the national or international standards is required.

Australian Standard AS 1391 specifies the tensile testing of metals, and outlines procedures
pertaining to the test, from test specimen preparation, performing test measurements under specified
conditions, and machine calibration. The types of test specimens are illustrated in Figure 2-3 and
Table 2-1 with their relative dimensions. The various shapes of test pieces before and after fracture
are also illustrated.

Reference is made in the standard to many factors, some of the most important being:
i. The position of the test pieces when machined from bars and extrusions, including pipes and
rods et cetera.
ii. Dimensions and accuracy of machining including surface finish.
iii. Removal of surface coatings, if any.
iv. Method of gripping test specimens.

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Chapter 2: Mechanical Properties

Figure 2-31 The form of the end of the test pieces shown in Figures 1, 3, 5 and 7 is intended as a guide only
(see Clause 9).

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Chapter 2: Mechanical Properties

Quantity
Term Unit symbol Text reference
symbol
A percentage elongation after fracture % Clause 19
At percentage total elongation at fracture % Clause 19
D outside diameter of a round tube mm Figure 5, Clause 7
Fm maximum force N Clause 18
Lc parallel length mm Figures 1, 3, 7
Le extensometer gauge length mm Clause 8.2
Lo original gauge length mm Figures 1, 3, 5, 7, Clause 8.1
Lu final gauge length after fracture mm Figures 2, 4, 6, 8
Clause 14, Appendix B, Figures
ReH upper yield stress MPa
B1 to B6, Appendix C
Clause 14, Appendix B, Figures
ReL lower yield stress MPa
B1 to B3, B6, Appendix C
Rm tensile strength MPa Clause 18
proof stress (non-proportional elongation) (e.g. Rp0.2 Clause 15, Appendix B, Figures
Rp MPa
= 0.2% proof stress) B4, B5, B7
permanent set stress (e.g. Rr0.2 = 0.2% permanent Clause 16, Appendix B, Figure
Rr MPa
set stress) B9
proof stress (total elongation) (e.g. Rt0.5 = total Clause 15, Appendix B, Figure
Rt MPa
elongation proof stress) B8
original cross-sectional area of the test piece within
So mm2 Figures 1, 3, 5, 7, Clause 7
the gauge length
Su minimum cross-sectional area after fracture mm2 Figures 2, 4, 6, 8
Z percentage reduction of area % Clause 20
Thickness of a flat test piece, average cross-
a sectional thickness of a product section test piece, mm Figures 3, 5, 7, Clause 7
or wall thickness of a tube
width of a flat piece, or average width of a product
b section test piece, or a longitudinal strip cur from a mm Figures 3, 7, Clause 7
tube
diameter within the gauge length of a test piece of
d mm Figure 1
circular cross-section
r transition radius mm Figures 1, 3, 7

Table 2-11 The quantity symbols used in Australian Standard AS 1391 are tabulated. Note that the figures in
the ‘Text reference’ column refer to Figure 9.2.

2.2.1 Proportional Test Pieces

Proportional test pieces have a specified relationship between the original gauge length Lo and the
original cross sectional area So. This international relationship is

Lo = 5.65 So (2-1)

For circular cross-sectional test pieces:

Lo = 5d (2-2)
Dimensional requirements for proportional circular section pieces from Australian Standard AS 1391
are given below in Figure 9.4 and Figure 9.5.

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Chapter 2: Mechanical Properties

Diameter Maximum Original Minimum Minimum Minimum

d variation of gauge length parallel free length transition
diameter of Lo = 5.65 So length between radius
paralled 1 grips r
length L=
c Lo + d Lo + d
2
20.0 ± 0.4 0.05 100 ± 2.0 110 120 20
15.0 ± 0.3 0.04 75 ± 1.5 83 90 15
10.0 ± 0.2 0.03 50 ± 1.0 55 60 10
5.0 ± 0.1 0.02 25 ± 0.5 28 30 5
Table 2-21 Dimensional requirements for proportional circular section test pieces.

Width Maximum Minimum Original Minimum Minimum Minimum

b variation test piece gauge parallel free length transition
of width thickness length length between radius
within the Lo 1 grips r
parallel L=
c Lo + b Lo + b
2
length of a
test piece
40 ± 2 0.2 3 200 ± 4 220 240 20
20 ± 1 0.1 0.3 200 ± 4 210 220 20
20± 1 0.1 0.1 80 ± 1.6 90 100 20
12.5 ± 0.6 0.06 - 50 ± 1.0 56 63 15
6 ± 0.3 0.04 - 24 ± 0.5 27 30 6
3 ± 0.2 0.04 - 12 ± 0.2 14 15 3
Table 2-3 Dimensional requirements for rectangular section test pieces (reduced section and parallel-sided)

2.2.2 The Tensile Test – Key Points

Full details are given in the Australian Standard but key points are listed for background information:
i. Measurement of gauge length and marking of gauge length.
ii. Measurement of cross-sectional area.
iii. Test grips – types
iv. Strain rate is the time rate of increase of strain. The standard strain rate is 8×10-4s-1 within
the range 2.5×10-4 – 2.5×10-3s-1-.
v. Determination of percentage elongation and percentage reduction of area after fracture.

2.2.3 Definition of Terms

2.2.3.1 Engineering Stress (σ)

Engineering stress, σ , is the instantaneous load applied to a specimen divided by its original cross
sectional area. Stress is measured in SI units, that is Pa, which equals N/m2.

F
σ= (2-3)
A0
Where F = instantaneous load applied perpendicular to cross section in newtons
A0 = original cross sectional area in meters2.

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Chapter 2: Mechanical Properties

2.2.3.2 Engineering Strain (ε)

Engineering strain, ε , is the increase in length per unit length.

li − l0
ε= (2-4)
l0
Where li = instantaneous length
l0 = original length

Equation (2-4) can also be written as:

∆l
ε= (2-5)
l0
Where ∆l = change in length at some instant.

2.3 The Compression Test

The compression test can be applied to metals, but is more commonly applied to ceramics and
concrete. The concepts of compressive stress and strain are analogous to tensile stress and strain.

2.4 Shear and Torsional Tests

Shear forces are applied parallel to the upper and lower faces as illustrated in Figure 2-1.
F
τ= (2-6)
A0
Where τ = shear stress
F = instantaneous load applied perpendicular to cross section.
A0 = original cross sectional area.
γ = tan θ (2-7)
Where γ = shear strain
θ = strain angle

2.5 Elastic Deformation

Elastic deformation is defined as deformation that is non-permanent, that is, totally recovered upon
release of the applied stress. According to Hooke’s Law, stress is proportional to strain within in the
elastic region.
σ ∝ε

𝜎𝜎 = 𝐸𝐸 𝜀𝜀 (2-8)
Where σ = engineering stress
E = modulus of elasticity or Young’s modulus
ε = engineering strain

For most metals E ranges between 45 – 400 GPa.

Where 1 Giga Pascal = 109 Pascals = 109 N/m2 = 103 MPa

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Chapter 2: Mechanical Properties

A graph of stress against strain is linear within the elastic region. The slope of the graph is equal to
the modulus of elasticity, E. This is illustrated in Figure 2-4.

Figure 2-43 Schematic stress-strain diagram showing linear elastic deformation for loading and unloading
cycles.

E may be thought of as a measure of stiffness, or alternatively as the materials resistance to

deformation. Certain materials such as concrete, grey cast iron and polymers show non-linear stress-
strain behaviour, and thus do not obey Hooke’s law. In such cases the modulus of elasticity E is taken
as the tangent to the curve at a specified value of stress, or as the slope of a secant, drawn from the
origin to a specified point on the stress-strain curve.

Strain on the macroscopic level is actually a manifestation of the stretching of interatomic bonding
forces in the metal.

Figure 2-5 is a stress-strain curve for a single atomic bond stretching beyond its equilibrium position.
This curve is identical to the net force-inter-atomic spacing diagram in Figure 2-2. The instantaneous
slope of this curve at the zero point represents the modulus of elasticity of a material, a fundamental
mechanical property, and re-affirms the direct link between elastic properties of materials and the
bulk electrical forces that bind atoms together, as discussed in section 2.1.

Figure 2-59 The stress-strain curve for a single atomic bond illustrating stretching beyond the equilibrium
spacing a0

Elastic deformation can also be induced by compressive, shear and torsional forces.

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τ ∝γ
∴τ = G γ (2-9)
Where τ = shear stress
G = shear modulus
γ = shear strain
It is the general rule for metals that elastic deformation is independent of time, that is, upon removal
of the stress, the strain is totally recovered. However, for some polymeric materials, elastic strain is
not immediately recovered upon removal of the stress, and may vary during stress application. Time
dependant elastic behaviour is known as anelasticity or viscoelastic behaviour.

2.5.1 Elastic Properties of Materials – Tensile Forces Poisson’s Ratio and Elastic
Modulus
Elastic properties may be dependent upon crystallographic orientation, but since most metals are
polycrystalline, the materials are considered to be isotropic, that is, the properties will be the same in
all directions due to an average of all the random orientations. When a tensile test specimen is under
stress, there is an elastic elongation in the direction of the applied stress (usually taken as the z
direction, ). Simultaneously there will be a contraction in the x and y directions, perpendicular to the
direction of the applied force. This is illustrated in Figure 2-6. Hence compressive strains ε x and εy
can be determined.

Figure 2-63 Axial (z) elongation (positive strain) and lateral (x and y) contractions (negative strains) in
response to an imposed tensile stress. Solid lines represent dimensions after stress application; dashed lines,
before.

For isotropic materials, ε x = ε y , and the Poisson ratio is defined as:

ε ε
ν=
− x=− y (2-10)
εz εz
Where ν = Poisson’s ratio
ε x = compressive strain in the x direction
ε y = compressive strain in the y direction

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From Equation (2-10) it can be deduced that Poisson’s ratio, ν , is the negative ratio of the lateral and
axial strains. On a practical level ν gives the relative dimensional change in two dimensions of a
specimen under stress. Values of ν range between 0.25 and 0.35.

2.5.2 Shear and Torsional forces

Shearing forces are commonly present in tensile loading and bending of structural members. Torsion
is a variation of pure shear, when a structural member is twisted in a manner illustrated in Figure
2-1(d). The inter-relationship between the common forces present in a loaded rectangular beam and
a shaft of circular cross-section loaded in torsion is illustrated in Figure 2-7.

Figure 2-79

The shaded regions in Figure 2-7 represent strain distribution for a bending beam and a rotating shaft,
and by implication stress distribution, since Hookes law is obeyed in elastic deformation.

Comparative modes of loading and states of stress are further illustrated in Figure 2-8.

Figure 2-89

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Engineering components can have many shapes and configurations; however no matter how complex,
the stresses in a small element within the structure may always be described by a combination of
tension, compression and shear. The single property that determines the magnitude of the deforming
force is the elastic or shear modulus of the material, referred to in earlier sections. Figure 2-9 further
illustrates the inter-connection between stress, strain and elastic moduli.

Figure 2-99

For isotropic materials the elastic and shear modulus, E and G, are related to the Poisson ratio as in
Equation (2-11).

=E 2G (1 +ν ) (2-11)

Where E = elastic modulus

G = shear modulus
ν = Poisson’s ratio

Also, for most metals G ≈ 0.4E

Values of E, G and ν for important alloys are given in Table 2-4.

Metal alloy Modulus of Elasticity Shear Modulus Poisson’s ratio

GPa GPa
Aluminium 69 25 0.33
Brass 97 37 0.34
Copper 110 46 0.34
Magnesium 45 17 0.29
Nickel 207 76 0.31
Steel 207 83 0.30
Titanium 107 45 0.34
Tungsten 407 160 0.28
Table 2-43 Room-temperature elastic and shear moduli, and Poisson’s ration for various metal alloys.

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2.5.2.1 Elastic bending of beams

When a beam is subjected to a bending moment its original straight axis is deformed to a curve of
radius R illustrated in Figure 2-7. Its curvature к is defined as the reciprocal of the radius of curvature,
that is к = 1/R. The curvature generates a linear variation of stress and strain across the section, with
tension on one side and compression on the other side. The position of zero stress is along the neutral
axis. The stress increases with distance from the neutral axis y. Since the material is more effective at
resisting stress at greater distances y from the neutral axis, the cross-sectional shape is of prime
importance. The geometry of the beam is incorporated into an important term known as the second
moment of area I, which appears in the general bending equation,
𝜎𝜎 𝑀𝑀 𝐸𝐸
= = (2-12)
𝑦𝑦 𝐼𝐼 𝑅𝑅

Where σ = stress in Pa, y = displacement parallel to the y axis in m, M = bending moment in Nm, I =
second moment of area in m4, E = modulus of elasticity in Pa and R = radius of curvature of the loaded
beam in m.

𝑑𝑑/2
For a rectangular cross-section, illustrated in Figure 2-10, the second moment of area IXX = ∫−𝑑𝑑/2 𝑦𝑦 2 b
dy, where b dy is the area of the element section at distance y.

Figure 2-1012

The second moment of area I may also be expressed as ∫ 𝑦𝑦 2 dA . Figure 2-11 tables expressions for
values of I for several common beam cross-section geometries.

Figure 2-119

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It should be noted that the second moment of area characterizes the resistance of the structural
member to bending, taking into account the effects of size and shape. In its general form as ∫ 𝑦𝑦 2 𝑑𝑑𝑑𝑑, it
appears in derivations for bending and twisting relationships.

The differential equation for the deflection of a beam may also be obtained from elastic beam theory,
and is,
𝑑𝑑2 𝑦𝑦
M = EI (2-13)
𝑑𝑑𝑥𝑥 2
𝑀𝑀
The ratio of moment to curvature is called the flexural rigidity, and is equal to EI. The SI units are
к
Nm2. The maximum deflection of the beam D(y) when the force F is applied to the centre of the beam,
may be calculated by integrating equation (2-13) twice. For a beam centrally loaded as illustrated in
Figure 2-12, the maximum deflection can be calculated as,
𝐹𝐹𝐿𝐿3
D(y) = (2-14)
48𝐸𝐸𝐸𝐸

Figure 2-129

NOTE: Detailed derivations of all relevant equations relating to the elastic deformation of beams is
presented in Supplement 1on MyLO.

Further application of elastic beam theory is covered in section 2.15, where it is associated with
flexural testing of composites using the three-point bend test.

Solved problems associated with beams are included at the end of this chapter.

2.5.2.2 Torsion of shafts

Consider a tangential force F acting upon a body moving in a circular path of radius r, and angular
displacement 𝜃𝜃 radians, and illustrated in Figure 2-13.

Figure 2-1312

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Torque T = tangential force x radius = F r. The circumferential displacement = r 𝜃𝜃.

The work done by the force = force x distance = F r 𝜃𝜃 = T 𝜃𝜃.

If the body rotates about a central axis O at N revolutions per minute, the angle displaced per minute
= 2π N radians, and the work done per minute = 2πNT J/min. Thus the work done per minute is the
2𝜋𝜋𝜋𝜋𝜋𝜋
power in watts = . Since power is the work done per second,
60
2𝜋𝜋𝜋𝜋𝜋𝜋
Power = (2-15)
60
When a torque T is applied to the ends of a bar of uniform cross-section a shear stress τ is generated.
For circular sections the shear stress varies with radial distance r (Figure 2-7).

The general twist formula for a rotating circular shaft illustrated in Figure 2-1(d) is,
𝑇𝑇 𝜏𝜏 𝐺𝐺 ∅
= = (2-16)
𝐽𝐽 𝑟𝑟 𝐿𝐿

where T = torque in Nm, J = polar second moment of area in m4 , τ = shear stress in Pa, r = radius in
m, G = shear modulus in Pa, ∅ = angle of twist in radians and L = shaft length in m. It will be noted that
equation (2-16) is analogous with equation (2-12) for beams.

∅ 𝑇𝑇 𝑇𝑇
In equation (2-16), the twist per unit length is , and the ratio of torque to twist, per unit length
𝐿𝐿 ∅ ∅𝐿𝐿
= GJ, which is the torsional rigidity. Note the analogy between flexural rigidity EI for beams, and
torsional rigidity GJ for shafts.

The polar second moments of area J are determined using the same technique as for second moments
of area I. The Theorem of perpendicular axes relates normal and polar second moments about X, Y
and R axes as: IXX + IYY = J . Thus for shafts of circular cross-section, either solid or hollow, with
outside diameter = d0 and inside diameter = di , respectively,
𝐽𝐽 𝜋𝜋𝑟𝑟 4 𝜋𝜋𝑑𝑑4
IXX = IYY = = = (2-17)
2 4 64

𝐽𝐽 𝜋𝜋 𝜋𝜋
IXX = IYY = = (r04 - ri4) = (d04 - di4) (2-18)
2 4 64
Several solved problems on torsional and shear stresses are included at the end of this chapter. Full
details of formula derivations for twisting may be found in Supplement 2 on MYLO.

2.6 Plastic Deformation

Elastic deformation only occurs for very low values of strain, in the order of 0.005. Beyond this strain,
Hooke’s law does not apply, and permanent strain results from plastic deformation.

2.6.1 Plastic Deformation by Slip

Two models were proposed to explain the mechanism of plastic deformation. The first, proposed a
“bulk” movement of rows of atoms, where the motion was caused by shearing forces. This model is
illustrated in Figure 2-14. However the estimation of stresses required for this mechanism, based on
bond strength, was many orders of magnitude greater than that observed from testing, and as a
consequence, this model was rejected.

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Figure 2-144

The second model proposed was based upon the observed presence of the ubiquitous dislocation,
discussed in section 1.10.

The observation of step markings on metals stressed beyond their elastic limit, led to the association
of plastic deformation with slip planes. During the process of plastic deformation slip was postulated
to occur along preferred crystallographic planes, known as slip planes, where the resolved shear
stress was considerably less than other regions of the crystalline net work. Figure 2-15 illustrates the
step markings in a crystal of hexagonal close packed zinc.

Figure 2-155

On the basis of the observed slip steps, the current model of plastic deformation was described as
being by a slip mechanism, promoted by the movement of dislocations, via the dislocation defect. This
mechanism successfully accounts for the fact that the shearing forces required are only a fraction of
those based upon the earlier model, since the mechanism involves a series of only single step atomic
shear movements. This single step shear mechanism is only possible because of the missing row of
atoms in the dislocation, which is where the “action”takes place. The mechanism of dislocation
movement under an applied shear force is illustrated in Figure 2-16.

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Figure 2-166

Careful observation of the slip mechanism illustrated in Figure 2-16 will indicate that the step-wise
mechanism will be facilitated if the inter-atomic distance is decreased. As a result, slip occurs more
readily in a plane of high packing density. This point was made earlier in section 1.7. Figure 2-17
justifies the case that slip is more likely in a plane with high packing density.

Figure 2-176

Figure 2-18 provides a novel alternative model for plastic deformation by the movement of
dislocations via slip planes, employing “Goldie the caterpillar”.

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Figure 2-186

In the illustration, Goldie wriggles along easily, by passing a dislocation along the length of her body!
Figure 2-19 illustrates the major slip systems for the three basic crystal structures associated with
metals. The process of plastic deformation in metals will occur by the movement of dislocations along
these preferred slip planes.

Figure 2-196

2.6.2 Plastic Deformation by Twinning

Plastic deformation, and hence dislocation movement may also occur by transmission via twin
boundaries. Twins are produced when a shear force produces atomic displacements such that on one
side of a plane known as the twin boundary, atoms are located in mirror image positions of atoms on
the other side. The way this displacement occurs is illustrated in Figure 2-20. See also section 1.11.4.2.

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Figure 2-207

Twinning only occurs on a specific crystallographic plane, in BCC and HCP crystals, but not in FCC
systems. For BCC systems, the twin plane is (112), and the direction is [111].
Mechanisms of deformation by slip and by twinning are illustrated in Figure 2-21.

Figure 2-213

There are several major differences between slip and twinning deformations, namely:

1. For slip the crystallographic orientation above and below the slip plane is the same before
and after deformation. For twins there is a re-orientation across the twin boundary.
2. Slip occurs in multiples of atomic spacings, while for twinning the atomic displacement is
less than one inter-atomic spacing.

2.6.3 Plastic Deformation of Polycrystalline Metals

All engineering alloys are polycrystalline, that is, grains of random orientation are separated by
discontinuous regions known as grain boundaries. The atomic packing at grain boundaries is lower
than in the body of the crystal, which is much more ordered. Thus the grain boundary will act as a
deterrent to the movement of dislocations during the process of deformation. During deformation,
dislocations moving in a particular slip plane will move freely within the grain, but will be impeded
in their progress by the next grain boundary. Furthermore each grain has a different orientation to
its neighbour, with a different set of slip planes, and this will cause a change in direction of dislocation
movement from grain to grain. It therefore follows that with finer grained metals, with a
correspondingly larger total surface area of grain boundaries, the restriction to the movement of
dislocations will be greater than for coarse grained metals.

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As the process of plastic deformation continues there will be a “pile up” of dislocations at grain
boundaries, which results in work hardening and a strengthening of the metal. Figure 2-22 illustrates
the slip lines in differing orientations at the grain boundaries of a polycrystalline material.

Figure 2-223

As the deformation progresses the original equiaxed grains become more elongated in the direction
of the applied stress, and this is illustrated in Figure 2-23.

Figure 2-233

It should be noted here that the effectiveness of surface defects in interfering with the slip process
will depend upon their surface energies. For most engineering metals the energy of the grain
boundary is about 4-15 times greater than for a twin boundary, and thus the grain boundary is a far
greater factor in promoting strain hardening than the twin boundary.

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2.6.4 Strengthening Mechanisms for Metals

There are several methods by which metals may be strengthened in practice. They are:

1. Grain size reduction: The case has been made above for increasing the strength of metals by
reducing the grain size. In practice the grain size can be reduced by more rapid cooling of the
molten metal, by the use of grain refining nucleating agents added to the molten metal, and by
heat treatments, post deformation.

2. Cold working/Work hardening: The history of mechanical working by processes such as

rolling, extrusion, deep drawing and forging of the cold metal, will all lead to it being strain
hardened. The process of cold working will promote the formation of more dislocations and
more dislocation pile ups at grain boundaries. The mutual repulsion of dislocations as a result
of their negative charge will hinder further their movement. As the deformation process
continues the material becomes harder and stronger, but at the cost of ductility, which is
reduced. The effect of elastic strain recovery and strain hardening is illustrated in section 2.13,
where as a result of cold working, the yield point was increased over and above its original
value.

Excess deformation will ultimately lead to brittleness, which can be relieved by various types
of heat treatment, (see section 6.2). Figure 2-24 illustrates the relationship between the
percent of cold work and the change in mechanical properties.

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Figure 2-24

The following equation illustrates the relationship between the % of cold work, and the degree
of plastic deformation.
 A − Af 
=
%CW  0  × 100 (2-19)
 A0 
Where A0 = original cross-sectional area
Af = final cross-sectional area

It can be seen that this equation is the well known % reduction in cross-sectional area,
determined in section 2.9.

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3. Solid solution strengthening: Any structural change to the metal that will impede the
movement of dislocations will aid strain hardening. If alloying elements are introduced into
metals, an alloy is formed. In almost all respects alloys are stronger than the pure metal itself.
Impurity atoms when introduced may form solid solutions with the base metal. For example
zinc and tin introduced into copper form a series of solid solutions in brass and bronze
respectively. Similarly nickel introduced into copper will alter the mechanical properties of
copper, depending upon how much nickel is introduced. These changes are summarized in
Figure 2-25.

Figure 2-252 Variation with nickel content of (a) tensile strength, (b) yield strength, and (c) ductility
(%EL) for copper-nickel alloys, showing strengthening.

The impurity atom strain hardens a metal by introducing a strain field into the crystal lattice,
and therefore will serve to impede dislocation motion. This is depicted in Figure 2-26.

Figure 2-266

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2.7 Tensile Strength

The standard tensile test provides useful yield properties and information relating to ductility. The
yield strength σy is the stress required to produce a very slight yet specified amount of plastic strain.
For materials that have a sharp transition from elastic to plastic deformation, the yield point is taken
at the first onset of change as illustrated in Figure 2-27(b) typical of certain steels. For other types of
materials, there is no well defined yield point after the limit of proportionality is reached, and here σy
is associated with 0.2% proof stress, that is the point at which the stress-strain curve deviates by a
strain of 0.2%. A line is drawn from 0.2% strain parallel with the linear section of the stress-strain
curve. Where this line intersects the stress axis is the 0.002 proof stress, illustrated in Figure 2-27(a).

Figure 2-273

Figure 2-28

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After yielding, the stress increases to a maximum at M, afterwards decreasing to the fracture point F.
The tensile strength is the stress corresponding to the maximum M on the engineering stress-strain
curve depicted in Figure 2-28.

If this stress is maintained, fracture will result. All deformation up to this point is uniform throughout
the narrow neck of the specimen. At the maximum M, a small constriction will occur, and a neck begins
to form. From here on all subsequent deformation will occur at the neck. This phenomenon is called
'necking'. Tensile strengths vary from 50MPa for aluminium to 3000MPa for certain steels.

2.8 Ductility
Ductility is the amount of plastic deformation that has been sustained at fracture. A material that
experiences very little deformation before fracture is termed brittle. Conversely a ductile material
will experience varying degrees of deformation. Ductility can be expressed as percent elongation, or
percent reduction in cross-sectional area.
l f − l0
=
%EL ×100 (2-20)
l0
Where %EL = the percentage elongation
lf = final length between original gauge marks
l0 = original gauge length
A0 − Af
=
%RA ×100 (2-21)
A0
Where %RA = the percentage reduction of cross-sectional area.
A0 = original cross-sectional area
Af = final cross-sectional area

Note that brittle materials usually have fracture strains of <5%.

Figure 2-29 contrasts tensile stress-strain behaviour for ductile and brittle materials.

Figure 2-293 Brittle and ductile materials.

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A knowledge of the ductility of a material is important in engineering design, since it indicates to the
designer the degree to which a structure will deform before failing. Secondly, it specifies the allowable
degree of deformation during operation. Table 2-5 lists typical mechanical properties obtained from
tensile stress-strain tests.

Metal Alloy Yield Strength Tensile Strength Ductility, %EL

MPa MPa [in 50mm (2 in)]
Aluminium 35 90 40
Copper 69 200 45
Brass (70Cu-30Zn) 75 300 68
Iron 130 262 45
Nickel 138 480 40
Steel (1020) 180 380 25
Titanium 450 520 25
Molybdenum 565 655 35

Table 2-5

It should be noted that the values quoted in above table are sensitive to prior deformation, heat
treatment, and environment temperature. The effects of temperature on the stress-strain curve are
shown, and illustrates that reduction in strength accompanies an increase in temperature.

Figure 2-303 Engineering stress-strain behaviour for iron at three temperatures.

2.9 Resilience
Resilience is the capacity of a material to absorb energy when it is deformed, and then upon unloading
to have this energy recovered. "Resilience = to bounce back". The associated quantitative property is
the modulus of resilience Ur, which is equal to the area under the stress-strain curve up to the yield
point. Figure 2-31 illustrates the computation of resilience for the shaded area of the stress-strain
curves.

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Figure 2-316

For a non linear curve, Figure 2-31 (a):

εy
U r= A= ∫
0
σ y dε (2-22)

Where ε y = yield strain

σ y = yield stress

For a linear curve, Figure 2-31 (b):

1
U r= A= ε yσ y (2-23)
2
Where ε y = yield strain
σ y = yield stress
The units for Resilience, Ur, are Pascals, Pa = J/m3.

The relationship as depicted in equation (2-9) may be substituted into equation (2-23) which will
yield:
1
U r = ε yσ y
2
1 σ
= × y ×σ y
2 E
σ y2
Ur =
2E

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Thus resilient materials, such as, spring steel having high yield strengths, and low moduli of elasticity
will have a large modulus of resilience.

2.10 Toughness
Toughness is the ability to absorb energy up to fracture, and is thus similar to resilience. Hence
toughness is equal to the area under a stress-strain curve up to the point of fracture (for low strain
rate). Toughness is affected by the rate of application of stress, and also by the presence or absence
of a notch or stress raiser. Generally speaking, ductile materials are tougher than brittle materials.
Toughness is generally determined by the notch toughness impact test. The shaded areas in Figure
2-29 are equivalent to toughness. The units are J/m3 as for resilience.

2.11 True Stress and Strain

The engineering stress-strain curve illustrated in Figure 2-28 indicates that after point M (maximum
stress), the material is getting weaker because the curve drops. This is not the case; the stress is
actually increasing, but simultaneously the cross sectional area is diminishing. This is not taken into
account when calculating σ , as the original CSA is used even after necking starts.

It should be noted that work hardening occurs simultaneously with reduction in CSA. A plot of true
stress versus strain, as in Figure 2-32, illustrates the actual changes.

Figure 2-323 A comparison of typical tensile engineering as stress-strain and true stress-strain behaviour.
Necking begins at point M on the engineering curve, which corresponds to M' on the true curve. The
'corrected' true stress-strain curve takes into account the complex stress state within the neck region.

Here true stress:

F
σT = (2-24)
Ai
Where σT = true stress

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F = instantaneous load applied perpendicular to cross-section

Ai = instantaneous cross-sectional area

∆l i dl
l

ε
Similarly true strain, T = lim ∑ l =∫ l
i l0 i

li
ε T = ln (2-25)
l0
Where εT = true strain
li = instantaneous length
l0 = original length

The relationship between true stress and engineering stress and strain is:

σ=
T σ (1 + ε ) (2-26)

Where σT = true stress

σ = engineering stress
ε = engineering strain

The relationship between true strain and engineering strain is:

ε T ln (1 + ε )
= (2-27)

Where εT = true strain

ε = engineering strain

The complex stresses present at necking include a strain hardening factor, in addition to a component
of axial stress. Thus the axial stress is slightly less, due to the presence of the developing strain
hardening component, and is shown as the corrected stress. Empirical studies have attempted to fit
an equation to represent the relationship between true stress and true strain from P, the onset of
plastic strain to the onset of necking, taking into account the strain hardening component. The
empirical relationship is given by:

σ T = K ε Tn (2-28)

Where σT = true stress

K = a constant for the material, taking into account its history of heat treatment and work
hardening
εT = true strain
n = a constant, representing the strain hardening exponent

Table 2-6 shows K and n values for various alloys.

Material n K (MPa)
Low-carbon steel (annealed) 0.21 600
4340 steel alloy (tempered @ 315°C) 0.12 2650
304 stainless steel (annealed) 0.44 1400
Copper (annealed) 0.44 530
Naval brass (annealed) 0.21 585
2024 aluminium alloy (heat treated-T3) 0.17 780

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AZ-31B magnesium alloy (annealed) 0.16 450

Table 2-63 Tabulation of n and K values from equation (2-28) for several alloys.

2.12 Elastic Recovery after Plastic Deformation

When the load applied during the course of a stress-strain test is released, some fraction of the total
deformation is recovered as elastic strain, that is, the specimen will contract in part back towards its
original dimension. The phenomenon is shown in Figure 2-33 where elastic recovery and strain
hardening occur.

Figure 2-333 Schematic tensile stress-strain diagram showing the phenomena of elastic strain recovery and
strain hardening. The initial yield strength is designated as σ y0 ; σ yi is the yield strength after releasing the
load at point D, and then upon reloading.

In Figure 2-33 note that σ yi > σ y0 due to strain hardening.

2.13 Impact and Fracture

Fracture is the separation of a body into two or more pieces in response to a stress at ambient
temperature. It may be tensile, compressive, shear or torsional. Fracture may be brittle or ductile.

i. Ductile fracture is where the materials experience plastic deformation associated with high
energy absorption.
ii. Brittle materials experience little or no plastic deformation with low energy absorption. The
contrasting modes of fracture are illustrated in Figure 2-34 and Figure 2-35.

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Chapter 2: Mechanical Properties

Figure 2-343 (a) Highly ductile fracture in which the specimen necks down to a point. (b) Moderately ductile
fracture after some necking. (c) Brittle fracture without any plastic deformation.

Figure 2-353 Stages in the cup-and-cone fracture. (a) Initial necking. (b) Small cavity formation. (c)
Coalescence of cavities to form a crack. (d) Crack propagation. (e) Final shear fracture at a 45° angle relative to
the tensile direction.

Cup and cone fracture in aluminium, and brittle fracture in steel are illustrated in Figure 2-36.

45˚

Figure 2-363 (a) Cup-and-cone fracture in aluminium (b) Brittle fracture in a mild steel.

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Ductile fracture is usually dull and fibrous in appearance, and upon magnification can appear
'dimpled', being one half of a micro void. Shear forces contribute to ductile fracture.

A typical fracture pattern for ductile materials is that of the cup and cone, illustrated in Figure 2-36(a).
During the tensile test, the tensile stress creates shear stress on planes that lie at an angle to the
longitudinal axis of the test piece. Deformation will proceed via the movement of dislocations on those
shear planes with the highest stress.

The force diagram illustrated in Figure 2-37 shows the tensile force F acting on the shaft of the test
piece of cross-sectional area A. If this force is resolved parallel to a plane with a normal that lies at an
𝐴𝐴
angle 𝜃𝜃 to the axis of tension, it yields a shear force τ = F sin 𝜃𝜃. The area of the shear plane is
𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
.

Figure 2-379

𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝐹𝐹 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠
Thus the shear stress on the plane shown = τ = = = σ sin𝜃𝜃 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐, where σ = F/A .
𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝐴𝐴/𝑐𝑐𝑜𝑜𝑜𝑜𝑜𝑜

When the shear strength is plotted against 𝜃𝜃, the maximum shear occurs at an angle of 45° to the
applied tensile force. Careful observation of cup and cone fractures shows this basic analysis to hold
in practice. See also Schmidt’s law in section 1.14.5.2.

Brittle fracture is where the surface is usually flat and shiny, often with chevron markings. For most
brittle materials fracture results from the repeated breaking of atomic bonds along crystallographic
planes known as cleavage. This type of cleavage is transgranular as pictured in Figure 2-38.

Brittle fracture in metals is believed to take place in three stages:

1. Plastic deformation concentrates dislocations on the slip or twin planes.

2. Shear stresses build up where dislocation movement is blocked, and micro-cracks are
nucleated at these sites.
3. Further stress will cause the micro-cracks to coalesce into macro-cracks, which then
propagate through the metal and result in failure.

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Figure 2-383 Schematic cross-sectional profile showing crack propagation through the interior of grains for
transgranular fracture.

Brittle fracture results from crack propagation at right angles to direction of stress. In some metals
crack propagation is along grain boundaries, that is, intergranular as shown in Figure 2-39.

Figure 2-393 Schematic cross-section profile showing crack propagation along grain boundaries for
intergranular fracture.

Grain boundaries can be embrittled by the deposition of carbides or by a corrosive environment.

2.13.1 Impact Fracture Testing

These tests measure the energy absorbed during the impact of a notched specimen of standardized
geometry. This parameter is useful in assessing the ductile to brittle transition. The test is qualitative,
and is useful for comparing materials, but not for design calculations. The Charpy V notch test is
outlined in Australian Standard AS 1544.

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Figure 2-403 (a) specimen used for Charpy and Izod impact tests. (b) A schematic drawing of an impact
testing apparatus. The hammer is released from fixed height h and strikes the specimen; the energy expended
in fracture is reflected in the difference between h and the swing height h'. Specimen placements for both
Charpy and Izod tests are shown.

The test piece specifications as outlined in AS 1544 is reproduced in Figure 2-41, Figure 2-42 and
Table 2-7.

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Figure 2-412 Arrangement of supports, test piece and striker. Dimensions are in millimetres.

Figure 2-422 Standard and subsidiary test pieces. Dimensions are in millimetres.

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Nominal Machining
Characteristic
dimension tolerance
Length 55 mm ±0.60 mm
Standard test piece 10 mm ±0.11 mm

Thickness
Subsidiary test piece 7.5 mm ±0.11 mm
Subsidiary test piece 6.7 mm ±0.06 mm
Subsidiary test piece 5 mm ±0.06 mm
Subsidiary test piece 2.5mm ±0.06 mm
Width 10 mm ±0.06 mm
Root radius of notch 0.25 mm ±0.025 mm
Depth below notch 8 mm ±0.06 mm
Distance of centre of notch from one end
27.5 mm ±0.42 mm
of test piece
Angle between plane of symmetry of
90° ±2°
notch and longitudinal axis of test piece
Angle of notch 45° ±2°
Angle between adjacent longitudinal faces
90° ±20°
of test piece
Table 2-72 Dimensions and tolerances of test pieces.

The hammer of the impact tester is raised to a set height, h, and then released. The hammer impacts
on the test piece as shown in Figure 2-41 for the Charpy test. Impact energy is absorbed by the
specimen at fracture, such that the hammer loses energy. The height after impact is h'. The dial on the
tester will record the energy lost by the pendulum, which is proportional to h – h'. This is equivalent
to the notch impact energy, usually read directly in joules from the scale.

2.13.2 Ductile to Brittle Transition

This is exacerbated by lowering the temperature. At lower temperatures, brittle fracture is more
likely to occur, and is accompanied by a reduction in impact energy.

Figure 2-433 Temperature dependence of the Charpy V-notch impact energy (curve A) and percent shear
fracture (curve B) for an A283 steel.

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The percentage of shear fracture is a measure of ductility fracture and this property increases with
increase in temperature. It can be seen from the impact energy-temperature diagrams below that an
alloys crystal structure and composition significantly alter impact energies at different temperatures.

Figure 2-443 Schematic curves for the three general types of impact energy-versus-temperature behaviour.

Figure 2-453 Influence of carbon content on the Charpy V-notch energy-versus-temperature behaviour for
steel.

Note the CVN (Charpy V notch) transition temperatures are approximately -50°C and 20°C for 0.11%C
steel and 0.22%C steel respectively.

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2.13.3 Assessment of Ductile/Brittle Fracture

Australian Standard AS 1544.5 provides a method for visually assessing brittle-ductile fracture.
Figure 1 of AS 1544.5 is reproduced below. Other relevant details for the quantitative assessment will
be included in the laboratory hand out.

Figure 2-46Fracture appearance assessment charts for 10mm×10mm test pieces. Dimensions in millimetres.

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2.13.4 Fracture Mechanics

Impact fracture testing, covered in section 2.13.1, provides comparative information on a material’s
toughness under a fairly rigid set of conditions. This test uses a notched stress raiser of fixed
geometry, and the impact is carried out at very high strain rates. It was found very difficult to
extrapolate the results of charpy or izod testing and achieve correlation with actual cases of structural
failure. As a consequence, the field of fracture mechanics has evolved. This has led to a more
fundamental understanding of the mechanism of failure, and has enabled quantitative relationships
to be developed relating the material properties and applied stresses.

2.13.4.1 Stress Concentration

Microscopic flaws present in all materials have the potential to amplify stresses, at their tips. The
magnitude of the stress concentration depends upon the size, shape, and orientation of the flaw.
Stress levels can be amplified to such an extent that ductile materials can fail catastrophically.
Typical flaws include microscopic cracks, as well as macroscopic internal discontinuities such as
voids, sharp corners and notches. These stress raisers can be on the surface or inside the structure.
Figure 2-47 illustrates the stress profile across the cross-section of an internal crack. The stress σm is
a maximum at the crack tip, reducing to the nominal stress σ0 away from the crack.

Figure 2-473

It can be shown that for an elliptical hole in a metal plate, oriented perpendicular to the applied stress,
the maximum stress at the crack tip σm is given by:
𝑎𝑎
σm = 2σ0 (𝜌𝜌 )1/2 (2-29)
𝑡𝑡

where a = length of a surface crack or half the length of an internal crack, and ρt = the radius of the
𝑎𝑎
crack tip. It can be seen that if ρt is very small, the term in equation (2-29) will be very large. Thus
𝜌𝜌𝑡𝑡
cracks with very small tips will greatly amplify the stress, and crack propagation will be initiated.
Stress raisers are more significant in brittle than in ductile materials. In ductile materials, plastic
deformation will occur when the applied stress exceeds the yield stress. In such materials the stress
distribution around the defect will be less than the theoretical maximum stress σm, and more
uniformly distributed than for a brittle material. In brittle materials the stress distribution around the
stress raiser will be close to the theoretical σm, as predicted by equation (2-29). When the magnitude
of the applied stress at the tip of a flaw exceeds the critical stress σc, a crack forms and propagates,
and this results in fracture.

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2.13.4.2 Fracture Toughness

Fracture toughness Kc is defined as the measure of a material’s resistance to fracture when a crack is
present.The relationship between the variables involved in the mechanism of crack initiation is given
by:
Kc = Yσc√𝜋𝜋𝜋𝜋 (2-30)
Where Y is a dimensionless constant, its value, depending upon crack geometry, material thichness,
and the mode of crack surface displacement. For fracture toughness, the units are MPa√𝑚𝑚. In order
to simplify calculations, and minimize the factors influencing the value of Y, certain initial conditions
have been specified that cover the most common situations, namely:

1. That crack dimensions are small relative to the bulk size of the component,
2. That the mode of crack surface displacement is specified as being 1 tensile, 2 sliding or 3
tearing. These modes are illustrated in Figure 2-48.

Figure 2-483

Under simplified conditions, a new term plane strain fracture toughness K1c may be defined as the
fracture toughness for bulky components, when the mode of crack surface displacement is type 1, or
tensile, as shown in Figure 2-48. This represents the most commonly encountered conditions in
practice.

K1c may be expressed as:

K1c = Yσ√𝜋𝜋𝜋𝜋 (2-31)
Table 2-8 lists plain strain fracture data for selected engineering materials.

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Table 2-83

2.13.4.3 Applications to Problem Solving

Equations (2-29)-(2-31), together with the data in Table 2-8, enable engineers to choose materials
with optimal properties to resist fracture and risk of failure. There are three variables in equations
(2-30) and (2-31). If any two are specified, the third is fixed. For example, if the stress level σ, and the
plain strain fracture toughness are fixed by design constraints, then the crack size a will be
determined by the numerical value of these factors. Under these conditions the maximum or critical
flaw size ac will be given by rearranging equation (2-31), where :
1 𝐾𝐾1𝑐𝑐 2
ac = ( ) (2-32)
𝜋𝜋 𝜎𝜎𝜎𝜎

Under these specified circumstances, ac would be determined, and non destructive tests carried out
on the component to determine whether any flaws were present, and if so, what size were they. There
are a number of test methods suitable for this type of detection, including dye penetrant, ultrasonic,
Xray, and optical microscopy.

2.14 Hardness Testing

Hardness is a measure of a materials resistance to localized plastic deformation. The original Moh’s
hardness test is still performed on minerals, indicating their relative position on the Moh scale.

In Moh’s hardness test, 10 representative minerals are arranged in increasing order of hardness
ranging from 1-10.

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Mineral Moh hardness

Talc 1
Gypsum 2
Calcite 3
Fluorite 4
Apatite 5
Orthoclase feldspar 6
Quartz 7
Topaz 8
Sapphire (corundum) 9
Diamond 10
Table 2-93 Moh’s hardness scale.

A mineral is selected from the above, which just scratches the unknown, thus the hardness number is
assigned.

Modern tests force an indenter into the surface of the metal. The depth of penetration or the
dimensions of the indent is then measured. Hardness tests are relative, but because of their ease of
performance are very commonly used for quality control. There is some level of correlation between
hardness and other mechanical properties.

2.14.1 Rockwell Hardness

This is the simplest and most widely used of the hardness tests. It involves making an indentation into
the specimen with a hard steel ball of set diameter, or a conical diamond for harder materials. The
hardness is determined by the difference in depth of penetration of the minor and major loads. The
minor load is 10 kg. The tables in Table 2-10 and Table 2-11 relate ball diameter and major load to
the various Rockwell scales.

Scale symbol Indenter Major Load (kg)

A Diamond 60
B 1
16 -in. ball 100
C Diamond 150
D Diamond 100
E 1
8 -in. ball 100
F 1
16 -in. ball 60
G 1
16 -in. ball 150
H 1
8 -in. ball 60
K 1
8 -in. ball 150
Table 2-103 Rockwell hardness scales.

Superficial Rockwell scales are used for soft or thin specimens. For reproducible tests, the specimen
thickness must be greater than ten times the depth of penetration.

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Scale symbol Indenter Major Load (kg)

15N Diamond 15
30N Diamond 30
45N Diamond 45
15T 1
16 -in. ball 15
30T 1
16 -in. ball 30
45T 1
16 -in. ball 45
15W 1
8 -in. ball 15
30W 1
8 -in. ball 30
45W 1
8 -in. ball 45
Table 2-113 Superficial Rockwell hardness scales.

2.14.2 Brinell Hardness (HB)

In this test, a 10mm ball is impressed, using loads ranging from 500-3000 kg. The diameter of the
indentation is measured with a hand microscope, and the Brinell hardness (HB) calculated using a
chart for the load employed. Equation (2-33) shows the relationship between the load, ball and
indentation diameters for Brinell hardness is:
2P
HB = (2-33)
π D D − D2 − d 2 
 
Where P = load applied in kg
D = diameter of the sphere in mm
d = diameter of the indentation in mm

2.14.3 A Summary of Hardness Measuring Techniques

Figure 2-493 Hardness-testing techniques

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2.14.4 Hardness Inter-Conversion

The comparison of several hardness scales is reproduced below, but inter-conversion needs to be
approached with some caution, unless the materials are similar.

Figure 2-503 Comparison of several hardness scales.

2.14.5 Correlation between Hardness and Tensile Strength

Since both properties, hardness and tensile strength, are a function of the metals resistance to plastic
deformation, they are roughly proportional, and equation (2-34) can be applied.
TS ≅ 3.45 × HB (2-34)
Where TS = tensile strength in MPa
HB = Brinell hardness

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2.15 Flexural Strength and the Three-point Bend Test

With the increasing popularity and widespread use of polymers and composites in engineering, it is
logical to present the mechanical behaviour of these materials in a format similar to that used for
metals. Although tensile strength and elastic modulus are important parameters for these materials,
design applications frequently require consideration to be given to the bending, rather than the
tensile mode. For this reason flexural properties are often most useful.

The important parameters frequently quoted are, flexural stress, flexural strength, flexural strain, and
flexural or bending modulus. These quantities can all be determined by using a bend test, either three
or four point, outlined in the ASTM standard D790-10. In this test a specimen of circular or
rectangular cross-section is loaded at its centre. Under these conditions the top surface is subject to
compression, and the lower surface to tension. Thus this one test allows compressive and tensile loads
to be applied, and their effects to be quantified. The load is applied until such time as the lower surface
fractures.

The three point bend test is illustrated schematically in Figure 2-51, where a test beam of span L is
subject to vertical loading P.

Figure 2-513

In the following subsections, the four flexural properties derived from the three-point bend test will
be discussed. The derivations of the formulae for each of these key properties is presented in full in
supplement 1 on MyLO.

2.15.1 Flexural Stress

Flexural Stress σf, is the stress at the midpoint of the outer surface of the beam, corresponding to any
point on the load-deflection curve. The flexural stress may be calculated from the equation (2-35).
3𝑃𝑃𝑃𝑃
σf = (2-35)
2𝑏𝑏𝑏𝑏2
Where P = applied load in N
L = span in mm = 16 d = 16 × thickness (mm)
b = width in mm
d = thickness in mm
σf = flexural stress in MPa

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2.15.2 Flexural Strength

Flexural Strength σfM, is the maximum flexural stress sustained by the test specimen during a bending
test, and may be calculated by substituting the stress corresponding to the yield point Y as indicated
in Figure 2-52. In this figure curve a represents a specimen that breaks before yielding, b represents
a specimen that yields and then breaks before the 5 % strain limit, and c represents a specimen that
neither yields nor breaks before the 5 % strain limit.

Yields and breaks before

Breaking before yielding
5% strain limit

Neither yields nor breaks

before 5% strain limit

Figure 2-524

2.15.3 Flexural Strain

Flexural Strain εf, is the nominal fractional change in the length of an element of the outer surface of
the test specimen at midspan, where the maximum strain occurs. It may be calculated for any
deflection D using equation (2-36).
6𝑑𝑑𝑑𝑑
εf = (2-36)
𝐿𝐿2

2.15.4 Flexural Modulus

Flexural Modulus, (modulus of bending, modulus of rupture), EB is defined as the ratio, within the
elastic limit, of stress to corresponding strain. It is calculated by drawing a tangent to the steepest
initial straight line portion of the load deflection curve illustrated in Figure 2-53, and using equation
(2-37).
𝑚𝑚𝑚𝑚3
EB = (2-37)
4𝑏𝑏𝑏𝑏3

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Symbols used in equations (2-35)– (2-37):

P = load at a given point on the load-deflection curve, N,

L = support span, mm,
b = width of beam tested, mm,
d = depth or thickness of beam tested, mm,
D = maximum deflection at the centre of the beam, mm,
m = slope of the tangent to the initial straight line portion of the load-deflection curve,
N/mm, and illustrated in Figure 2-53. See also problem and answer of Q9.7 and Q9.7a.

Figure 2-534

The slope m is for the tangent to the linear portion of the curve, CD, where B is taken as the new origin,
after applying “toe compensation”.

The standard method for performing flexural tests on unreinforced and reinforced plastics is outlined
in ASTM standard D790-10.

2.16 Fatigue and the Fatigue Test

Fatigue is defined as failure of structures at relatively low stress levels, when they are subjected to
cyclic and fluctuating stresses, often over long periods. Approximately 90 % of all field failures of
metals, polymers and ceramics is due to fatigue. Fatigue failure is usually brittle-like, even in ductile
materials. The effect of long periods of stress can cause brittle failure at stresses considerably below
the tensile stress as illustrated in Figure 2-54. Such failures can be sudden and catastrophic.

Figure 2-547

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Fatigue testing can be simulated by well designed apparatus set up in the laboratory to reproduce the
type of cyclic stresses experienced in practice. Figure 2-55 illustrates such an apparatus.

Figure 2-557

In fatigue testing a plot of the load amplitude S against the logarithm of the number of cycles N, yields
what is known as an S-N curve. Analysis of this graph can provide useful predictive information that
will enable the engineer to correctly design the component to meet the environmental requirements.

Figure 2-56 illustrates typical S-N curves for a material that shows a fatigue limit in (a), and no fatigue
limit in (b).

Figure 2-563

It must be realised that the S-N curves depicted are made up of many fatigue test data, usually
beginning with high stress amplitude, and a low number of cycles, and progressing to a lower stress
amplitude with a correspondingly higher number of cycles. For many ferrous metals a fatigue or an

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endurance limit is reached, below which fatigue failure will not occur. This limit is usually within 35
% to 60 % of the tensile strength.

For most non-ferrous metals, copper, aluminium etc, the S-N curve continues downwards, as in (b).

For these metals, a fatigue strength is specified that is the stress level at which failure occurs
corresponding to some specified number of cycles.

Statistical methods of analysis are applied to S-N curve interpretation, due to the very wide spread of
data obtained from these tests.

2.16.1 Mechanism of Crack Formation

There are three steps involved in failure by fatigue. They are:

1. Crack initiation, whereby a crack begins at a surface imperfection, which acts as a stress
raiser because of its higher level of surface energy.
2. Crack propagation, whereby the crack advances incrementally with each cycle of stress.
3. Final failure where the crack reaches a critical size, and rapidly advances causing sudden
failure.
It is beneficial to study the surface appearence of the fatigued surface. This is illustrated in Figure
2-57.

Figure 2-573

The fractured surface illustrates the point of origin, which would have been a stress raiser, and the
concentric rings originating from the origin of the crack, known as beach marks. These markings
indicate an interupted history of propagation during the life cycle. The many striations that make up
this macrostructure are called striations, and are only visible under elecron microscopy. Each
striation is considered to be part of a new crack front during a single load cycle. These striations are
illustrated in Figure 2-58.

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Figure 2-583

The reason for the decay in strength during stress-cycling is subtle, since it is due to changes at the
atomic level. The repeated stressing gives rise to areas of localized plastic deformation by slip
processes, leading ultimately to sharp surface discontinuities in the form of micro ridges and hollows.
(Refer also to section 2.7). These are the striations pictured in Figure 2-58, and illustrated
schematically in Figure 2-59.

Figure 2-597

The beach marks and striations associated with fractured surfaces are only associated with the slow
propagating stage of crack propagation. Once the crack reaches its critical size, final propagation is
rapid. The two types of surface are illustrated in Figure 2-60, where the smooth top section
corresponds to the slow speed of propagation, and the lower dull fibrous surface to the rapid ductile
fracture.

Figure 2-603

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2.16.2 Factors affecting Fatigue Life

The fatigue behaviour of engineering materials is very sensitive to a number of variables, any one of
which can promote fatigue. The most common variables are listed.

1. The mean stress experienced by the component as stress amplitude in the S-N test is very
significant, higher values resulting in earlier failures.
2. Surface effects and surface treatments are important elements in fatigue. Stress amplification
occurs at stress raisers such as surface imperfections like sharp edges, small nicks and
defects, and as already mentioned give rise to crack initiation. On the otherhand there are
several surface treatments readily available for stuctures and components that will render
the surface less susceptible to stress amplification.
Since many components are subject to external tensile forces, surface compressive forces will
partially nullify these forces and promote longer life. Treatments such as peening and case
hardening put the surface in compression. Peening involves bombarding the surface with ball
bearings and creating a series of continuous indentations, an array of compression sites. Case
hardening achieves the same compressive effect using a different procedure, (see section
6.11).
Surfaces are also greatly improved by smoothing or polishing, thus at least partially removing
the source of surface stress raisers.
3. Thermal and corrosive environments make major contributions to exacerbating premature
fatigue, and must be taken into account at the design stage.

2.17 The Collapse of the Twin Towers

The property of ferromagnetism is due to the direct influence of two effects that stem from quantum
mechanics, namely magnetic spin, and the Pauli exclusion principle.

The spin of an electron results in a magnetic dipole, which creates a magnetic field.

For many materials the total dipole moment of all the electrons is zero because the electron orbitals
are filled. Remember the Pauli exclusion principle allows only two electrons per orbital, and these
must have opposite spins.

For a metal such as iron there are many partially filled orbitals, ie. electrons with unpaired spins.
When these tiny dipoles are aligned in the same direction they create a measureable magnetic field.
In ferromagnetic materials as distinct from other materials the dipoles tend to align spontaneously in
the absence of an applied field. This is purely a quantum mechanical phenomenon.

If an ordinary piece of iron is placed in a magnetic field the dipoles will orientate themselves into
magnetic domains, and remain “snagged” or pinned on defects in the crystal lattice of the iron.These
domains are illustrated in Figure 2-61.

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Figure 2-61

The Curie temperature

This is the temperature beyond which the magnetic properties disappear. The magnetism is
destroyed by the increase of thermal vibrational motion, and the increase of entropy that ultimately
breaks down the symmetry of the magnetic domains.Typical Curie points are:

cobalt 1388 K
Iron 1043 K
Nickel 627 K

The collapse of the twin towers has been attributed to the loss of ferromagnetism in the steel structure
of the buildings at elevated temperatures.

Dr. Serge Dudarev has proposed that when steel is heated to a temperature of 5000C or greater, it
loses its strength. This weakening is due to the loss of the ordered magnetic domains which are
instrumental in sustaining the structural stability of the steel. The steel becomes soft, and the atoms
slide past each other more readily. This phenomenon is shown below:

Figure 2-62

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The steel backbone of the twin towers was probably exposed to temperatures close to 5000C or
greater when the thermal insulating panels became dislodged upon impact with the aircraft. The
roaring fire midway up the building heated the steel struts, and hence the structure became plastic
and collapsed, due to the weight of the floors above.

2.18 Questions and Answers – Mechanical Properties

Q9.1 A cylindrical specimen of a nickel alloy having an elastic modulus of 207 GPa and an original
diameter of 10.2 mm will experience only elastic deformation when a tensile load of 8900 N is applied.
Compute the maximum length of the specimen before deformation if the maximum allowable
elongation is 0.25 mm.

Q9.2 A load of 140,000 N is applied to a cylindrical specimen of a steel alloy displaying the stress-
strain behaviour shown in figure 1. It has a cross-sectional diameter of 10 mm.

(a) Will the specimen experience elastic/plastic deformation? Why?

(b) If the original specimen length is 500 mm, how much will it increase in length when this load
is applied?

Q9.3 A 10mm Brinell hardness indenter produced an indentation 2.50 mm in diameter in a steel alloy
when a load of 1000 kg was used.
(a) Compute the HB of this material.
(b) What will be the diameter of an indentation to yield a hardness of 300 HB when a 500 kg load
is used?
(c) Estimate the tensile strength of the steels tested above.

Q9.4 A piece of flat steel has to be bent around a drum 1.8 m in diameter. What is the maximum
thickness of the strip that can be made so that there shall be no permanent deformation when it is
removed from the drum? The elastic limit of the steel is 200 MPa and E is 200GPa.

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Q9.5 A beam is supported at both ends and uniformly loaded at its centre. The beam is 4.0 m long and
the load is 200kN. Given that the modulus of rigidity is 300 x 106 Nm2 , determine: (i) the slope at the
ends and (ii) the deflection at the beams centre.

Q9.6 A shaft of diameter 80 mm is running at 300 revs per minute, and transmits 50 kW of power.
Find

(a) the maximum stress in the shaft

(b) the angle of twist in degrees in a length of 30 m.

The shear modulus is 80 GPa.

Q9.7 The load-extension curve below was obtained from a three-point bend test carried out in
accordance with ASTM 790-10. The test piece was taken from a composite panel manufactured from
a 5 mm PVC foam core and clad with Kevlar/glass/epoxy. The dimensions of the test piece were width
= 11.1 mm, depth = 11.1 mm and span = 179 mm. Determine,

(a) the flexural strength at the yield point

(b) the maximum flexural strength

(c) the flexural modulus

(d) the flexural strain at the maximum load

(e) the mode of fracture.

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A9.1
Given: E = 207 GPa
d = 10.2 mm = 10.2 x 10-3 m
F = 8900 N
∆l = 0.25 mm

Cross-sectional area A = πd2/4 = π x (10.2 x 10-3)2 m2

= 81.71 x 10-6 m2
σ = F/A = 8900 N/81.71 x 10-6 m2
= 108.92 x 106 Pa
108.92 𝑥𝑥 106
But ε = σ/E =
207 𝑥𝑥 109
= 5.26 x 10-4,
and ε = ∆l/l
l = ∆l/εz = 0.25 mm/5.26 x 10-4 mm
= 475 mm.

A9.2
(a) From the graph in Figure 1, it can be seen that the maximum stress corresponding to the elastic
or linear portion of the curve is 1300 MPa. If the actual stress applied is greater than this value, then
the cylindrical specimen will be experiencing plastic deformation.
CSA of specimen = πd2/4 = π x( 10 x 10-3)2/4 m2 = 78.54 x 10-6 m2
But σ = F/A = 140,000 N/78.54 X 10-6 m2 = 1783 MPa.
Since σapplied > σyield
∴ 𝑡𝑡ℎ𝑒𝑒 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑖𝑖𝑖𝑖 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑.
(b) Given, l0 = 500 mm, find the change in length, ∆l.
But σ = εE = (∆l/l) E, where E is the elastic modulus.
The value of the elastic modulus may be estimated from the slope of the stress/strain curve
in the elastic region. The estimate is 200,000 x 106 Pa.
Hence ∆l = l σ /E
0.500 𝑥𝑥 1783 𝑥𝑥 109
= 200,000 𝑥𝑥 106
m
= 4.5 mm.

A9.3
(a) Given: D = 10mm, d = 2.5 mm, L = 1000kg
2𝑃𝑃 2000 2000
HB = = = = 200.5
𝜋𝜋𝜋𝜋�𝐷𝐷−√𝐷𝐷 2 − 𝑑𝑑 2 � 10𝜋𝜋(10−√100−6.25 ) 10𝜋𝜋(10−9.682 )

(b) Given HB = 300, D = 10 mm, P= 500kg

Substituting into the formula for Brinell hardness in part (a) gives:
1000
300 =
10𝜋𝜋(10− √100− 𝑑𝑑2 )

300π(10 – √100 − 𝑑𝑑 2 )= 100

10 – √100 − 𝑑𝑑2 = 1/3π
100 – d2 = (10 – 1/3π)2 = 97.889

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d = √100 − 97.889 = 1.45 mm

(c) Given, TS (MPa) = 3.45 HB,
When HB = 200.5,
TS (MPa) = 3.45 x 200.5
= 692.
When HB = 300,
TS (MPa) = 3.45 x 300
= 1035

A9.4
The figure below illustrates the drum for bending the steel strip.

𝜎𝜎 𝐸𝐸
Using the general bend equation, = , and given σ = 200 x 106 Pa, y = 0.5t, E = 200 x 109 Pa,
𝑦𝑦 𝑅𝑅

200 𝑥𝑥106 200 𝑥𝑥 109

R = 0.9 + 0.5t. Substitute these values into the bend equation, giving 0.5𝑡𝑡 = 0.9+0.5𝑡𝑡 . Solving this
equation for t gives t = 0.0018 m, that is the maximum thickness of steel that can be bent without
causing permanent deformation is 1.8 mm. It should be noted that the value given for the elastic limit
is actually the yield strength σy which is the maximum stress that can be applied before plastic or
permanent deformation occurs.

A9.5
𝑑𝑑𝑑𝑑 𝑊𝑊𝐿𝐿2
(a) The slope at the ends of the beam is = 16𝐸𝐸𝐸𝐸 , (see Supplement 1 equation 17), where W =
𝑑𝑑𝑑𝑑
load, L = beam length and EI = modulus of rigidity. The slope at the ends of the beam =
200 𝑥𝑥 103 𝑁𝑁 𝑥𝑥 42 𝑚𝑚2
16 𝑥𝑥 300 𝑥𝑥 106 𝑁𝑁𝑚𝑚2
= 0.00067

𝑊𝑊𝐿𝐿3 200 𝑥𝑥 103 𝑁𝑁 𝑥𝑥 43 𝑚𝑚3

(b) The equation for the deflection of the beam is y = 48𝐸𝐸𝐸𝐸
= 48 𝑥𝑥 300 𝑥𝑥 106 𝑁𝑁𝑁𝑁2
= 0.89 mm

A9.6
The rotating shaft with angle of twist ∅ is illustrated below.

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Chapter 2: Mechanical Properties

𝐺𝐺∅
(a) The general twist equation is T/J = τ/r = , and the power developed by a rotating shaft
𝐿𝐿
= 2πNT/60. Solving for T, the maximum torque is,
𝐽𝐽
𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑥𝑥 60 50,000 𝑋𝑋 60 𝑠𝑠/𝑚𝑚𝑚𝑚𝑚𝑚
T = = 𝑆𝑆
= 1592 Nm
2𝜋𝜋𝜋𝜋 2𝜋𝜋 𝑥𝑥 300 𝑟𝑟𝑟𝑟𝑟𝑟/𝑠𝑠

(b) J the polar second moment for a circular cross-section is,

𝜋𝜋 𝑥𝑥 44 𝑥𝑥 10−8 𝑚𝑚4
J = πr4/2 = 2
= 402 x 10-8 m4
𝑇𝑇𝑇𝑇 1592 𝑁𝑁𝑁𝑁 𝑥𝑥 40 𝑥𝑥 10−3 𝑚𝑚
From the general twist equation, the shear stress τ = = = 158.4 N/m2
𝐽𝐽 402 𝑥𝑥 10−8 𝑚𝑚4
𝑇𝑇 𝐺𝐺∅ 𝑇𝑇𝑇𝑇 1592 𝑁𝑁𝑁𝑁 𝑥𝑥 30 𝑚𝑚
Since = , ∅ the angle of twist = =
𝐽𝐽 𝐿𝐿 𝐽𝐽𝐽𝐽 402 𝑥𝑥 10−8 𝑚𝑚4 𝑥𝑥 80 𝑥𝑥 109 𝑁𝑁/𝑚𝑚2

∅ = 0.145 rad = 0.145 rad x 57.30 / rad = 8.510

Q9.7A

Refer to the above load-extension curve for answers to this question.

(a) The yield load P = 9000 g = 9.00 kg x 9.82 m/s2 = 88.3 N
3𝑃𝑃𝑃𝑃 3 𝑥𝑥 88.3 𝑁𝑁 𝑋𝑋 179 𝑚𝑚𝑚𝑚
Flexural yield stress σf = = = 17.3 MPa
2𝑏𝑏𝑑𝑑 2 2 𝑥𝑥 11.1 𝑚𝑚𝑚𝑚 𝑥𝑥 11.12 𝑚𝑚𝑚𝑚2

(b) Pmax = 11,000 g = 11.0 x 9.81 = 107.9 N

3𝑃𝑃𝑚𝑚𝑚𝑚𝑚𝑚 𝐿𝐿 3 𝑥𝑥 107.9 𝑥𝑥 179
σfM = = = 21.2 MPa
2𝑏𝑏𝑑𝑑 2 2 𝑥𝑥 11.1 𝑥𝑥 11.12
𝐿𝐿3 𝑚𝑚 1793 𝑚𝑚𝑚𝑚3 𝑥𝑥 30.4 𝑁𝑁/𝑚𝑚𝑚𝑚
(c) Flexural modulus EB = = = 2871 MPa = 2.87 GPa, where m = slope
4𝑏𝑏𝑑𝑑 3 4 𝑥𝑥 11.1 𝑚𝑚𝑚𝑚 𝑥𝑥 11.13 𝑚𝑚𝑚𝑚3
of the elastic region of the load-extension curve, (see above figure).
6𝑑𝑑𝑑𝑑 6 𝑥𝑥 11.1 𝑚𝑚𝑚𝑚 𝑥𝑥 4.0 𝑚𝑚𝑚𝑚
(d) Flexural strain εf = 2 = = 0.0083 = 0.83 %, where D = maximum
𝐿𝐿 1792 𝑚𝑚𝑚𝑚2
deflection = 6.5 – 2.5 = 4.0 mm.

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Chapter 2: Mechanical Properties

(e) The test sample neither yields or breaks before the 5 % strain limit, (see stress-strain curves
section 2.16.2.
References

7 AS 1391
8 AS 1544
9 Callister, Jr., William D. Materials Science and Engineering an Introduction. 7th ed. York,
PA: Techbooks, 2007
10 ASTM Standard D790-10.
11 Van Vlack, L. H, Elements of Materials Science and Engineering, 3rd ed., Addison-
Wesley, 1975.
12 Smith, W. F, Hashemi, J, Foundations of Materials Science and Engineering, 5th ed.,
McGraw-Hill, 2010.
13 Shackelford, J. F, Introduction to Materials Science for Engineers, 3rd ed., Macmillan,
1992.
14 Askeland, D. R, The Science and Engineering of Materials, 2nd ed., PWS-Kent, 1989.
15 Shackelford, James, F., Introduction to Materials Science for Engineers, 3rd ed.,
Macmillan, 1992.
16 Fusion power seeks super steels by Jennifer Carpenter,Science reporter,BBC
news,Liverpool,UK.
17 Ferromagnetism hyperphysics.phy-astr.gsu.edu/Hbase/Solids/ferro.html
18 Stephens, R.C., Ward, J. J. Applied Mechanics, 3rd edition, Macmillan, 1972

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Chapter 3: Polymers

Polymers

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Chapter 3: Polymers

3.1 Introduction
A polymer is a molecular compound with a high molecular weight, consisting of “many parts”. The
two broad groups of polymers of greatest interest in the industrial world are plastics and elastomers.
Plastics are a wide and diverse group of synthetic materials made from petrochemicals, and processed
by forming and molding into shape. The two broad classes of plastics are thermoplastics and
thermosets. Thermoplastics can be softened by partial melting, and are therefore readily shaped
because of their plasticity. They can also be recycled easily. Examples include polyethylene,
polypropylene and polyvinylchloride. Thermosets cannot be melted without degradation, and once
polymerized cannot be re-molded. Typical examples include epoxy, phenolic and urea-formaldehyde
resins.

Elastomers or rubbers are another broad class of plastics which can be deformed by a large amount
and then return to their original shape.

In engineering materials there is a strong link between structure and properties. This is particularly
the case with polymers, because of the great number of structures possible for chains of carbon atoms,
both open and closed, and both unbranched and branched. Although the covalent carbon-carbon
bonding within the polymeric chain is of prime importance in providing structural integrity to all
classes of polymers, it is more often the presence or absence of intermolecular bonds that impart
special characteristics within a family of polymers. A good example of this is to be found in the group
known as the vinylidene family, including polyethylene, polyvinylchloride and polystyrene discussed
in detail in section 3.6.2.

It is the strong connection between polymer morphology and the nature of the intermolecular
bonding resulting from, or contributing to that structure, that gives rise to the large variation of
mechanical, thermal and electrical properties encountered for example, in the family of polyethylene
polymers.

In section 3.2 we will examine the nature and characteristics of both the covalent bond and the various
forms of intermolecular bonding in polymers.

3.2 Bonding in Polymers

3.2.1 The carbon-carbon covalent bond

Of all the elements in the periodic table, carbon is quite unique in one property. This is the ability to
bond to itself in the form of chains and rings. This characteristic has led to the potential for a huge
number of complex molecules, and ultimately to the evolution of diverse life forms that make up the
animal and plant kingdoms.

The nature of the bond between carbon atoms depends as do all other forms of chemical bonding, on
the electron configuration of its atoms. Carbon is element number 6 in the periodic table, and its
electronic configuration may be written as 1s2 2s2 2p2. In accord with quantum mechanical principles,
the Pauli exclusion principle, and Hund’s rule, we may represent the electrons in their respective
orbitals, schematically shown as “boxes” as in Figure 3-1.

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Chapter 3: Polymers

Figure 3-12

Each half arrow in the box represents an electron with opposite spins.

In bond formation, the two carbon atoms approach each other until the attractive and repulsive forces
balance. This stable state of bonding equates with a state of minimum energy, in line with
thermodynamic principles, as illustrated below. In this bonded state there is an overlap of electron
orbitals in a configuration that promotes the most stable bond possible.

Figure 3-21

Figure 3-2 shows the optimal bond distance of 0.74A0 which is associated with minimum energy.

The most stable bonding state is achieved when there is some hybridization associated with the
overlapping orbitals. This is illustrated below for sp2 hybridization, which is associated with a carbon-
carbon double bond, commonly encountered in monomers.

Figure 3-33

This more favourable electron state is achieved first by the promotion of one of the 2s electrons to
the 2p orbital, and then a hybridization of two electrons from the 2p orbital with one from the 2s
orbital, giving the fully hybridized sp2 orbital, pronounced sp two. The figure below illustrates the
three sp2 orbitals of carbon in the horizontal plane at angles of 1200, with the remaining p orbital
perpendicular to the plane.

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Chapter 3: Polymers

Figure 3-41

THE ETHENE LINKAGE

Since ethene, and similar molecules like propene represent a family of monomers producing some of
the most commonly used polymers, we will now examine the molecular geometry of this compound,
and in particular its key feature, the double bond. The figures below show the geometry of ethene as
discussed in relation to the carbon atom.

Figure 3-51

The σ bonds between the H and C atoms result from the overlap between the sp2 orbital from carbon
and the 1s orbital from hydrogen, and are a single covalent bond. A σ bond also links the two C atoms.
The additional presence of the 2p electrons, one from each of the carbon atoms occupy a space
perpendicular to the plane of the molecule, and overlap as shown. This overlap produces a diffuse
electrical cloud, or π bond. The combination of σ and π bonds forms what is commonly called the
double bond. The two major effects of this type of bond is that firstly it prevents free rotation of the
two carbon atoms, and secondly imparts high chemical reactivity to any molecule where it is present.
The ease with which alkenes, and in particular ethene react is due to high electron density
surrounding the double bond. The concentration of negative charge will inevitably attract electron
seeking, or electrophilic reagents. This is the key to polymerization reactions.

It should be pointed out that the molecular geometry is determined by the type of hybridisation of
the organic compound , other combinations being sp3 associated with single bonds and tetrahedral
geometry, and sp associated for the triple bond, eg in acetylene.

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3.2.2 Intermolecular Bonding

There are in fact four fundamental forces at play in the universe. In order to gain a perspective on the
bonding forces in materials, and to see these in context, it will be useful to list and briefly define these
four fundamental forces at the outset. They are:

i. The strong nuclear force. This is the force that holds the nucleus of atoms together.

ii. The electromagnetic force. This is the force that holds atoms and molecules together and is
involved in chemical bonding.

iii. The weak nuclear force. This is a nuclear force responsible for beta decay processes in
radioactive elements.

iv. Gravity. This is the weakest force and plays no role in chemical bonding. Its effect however on
a cosmic scale is profound.

The relative strength of these forces are 1 : 0.007 : 10-6 : 6 x 10-39 respectively.

The basic electrostatic or coulombic forces present between atoms has been outlined in sections
1.2.1.4 and 2.1, and should be reviewed before proceeding.

Intermolecular bonds are defined as energies between molecules, not between atoms within a
molecule. They are considerably weaker than ionic, covalent and metallic bonds, with bond energies
that range between 4 and 30 kJ/mol. Intermolecular bonds often known collectively as secondary
bonds arise from atomic or molecular dipoles.

A dipole may be defined as a pair of equal and opposite charges that are separated by a small distance.
Dipoles result from a difference in electronegativity between atoms in a molecule. The net dipole
moment of a molecule results from the vector sum of the individual dipoles. In symmetrical molecules
the net dipoles will cancel. In asymmetric molecules a net dipole moment will result.

Electronegativity is the tendency for atoms to attract electrons to themselves. Non-metals on the
right hand side of the periodic table exhibit this property. Figure 3-6 illustrates the electronegativities
of the elements, together with numerical estimates of comparative magnitude, as determined by
Pauling.

Figure 3-62: Periodic table of Pauling electronegativities

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Dipoles: Dipole interactions may occur between (i) induced dipoles, (ii) induced dipoles and polar
molecules and (iii) polar molecules.

The bonding that occurs between dipoles results from the electrostatic attraction between the
positive end of one dipole and the negative region of the adjacent one, as illustrated in Figure 3-7.

Figure 3-72: Dipole-dipole interaction

Van der Waals or Dispersion Bonding

All molecules above absolute zero temperature are in a constant state of random motion. As such,
random distortions of their electrical symmetry occurs. The result of these distortions are short lived
induced dipoles. These transient dipoles will induce dipoles in adjacent molecules, resulting in a short
range chain reaction. These weakly attractive forces are temporary and fluctuate, but have a
cumulative net effect, particularly in polymers where the number of atoms are large. The effect of
these dispersion forces can produce significant changes in mechanical and thermal behaviour in some
polymers. Figure 3-8 illustrates schematically the formation of a temporary induced dipole that
results in the formation of this type of intermolecular bond.

Figure 3-82: Formation of an induced dipole, (dispersion bonding)

The dispersion bond is present to a greater or lesser extent in all materials.

Dipole-Dipole Bonds

Permanent dipoles can exist in certain molecules because of their asymmetry and also because of
differences in the electronegativities of the atoms that make up the molecule. In hydrogen chloride
for example, the difference in Pauling electronegativities between hydrogen and chlorine is 2.9-
2.1 = 0.8. In spite of the symmetry of the HCl molecule, charge separation will occur, with the
distribution of the negative charge concentrating on the more electronegative chlorine, and the
resultant positive charge on the hydrogen. The net effect is the production of a permanent dipole on
HCl as illustrated in Figure 3-9.

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Chapter 3: Polymers

Figure 3-9: The permanent dipole for HCl

The polar HCl molecule will induce a dipole in an electrically symmetrical molecule as illustrated in
Figure 3-10. The electrically symmetrical molecule could be butane C4H10, a simple hydrocarbon.

Figure 3-102: Induced dipole by a permanent dipole

Hydrogen Bonds

The hydrogen bond is a special case of dipole-dipole bonding between two molecules with permanent
dipoles, and is the strongest of all the secondary bonds. When hydrogen is coupled with strongly
electronegative elements fluorine, nitrogen and oxygen as in HF, NH3 and H2O, a strong permanent
dipole will exist, with the positive end of the dipole on the hydrogen atom. In a cluster of these
molecules the electronegative element F, N or O will draw the single valence electron of the hydrogen
atom to itself, and become negative. The hydrogen atom thus becomes a proton. Its positive charge is
stronger because it is unhindered by inner shells of electrons. Therefore the negative dipole can more
closely approach the unshielded proton, thus strengthening the bond. This last point is crucial, since
all secondary bonds are short range acting and diminish rapidly with distance separation, in accord
with the inverse square law.

The atypical properties of water result from its hydrogen bonding. Polymers containing N, F and O in
their structure, for example nylon, will exhibit superior physical properties due to hydrogen bonding.
Figure 3-11 illustrates the nature of the hydrogen bond between two molecules of water.

Figure 3-111: A hydrogen bond

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The strength of the hydrogen bond may be as high as 50 kJ/mol.

Secondary bonds although considerably weaker than ionic, covalent and metallic bonds are
responsible for a range of properties such as solubility, surface tension, vapour pressure, volatility
and viscosity. With respect to polymers they have profound effects on bulk properties such as
strength, stiffness, softening temperature and the glass transition temperature Tg as discussed in
sections 3.4.2 and 3.4.3.

3.3 Polymerization and Polymers

3.3.1 Introduction

Polymers include such diverse materials as plastics, rubbers, and adhesives, and are giant molecules
with molecular weights ranging from 10,000 to 1,000,000 g/mol. They are classified as organic
polymeric molecules which are made by joining together very large numbers of simple reactive
molecules called monomers.

Polymers are light weight, corrosion resistant, inexpensive materials, widely used because of their
range of properties which include transparency, low coefficient of friction, and electrical insulation.
Applications include coatings, paints, adhesives, fabrics, tyres, foams, packaging, prostheses, sporting
goods, and many others.

The source of monomers for the manufacture of polymers are petrochemicals, which are naturally
occurring, but non renewable.

3.3.2 Classification

The three common methods of polymer classification are summarised in the following table.

Behaviour General Structure Monomer Joining Mechanism

Thermoplastic Flexible linear chains Addition or condensation
Thermosetting Rigid three dimensional network Condensation to produce the cross-links
Elastomer Linear cross-linked chains Addition produces chains and cross-links
Table 3-1

3.3.3 Polymer Structure

Linear polymers form long chains, which are made by either addition or condensation
polymerization. The individual chains are strong due to the covalent bonds present, but between
chains the bonding is weak secondary or Van der Waals bonds. Linear polymers are flexible because
of this morphology.

Network polymers are cross-linked in three dimensions, and are therefore rigid and strong.

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3.3.4 Polymer Behaviour

Thermoplastic polymers are plastic, ductile, and may be heated and cooled repeatedly without
structural damage. This property enables these polymers to be reprocessed, reclaimed, and moulded
and extruded into any desired shape by mass production.

Thermosetting polymers being cross-linked are hard and rigid, and cannot be melted without
decomposing.

Elastomers show intermediate behaviour. They can be elastically deformed to a large extent, without
permanent change to their shape.

3.3.5 Structure Representation

Figure 3-12

The above diagram illustrates the ways in which polymer structures may be represented. Each style
has its own particular merits.

i. (a) and (b) are 3D models showing the tetrahedral linkages.

ii. (c) and (d) show the structure in 2D, and are easier to draw.
Polymers more than most materials demonstrate the close link between structure and properties.

3.3.6 Polymerization of Ethene to Polyethylene

Ethene is an alkene, and alkenes react by addition across the double bond. Addition polymerization
requires a catalyst-initiator to start the reaction. The most common initiator is a peroxide, a very
reactive and toxic compound. Because the peroxide linkage is fairly weak, the peroxide will cleave in
the presence of UV radiation, (step 1). Free radicals form, which then initiate the polymerization
reaction, (step 2). A free radical is a chemical fragment with only one electron. It seeks out a site of
available electrons, in this case the double bond of ethene. In so doing it satisfies the need for a
bonding pair, linking in consequence to a molecule of ethene. This process is repeated many times,
and the molecular chain is propagated, (step 4). The final stage in the polymerization process is
termination, (step 5). Here two polymeric free radicals unite to form the final polymer, regenerating

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the peroxide catalyst as a second product. These 5 stages of the polymerization process are shown
below in Figure 3-13.

Figure 3-13

3.3.7 Other Important Addition Polymers

The mechanism for the polymerization of ethene is applicable to other important polymers whose
monomers are based on small variations to the ethene molecule. These polymers include
polypropylene, polyvinylchloride, polystyrene, and polytetrafluoroethylene. The similarities between
these polymers and their monomers can be seen from the table below.

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Chapter 3: Polymers

Figure 3-14

3.3.8 Chain Formation and Functionality

Addition polymerization occurs when the monomer contains a double bond. Any compound
containing a double bond has a functionality of two, and is termed bifunctional. That is there are two
locations at which molecules can be attached, and these are the two carbon atoms either side of the
double bond. The resulting polymer will be chain like, and two dimensional in shape. A monomer
which is trifunctional will have three bonding sites, and will form a three dimensional polymer
network. 3D polymers are generally stronger than 2D, or chain polymers. The figure below illustrates,
(a), bifunctional ethene,

Figure 3-15 (b), trifunctional ethyne, and (c), phenol, which is trifunctional or greater.

3.3.9 Chain Formation by Condensation Polymerization

Linear polymers are also formed by condensation polymerization, giving structures and properties
similar to addition polymers. In condensation polymerization, a simple molecule like water is
eliminated as a by-product of monomer combination during the reaction, unlike addition reactions.
An important polymer manufactured by condensation polymerization is 6, 6- nylon. The reaction of
the two monomers to form nylon is illustrated below.

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Chapter 3: Polymers

Figure 3-16

The monomers are hexamine-1,6-diamine, and adipic acid. One of the amine groups condenses with
one of the carboxylic acid groups forming the amide linkage, with the simultaneous elimination of a
molecule of water. This process continues, thus building a long chain polymer. It will be noted that
each monomer has a functionality of two, and therefore nylon is a linear polymer.

3.3.10 Chain Shape and Stereoisomerism

A polymer consists of random coils and entanglements as shown in Figure 3-17.

Figure 3-172 Schematic representation of a single polymer chain molecule that has numerous random kinks
and coils produced by chain bond rotations.

This structure results in a number of special characteristics associated with polymers such as high
elasticity, usually associated with rubbers. Certain mechanical and thermal properties can be
explained by considering molecular shape, for example, rotational flexibility. The flexibility is due to
the freedom of polymer chains to rotate about their single bonds.

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Rotational flexibility, such as in polythene, is reduced when double bonds or large bulky side groups
are introduced into the chain. Polystyrene is therefore more rigid than polyethylene.

Figure 3-182 Schematic representation of (a) linear, (b) branched, (c) cross-linked, and (d) network (three-
dimensional) molecular structures. Circles designate individual repeat units.

3.3.11 Degree of polymerization

The physical properties of polymers are very significantly affected by their molecular weight, which
is determined by how far the polymerization is allowed to proceed. Factors such as the quantity of
initiator added, as well as the type of catalyst used, and the temperature and viscosity of the reaction
mixture will affect the final molecular weight. In practice the chains are not all of the same length, and
hence each chain will have a different weight. Under these conditions a statistical approach is
required to determine the molecular weight, where the chains are divided into size ranges, and the
fraction of chains having molecular weights within this range determined. The weight average
molecular weight 𝑀𝑀 � w is expressed as:
�w
𝑀𝑀 = Σfi Mi /Σfi
where Mi is is the mean molecular weight of each range, and fi is the weight fraction of the polymer
having chains within that range.

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3.3.12 Polymer Classification Scheme

Figure 3-192 Classification scheme for the characteristics of polymer molecules.

3.4 Effect of Heat on Thermoplastics

3.4.1 Crystalline Materials

In this section we will investigate the structural changes that occur when a thermoplastic is cooled
from the liquid state. Before we deal with plastics it will be useful to review the solidification
behaviour of pure crystalline materials like metals, alloys, salts and organic chemicals.

Figure 3-204

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Figure 3-20 (a) and (b) represent the temperature-time melting and solidification curves for
naphthalene, melting point 800C. Several points need to be emphasised. During the period when the
substance is melting, the temperature is constant. For melting, it is during this period represented as
B in figure (a) that latent heat of fusion is absorbed. Only when this phase change is complete will the
temperature begin to rise again. Curve (b) represents the cooling curve for naphthalene. At B the
latent heat of fusion is released, after which the temperature of the naphthalene continues to drop
again.

There is a further change associated with phase change, and that is an accompanied change in volume.
For most solids the volume decreases as the substance freezes, two notable exceptions being water
and cast iron.

Curve (c) represents an amorphous material such as glass and many polymers. It will be noted that
the process of freezing occurs over a range of temperature, unlike the pure crystalline naphthalene.
During this period the material transforms from a plastic to a final glassy state, which may be likened
to a ductile to brittle transition. As these changes occur there is also a reduction in volume, but less
marked than for crystalline materials.

3.4.2 Solidification of noncrystalline thermoplastics

When noncrystalline thermoplastics are slowly cooled, there is no sudden change in specific volume
and no sudden thermal arrest plateau as with crystalline substances. This is illustrated in Figure 3-21.

Figure 3-215

The section of curve represented by A,B,C indicates a slow change in specific volume when the plastic
is in a “rubbery”state. The change in slope occurs at a temperature marked Tg known as the glass
transition temperature. At Tg the plastic changes from a flexible rubbery state to a brittle glassy state.
This brittle state corresponds to a significant reduction in molecular chain motion at lower
temperatures, and consequently a change in mechanical properties, in particular a decrease in
toughness. The value of Tg is profoundly affected by the molecular structure of the particular polymer,
which is in turn determined by the conditions applying at the time of polymerization, including the
type of catalyst employed.

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3.4.3 Solidification of a partly crystalline thermoplastic

Figure 3-21 illustrates the cooling curve marked B, E, F for a partly crystalline thermoplastic. It will
be noted that there is a partially defined freezing/melting point marked Tm, in contrast to the
noncrystalline amorphous plastic. Also BE represents a reduction in volume which is a direct result
of the phase change. Section E corresponds to a transformation, during which crystalline phase and
supercooled viscous liquid co-exist. After the glass transition temperature is passed, the material
changes to the glassy state that consists of crystalline regions in a glassy noncrystalline matrix.

Figure 3-22 illustrates possible model structures for a partly crystalline thermoplastic. Note that
tangled chains represent amorphous regions, and the more ordered parallel and uniformly folded
chains represent crystalline regions.

Figure 3-225

The following table gives the glass transition temperatures for selected thermoplastics.

PLASTIC Tg (0C)
Polyethylene -110
Polypropylene -18
Polyvinylchloride 29
Polystyrene 75-100
Polymethylmethacrylate 72
PTFE 115
PAN 95
Table 3-2

3.5 The Structure of Thermoplastics

3.5.1 The Structure of partly crystalline thermoplastics

Microscopic examination of selected polymers has shown that they consist of regions with small
crystals, dispersed between regions which are non-crystalline, or amorphous. The crystalline
component of the polymer consists of thin platelets or lamellae up to 20nm thick and 10,000nm long,
illustrated in Figure 3-23.

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Figure 3-232 Electron micrograph of a polyethylene single crystal. 20,000×.

The molecular chains of each molecule within each platelet are regularly folded as depicted in Figure
3-24.

Figure 3-242 The chain-folded structure for a plate-shaped polymer crystallite.

Many polymers are semi-crystalline, and exhibit a "spherulite" structure when crystallized from the
melt. The bulk spherulite consists of radiating regions of crystallites showing the folded chain
structure, in between are regions of amorphous material as illustrated in Figure 3-25.

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Figure 3-252 Schematic representation of the detailed structure of a spherulite.

As the crystallisation process nears completion the boundaries of the many spherulites interact,
forming planar boundaries, analogous to grain boundaries in polycrystalline metals. The crystal
structure is illustrated in Figure 3-26 for polyethylene, and is similar to that shown by Kevlar.

Figure 3-262 A transmission photomicrograph (using cross-polarized light) showing the spherulite structure
of polyethylene. Linear boundaries form between adjacent spherulites, and within each spherulite appears a
Maltese cross. 525×.

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During non-equilibrium cooling of polymers, various types of defects occur. Again these are similar
to those found in metals, as illustrated in Figure 3-27.

Figure 3-27 Schematic representation of defects in polymer crystallites.

3.5.2 Stereoisomerism in thermoplastics

Properties such as the glass transition temperature and the proportion of crystalline and amorphous
structure in a thermoplastic have a significant effect on the mechanical and physical properties. These
properties are also in turn determined by the molecular structure, ie the shape, the degree of
branching, and the intermolecular forces acting between the chains in the polymer.

Certain thermoplastics such as polypropylene can exist in three different stereoisomeric forms, with
each isomer possessing different physical properties. Stereoisomers of a compound have the same
chemical composition, but differ in their three-dimensional structure. The three stereoisomeric forms
are atactic, isotactic and syndiotactic. These terms refer to the location of a side group with respect to
the parent chain in the polymer. Figure 10.21 illustrates the three stereoisomers of polypropylene
with respect to the position of the methyl group.

For the atactic form the methyl groups are randomly distributed along the main chain.
For the isotactic form the distribution of methyl groups are all on the same side.
For the syndiotactic form the distribution of methyl groups alternates from side to side.

The discovery of a stereospecific catalyst by Ziegler and Natta in 1963 enabled the highly crystalline
iso form of polypropylene to be commercially produced. With a melting point of 165-1750C, this
highly ordered crystalline form possesses superior strength and heat deflection temperatures than
the atactic form.

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Least Crystalline

Most Crystalline

Figure 3-285 (a)= Atactic, (b) = Isotactic and (c) = Syndiotactic

3.6 Commercially important thermoplastics

3.6.1 Introduction

This section will cover a selected number of important thermoplastics, and deal with their structure,
processing, properties and uses. Plastics to be covered are, polyethylene, polypropylene, polystyrene,
polyacrylonitrile, polymethylmethacrylate and polytetrafluoroethylene.

3.6.2 Vinyl and vinylidene polymers

A broad range of useful polymers are based on the polyethylene molecule. These structures are
obtained by substituting one or more of the hydrogen atoms of the repeating -(C2H4)- unit with
another atom, or group of atoms. These substitutions produce a family of polymers known as vinyl or
vinylidene polymers respectively.

The general reaction for the polymerization of vinyl polymers is illustrated in Figure 3-29, where one
hydrogen atom is substituted. For vinylidene polymers two or more hydrogens are substituted.

The values for R1, the substituted group are listed below where, CH3 gives polypropylene, Cl gives
polyvinylchloride, C6H5 gives polystyrene, CN the nitrile group gives polyacrylonitrile (PAN), F gives

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polytetrafluoroethylene, and CH3 together with an ethanoate group, COOCH3, gives

polymethylmethacrylate. Their repeat formulas are illustrated in Figure 3-29.
The properties of these selected thermoplastics are tabled below.

Density, Impact Strength Tensile Strength,

Material E, GPa
g/cm3 J/m MPa
PE-Low density 0.92-0.93 53-480 6-17 0.17-0.28
PE- High density 0.95-0.96 21-214 20-37 1.08
PVC 1.49-1.58 - 52-62 2.4-4.1
PP gen. purpose 0.90-0.91 21-54 33-38 1.14-1.55
Polystyrene 1.05 19-24 22-55 2.3-3.3
PAN 1.15 80-256 62 3.5-4.0
PTFE 2.1-2.3 160 14-48 0.4-0.55
Table 3-3

Figure 3-29

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3.6.3 Polyethylene

The repeat unit structure of polyethylene is illustrated in Figure 3-29. It is the most commonly used
plastic because of its cheapness, its toughness and flexibility at low temperatures, its excellent
corrosion resistance and insulating properties, and its very low permeability to water vapour.

There are four major types of polyethylene, low density, linear-low density, high density and ultra
high molecular weight. The two low density polyethylenes are characterised by a certain amount of
branching from the main chain. The presence of these branches reduces the inter-molecular packing,
and hence the magnitude of the van der Waals bonds between the chains. Because the polyethylene
molecule is completely nonpolar, there are no other intermolecular forces apart from these
dispersion forces. Although these forces are weak, the high molecular weight results in long chains,
and a multiplier effect. Thus the higher the molecular weight the higher the bond strength, which
raises in turn the melting point and strength, in proportion.

By contrast high density polyethylene is essentially free from chain branching as a result of the use of
the stereo- specific Phillips and Ziegler catalysts during the polymerization process. As a result the
chains pack together more closely, and therefore the intermolecular bonding is much stronger than
for the low density forms.

The mechanical and physical properties of the family of polyethylenes are a direct result of their
different molecular structures illustrated in Figure 3-30, with (a) high density, (b) low density, and
(c) linear-low density.

Figure 3-305

Ultra high molecular weight polyethylene, UHMWPE, is another interesting member of the
polyethylene family. It consists of very high molecular weight macromolecules with weights ranging
from 2-6 million. This characteristic leads to very high toughness on account of the very long straight
chains, which have the capacity to transfer and disperse high loads along their length. It is nonpolar,
has a negligible coefficient of friction, is very abrasive resistant, and lends itself to extrusion into
fibres. Because of the regular arrangement of its chains, it possesses a high level of crystallinity, and
can therefore be heat treated like steel. As a consequence of this unique structure it can be
mechanically worked, extruded, hardened, annealed and softened and toughened like many alloys.

Its uses include ballistic vests, ultra strong rope, skis, and joint replacement prostheses.

The table below lists some further characteristic properties of three classes of polyethylene.

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EL., %
Polymer Type E, GPa σy, MPa TS, MPa ρ, g/cm3 Tm, 0C Tg, 0C Crystallinity, %
avg
LDPE 0.25 12 8-31 0.93 380 115 -110 65
HDPE 1.0 30 26 0.95 250 137 - 95
25
UHMWPE 0.69 2400 45 0.96 150 148 - -
fibre
Table 3-4

3.6.4 Polyvinylchloride, PVC

The repeat structure for PVC is illustrated in Figure 3-29. The presence of the large polar chlorine
atom on every second carbon atom causes the chains to stiffen, and become more chemically resistant.
This results from electrostatic repulsion and steric hindrance produced by the chlorine atoms, with a
consequent restriction of free rotation of the chains. Due to the asymmetry of the vinyl chloride
monomer, the structure of PVC is essentially non-crystalline. The applications of PVC are many and
varied, and include rigid pipes, window frames, electrical conduit and other items used in the building
and construction industries.

3.6.5 Polypropylene

The stereoisomeric forms of polypropylene are discussed in section 3.5.2. The presence of the bulky
non-polar methyl group on every alternate carbon atom restricts chain rotation. Like PVC,
polypropylene is harder, stronger and more rigid than LDPE. Isotactic polypropylene due to its high
level of crystallinity has a melting point of 1650C, (high for a plastic), and can be heated to 1200C
without deforming. It is used widely for packaging, liquid storage, battery cases and many other
applications where strength, heat resistance and chemical inertness are required. In this repect it is
superior to LDPE, although it is more costly.

3.6.6 Polystyrene

Polystyrene is a clear, rigid, brittle plastic. The presence of the large flat phenylene ring causes
significant steric hindrance and makes polystyrene inflexible at room temperature. The impact
properties can be improved by copolymerizing with about 10% polybutadiene, -(CH2CH=CHCH2)- ,
an elastomer. Typical uses are for knobs, housings, dials in automobiles and in a variety of fittings in
the home.

3.6.7 Polyacrylonitrile

The nitrile group is bulky and polar. This group therefore imparts rigidity, which is further enhanced
by the formation of hydrogen bonds between the nitrogen atom from one chain and a hydrogen atom
of an adjacent chain. Additionally the mutual repulsion between the polar nitrile groups forces the
chains into stiff rod-like configurations. As such PAN is used in the form of drawn fibres to make
clothing and woolly fabrics.

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3.6.8 Polytetrafluoroethylene

The small size of the fluorine atom, and the symmetry of the PTFE chain produces an ordered
crystalline structure. The close packing of the polymer chains results in PTFE having a high density of
2.15g/cm3. PTFE has exceptional chemical resistance and an extremely low coefficient of friction. It is
also stable over a wide temperature range between -2000C and 2600C. Its impact strength is high, but
its tensile strength is low when compared to other engineering plastics. Fillers such as fibre glass can
be used to increase its strength. PTFE is used in a wide range of applications where chemical
resistance is required such as pipes, gaskets, seals and O rings. Its low coefficient of friction means
that is used in self lubricating bushes and bearings, and in non-stick cookware.

3.6.9 Nylon

Nylon is produced by condensation polymerization, (section 3.3.9). Nylon is a high strength polymer,
because it is very crystalline. This is due to a high level of symmetry within the polymer chains. Also
the presence of an amide linkage, (CONH), will further strengthen inter-chain bonding by the
formation of strong hydrogen bonds between the chains. Nylon is mechanically strong, and has good
chemical and high temperature stability. The long flexible chains result in low surface friction and
high surface lubricity. However the highly polar nature of the intermolecular bonding means that the
absorption of polar solvents like water is high. Nylon is used widely as an engineering material in
bearings, anti-friction parts, in high temperature applications, and for components requiring strength
and high impact resistance.

3.7 Deformation Mechanisms for Thermoplastics

Thermoplastics, like metals can deform elastically, plastically, or by a combination of both
mechanisms. As a thermoplastic is heated above its glass transition temperature, thermal vibrations
weaken the secondary intermolecular bonds between the polymeric chains, and the plastic is
weakened. As the temperature rises the tensile and yield strengths decrease, and the ductility
increases. Below the glass transition temperature, the deformation is elastic. Above, the deformation
is plastic. Figure 3-31 illustrates the stress-strain behaviour for polymethylmethacrylate, PMMA. It
can be seen that a ductile to brittle transition occurs between 680C and 1220C. This is because the
glass transition temperature is 720C, ie between these values.

Figure 3-315

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Figure 3-32 illustrates the three mechanisms by which molecular changes occur during elastic and
plastic deformation. In (a) elastic deformation occurs when the tetrahedral covalent bonds are
stretched. In (b) elastic or plastic deformation occurs when the main chain uncoils. In (c) plastic
deformation occurs when the chains which are bound strongly by intermolecular forces are caused
to slip past each other.

Elastic
deformation

Plastic
deformation

Figure 3-325

3.8 Strengthening mechanisms for thermoplastics

There are two major methods of strengthening thermoplastics. One method is to add reinforcing
fibres such as glass or carbon fibre. These techniques are fully covered in chapter 4 under composites.

By far the most common methods however are those based upon the idea of altering the structure of
the polymeric chains to effect property change. In this sense it is possible to a significant degree to
design a polymer by understanding the relationship between structure and properties. These methods
include changing the molecular weight, altering the degree of crystallization, and introducing bulky
or polar pendant groups into the main chain. These methods will be discussed in the sections
following.

3.8.1 Changing the molecular weight

Whilst it follows that the strength of a particular polymer will increase with the average molecular
weight, this method is not used as such. This is because there are more effective methods, and also
because there are upper limits of molecular weight achievable in practice. Furthermore after a critical
molecular weight is achieved there is little further increase in strength if the molecular weight is
raised. The molecular weight of a polymer is directly related to the degree of polymerization.

𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤ℎ𝑡𝑡 𝑜𝑜𝑜𝑜 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝

Degree of polymerization =
𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤ℎ𝑡𝑡 𝑜𝑜𝑜𝑜 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚

= Number of repeating units/polymer chain.

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Typical values are tabled below.

Thermoplastic Molecular weight, g/mol Degree of polymerization

Polyethylene 28,000-40,000 1000-1500
Polyvinylchloride 67,000 avg. 1080
Polystyrene 60,000-500,000 600-6000
Nylon 6,6 16,000-32,000 150-300
Table 3-5

3.8.2 Changing the Proportion of Crystallinity

It is a general rule that as the amount of crystallinity of a polymer increases so does the tensile
strength, the elastic modulus, and the density.
The ratio of crystalline to amorphous regions in a polymer is dependent upon how close the polymeric
chains are able to pack together in order to optimise the intermolecular bond strength. The efficiency
of packing is a function of the chain shape. Chains that are not branched will pack more tightly together
than chains that are branched; for example HDPE is less branched than LDPE, and as a consequence
HDPE has a higher proportion of crystalline to amorphous structure. It is therefore stronger. To carry
this argument one stage further, consider UHMWPE. This material is highly crystalline, and is very
strong, particularly when it is extruded into filaments that are then twisted together into ropes or
twine.

Figure 3-33 illustrates the comparative strength of high and low density polyethylene as a function of
their crystallinity.

Figure 3-335

3.8.3 Adding Bulky Pendant Groups

Chain slippage during the plastic deformation stage of a thermoplastic under stress, can be reduced
by adding bulky pendant groups such as methyl, CH3, and phenyl, C6H5. The presence of these groups
on the main chain impedes the inter-chain slip mechanism, and therefore increases the strength and
stiffness of the polymer.

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These effects are illustrated in the table below for polyethylene, for polyethylene to which a CH3
pendant group has been added, producing polypropylene, and for polyethylene to which a C6H5 group
has been added, producing polystyrene.

Polymer E, GPa % Elongation

HDPE 0.9 750
Polypropylene 2.25 425
Polystyrene 3.1 2
Table 3-6

Note that as the modulus of elasticity is increased by increasing the size of the added pendant groups,
the ductility decreases in proportion.

3.8.4 Adding Polar Pendant Groups

Typical polar atoms added to polyethylene are the halogens, fluorine and chlorine. These atoms are
strongly electronegative, with high values of 4.0 and 3.0 on the Pauling scale, respectively. The
introduction of such a polar atom will increase the dipole-dipole bonding between chains, and as a
consequence the strength and stiffness of the polymer is increased, resulting from reduced inter-
chain slippage. In Figure 3-34 the stress-strain behaviour of polyvinylchloride is compared to
polystyrene.

Inter-chain slippage (Plastic Deformation)

Figure 3-345

The yield point, σy at the top of the linear elastic region corresponds to the onset of plastic
deformation, at which point the tensile test piece begins to neck. This is also the onset of inter-chain
slippage. The average yield points of polyethylene, PVC and polystyrene are 30, 42 and 55 MPa
respectively, and reflect the trends dicussed above.

Note that the large phenylene group present in polystyrene is even more effective than the chlorine
atom in reducing the chain slippage. It therefore follows that polystyrene has a higher modulus of
elasticity and a higher tensile strength than polyvinylchloride.

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3.8.5 Introducing O and N Atoms

Oxygen and nitrogen, although less electronegative than chlorine and fluorine, will still introduce an
element of polarity into the chain, and hence strengthen the dipole-dipole bonding. The addition of
oxygen, and the subsequent formation of an ether linkage -CH2-O-CH2 - into the main chain, will
therefore strengthen the polymer. The additional introduction of a nitrogen atom, as in the amide
linkage, (present in nylon), produces hydrogen bonding, the strongest type of intermolecular
bonding. These factors lead to a further significant increase in tensile strength and elastic modulus.

3.8.6 Adding Phenylene Rings and other Atoms

The effect of introducing a single phenylene group into the polyethylene chain was discussed in
section 3.6.6 under polystyrene. The effect of adding more than one phenylene ring into the main
polymer chain will further increase the strength and rigidity of the resultant polymer. Polycarbonates
are a good example of this type of combination. The repeat unit for polycarbonates is illustrated in
Figure 3-35.

Figure 3-35

The presence of the two phenylene groups impart strength and stiffness, and the single C-O bonds in
the carbonate unit introduce a degree of flexibility and toughness to the otherwise rigid, brittle
polymer. With this balance between flexibility and rigidity, the resultant mechanical properties of
polycarbonates find many uses in engineering products.

Typical mechanical properties for polycarbonate are: σy = 62MPa, TS = 63-72MPa, % elongation =

110-150, and fracture toughness = 2.2 MPa√𝑚𝑚. The fracture toughness of polypropylene is
3.7MPa√𝑚𝑚 for comparison. It can be noted that although polycarbonates are very strong they are also
quite tough, less so than polypropylene, but considerably tougher than thermosets. Uses include
safety shields and helmets, clear roofing panels, and many engineering applications where high
strength is required.

3.9 Methods of Forming Polymers

There are four major methods for producing polymer shapes. These are moulding, extrusion,
manufacture of films or sheets, and manufacture of fibres.

Thermoplastics lend themselves to the greatest variety of forming techniques. Here the polymer is
heated to near or slightly above its melting point and cast or injected into a mould or die to make the
desired shape. The various processes are illustrated in Figure 3-36.

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Figure 3-36 (a) is extrusion, (b) blow moulding, (c) injection moulding, (d) thermoforming, (e) calendaring,
and (f) spinning.

EXTRUSION: A screw mechanism forces the molten polymer into a mould where air is introduced to
shape the hollow object, (a and b), or direct injection into a mould for a solid object, (c).

THERMOFORMING: Here the polymer sheet is heated into the plastic condition, and pressed between
two sets of dies, using air pressure or a vacuum, (d).

CALENDARING: The molten plastic is poured between two rollers, which may be embossed with a
pattern to form objects such as tiles, shower curtains, or films, (e).

SPINNING: Plastics are forced through a die containing many holes, and this die or spinnerette is then
rotated to produce a yarn or rope. The extrusion process involves stretching, and aligning of the
chains, and greatly strengthens the polymer, (f).

FOAMS: The polymer is made into small beads into which a foaming agent is introduced. These beads
may be injected into a mould and then heated. The heating process causes the foaming agent to release
a gas, usually carbon dioxide or nitrogen.

Thermosetting polymers are more difficult to form than thermoplastics, and in all methods the mixed
liquid resins are immediately injected, and heated. The moulding and curing processes thus occur
simultaneously. Finally the moulded object is ejected. The two major processes used for
thermosetting polymers are compression moulding, and transfer moulding illustrated as (a), and (b)
respectively in Figure 3-37.

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Figure 3-37

3.10 High Strength Fibres

3.10.1 Carbon Fibre

This material consists of extremely thin fibres 0.005 to 0.010 millimetres in diameter, and is
composed almost exclusively of carbon atoms. The strength of this material derives mainly from the
fact that the carbon crystals are almost totally aligned in each fibre. The yarn is manufactured from
several thousand fibres twisted together. The yarn may be woven into a fabric and is often combined
with a resin to produce an extremely strong composite material. Carbon fibre has a very high tensile
strength, a typical value being from 2000 to 7000 MPa, (low carbon steel 180 MPa). The density is
1.75 g/cm3, and like other high strength polymers, carbon fibre has a superior strength to weight
ratio, relative to metals.

Carbon fibre used in composites is made from a precursor fibre such as polyacrylonitrile, by a process
that involves stretching the PAN fibre while it is being heated. The three stages are, 1. stabilization, 2.
carbonization, and 3. graphitization.

In the stabilization stage the fibre is heated to about 2000 C, and stretched to align the PAN fibrils.

The carbonization stage involves pyrolyzation at temperatures around 12000 C in an inert

atmosphere, when O, H, and N are eliminated from the precursor fibre as gaseous products, leaving
behind a graphite like network of carbon fibres. This part of the process leads to a high strength fibre,
due to the graphene structure of the sheets of carbon atoms, which may be haphazardly folded or
crumpled together. This morphology is known as turbostratic.

The graphitization stage involves further heating to round 18000 C, where additional morphological
changes produce a more ordered graphitic structure. This form has a higher elastic modulus than the
turbostratic structure.
Figure 3-38 illustrates several stages in the manufacture of carbon fibres. These may be summarised
as (1) the polymerization of acrylonitrile, (2) the cyclization of PAN into polycyclic chains, and (3) the
elimination of H and N, when the chains are joined into graphite like sheets at high temperatures.

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The table following compares the mechanical and electrical properties of two of the strongest
reinforcing fibres with steel and carbon nanotubes.

Tensile Strength, Thermal Conductivity

Material Elastic Modulus, GPa
MPa W/m.K
Carbon fibre 3450 228 8-105
Kevlar 3600 131 -
Steel 1040 (cold drawn) 600 200 52
Carbon nanotube 45,000 1300 > 3000
Table 3-7

The extremely high strength of carbon and Kevlar fibres, are in direct contrast to a typical medium
plain carbon steel. Furthermore, when the strength to weight ratio is considered, carbon fibre is about
25x stronger than steel!

Figure 3-383

3.10.2 Carbon Nanotubes

The extreme strength of the carbon nanotube is an interesting reference point for comparing the
properties of carbon fibres in general, although at this point in time their potential has been far from
fully realised. Their unique strength stems from the high purity graphene structure formed into a
tube, joined down its length, and sealed at the ends with two hemispheres of fullerene. The carbon
nanotube is depicted in Figure 3-39.

Figure 3-395

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The fullerene molecule, C60, is yet another polymorph of carbon, along with the better known diamond
and graphite. This polymorph is often referred to as buckyball, or buckminsterfullerene. It is a highly
symmetric ball like structure of 60 carbon atoms arranged to form 12 pentagons and 32 hexagons as
illustrated in Figure 3-40.

Figure 3-401

Analysis has shown that the structure under-pinning high strength carbon fibres is that of the
graphene sheet, present in naturally occurring graphite, and illustrated in Figure 3-41. The graphene
structure is the name given to the individual layers present in graphite, that is, without the weak
dispersion forces that connect them.

Figure 3-415

Carbon nanotubes can be made in either multiwalled or single-walled forms. Depending upon how
the graphite sheet is rolled up, and what its diameter is, nanotubes can behave as metals or
semiconductors. The capacity for a semimetal like carbon or silicon to conduct electricity is a measure
of its ability to transfer electrons into the conduction band. As the size, or the number of atoms
decreases the conduction band gap increases in size, and the material becomes non-conducting. Thus
the diameter of the nanotube will determine the degree of conductivity. On the basis of this behaviour,
there is great interest in using carbon nanotubes for electronic circuits.

Carbon nanotubes are very anisotropic, being excellent electrical and thermal conductors along their
length, but nonconducting at right angles. Another interesting characteristic of carbon nanotubes is
their almost complete absence of defects at the atomic level, due to their regular covalent bonding. In
this respect they are greatly superior to metals, which have high levels of linear defects in the form of
dislocations. These imperfections become even more pronounced at the nano-scale, towards which
electronic circuits are now trending. As circuits become more miniaturised, the efficient cooling of the
metallic connecting wires becomes a barrier to further size reduction.

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The characteristics of carbon nanotubes discussed in terms of their electrical properties also account
for their superior mechanical properties compared to metals. As a group, carbon nanotubes can now
be made with diameters ranging from < 1 nm up to 50 nm, and lengths up to several centimetres.

3.10.3 Kevlar

This material was originally developed to replace steel belting in automobile tyres in the 1970’s.
However its unique strength and durability resulted in wider applications. When woven into a fabric
it exhibited an ability to stop a lead bullet, hence, the bullet proof vest, illustrated in Figure 3-42.

Figure 3-427 Police wear bullet vests made of Kevlar as pictured.

In terms of strength it approaches carbon fibre. Typical ultimate tensile strength values of 3000 MPa
and a density of 1.44 g/cm3 result in exceptional strength to weight ratio.

It is produced by the condensation polymerization between H2N NH 2 and

O 1,4-phenylene diamine
||
Cl − C − − C − Cl , liberating HCl in the process.
||
O
terephthaloyl chloride

The reaction is illustrated in Figure 3-43.

Figure 3-438

The strength of Kevlar derives in part from strong intermolecular bonds, and in particular H bonds as
illustrated, and π bonding between the stacked benzenoid rings.

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Figure 3-448 Steric hindrance increase rigidity (Benzene Rings)

Kevlar’s structure consists of relatively rigid molecules which tend to form planar sheet-like
structures as shown in Figure 3-44. Kevlar has good resistance to high and low temperatures between
-160°C to 196°C. Apart from bullet proof vests Kevlar finds wide application in body armour, rope,
cable, and sporting equipment like kayaks and rowing hulls. It is commonly used as a composite with
carbon fibre, bonded with epoxy resin. In this form it is used in boat hulls, racing car bodies, and
helicopter blades. Figure 3-45 illustrates its use in windsurfing sails.

Figure 3-457 Windsurfing sails can withstand the force of 100 kph winds and don’t rip easily and are made of
Kevlar.

Figure 3-46 shows an x-ray picture of a cross-section of a Kevlar fibre. This image is similar to the
spherulitic structure of polymers discussed in section 3.5.1, Polymer Crystals.

Figure 3-467

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3.11 Thermosetting Polymers

Thermosetting polymers are formed by first producing linear chains, and then cross-linking to
produce a 3D network polymer. Quite often the components are two liquids, which are mixed prior
to use. As previously noted, for a polymer to be thermosetting, the monomers must be tri-functional
or better. The three most common groups are:

(a) Epoxies, common trade name araldite, and epicote.

(b) Phenolics, common name Bakelite.
(c) Polyesters, common name aropol.
(d) Urea-formaldehyde.

3.11.1 Urea Formaldehyde

The formation of urea-formaldehyde will serve to illustrate the initial chain forming mechanism, plus
the subsequent cross-linking in the production of this resin.

(i) The condensation reaction between two molecules of urea, and one molecule of
formaldehyde, and the elimination of water is illustrated in Figure 3-47.

Figure 3-47

(ii) The length of the urea-formaldehyde chain can be extended continuously while the
condensation reaction proceeds.
(iii) If excess formaldehyde is present the cross-linking process will begin, the extent to
which it networks depending upon the time, and the amount of excess formaldehyde
added. This cross-linking is shown Figure 3-48.

Figure 3-48

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3.11.2 Epoxy Resin

The production of this thermosetting resin is by condensation polymerization using the di-functional
monomers bis-phenol A and epichlorohydrin. The pre-polymer therefore consists of chains of
polymer from the two monomers alternating along the chain length. Active epoxide groups occur at
either end of these chains. When the stoichiometric addition of a difunctional amine is added, cross-
linking of the chains occur between the active epoxide sites and the diamine hardener, producing a
hard, tough resin. In contrast to the polymerization of other thermosetting resins where a catalyst is
used to .promote cross-linking, the amine added for epoxy resin formation is referred to as a hardener,
since it cross-links by a different mechanism, and may be considered to be acting as a third monomer.

The two di-functional monomers are illustrated in Figure 3-49.

Figure 3-49

Figure 3-50 illustrates the pre-polymerization of 1mole of epichlorohydrin with 1mole of bis-phenol
A by condensation polymerization. During this process 3 moles of hydrogen chloride are eliminated.
The product is epoxy pre-polymer, commonly purchased as “resin”.

Figure 3-50

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Chapter 3: Polymers

Figure 3-51 illustrates the di-functional hardener N,N’- diethylamine, which links the ends of the pre-
polymer chains together. The functional groups are indicated by asterisks.

Figure 3-51

The hardening mechanism involves the di-functional amine hardener reacting with the free epoxy
groups on each end of the pre-polymer chains, and linking them together. This mechanism is
illustrated in Figure 3-52.

Figure 3-52

Figure 3-53 shows the linked ends of two polymer chains. By this process the cross-linking produces
a hard tough thermosetting resin.

Figure 3-53

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Chapter 3: Polymers

Finally Figure 3-54 represents a schematic representation of the epoxy resin structure.

Figure 3-54

3.11.3 Properties of Thermosets

The properties, applications, and repeat units of selected thermosetting polymers are listed in the
table below and in Figure 3-55.

Density Modulus of Tensile Major application Typical

Polymer type
g/cm3 elasticity GPa strength MPa characteristics applications
Mouldings,
Good mechanical
coatings,
Epoxies 1.11-1.4 2.41 28-90 properties,
fibre glass
adhesion, stable
matrix
Motor
Thermal stability,
housings,
Phenolics 1.28 2.76-4.83 35-62 compatible with
electrical
fillers, resins etc
fixtures
Helmets,
Good electrical
fibre glass
Polyesters 1.04-1.46 2.06-4.41 41-90 insulator, fibre
boats, auto
reinforced
body parts
Durable, water Glues,
Urea-
1.4-1.8 - 27-58 resistant, good switches,
formaldehyde
strength,insulator plugs
Table 3-8

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Figure 3-55

3.11.4 Additives to Polymers

(i) PIGMENTS: Commonly used to produce colour into the polymer.

(ii) STABILIZERS: Prevent deterioration due to UV radiation, and heat during processing.
Antioxidants are added to ABS, polyethylene and polypropylene.
(iii) ANTISTATIC AGENTS: Most polymers are poor electrical conductors, and attract static
electricity. These agents attract moisture, and reduce the risk of sparking.
(iv) FLAME RETARDENTS: Most polymers are flammable because they are organic in origin.
Additives like metallic salts reduce the likelihood of ignition.
(v) PLASTICIZERS: These additives are low molecular weight polymers which reduce the
glass transition temperature. A lower Tg renders the polymer more plastic, and therefore
improves the ease with which forming processes may be carried out. This is particularly
important for polystyrene, Tg = 85-1250C, and polyacrylonitrile, Tg = 1070C.
(vi) FILLERS: These materials are added to improve strength and wear resistance, the best
known being carbon black in rubber. Other types of fillers are inorganic flakes and fibres.
Extenders are added to increase the bulk volume of the polymer, thus reducing costs.
Calcium carbonate, silica, and clay are commonly used extenders.
(vii) REIFORCEMENTS: The strength and rigidity of polymers is greatly improved by
incorporating fibres into the matrix. Examples include glass, polymer and carbon fibre

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3.12 Polymers Terms and Definitions

1. Polymer: A compound of high molecular weight, the structure being composed of chains of small
repeat units.
2. Macro-Molecule: A huge molecule made up of thousands of atoms.
3. Monomer: A stable molecule from which a polymer is synthesized.
4. Functionality: The number of covalent bonds that a monomer can form when reacting with other
monomers. For example a bi-functional monomer like ethylene forms a 2D structure in
thermoplastic polyethylene. A tri-functional monomer(s) is phenol plus formaldehyde that forms
bakelite, a 3D thermosetting polymer.
5. Homopolymer: A polymer having a chain structure in which all repeat units are the same.
6. Copolymer: A polymer that consists of two or more repeat units combination.
7. Elastomer: A polymeric material that may experience large and elastic deformations.
8. Thermoplastic Polymer: A semi-crystalline polymeric material that softens when heated, and
hardens upon cooling. While in the softened state articles may be formed by moulding or
extrusion.
9. Thermoplastic Elastomer: A copolymer that exhibits elastomeric behaviour, yet is thermoplastic
in nature. At the ambient temperature domains of one repeat unit form at molecular chain ends
that crystallize to act as physical cross-links.
10. Thermosetting Polymer: A polymeric material, that once having cured or hardened by a chemical
reaction will not soften or melt when subsequently heated.
11. Glass Transition Temperature Tg: The temperature at which upon cooling, a non-crystalline
polymer transforms from the super cooled liquid or rubbery phase, to a rigid glass.
12. Crystallinity: A synthetic polymer may be described as crystalline if it contains region of 3D
ordering on an atomic scale. This ordered structure may result from regular folding or stacking of
adjacent chains. Polymers may consist of both crystalline and amorphous regions, and their
degree of crystallinity may be quantitatively expressed in terms of a weight or volume fraction.
Polymers with micro-crystalline regions are generally tougher, more flexible, and more impact
resistant than totally amorphous polymers because of more regular packing at the molecular
level.

3.13 Comparative Properties of Metals and Polymers

Figure 3-562 Bar-chart of room-temperature density values for various metals, ceramics, polymers and
composite materials.

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Chapter 3: Polymers

Figure 3-572 Bar-chart of room-temperature stiffness (i.e., elastic modulus) values for various metals,
ceramics, polymers and composite materials.

Figure 3-582 Bar-chart of room-temperature strength (i.e., tensile strength) values for various metals,
ceramics, polymers and composite materials.

Figure 3-592 Bar-chart of room-temperature resistance to fracture (i.e., fracture toughness) values for
various metals, ceramics, polymers and composite materials.

Figure 3-602 Bar-chart of room-temperature electrical conductivity ranges for various metals, ceramics,
polymers and composite materials

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Chapter 3: Polymers

References

1 Brown, Theodore L., H E. LeMay, Jr., and Bruce E. Bursten. 10th ed. USA: Pearson,
Prentice Hall, 2006.
2 Callister, Jr, William D. Materials Science and Engineering an Introduction. 7th ed.
York, PA: John Wiley & Sons, 2007.
3 "Carbon Fiber." Wikipedia. 11 June 2008. 21 June 2008
<http://en.wikipedia.org/wiki>.
4 Martin, S.L., Connor, A.K., Basic Physics, Revised first edition, Whitcomb and Tombs,
1968
5 Smith, W.F., Hashemi, J., Foundations of Materials Science and Engineering, Fifth
edition, McGraw Hill, 2010.
6 James, Maria, Maida Derbogosian, Sholto Bowen, Santina Raphael, and Jennifer
Moloney. Chemical Connections. 3rd ed. Vol. 1. Milton, Queensland: John Wiley & Sons,
1999.
7 "Kevlar - the Wonder Material." MicroWorlds. E.I. Du Pont De Nemours and Company.
21 June 2008 <http://www.lbl.gov>.
8 "Kevlar." Wikipedia. 17 June 2008. 21 June 2008 <http://en.wikipedia.org/wiki>.
9 Askeland, D.R., The science and engineering of materials, 2nd. Edition,PWS-Kent 1989.

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Chapter 4: Composites

Composites

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Chapter 4: Composites

4.1 Introduction
Composites are produced by combining two or more materials which together produce properties
that cannot be achieved from the individual components. By careful selection of materials,
combinations with superior properties such as strength, hardness, weight, corrosion resistance, and
high temperature performance can be made.

Composites of metal-metal, metal-ceramic, metal-polymer, and polymer-polymer produce a varied

and characteristic range of possible properties. In this discussion emphasis will be placed on polymer-
polymer combinations.

Composites can be divided into three categories, specifically particulate, fibre, and laminar, based
upon the shape of the dispersed phase or the material structure. For example concrete is particulate
with sand and gravel in a cementitious matrix, fibreglass is a fibre reinforced matrix of a
thermosetting resin, and plywood is a laminated structure of wood joined by glue. If the reinforcing
components are randomly orientated, particulate composites will be isotropic.

Fibre composites can be either isotropic or anisotropic, while laminates will always be anisotropic.
Figure 4-1illustrates (a) particulate, (b) fibre, and (c) laminar composite materials.

Figure 4-1

4.2 Dispersion Strengthened Composites

A common example of ceramic-metal dispersion strengthened composite is silicon or tungsten
carbide embedded in a metal matrix like cobalt. This material is widely used in cutting tools where
the very hard, brittle, and abrasive carbide particles are held together by the cobalt metal binder. As
the carbide cutting particles dull they fracture or pull away from the matrix, exposing new particles.
Other examples include carbon black dispersed in rubber, which increases the stiffness and wear
resistance of rubber tyres, and silica, a high melting point solid in a matrix of resin, which may be
moulded into a desired shapes and used as refractory vessels for holding molten metal.

4.3 Fibre Reinforced Composites

When stiff fibres are embedded in a matrix which acts as a binder, the composite increases in strength,
fatique resistance, stiffness, and strength to weight ratio. Examples of widely used composites include
steel re-inforcing in concrete and fibre glass in a polymeric matrix. Composites possess superior
properties to their individual constituents because the matrix transmits and spreads the load to the
fibres giving improved ductility and toughness.

Properties depend upon several factors, one of the most important being the orientation of the fibres.
Short randomly oriented glass fibres as present in fibre glass yield anisotropic properties.
Unidirectional fibres give maximum strength parallel to the fibre orientation, and this type of material

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Chapter 4: Composites

is classified as isotropic in one direction. Fibres may also be woven into fabrics with a large
combination of weaves to give a corresponding variety of isotropic properties in several directions.

Figure 4-2 illustrates, (a) unidirectional fibres, (b) randomly oriented discontinuous fibres, (c) fibres
oriented at rightangles, and (d) multi-ply continuous fibres randomly oriented.

Figure 4-2

One of the major advantages of these types of composites is the ability to mould them into complex
shapes.

STRESS-STRAIN CURVES: Figure 4-3 illustrates the difference between composites, common metals
and alloys, and non-reinforced plastics.

Figure 4-3

For composites the yield point and ultimate strength occur at the same point, for metals the yield
point is always lower than the ultimate strength, and for non-reinforced plastics the stress-strain
curve is non-linear with a non-defined yield point.

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4.4 The Rule of Mixture: Predicting the Properties of Composites

The rule of mixtures can be used to calculate certain bulk properties of composites, where that
property depends only upon the relative amounts and properties of the individual components.
Properties such as density and modulus of elasticity fall into this category. Hardness and strength
cannot be predicted by the rule of mixture.

4.4.1 Density

Using density as an example the rule of mixtures may be stated as:

ρc = Σfiρi = f1ρ1 + f2ρ2 + …. + fnρn
Where ρc = the density of the composite, ρ1, ρ2 ----ρn are the densities of each constituent in the
composite, and f1, f2, …, fn are the volume fractions of each constituent. Figure 4-4 illustrates this
principle of mixtures for a ceramic reinforced polymer, where the composite modulus of elasticity and
density fall between the individual values for the components, as a function of the volume fraction of
each component.

Figure 4-4

4.4.2 Isostrain (Longitudinal), Conditions for a Lamellar Composite

4.4.2.1 The Elastic Modulus, E

Consider a lamellar composite with a continuous structure, and a strong and coherent bond between
the fibre and matrix during the application of the load as illustrated in Figure 4-5.

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Chapter 4: Composites

Figure 4-57

With the layers parallel to the direction of the applied load, the strain on each component of the
composite will be the same, ie
εc = εf = εm (4-1)
where subscripts c, f and m refer to composite, fibre and matrix respectively. With this configuration
the load F on the composite is the sum of the loads on the fibre and matrix, ie
Fc = Ff + Fm. Since F = σA,
σcAc = σfAf + σmAm
where A = fractional areas.

Since the length l of each layer is equal, the area fractions can be replaced with volume fractions, V,
and since Vc = 1, therefore,
σc = σfVf + σmVm (4-2)
Dividing equation (4-2) by (4-1) gives,
Ec = EfVf + EmVm (4-3)

4.4.2.2 Fraction of Load Carried by the Fibre

Since F = σA, the distribution of the load F between the fibre and the matrix is,
𝐹𝐹𝑓𝑓 𝜎𝜎𝑓𝑓 𝐴𝐴𝑓𝑓 𝐸𝐸𝑓𝑓 𝜀𝜀𝑓𝑓 𝐴𝐴𝑓𝑓
= = ,
𝐹𝐹𝑚𝑚 𝜎𝜎𝑚𝑚 𝐴𝐴𝑚𝑚 𝐸𝐸𝑚𝑚 𝜀𝜀𝑚𝑚 𝐴𝐴𝑚𝑚

because σ = Eε. Since under isostrain conditions, εf = εm, therefore,

𝐹𝐹𝑓𝑓 𝐸𝐸𝑓𝑓 𝐴𝐴𝑓𝑓 𝐸𝐸𝑓𝑓 𝑉𝑉𝑓𝑓
= = (4-4)
𝐹𝐹𝑚𝑚 𝐸𝐸𝑚𝑚 𝐴𝐴𝑚𝑚 𝐸𝐸𝑚𝑚 𝑉𝑉𝑚𝑚
But the load on the composite is the sum of the loads on fibre and matrix respectively, therefore, Fc =
Ff + Fm. Thus from 4.4,
𝐹𝐹𝑓𝑓 𝐸𝐸𝑓𝑓 𝑉𝑉𝑓𝑓
= (4-5)
𝐹𝐹𝑐𝑐 𝐸𝐸𝑓𝑓 𝑉𝑉𝑓𝑓 + 𝐸𝐸𝑚𝑚 𝑉𝑉𝑚𝑚

Hence the fraction of the load carried by the fibre under isostrain conditions is given by equation
(4-5).

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4.4.3 Isostress (Transverse), Conditions for a Lamellar Composite

4.4.3.1 The Elastic Modulus, E

Consider a lamellar composite with a continuous structure and a strong coherent bond as illustrated
in Figure 4-5, but with the layers at right angles to the applied stress. This composite is illustrated in
Figure 4-6.

Figure 4-67

Because the area of each layer receiving the load is the same, it follows that the stress on each layer
will be equal.

Thus, σc = σf = σm, and therefore the total strain on the composite, is equal to the sum of the strains on
the individual layers, ie
𝜀𝜀 c = εf + εm.
Assuming that the area perpendicular to the applied load remains unchanged as a result of the
loading, and assuming also unit length for the composite after loading,
εcVc = εfVf + εmVm.
But Vc = Vf + Vm = 1, and therefore
εc = εfVf + εmVm (4-6)
Assuming that Hooke’s law is obeyed during deformation, the individual strains are given by,
𝜎𝜎 𝜎𝜎 𝜎𝜎
εc = 𝐸𝐸𝑐𝑐
, εf = 𝐸𝐸 , and εm = 𝐸𝐸
𝑓𝑓 𝑚𝑚·

Substituting these values of strain into equation (4-6) gives,

𝜎𝜎 𝜎𝜎𝑉𝑉𝑓𝑓 𝜎𝜎𝑉𝑉𝑚𝑚
𝐸𝐸𝑐𝑐
= +
𝐸𝐸𝑓𝑓 𝐸𝐸𝑚𝑚·

Dividing this equation by σ gives,

1 𝑉𝑉 𝑉𝑉 𝐸𝐸𝑚𝑚 𝑉𝑉𝑓𝑓 + 𝐸𝐸𝑓𝑓 𝑉𝑉𝑚𝑚
𝐸𝐸𝑐𝑐
= 𝐸𝐸𝑓𝑓 + 𝐸𝐸𝑚𝑚 = ,
𝑓𝑓 𝑚𝑚 𝐸𝐸𝑓𝑓 𝐸𝐸𝑚𝑚

and solving for the elastic modulus Ec, gives

𝐸𝐸𝑓𝑓 𝐸𝐸𝑚𝑚
Ec = 𝑉𝑉 (4-7)
𝑓𝑓 𝐸𝐸𝑚𝑚 + 𝑉𝑉𝑚𝑚 𝐸𝐸𝑓𝑓

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Chapter 4: Composites

Figure 4-7shows that for a given volume fraction of fibre and resin, a composite loaded under
isostrain conditions will have a higher modulus of elasticity, and hence a lower flexibility than an
identical composite when loaded under isostress conditions.

Figure 4-77

The stress-strain curve for a fibre reinforced composite under isostrain, or longitudinal loading, is
shown in figure 4.8. At low stresses the modulus of elasticity is given by the rule of mixtures. For loads
applied parallel to the continuous fibres, the bulk modulus is given for section I of the curve. At higher
stresses the matrix deforms and the curve is no longer linear. Under these circumstances the rule of
mixtures is no longer obeyed, and the bulk modulus is sustained by the fibres only, with the
approximate value as given in region II of the curve.

When the load is applied perpendicular to the fibres, each component behaves independently of the
1 𝑉𝑉 𝑉𝑉
other, and the bulk modulus is the sum of the reciprocals given by = 𝑓𝑓 + 𝑚𝑚 , .from which equation
𝐸𝐸𝑐𝑐 𝐸𝐸𝑓𝑓 𝐸𝐸𝑚𝑚
(4-7) is derived.

Figure 4-88

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Chapter 4: Composites

It should be noted that the strength of composites is usually less than that predicted by the rule of
mixtures. This is because the strength depends largely upon the bond strength between fibre and
matrix, which is limited by the deformation of the matrix.

Whilst tensile and shear strength tests are performed on composites, the flexure test is particularly
useful in that flexural loads are combinations of tensile, compressive and shear loads being induced
into the composite. Figure 11.9 illustrates the interaction of these three forces.

Figure 4-9

The flexure test may be a three point or four point bend test, depending upon the stiffness of the
material. The widely used three point bend test is described in detail in ASTM Standard D790-10. The
four point test is found in ASTM6272. The three point bend test is discussed in detail in section 4.9.

4.4.4 Specific Strength- Strength to Weight Ratio

An important characteristic of many materials is their specific strength, which is the strength to
density ratio. Even though a material may have a lower tensile strength in comparison to a more dense
material (such as steel), on a weight basis it will be able to support a higher load. This characteristic
is particularly useful in comparing the relative strength and modulus of elasticity of polymers and
composites with metals.

Specific strength = σ/ρ = (N/m2)/(kg/m3 ) = Nm/kg.

Similarly specific modulus = E/ρ, with the same units as for specific strength. Characteristic
properties for a selection of reinforcing fibres are illustrated in Figure 4-10 below.

Figure 4-10

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4.5 Fibre Reinforcing

There are many different types of material used in fibre reinforcing, most commonly glass of different
compositions, carbon, aramids which include kevlar, and hybrids of the above types. These materials
may be obtained in various forms such as chop strand mat for glass, and as woven cloths employing
different weaves. Each form has their own special properties and applications.

4.5.1 Aspect Ratio

The aspect ratio is the ratio of length to diameter = l/d. In general the strength is improved with high
aspect ratios. This is because when the diameter is very small the surface area is small, and
consequently the number of surface flaws is low. It is the presence of surface imperfections or stress
risers, that exacerbates the likelihood of brittle fracture, (see also section 2.13.4). In addition long
fibres distribute the load along the fibre length, thus increasing the load carrying capacity. In a
composite there is a critical fibre length lc where the load is concentrated exactly at a point in the
centre of the fibre. Fibres where l > 15lc are classified as continuous. Figure 4.11 illustrates the
distribution of stress along the fibre for multiples of lc, when the applied stress equals the tensile
strength of the fibre, σ*f

Figure 4-11

In Figure 4-11 (a), l = lc, in (b), l > lc , and in (c), l < lc . It will be noted that when the fibre length is less
than the critical length the fibre fails because the applied stress is not transferred along the fibre.
Hence such fibres offer no reinforcement potential. A typical critical length for glass, carbon and
aramid fibres is about 1mm.

As an example of the significance of fibre aspect ratio, the following tensile strengths for nylon
reinforced with carbon fibres were obtained. For an aspect ratio of 30 the tensile strength was 110
MPa, and for an aspect ratio of 800 the tensile strength was 242MPa.

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4.5.2 Volume Fraction of Fibres

A greater volume fraction of fibres will result in an increase in strength and stiffness of the composite
up to a maximum of 80%v/v. Beyond this value there is not sufficient resin in the matrix to completely
surround and bond to the fibres.

4.5.3 Orientation of the Fibres

Randomly oriented fibres with a small aspect ratio will exhibit isotropic behaviour, but may not
achieve optimal properties. When a composite is made that has unidirectional fibre orientation,
maximum strength will occur parallel to the fibre, and then diminish as the orientation approaches
90° , that is at right angles to the fibres. The change in modulus of elasticity and tensile strength when
the direction of the applied stress is changed is illustrated in Figure 4-12.

Figure 4-12

Fortunately it is possible to tailor make composites to achieve a specified property. Multiple plies of
fibres with different orientation in each ply can be laid down, or fabrics of different weaves and
orientations can be used. Figure 4-13 illustrates uni and multidirectional plies for a laminate.

Figure 4-13

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Many different types of weaves produce a range of fabrics. Basket weave is illustrated in Figure 4-14.

Figure 4-14

Figure 4-15 illustrates 0°-90° x ± 45° double bias fabrics. Double bias fabrics give conformability,
torsional strength and shear strength. Double bias fabrics are also used to reduce panel edge cracking,
and cracking at fastener locations.

Figure 4-15

Comparatve properties of the more commonly used fibre materials in a unidirectional prepreg form
in a matrix of epoxy resin are illustrated in Figure 4-16.

Figure 4-16

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These graphs show the strengths and maximum strains of different composites at failure. The
gradient of each curve indicates the stiffness,(modulus of elasticity), the steeper gradients
corresponding to greater stiffness. Note the unusual behaviour of aramid in compression, compared
to tension.

Impact strength of laminates are illustrated in Figure 4-17. Note the very poor performance of carbon.
For this reason, in critical situations, carbon is often coupled with other materials into a hybrid
combination.

Figure 4-17

It is useful to compare the specific strength and modulus of metals, polymers, composites, and
reinforcing fibres. These values enable materials to be ranked in terms of their strength to weight
ratio, and provide another criteria for informed material selection. Figure 4-18 illustrates in
particular the superior characteristics of glass, aramid and carbon fibres relative to other material
categories.

Figure 4-18

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4.6 The Matrix

General characteristics
The matrix in contast to the fibres is usually ductile and tough. This property enables the matrix to
adequately support the fibres by transmitting the load uniformly, thus minimizing the risk of fibre
damage. It is essential that strong bonds form between fibre and matrix. Sound bonds are produced
when there is chemical compatibility between the two materials. The general rule is that like bonds to
like. For example fibres with polar units will bond to a matrix with polar groups. Similar factors also
determine water resistance. As a general rule less polar epoxy resins are much more water resistant
than polyesters, where the polar ester groups bond with water. Thus in marine applications epoxies
are much preferred to polyesters, although the former are more costly.

Another important property that strongly influences bond formation is the similarity of the
coefficients of thermal expansion for the two materials. If one component of the composite expands
and contracts at a rate much different from the other, bonding will be disrupted and premature failure
will occur. Other factors that promote bonding are the surface roughness of the fibres, and their
surface area, the latter being a function of their aspect ratio.

To illustrate the vital importance of a strong fibre to matrix bond, consider the progressive effects of
a tensile force on the composite shown in Figure 4-19.

Figure 4-19

When a crack develops in the matrix, the fibres remain intact and bridge the crack. With strong
fibre:matrix bonding, debonding and pull-out are minimized, and the propagation of the crack is
contained. Thus the onset of failure will be considerably delayed because the ultimate cracking will
be statistically distributed across all fibres. This is only possible if interfacial bonding is strong.
The three most common thermosetting resins used in composites are polyesters, vinylesters, and
epoxies. The main advantages and disadvantages are tabled below in Figure 4-20.

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Figure 4-20

The comparative mechanical properties are illustrated in Figure 4-21.

Figure 4-21

The detailed chemistry of epoxy resin is outlined in section 3.11.2

4.7 Mechanical Properties of Fibre Reinforced Composites

The strength of fibre-reinforced composites depends upon the orientation of the fibre relative to the
direction of the applied stress, being a maximum when they are parallel to each other. It is generally
the case that the fibre is brittle relative to the matrix. Figure 4-22(a) illustrates the stress-strain
relationship for the individual components of the composite, where the mode of deformation is brittle
for the fibre, and ductile for the matrix.

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Figure 4-2213. Stress-strain curves for a composite

Figure 4-22(b) reproduces the stress-strain data from (a), to which has been added the bulk curve for
the composite, equivalent to the fibre + matrix curves. There are two stages in the deformation of the
composite. In stage I both fibre and matrix exhibit elastic behaviour; that is this region of the stress-
strain curve is linear. In stage II the fibre continues to deform elastically, while the matrix deforms
plastically. This is due to the fact that the tensile strength of the fibre is significantly greater than the
matrix. In passing from stage I to stage II, the majority of the load is borne by the fibres.
The onset of failure begins as the fibres begin to fracture, corresponding to a strain of εf. The mode of
failure is however not catastrophic, as not all the fibres break together, and the matrix is still intact.
This mode of failure is typical for fibre reinforced composites, so long as the bond strength is strong
enough to withstand the high shearing forces.

The bond strength is crucial for sandwich laminates, particularly when wooden or polymeric cores
are used in conjunction with fibre reinforced layers. In these materials, low bond strength between
core and adjacent layers will lead inevitably to complete premature failure.

Table 4-1 lists comparative physical and mechanical properties for the commonly used composites
and metals.

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Table 4-19

Table 4-2 lists physical and mechanical properties for fibres used in composites.

Table 4-29

Comparison of some of the data from tables 1 and 2 are useful. Major points are:
1. Composites have low elongations, (1-4.4%) compared to metals, (up to 40%).
2. The deformation of unidirectional composites is elastic up to the point of failure. In contrast
the elastic limit for metals corresponds to a strain of about 0.2%.
3. Compared to metals, composites have low stiffness, (flexural modulus). However there are
various manufacturing techniques to readily stiffen composites, namely;
(i) Increase the local thickness where required,
(ii) Laminate ridges onto the underside of the panel,
(iii) Use multi-axial fabrics, (see section 4.5.3),
(iv) Employ a sandwich construction, (see section 4.7).

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4.8 Sandwich Structures

4.8.1 Introduction

The flexural stiffness of a panel when subjected to a simple three point bend test as outlined in ASTM
D790, is proportional to the cube of the panel thickness. Thus the purpose of the core of a composite
panel is to increase the laminates stiffness by “thickening “it with a low density core material.

A sandwich panel may be considered therefore to be a class of structural composites designed to be

a light-weight beam, with high stiffness and strength, and low weight. Sandwich panels are used in a
wide variety of applications, including buildings, aircraft, boats, and sporting gear.
Figure 4-23 and Figure 4-24 illustrate a cored laminate under a bending load. Here the laminate may
be likened to an I-beam, where the laminates upper and lower skins act as the I-beams flange, and the
core acts as the I-beams web.

Figure 4-239

Figure 4-241

The outer sheets of the panel are made from relatively stiff, strong material, bonded to the core.
Typical materials are fibre-reinforced plastics, metal, or wood.

The core material is lightweight, and normally has a low modulus of elasticity. Core materials are
usually rigid polymeric foams, wood, or honeycombs. Structurally the core must provide continuous
support to the faces, possess sufficient shear strength to withstand transverse shear stresses, and also
be thick enough to provide high shear stiffness; that is to prevent buckling under load.
The composite sandwich structure must be strong enough to withstand compressive, impact, and
tensile forces that result from loading in the working environment.

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Figure 4-25 illustrates a simple sandwich panel, and Figure 4-26 a composite panel with a honeycomb
core.

Figure 4-25

Figure 4-26

4.8.2 Core Materials and their Properties

4.8.2.1 Closed Cell PVC Foam

This material comes as a non-crosslinked polymer which is flexible and tough, but not as strong as
the crosslinked form, which tends to be harder and more brittle. They have a large operating
temperature range from -2400C to +800C, and are quite flammable. They may be treated with fire-
retardants to minimize flammability.

4.8.2.2 Polystyrene Foam

This material although widely used in sail and surfboard manufacture, and is a lightweight material,
does not possess the mechanical strength of most other polymeric foams.

4.8.2.3 Polyurethane Foam

This polymer has only moderate mechanical strength, but is widely used in panels subject to low
loads, where good thermal insulation and acoustic absorbance is required.

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4.8.2.4 Honeycombs

These materials are most commonly made from paper or aluminium. They are extremely lightweight,
the paper based materials being used in domestic panels such as doors and partitions, and the
aluminium honeycombs in aircraft and other high performance applications where high strength to
weight ratios are needed. Nomex is a trade name for Kevlar paper which is strengthened by dipping
in a phenolic resin. This material is used in panels in aircraft and also in racing yacht hulls.

Figure 4-27 illustrates a typical honeycomb structure with regular hexagons. It should be noted that
over expanded forms with hexagon angles greater than 1200 are also available. This type of
honeycomb facilitates being fitting around curves, without the distortion of the cell structure.

Figure 4-27

An advantage of honeycomb core materials is their tendency to absorb smaller amounts of resin than
their foam counterparts, assuming that the most compatible resin is selected. This enables the density
of the panel to remain low. Figure 4-28 compares the core-laminate bond for foams and honeycombs.

Figure 4-28

It should be noted that aluminium honeycombs are not compatible with carbon fibre skins. Carbon is
strongly cathodic with respect to aluminium in the galvanic series. Aluminium will therefore corrode
freely unless it is electrically insulated from the carbon fibre. Aluminium honeycombs also have the
problem that they lack a mechanical memory. That is, upon impact they will deform irreversibly, in
contrast to nomex, for example.

4.8.2.5 Wood

Wood itself is a naturally occurring composite material, consisting of longitudinal fibres of cellulose
embedded in a complex binding matrix. The longitudinal fibres and their alignment provide the
strength. The matrix consists of lignin and hemicellulose, which bind the fibrous cells together. Lignin
is a phenolic polymer, and hemicellulose is a low molecular weight polymeric cellulose. The
microstructure of wood is illustrated in Figure 4-29.

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Figure 4-297

The dominant features of the microstructure are the large tubelike cells L, oriented vertically, and
aligned with the vertical axis of the tree. These cells carry water, sap, and other fluids essential for the
growth process. The cellulose fibres that make up wood are analogous to the fibres in fibre-
reinforced- composites. The radial cells R, perpendicular to the longitudinal ones, store food for the
growing tree. Tangential cells are denoted T.

The complex chemistry and microstructure of wood are manifest in a highly anisotropic
macrostructure illustrated in Figure 4-30. The mechanical properties of wood vary significantly with
orientation of the fibres, and also with the moisture content. Wood is very susceptible to moisture
absorption, and much care needs to be taken to ensure that when used in sandwich construction, the
wooden core is sealed off from water ingress.

Figure 4-3011
Woods are classified broadly as hard or soft, based more upon their botanical characteristics, rather
than whether they are necessarily hard or soft in property. Students who wish to investigate this
fascinating subject further are directed to Wood in Australia, 2nd ed., by Keith Bootle, (see reference 12,
chapter 4). Wood is highly anisotropic in its structure, and is much stronger in a direction parallel to
the grain than at right angles. Furthermore wood, because of its ability to absorb moisture, is usually
kiln dried, in which form it has significantly better mechanical properties than in the green state.

Table 4-3 illustrates the full range of mechanical properties for selected American woods.

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Shear
Flexural Modulus of Compression Compression
Density parallel
Species Condition Strength Elasticity parallel to perpendicular
g/cm3 to Grain
MPa GPa Grain MPa to Grain MPa
MPa
Hickory-
Green 0.60 68 9.5 27.5 5.4 10.2
pecan
Kiln dried 0.66 95 11.9 54.1 11.9 14.4
Maple- red Green 0.49 53 9.6 22.6 2.8 7.9
Kiln dried 0.54 92 11.3 45.1 6.9 12.8
Oak-white Green 0.60 57 8.6 24.6 4.6 8.6
Kiln dried 0.68 105 12.3 51.3 7.4 13.8
Cedar Green 0.31 36 6.5 19.1 1.7 5.3
Kiln dried 0.32 52 7.7 31.5 3.2 6.8
Redwood Green 0.34 41 6.6 21.5 1.9 6.1
Kiln dried 0.35 55 7.6 36.0 3.6 7.7
Table 4-37

Table 4-4 compares the properties of selected Australian woods.

Density Flexural Modulus of Max. Crushing

Species Condition
g/cm3 Strength MPa Elasticity GPa Strength MPa
Ash Alpine, E.
Green 1.05 63 11 33
Delicatensis
Dry 0.62 110 15 60
Gum Manna, E.
Green 1.1 74 13 34
Viminalis
Dry 0.75 108 14 61
Messmate, E.
Obliqua Green 1.08 75 14 49
Tasmanian Oak
Dry 0.78 118 15 73
Mountain Ash, E.
Green 0.103 63 13 30
Regnans
Dry 0.68 110 16 63
Sassafras, A.
Green - - - -
Moschatum
Dry 0.63 99 12.6 47
Shining Gum, E.
Green 0.105 62 10 31
Nitens
Dry 0.7 99 14 58
Silver Wattle, A.
Green 0.8 60 10 30
Dealbata
Dry 0.68 87 12 52
Table 4-412

4.8.2.5.1 Balsa Wood

This material is most commonly used in its end-grain form, sandwiched between two layers of glass
or carbon fibre-resin for boat and yacht construction, where it forms a strong rigid sheet. End grain
balsa is readily available in sheet form, where it may be vacuum bagged with prepreg fibre-resin for
construction of sporting and engineering components. Balsa has high thermal, acoustic, and fire
resisting properties, but like all woods readily absorbs moisture. It is therefore necessary to ensure
that balsa cores are fully protected from moisture ingress if their integrity is to be maintained.

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4.8.2.5.2 Plywood

Plywood is a laminar composite that consists of layers of thin panels, each stacked with different
orientations of their fibres, and glued together. In this manner the composite can be tailored to
become more isotropic, compared to its individual layers, with required mechanical properties
optimised in any particular direction. In this respect plywood is similar to other fibre reinforced
composites using differing orientations of fibres or woven fabric in a resin matrix.

Figure 4-31 illustrates a composite comprising of successive layers of wood, with their fibre
orientations clearly shown.

Figure 4-3113

In Figure 4-31 the layers are oriented at 0-900 to each other. However any orientation can be chosen
to optimize properties, with another common arrangement being + or – 450 as illustrated in Figure
4-15. With either of these combinations the composite gains shear strength and torsional strength
over the individual layers. This effective strategy will also serve to reinforce edge cracking and
strengthen critical locations where fastenings are used.

Of significant importance in these types of laminates is not just the wood strength in different
directions, but the shear strength of the glue binding the layers. Failures in skateboards made using
commercial plywood cores has highlighted this weakness. Plywoods differ greatly in quality, and
therefore careful selection must be made.

If the core ply is to be hand-made from wood panel and glue, the appropriate wood species, thickness
and number of layers, together with the most compatible glue should be carefully researched. Of the
three most common resins, epoxy has better overall shear strength, tensile strength and elastic
modulus than either polyester or vinylester resins, (see also section 4.6).

4.8.2.6 Comparison of Cost and Mechanical Properties

Figure 4-32 and Figure 4-33, illustrate the relative cost, and the compressive and shear strengths with
respect to density, for a range of core materials.

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Figure 4-32

Figure 4-33

4.9 Manufacture of Core Panels

There are many processes for manufacturing composite panels. The method chosen will depend upon
the size and number of panels, and whether the process is manual or automated. However the
sequence of operations is the same whichever process is chosen.

4.9.1 Hand Lay up

In this technique resins are impregnated by hand into fibres in the form of woven, knitted or stitched
fabrics. The application of resin is commonly accomplished by brushing or rolling. Laminates are
usually left to cure under ambient conditions.
The technique is illustrated in Figure 4-34.

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Figure 4-3410

The main advantages of this method are that it is simple and easy to perform and requires no
expensive equipment. Its disadvantages are that the quality of finished product is highly dependent
upon the skill of the operators, and that there are health and safety issues due to the need to use less
viscous, more volatile resins.

4.9.2 Vacuum Bagging

Vacuum bagging is an extension of wet hand lay up, but where pressure is applied to the wet uncured
composite to enhance consolidation. This is achieved by encasing the composite in a sealed plastic
bag and removing the air using a vacuum pump. A pressure of up to one atmosphere can be obtained
which will remove all air and volatiles, and ensure effective consolidation and wetting of the fibre by
the resin.

The main advantages are that higher fibre contents can be used because of the improved wetting, and
lower void contents. Better health and safety outcomes are achieved due to a reduced exposure to
volatiles. The final quality of the composite is generally improved compared to ambient curing.
The main disadvantages are that the process is more costly, and that higher skills are required of the
operator, particularly with respect to obtaining efficient sealing of the plastic envelope against the
ingress of air. Futhermore proper mixing of resin and hardener are dependent on operator skill as
they are with hand lay up.

The process is illustrated schematically in Figure 4-35.

Figure 4-3510

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4.9.3 Prepregs and Their Use

4.9.3.1 Introduction

A prepreg consists of a combination of resin and fibre reinforcement in the required amounts,
conveniently combined in roll form from which it may be readily cut. The resin may be partly cured,
but optimal properties can only be obtained by vacuum bagging and oven curing, or by autoclaving
under pressure at elevated temperatures. The main advantage is in labour saving and quality of
finished composite. Its main disadvantage is the considerably higher material costs.
Prepregs are available in uni-directional reinforcement, ie one direction of reinforcement, and in
fabric form with several directions of reinforcement, illustrated in Figure 4-36.

Figure 4-361

The available fibre properties are illustrated in Figure 4-37.

Figure 4-371

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The weave style can be varied according to crimp and drapeability. Low crimp gives better mechanical
properties because straighter fibres can carry higher loads. High drapeability enables the fabric to lay
up easier over complex shapes. In addition to the three illustrated weaves, non-crimp fabrics can be
produced by stitching together uni-directional layers in pre-determined orientation. Three commonly
used weaves are illustrated in Figure 4-38, and non-crimp fabrics have been previously illustrated in
Figure 4-14.

Low drapeability/high crimp Good drapeability/low crimp Average drapeability and crimp
Figure 4-381

4.9.3.2 Applications

Prepregs are widely used in high-tech applications such as aerospace, railway, wind turbine blades,
marine vessels and sport and leisure equipment.

4.9.3.3 General Processing

The major types of processing are illustrated in Figure 4-39. They include vacuum bagging with oven
cure, autoclaving with pressure, match moulding, tube rolling and the pressure bag process. In these
notes we will only discuss vacuum bagging with oven cure.

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Figure 4-391

The vacuum bagging and autoclave processes are the most common in use for prepregs. Autoclaving
is costly because of the high equipment investment necessary. This process produces the highest
quality composites and is particularly suitable for thick sections. The vacuum bag process is cheaper
to set up, and produces good quality thin section composites.

4.9.3.4 Sandwich Processing

Sandwich constructions of thin sections can be laid up and cured as a single stage process. Figure
4-40and Figure 4-41 illustrate the vacuum bag lay up sequence and the make up of a sandwich
composite respectively.

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Figure 4-401

Figure 4-411

The role of each layer in the vacuum bag assembly is as follows:

• Release agent: Allows the release of the cured prepreg from the mould.
• Peel ply: Allows free passage of volatiles and resin during the cure. Can be removed after cure
to expose a smooth paintable surface.
• Bleeder fabric: Usually made from felt or glass wool to absorb excess resin.
• Release film: Prevents further flow of resin.
• Breather fabric: Provides a cavity to apply the vacuum and assists the removal of volatiles and
air as the vacuum is applied.
• Edge dam: Contains resin flow and component shape.
• Vacuum bag sealant tape: Provides a sealed bag to allow the efficient application of the
vacuum.

After the lay-up has been accomplished and the mould and wet composite have been sealed into the
vacuum bag, the process of curing is carried out in an oven with temperature/time control. The
temperature and time of curing will be advised by the supplier of the prepreg, but for epoxy resin the
curing temperature is 1200C.
A schematic diagram of the curing process and the curing cycle are illustrated in Figure 4-42 and
Figure 4-43.

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Figure 4-421

Figure 4-431

4.9.3.5 Properties of Fibre-Reinforced Composites

The fibres in a composite are strong and stiff, and support most of the applied load. The matrix
contributes to the toughness, protects the fibre from the environment, and is the medium that secures
the fibres in place, giving the composite its characteristic structure.

Unidirectional composites have their predominant mechanical properties in one direction and are
therefore anisotropic in nature. Woven fabric, depending upon the chosen weave may be isotropic.
Unidirectional fabrics can be laid up at different orientations to optimize properties, eg a tri-axial
arrangement on diagonal and longitudinal axes is useful for surf and skateboards. Refer to Figure 4-13
and to Figure 4-44.

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Equal properties Unequal properties

Figure 4-441

4.9.3.6 Storage of Prepregs

Prepregs should be stored as received in a cool dry place, or in a refrigerator. After removal from
refrigerator storage the prepreg should be allowed to reach room temperature before opening the
polyethylene bag. This will prevent condensation on the prepreg. A typical prepreg will have a
guaranteed shelf life of 12 months at -180C. Tack life at 230C depends upon the resin type, and is
clearly defined on the Product Data Sheet.

4.9.3.7 Typical Mechanical Properties for Selected Prepregs

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4.10 Use of Sandwich Laminates in Yacht Construction

Sandwich materials because of their high strength to weight ratio and their exceptional ability to
withstand impact, are being increasingly used in high performance yacht construction.

A wide range of possible combinations of bulk sandwich materials are now possible, by varying core
material, cladding, and number and sequence of layers within the sandwich. The modern boat
designer now has the opportunity to be truly innovative as never before, with the broad range of
polymeric composite materials currently available.

Students are encouraged to investigate this topic for themselves, and to visit a local boat building yard
to “see for themselves”.

Figure 4-45

4.10.1 Questions and Answers – Polymers

Q10.1 What conclusions can be made concerning the mechanical properties of polymers when
comparison is made between linear addition thermoplastics, linear condensation thermoplastics, and
thermosetting polymers?

A10.1 Refer to tables 3, 4, and 5, section 3.13 to answer this question. The maximum ranges of
properties from these references are tabled below.

Polymer Tensile Strength MPa % Elongation Modulus of Elasticity GPa

Linear addition
21 - 83 5 - 800 0.27 – 4.14
thermoplastics
Linear condensation
55 - 117 10 - 300 1.7 – 4.14
thermoplastics
Thermosetting polymers 28 - 104 0-6 3.45 – 11.0

The linear addition polymers have the lowest strength and stiffness, but the highest ductility. The
thermosetting polymers have the highest strength and stiffness, but are brittle. Most linear
condensation thermoplastics have intermediate properties. Their structure is usually more complex
than that of the addition polymers. They are not cross-linked as are the thermosetting polymers.

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References

1 www.hexcel.com/resources/datasheets/Prepreg_Technology.pdf
2 Ashby,M., Shercliff, H., Cebon,D., Materials engineering, science, processing and design,
Elsevier, First Ed., 2008.
3 www.ecocourses.au.edu/cgi_bin/ebook.cgi?doc=&topic=me&cha
4 Stephens, R.C., Ward, J.J., Applied Mechanics, SI Edition, Macmillan, 3rd Ed., 1972
5 www.testpacs.com
6 ASTM Standard D790-10, Standard Test Methods for Flexural Properties of
Unreinforced and Reinforced Plastics and Electrical Insulating Materials.
7 Smith, W.F., Hashemi, J., Foundations of Materials Science and Engineering, McGraw
Hill, 5th. Ed., 2010.
8 Askeland, R.A., The Science and Engineering of Materials, PWS-Kent, 2nd Ed., 1989.
9 Fgi Fibre Glass International Composite Handbook.
10 SP Guide to Composites .
11 Shackelford, James, F., Introduction to Materials Science for Engineers, 3rd ed.,
MacMillan, 1992.
12 Bootle, Keith, R., Wood in Australia, 2nd ed., McGraw-Hill, 2005.
13 Callister, William, D., Materials Science and Engineering, 7th ed., Wiley, 2007.

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Phase Diagrams

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5.1 Introduction
An understanding of phase diagrams is very important because the mechanical properties of alloys
are correlated to microstructure, which in turn is a function of heat treatments performed on the
alloy. The microstructure and the phase diagram are directly related, and provide a potent tool for
quality control, essential for the safety and functionability of engineering structures. A phase diagram
is a graphical representation of the relationship between temperature and composition, and the
regions of stable phases, under equilibrium conditions.

5.2 One Component Phase Diagrams

A great deal of information about the control of phase structure of a particular system may be
obtained from a phase diagram. Although binary phase diagrams are the major source of interest to
the materials engineer, the general concepts are more easily grasped by considering a simple unary
system, say that for water. The three external factors that affect phase structure are temperature,
pressure and composition. Figure 5-1 illustrates the phase diagram for water

Figure 5-13 Pressure-temperature phase diagram for H2O.

The following observations can be made from Figure 5-1:

i. The areas of phases present are solid (ice), liquid (water) and vapour (steam).
ii. The three curves Oa, Ob and Oc represent phase boundaries. At any point on these boundaries
the phases on either side are in equilibrium.
iii. Upon crossing a boundary, one phase will transform to another. For example, at 1 atmosphere
of pressure, during heating ice melts at point 2, at 0°C, and the liquid water vaporizes at point
3, 100°C. The reverse, cooling results in water vapour condensing at point 3, and the liquid
water freezing at point 2.
iv. Point O is a triple point at which all three phases are at equilibrium. This occurs only at
273.15°K and 6.04×10-3 atmospheres.

The term 'phase' may be defined as a homogeneous and physically distinct portion of a system
with uniform physical and chemical properties. The uniqueness of water and its phases has a
profound effect of life on earth, from its presence in microscopic cells, clouds, and ice crystals, to name
but a few. Part of this uniqueness is due to its molecular geometry shown in Figure 5-2.

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Figure 5-22 The water molecule is bent, with the two bonds between oxygen and hydrogen splayed at an
angle of 104.5° (a). To understand the structure of liquid water, we must also take into account the two 'lone
pairs' of electrons on the oxygen atom. The hydrogen atoms and the lone pairs sit more or less at the corners
of a tetrahedron (b). At the molecular scale, the structure of water is imprinted with this tetrahedral geometry.

Liquid water has an unusually high boiling point, because of strong hydrogen bonding shown in
Figure 5-3.

Figure 5-32 Water molecules – with hands representing hydrogens and feet representing lone pairs of
electrons – perform a dance that involves grabbing neighbours by the ankles. These clasps, due to hydrogen
bonding, lead to a tetrahedral arrangement of neighbours around each molecule. This is the central motif of
the structure of water, and the key to all its anomalous properties.

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Solid water in the form of ice is strangely less dense than the liquid phase, due to a change in molecular
geometry shown in Figure 5-4.

Figure 5-42 The structure of ice is no dance but an orderly tableau. Each water molecule is hydrogen-bonded
to four others in an arrangement that displays hexagonal symmetry. Here I have highlighted one of the
hexagonal rings in grey.

Strange and beautiful geometric patterns in the form of infinitely variable dendrites occur in the snow
flakes. Note the connection between the shape of the snow flake and the metal dendrite in Figure 5-5
and Figure 1-23

Figure 5-52 Snowflakes are crystals of ice that bear to nature’s inexhaustible pattern-forming capability.

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Finally the phase changes of water on a macroscopic scale are illustrated in the hydrological cycle
pictured in Figure 5-6.

Figure 5-62 The hydrological cycle carries water on an unending journey through streams, rivers and oceans,
the atmosphere, the ice sheets, living and the deep earth.

5.3 Pure Metals and Alloys

An alloy consists of two or more elements, usually metals. The major constituent is known as the base
metal, the minor constituent(s) are the alloying elements, together with impurities.

i. All metals and alloys are polycrystalline

ii. All pure metals are single phase
iii. An alloy may be single or multiphase
iv. A phase is a chemically homogeneous and physically distinct portion of a material.

5.3.1 Components in a Solid Alloy

When a liquid solution of two metals freezes, four situations can arise:

i. Both metals come out of solution, and separate totally into two phases. They are mutually
insoluble. For example, copper and lead, and aluminium and lead.
ii. Both metals remain in solution in the solid state and form a single phase solid solution. They
are mutually totally soluble. For example, copper and nickel, and copper and zinc up to 30%
zinc.
iii. Both metals form a range of partial solid solutions. For example, copper and zinc when zinc is
greater than about 35% zinc.
iv. The two metals react together during freezing, and form intermetallic compounds. For
example, portion of the aluminium and copper phase diagram.

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5.3.2 Solid Solutions and Compounds in Alloys

All solutions are homogeneous. For liquid solutions, the relative size of the solute and solvent
molecules is not important. For solid solutions, atomic size is important. The two types of solid
solutions are interstitial and substitutional.

5.3.2.1 Interstitial Solid Solution

This is where the solute atom is much smaller than the solvent atom. For example, carbon in iron.

5.3.2.2 Substitutional Solid Solution

This is where solute and solvent atoms are approximately the same size. For example, copper and
nickel, copper and zinc up to about 35% zinc. The various types of solid solutions are shown in Figure
5-7.

Figure 5-75 Interstitial and ordered and disordered substitutional solid solutions. The dark spheres represent
the interstitial or substitutional atoms in each case.

5.3.2.3 Intermetallic Compounds

i. Some obey the normal valence rules. For example, Mg2Sn and Mg3Bi2.
ii. Many do not obey valence rules, but may form covalent or ionic bonds. For example, Mg2Si
and CuAl2.
iii. 'Electron compounds' form where there is a fixed ratio of valence electrons and atoms.
Common ratios are 3:2, 21:13 and 21:12 (7:4). For example, CuZn:

Valence electrons 1 + 2 =
3
Cu Zn

Number of atoms = 2
Valence electrons 3
= = Ratio
Number of atoms 2

5.3.2.4 Interstitial Compounds

These are compounds formed between a large metal atom and a small non-metal atom, for example,
iron carbide, Fe3C (cementite). It is important to note that iron-carbide does not exist as a 'compound'
of Fe3C molecules, but rather the ratio of Fe:C in the crystal is in the proportion 3:1. The orthorhombic
structure of Fe3C is shown in Figure 5-8. The unit cell consists of 4 atoms of C and 12 atoms of Fe.

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Figure 5-85 The orthorhombic crystal structure of iron carbide (Fe3C).

It should be noted that all intermetallic compounds are hard and brittle, and affect the properties of
alloys in a profound way.

5.4 Thermal Equilibrium Phase Diagrams

The phase diagram is a graphical method of showing the phases present in an alloy system at different
temperatures for different compositions. All phases present result from slow, equilibrium cooling.

5.4.1 The Construction of a Phase Diagram

Phase diagrams are constructed from information obtained from a series of cooling curves, for a range
of alloy compositions. The cooling curves are illustrated below.

Figure 5-95 Cooling curves for pure metals and alloys. (A) for a pure metal, solidification occurs at constant
temperature as idicated by the horizontal line AB. (B) For a solid solution, solidification occurs over a
temperature range as indicated by the interval AB. (C) For a multi-phase alloy containing a eutectic mixture,
the solidification range is indicated by the interval ABC, the horizontal section line BC indicating the eutectic
reaction.

Eutectic Reaction: A two phase micro-structure resulting from the solidification of a liquid of eutectic
composition transforming iso-thermally into two intimately mixed solid phases. Phase: A chemically
homogeneous and physically distinct component of a system
The arrest points in Figure 5-9 represent the following:

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Cooling curve A for a pure metal: A phase change; in this case freezing.The line is horizontal, denoting
an isothermal process.

Cooling curve B for a solid solution of two metals: Here the mixture of metals freeze over a range of
temperature, and the phase change from liquid to solid does not occur isothermally as for a pure
metal.

CoolIng curve C for a multi-phase alloy: Not all binary alloys form solid solutions. Many form eutectoid
phases during which a solid phase transforms isothermally into two new intimately mixed solid
phases denoted α and 𝛽𝛽 and expressed by the equation,

Solid → α + 𝜷𝜷

In this cooling curve AB represents the freezing of a solid solution as for curve B.
BC represents the eutectoid reaction.

Figure 5-105 (a) A series of cooling curves for various alloys of the two metals, M1 and M2, which are insoluble
in the solid state. (b) Constructing the equilibrium diagram for the alloys of M1 and M2 using the data from the
cooling curves in (a). Note that the equilibrium diagram, unlike the cooling curves, does not show time as a
variable.

The line ABC is known as the liquidus, the line separating liquid and liquid plus solid. The line DBF is
called the solidus, the line below which all alloys are solid. The point B is the eutectic point, which
represents the point or temperature of solidification of the lowest melting point alloy.

The eutectic reaction is denoted by a liquid phase transforming isothermally into two intimately
mixed solid phases. (40%M1 and 60%M2). The area between the solidus and liquidus represents the
'mushy' metal, where both liquid and solid phases are present.

5.4.2 The Construction of a Copper-Nickel Phase Diagram

Details of construction using cooling curves are illustrated in Figure 5-11 and Figure 5-12.

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Figure 5-114 Relationship between cooling curves and equilibrium diagram for the system copper-nickel. (a)
Individual cooling curves for Cu, Ni and a 50-50 Cu-Ni alloy. (b) The cooling curves of (a) on time-
temperature-composition coordinates. (c)Surface generated by cooling curves for all possible alloys of Cu with
Ni. (d) Cu-Ni equilibrium diagram, which is the surface in (c) as viewed in the direction indicated by the arrow.

Figure 5-124 Schematic cooling curves for Cu-Ni alloy over-all composition Co. Points A and B correspond in
all three illustrations. (a) Location of Co on the equilibrium diagram. (b) Trace of cooling curve on three-
dimensional surface. (c) Cooling curve of alloy of composition Co.

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5.4.3 A binary single phase system (Cu-Ni)

Figure 5-13 (a)

Figure 12.133 (b) The copper-nickel phase diagram. (b) A portion of the copper-nickel phase diagram for
which compositions and phase amounts are determined at point B.

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5.4.3.1 Observations

i. Above 1453°C, all liquid, ∴melting point of Ni = 1453°C

ii. Below 1085°C, all solid, ∴melting point of Cu = 1085°C
iii. Above liquidus line, all liquid
iv. Below solidus line, all solid
v. α is the single phase (a solid solution of Cu and Ni)

5.4.3.2 Interpretation with Equilibrium Cooling

Refer to Figure 5-13(a), the phases present are:

i. Composition A, 60% Ni, 40% Cu, phase present is solid α .
ii. Composition B, 35% Ni, 65% Cu, phases present are solid α and liquid (L).

The phase composition for composition A is: α = 60% Ni, 40% Cu.
Determining the phase composition for composition B can be found in two different ways.
Refer to Figure 5-13(b). The first way of determining the composition for B is:

i. Draw the tie line, a horizontal line through B, intersecting liquidus and solidus lines.
ii. The composition of the liquid, L, is read from the intersection of the tie line with the liquidus,
projected down to the composition axis, namely CL.
CL = 31.5% Ni, 68.5% Cu.
The composition of α corresponds to the point of intersection with the solidus
Cα = 42.5% Ni, 57.5% Cu.
Percentage of phases using the lever rule:
Composition A = 100% α
Composition B: use the line through B, and apply the lever rule. Mass fraction of liquid phase,
S C − C0
=
WL = α (5-1)
R + S Cα − CL

Cα − C0 42.5 − 35
=WL = = 0.68
Cα − CL 42.5 − 31.5
Similarily:
R C − CL
=
Wα = 0 (5-2)
R + S Cα − CL
C0 − CL 35 − 31.5
=Wα = = 0.32
Cα − CL 42.5 − 31.5
Alternatively, R, S and R + S can be measured directly from the phase diagram using a millimetre rule,
assuming the scale is large enough for an accurate reading. equation (5-1) is used to illustrate reading
compositions from the phase diagram in Figure 5-13(b).
Cα − C0 20.5
=
WL = = 0.68
Cα − CL 30

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Note that Wα and WL are mass fractions, and Wα + WL = 1.0.

Consider an alloy of 35% Ni and 65% Cu. Solving in conjunction with Figure 5-14.

Figure 5-143 Schematic representation of the development of microstructure during the equilibrium
solidification of a 35 wt% Ni-65 wt% Cu alloy.

i. At a, T=1300°C, Phase = L. L= 65% Cu, 35% Ni

ii. At b, T=1270°C, Phases = L + a little α . L = 35% Ni, α = 46% Ni
iii. At c, T=1250°C, Phases = 72% L, 28% α (by lever rule) L = 32% Ni, α = 43% Ni
% L = 43-35 = 0.72 = 72%
43-32
% ∝ = 35-32 = .028 = 28%
43-32
iv. At d, T=1220°C, Phases = α + a little L. L = 24% Ni, α = 35% Ni.
v. At e, T=1190°C, Phases = α . α = 35% Ni
Note that considerable concentration gradients exist between the two phases as cooling proceeds. If
cooling is sufficiently slow, atomic diffusion will have time to occur, and the composition throughout
the equiaxed grains of α will be uniform. Such will not be the case if cooling is rapid. This is the rule
rather than the exception in the commercial production of alloys.

5.4.3.3 Effects of Rapid or Non-Equilibrium Cooling

Consider a 35% Ni, 65% Cu alloy when rapidly cooled as in Figure 5-15.

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Figure 5-153 Schematic representation of the development of microstructure during the nonequilibrium
solidification of a 35 wt% Ni-65 wt% Cu alloy.

Rapid cooling does not give the composition of the continuously freezing liquid solution time to adjust
its composition to equilibrium values, that is, diffusion is suppressed. Hence the composition of the
α grains is non uniform, being richer in the higher melting point metal, such as nickel, at their
centres. Thus the outside of the α grain is richer in copper, the lower melting point metal. This
phenomenon is known as coring, and results in weakening of the mechanical properties. If the alloy
is soaked at a temperature below the solidus, homogenization (diffusion) will occur, resulting in
improved properties. Figure 5-16 is a photomicrograph of a cored copper nickel alloy.

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Figure 5-161 Further examples of uneven composition (coring) in as-cast, solid solutions. Above: 90/10
copper-nickel alloy; below: 70/30 copper-zinc alloy. 200x.

5.5 Mechanical Properties of Isomorphous Alloys

It is a general rule that a pure metal is strengthened by the addition of a second metal, up to a
maximum or optimal value. This is illustrated for the Cu/Ni system where an alloy with 60% Ni has
maximum tensile strength and minimal ductility.

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Figure 5-173 For the copper-nickel system, (a) tensile strength versus composition, and (b) ductility (%EL)
versus composition at room temperature. A solid solution exists over all compositions for this system.

5.6 The Binary Euectic System (Pb-Sn)

Although some alloys exist as complete solid solutions, most commercially important alloys exhibit
only partial solid solubility. Certain alloys like copper-silver, lead-tin, steel, brass and bronze exhibit
more complex phase diagrams, containing a binary eutectic system as part of their phase diagram.
We will now consider the lead-tin system, to illustrate a typical binary eutectic alloy. At this point we
need to define two new terms, eutectic reaction and eutectic structure.

A eutectic reaction is a reaction where a liquid phase upon cooling transforms isothermally into two
intimately mixed solid phases. It is convention to label these phases using the Greek alphabet, usually
α and β . The eutectic reaction may be written as:
𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶
𝐿𝐿 ⇌ 𝛼𝛼 + 𝛽𝛽 (5-3)
𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻
A eutectic structure is a two phase microstructure which results from the cooling of liquid of eutectic
composition into two solid phases which exist as alternate lamellae, or fine layered structure.

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Liquidus

Solidus

Eutectic
Solvus

Figure 5-183 The lead-tin phase diagram.

5.6.1 Key Points for the Lead-Tin System

i. There are three phases present, α , β and liquid L.

ii. α is a solid solution of Sn in Pb. Solubility at room temperature is approximately 1-2% Sn.
iii. β is a solid solution of Pb in Sn of composition less than 1% Pb.
iv. The solubility of each of the solid phases is limited, and decreases with temperature.
v. The eutectic invariant point is at 61.9% Sn at 183°C.
vi. Solder is approximately 60% Sn and 40% Pb, being the composition with the lowest melting
point.

5.6.2 Analysis of Phases, Microconstituents for Pb-Sn System

Consider the cooling from the liquid state of alloys containing 1.5%, 15% 40% and 61.9% tin
respectively, as illustrated in Figure 5-19.

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Figure 5-193 The lead-tin phase diagram.

5.6.2.1 1.5% Sn Alloy 1

Point a: 1 phase = liquid = 1.5% Sn and 98.5% Pb.

Point b: Temperature = 323°C. 2 phases: L and α

Point c: Temperature = 267°C. 1 phase = α = 1.5% Sn and 98.5% Pb

The microstructure of equiaxed grains is below, in Figure 5-20.

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Figure 5-203 Liquid-phase region of a lead-tin alloy of composition C1.

5.6.2.2 15% Sn Alloy 2

Figure 5-213 Liquid-phase region of a lead-tin alloy of composition C2.

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Chapter 5: Phase Diagrams

Point d: Temperature ≈ 320°C. Phase = liquid = 15% Sn, 85% Pb

Point e: Temperature = 267°C. Phases = L and α .

Composition of phases: L = 23% Sn, α = 12% Sn
3 8
Percentage of phases (lever rule): % L = × 100 =27%, %α = × 100 =73%
11 11

Point f: Temperature = 190°C. Composition of phase = 15%Sn

Percentage of phase = 100% ∝

Point g: Temperature = 120°C. Phases = α and β .

Composition of phases: α = 6.5% Sn, β = 98% Sn
Percentage of phases (lever rule): % α = 90.7%, % β = 9.3%

Upon crossing the solvus line the solubility of α is exceeded and β is precipitated within the equiaxed
grains of α . The microstructure is illustrated below in Fig. 11.21.

5.6.2.3 61.9% Alloy 3

Figure 5-223 Lead-tin alloy of eutectic composition C3.

Point h: Temperature ≈ 250°C. Phases = 100% liquid, L = 61.9% Sn

Point i: Temperature = 180°C. At 183°C the eutectic reaction L → α + β occurs, and just below
183°C, the alloy is solid and is 100% eutectic, that is, α and β.

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Phase composition: α = 18.3% Sn, β = 97.8% Sn

Consider the eutectic change in a little more detail using equation (5-3).

𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶
𝐿𝐿(61.9% 𝑆𝑆𝑆𝑆) ⇌ 𝛼𝛼(18.3𝑤𝑤𝑤𝑤%
�� �������𝑆𝑆𝑆𝑆) �� + ��
𝛽𝛽(97.8%
������ 𝑤𝑤𝑤𝑤%
���𝑆𝑆𝑆𝑆)
��
𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻 𝑆𝑆𝑆𝑆 𝑖𝑖𝑖𝑖 𝑃𝑃𝑃𝑃 𝑃𝑃𝑃𝑃 𝑖𝑖𝑖𝑖 𝑆𝑆𝑆𝑆

For this change to occur atomic diffusion of Pb and Sn must occur. The resulting microstructure
consists of alternating layers or lamellae of the α and β phases, which form simultaneously.

Note the diffusion of Sn away from the α phase towards the β phase. Because the layers, or lamellae
are thin, diffusion occurs readily. The percentage of phases at point I from the tie line is:

97.8 − 61.9
=α =
×100 45%
97.8 − 18.3
61.9 − 18.3
=β =
×100 55%
97.8 − 18.3

Figure 5-233 Schematic representation of formation of the eutectic structure for the lead-tin system.
Directions of diffusion of tin and lead atoms are indicated by blue and red arrows, respectively.

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Chapter 5: Phase Diagrams

Figure 5-243 Photomicrograph showing the microstructure of a lead-tin alloy of eutectic composition. This
microstructure consists of alternating layers of a lead-rich α -phase solid solution (dark layers), and a thin
tin-rich β -phase solid solution (light layers). 375x.

5.6.3 40% Sn Alloy 4

Figure 5-253 Liquid-phase region of a lead-tin alloy of composition C4.

Point j: Temperature ≈ 310°C. Phases = liquid. L = 40% Sn

Point k: Temperature = 220°C. Phases = L and α

Composition of phases: α = 18% Sn, L = 46% Sn
46 − 40 40 − 18
Percentage of phases:
= α = 21%, = β = 79%
46 − 18 46 − 18

Point l: Temperature = 186°C. Phases = L and α

60 − 40 40 − 18
Composition of phases:
= α = 48%, =L = 52%
60 − 18 60 − 18

Point m: Temperature = 180°C. Phases = α and β . Microconstituents = α + eutectic

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Note that a microconstituent is an element of the microstructure having an identifiable and

characteristic structure, that is, primary α and eutectic. The eutectic consists of two phases, α and
β.

Figure 5-263 Photomicrograph showing the microstructure of a lead-tin alloy of composition 40 wt% Sn-60
wt% Pb. This microstructure is composed of a primary lead-rich α phase (large dark regions) within a
lamellar eutectic structure consisting of a tin-rich β phase (light layers) and a lead-rich α phase (dark
layers). 400x.
Since the eutectic microconstituent always forms from liquid having the eutectic composition, the
eutectic microconstituent will have a composition of 61.9% Sn and 38.1% Pb. It will consist of
lamellae of α and β .

Microconstituents: α + eutectic
Composition of α ' = 16% Sn
Composition of Eutectic = 61.9% Sn

61.9 − 40
of α '
Percentage = =
× 100 50%
61.9 − 18.3
40 − 18.3
Percentage of eutectic
= =
× 100 50%
61.9 − 18.3

Note that α' means the primary α , that is, α which precipitated out before the eutectic reaction
producing α and β .

Phases: α + β
Composition of α = 16% Sn
Composition of β = 97.8% Sn
97.8 − 40
Percentage of
= α ×=100 70.7%
97.8 − 16
40 − 16
Percentage of=β × 100
= 29.3%
97.8 − 16
It should be further noted that for non-equilibrium cooling the microstructure of alloy 4 at room
temperature will:

i. Possess cored grains of primary α .

ii. A higher proportion of eutectic than for equilibrium cooling.

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Alternatively for point m:

Figure 5-273 Lead-tin phase diagram.

P
=
%eutectic × 100
P+Q
Q
%α '
= × 100
P+Q

And fractions of total α , that is, primary and eutectic are:

Q+R
=%α × 100
P+Q+ R
P
= %β ×100
P+Q+ R
Tin balance for the 40% tin alloy at point m, Figure 5-25. It is often necessary to carry out a materials
balance in practice. For this system a stocktake of tin will illustrate the procedure.
Tin balance based on the microconstituents:
α ' 50% of 16% Sn = 8% Sn
eutectic 50% of 61.9% Sn = 30.95% Sn
Total Sn = 38.95% Sn
Tin balance on phases:
α = 70.7% of 16% Sn = 11.3% Sn
β = 29.3% of 97.8% Sn = 28.8% Sn
Total Sn = 40.1% Sn
38.95 + 40.1
Average Tin = = 39.5%
2

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This value is very close to 40% Sn in alloy 4, bearing in mind that all values have to be read off the
graphed phase diagram.

5.7 The Allotropy of Iron

Iron exists in three allotropic forms, each being stable over a certain temperature range. These
allotropic forms are illustrated in Figure 5-28.

Figure 5-283 The cooling curve for pure iron showing allotropic changes.

Changes occur at the following temperatures:

i. 1535-1400°C: the melting (freezing) point, delta Fe ( δ ) forms. This is body centred cubic.
ii. 1400-910°C: δ converts to gamma ( γ ) iron when cooled from 1400°C. This phase is
referred to as austenite and is non magnetic.
iii. 910-768°C: this is alpha, α , iron known as ferrite. It is body-centred cubic and is non
magnetic.
iv. 768°C: This is α iron, it is body-centred cubic and is magnetic. 768°C is known as the curie
point, and at this temperature there is a rearrangement of the valence electrons in iron
causing it to become magnetic.

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5.8 The Iron-Carbon Phase Diagram

5.8.1 Introduction

Plain carbon steels consist of iron and carbon with small amounts of Mn, Ni, Cr and Mo. However, it is
the different solubilities of carbon in iron which gives steel its basic properties, and allows steel to be
heat treated, which profoundly alters its mechanical properties. Figure 5-29 shows the iron-carbon
phase diagram.

Figure 5-293 The iron-carbon phase diagram.

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The composition axis on this diagram only extends to 6.7%C. At this composition an intermediate
compound, iron carbide (Fe3C), otherwise known as cementite forms. This is represented by a vertical
line. In practice irons and steels have carbon contents of less than 6.7%C, and hence only the iron rich
portion of the system is of value.

The following points of interest should be noted:

i. There is a general lowering of the freezing point of the alloy with increasing amounts of
carbon, until the eutectic composition of 4.3%C is reached at 1130°C. The eutectic reaction is:
L → γ + Fe3C .
ii. There is a progressive lowering of the upper critical temperature towards a minimum of
727°C for the alloy containing 0.76%C. At 727°C the eutectoid reaction occurs: γ → α + Fe3C
.
iii. A eutectoid reaction occurs when a cooling solid phase transforms isothermally into two new
solid phases that are intimately mixed. Like eutectic, the phases may exist as lamellae. It is
known as pearlite. This reaction is fundamental in the heat treatment of steel.
The phases and microconstituents important to the metallurgist and engineer are:

i. Austenite ( γ phase) which may hold up to 2.14% C in interstitial solution. It will also dissolve
other alloying constituents specifically Ni and Cr. Its microstructure is shown in Figure 5-30
below.

Figure 5-303 Photomicrograph of austenite. 325x.

ii. Ferrite ( α phase) is soft ductile iron, holding up to 0.008%C at room temperature. Ferrite
can also hold other elements such as Mn, which gives added strength. Its microstructure is
shown in Figure 5-31.

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Figure 5-313 Photomicrograph of α ferrite. 90x.

iii. Cementite Fe3C is a hard brittle intermetallic compound. Its presence hardens and
strengthens steel. It forms when the solubility of carbon in α at 727°C is exceeded.
iv. Pearlite is the eutectoid formed within the alloy system by the isothermal, simultaneous
precipitation of ferrite and cementite from austenite at 723°C.
γ → α +
Fe3 C
Austenite, 0.76% C         Ferrite, 0.02% C      Cementite, 6.67% C
        Pearlite ( ←    → )

It has fine to coarse alternating plates or lamellae of ferrite and cementite. Slow cooling gives
a coarse structure, while rapid cooling leads to very fine plates. Pearlite is a microconstituent.

Phase/ Tensile strength Elongation Brinell hardness

microconstituent MPa % HB
Ferrite 295 50 80
Difficult to measure due
Cementite - 600-650
to its extreme brittleness
Pearlite 770-1000 10 200-300
Table 5-13 General properties of ferrite, cementite and pearlite.

There are three main groups of ferrous alloys, namely:

i. Pure iron < 0.008%C

ii. Steels 0.008-2.14%C but usually >
/ 1.0%C.
iii. Cast irons 2.14-6.7%C but usually >
/ 4.5%C.

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5.8.2 Microconstituents and Phases in Hypoeutectoid Steels

This group of steels contain up to 0.76% carbon. We will examine the phase changes and resulting
microstructure of two such steels, specifically:
i. 0.76% carbon of eutectoid composition.
ii. 0.25% carbon
The microconstituents are ferrite plus pearlite.

5.8.2.1 Steel of Eutectoid Composition 0.76%C

Figure 5-323 Schematic representation of the microstructures for an iron-carbon alloy of eutectoid
composition (0.76 wt% C) above and below the eutectoid temperature.

Point a: Temperature = 800°C. The structure is 100% γ in the form of equiaxed grains. The
composition is 0.76% carbon.

Point b: Temperature = 720°C. The eutectoid structure is pearlite, formed as a result of the eutectoid
reaction, γ → α + Fe3C , occurring at 727°C. The eutectoid structure consists of fine lamellae of α
ferrite (light), and Fe3C cementite (dark). Its microstructure is shown in Figure 5-33.

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Figure 5-333 Photomicrograph of a eutectoid steel showing the pearlite microstructure consisting of
alternating layers of α ferrite (the light phase) and Fe3C (thin layers most of which appear dark). 500x.
Unless cooling is slow the structure of pearlite will be very fine and difficult to resolve under an optical
microscope. The structure of the eutectoid pearlite is similar to the lead-tin eutectic discussed in
section 5.6.3, 40% Sn Alloy 4.

Figure 5-343 Schematic representation of the formation of pearlite from austenite; direction of carbon
diffusion indicated by arrows.

5.8.2.2 Steel of 0.25% Carbon Content

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Figure 5-353 Schematic representation of microstructures for an iron-carbon alloy of hypoeutectoid

composition C0 (containing less than 0.76 wt% C) as it is cooled from within the austenite phase region to
below the eutectoid temperature.

Point c: Equiaxed grains of γ composition 0.25% C.

Point d: In this two phase region, α + γ , grains of α begin to grow at the γ grain boundaries. The
composition of α follows MN, and the composition of γ follows MO.

Point e: As the alloy is cooled to this point, the proportion of α increases, and that of γ decreases.

Point f: Just below 727°C. The microstructure will consist of proeutectoid, or primary α , and pearlite,
α + Fe3C, this is shown below for a 0.38% C steel.

Figure 5-363 Photomicrograph of a 0.38 wt% C steel having a microstructure consisting of pearlite and
proeutectoid ferrite. 635x.

Microconstituents: Proeutectoid α
and pearlite (see Figure 5-37)
U T
= α' = Pearlite
T +U T +U
Phases: α and Fe3C.
U +V + X T
= α = Fe3C
T +U +V + X T +U +V + X

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Figure 5-373 A portion of the Fe-Fe3C phase diagram used in computations for relative amounts of
( )
'
( )
'
proeutectoid and pearlite microconstituents for hypoeutectoid C0 and hypereutectoid C1 compositions.

The microstructure pictured in Figure 5-36 for 0.38% carbon will contain a little less α and a little
more pearlite than for the steel under consideration. The actual proportion of microconstituents will
be:
U 0.76 − 0.25
α=' = ×100= 69.1%
T + U 0.76 − 0.022
T 0.25 − 0.022
Pearlite= = ×100= 30.9%
T + U 0.76 − 0.022

By observing the proportion of the microconstituents in the microstructure it is possible to make an

estimate of the carbon content of the steel under investigation. The following values will be a guide
for this exercise.

Carbon content % microconstituents

0 100% ferrite α
50% α and 50%
0.4
pearlite
0.76 100% pearlite

5.8.3 Microstructures and Phases in Hypereutectoid Steels

Hypereutectoid steels contain more than 0.76% carbon usually up to a maximum of 1.6% carbon. The
microconstituents are pearlite plus cementite.

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5.8.3.1 Steel of Composition 1.1% Carbon

Figure 5-383 Part of the iron-carbon phase diagram.

Point g: Equiaxed grains of γ , 1.1% C

Point h: The two phase region γ + Fe3C. Grains of Fe3C (6.7% C) form at γ grain boundaries. The
proportion of Fe3C increases as the alloy continues to cool, the composition of γ following the line
PO.
Point i: The eutectoid line has been crossed. Microconstituents are proeutectoid or primary Fe3C plus
pearlite. The phases are α and Fe3C. Refer again to Figure 5-37.
V
Microconstituents: Proeutectoid Fe3C'. Composition = 6.7%. Proportion =
V+X
X
Pearlite. Proportion =
V+X
V +U + T
Phases: Fe3C proportion =
V +U + T + X
α proportion =
X
V +U + T + X
α composition ≈ 0.02% C

The microstructure for hypereutectoid steel is shown in Figure 5-39.

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Figure 5-393 Photomicrograph of a 1.4 wt% C steel having a microstructure consisting of a white
proeutectoid cementite network surrounding the pearlite colonies. 1000x.

The microstructure pictured in Figure 5-39 is for a 1.4% carbon steel. The steel under discussion
containing 1.1% carbon will contain slightly less cementite and slightly more pearlite. The
proportions of microconstituents can be calculated using the relationships given above.

V 1.1 − 0.76
=
Fe3C' = = 5.7%
V + X 6.7 − 0.76
X 6.7 − 1.1
= =
Pearlite = 94.3%
V + X 6.7 − 0.76
Proportion of phases:
V +U + T 1.1 − 0.022
=Fe3C = = 16.1%
V + U + T + X 6.7 − 0.022
X 6.7 − 1.1
=α = = 83.9%
V + U + T + X 6.7 − 0.002
The following calculation illustrates the procedure for carrying out a carbon balance for the 1.1%
carbon steel.

Using the proportion of the phases:

=
% Carbon 16.1% of 6.7%C + 83.9%
  of
0.022%C

in Fe3C in α

= 1.072 + 0.0185
= 1.09% (Nominal 1.1%)

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Using the microconstituents:

% Fe3C' = 5.7%
% pearlite = 94.3%
=
But total % Fe3C % Fe3C' + % Fe3C in pearlite
= 5.7% + % Fe3C in pearlite
16.1%
= 16.1% − 5.7%
% Fe3C in pearlite
= 10.4%
% α in pearlite
= 94.3% − 10.4%
= 83.9%

Since microconstituents = Fe3C1 + (Pearlite)

= Fe3C1 + (Fe3C + ∝)
∴ % Carbon = 5.7% of 6.67%C + (10.4% of 6.67%C + 83.9% of 0.022%C)
= 1.09 (nominal 1.1%C)

5.8.4 Effects of Non-Equilibrium Cooling

i. Phase changes may occur at temperatures other than those indicated in the diagram.
ii. Non equilibrium phases not in the phase diagram may appear at room temperature. This topic
is involved and will be covered in more detail in chapter 6. Heat Treatment of Alloys.

5.8.5 Effects of Alloying Elements

The effects of alloying elements on temperature and composition of the eutectoid reaction, that is,
γ → α + Fe3C , are illustrated in Figure 5-40 and Figure 5-41.

Figure 5-403 The dependence of eutectoid temperature on alloy concentration for several alloying elements
in steel.

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Chapter 5: Phase Diagrams

Figure 5-413 The dependence of eutectoid composition (wt% C) on alloy concentration for several alloying
elements in steel.

Figure 5-40 indicates the effect of alloying elements upon the temperature of the eutectoid reaction
in steels. It will be observed that the elements Ti, Mo, Si, W and Cr elevate the temperature, while
addition of Mn and Ni lower it.

Figure 5-41 indicates how alloying elements affect the carbon content of the eutectoid from the 0.8%
level for plain carbon steels. It can be seen that all alloying metals commonly used in steel
manufacture lower the carbon content of the eutectoid.

Since the eutectoid temperature and composition have profound effects on the phase diagram of steel,
it can be deduced that these phase transformations will result in significantly different methods of
heat treatment and hence steel properties. Further treatment of this topic is outside the scope of this
subject, but its relevance should be noted in connection with the important group of stainless steels
(see section 6.11.4).

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5.9 Plain Carbon Steels

5.9.1 Some Applications of Plain Carbon Steels

%
Type of steel Uses
carbon
Chains, stampings, rivets, nails, seam-welded pipes, tin plate,
Dead mild 0.05-0.15
automobile body steel, and material subject to drawing and pressing.
Structural steels, universal beams, screws, drop forgings, case
0.10-0.20
hardening steel.
Mild steels
Machine and structural work, gears, free-cutting steels, shafting and
0.20-0.30
forgings.
Connecting rods, shafting, axles, crane hooks, forgings.
0.30-0.40
Crankshafts, axles, gears, shafts, die-blocks, rotors, tyres, skip
0.40-0.50
Medium carbon wheels.
0.50-0.60
Loco tyres, rails, wire ropes.
0.60-0.70 Drop-hammer dies, saws, screwdrivers.
0.70-0.80 Band saws, anvil faces, hammers, wrenches, laminated springs, cable
High carbon
wire, large dies for cold presses.
0.80-0.90 Cold chisels, shear blades, punches, rock drills.
Axes, knives, drills, taps, screwing dies, picks.
0.90-1.10
Tool steels Ball bearing, files, broaches, razors, boring and finishing tools,
1.10-1.40
machine parts where resistance to wear is essential.
Table 5-2

5.9.2 A Simple Classification of Plain Carbon Steels

i. Dead mild: 0.07-0.15% C – easily cold worked into solids or tubes.

ii. Mild steels: 0.15-0.25% C – these are the most common steels and are easily welded and do
not harden appreciably when quenched.
iii. Medium carbon steels: 0.25-0.55% C.
• These steels respond to heat treatment.
• General forging: 0.25-0.35% C.
• Shafts, axles, wire etc: 0.35-0.45% C.
• Wear resisting steels, rails, cylinders and dies: 0.45-0.55% C.
iv. High carbon steels: 0.55-0.9% C – possesses high strength and wear resistance.
v. Carbon tool steels: 0.9-1.6% C – very hard, and abrasion resistant.

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5.10 Questions and Answers – Phase Diagrams

Q11.1 Refer to the iron-carbon phase diagram in Figure 5-42 to answer this question.

(a) Consider a plain carbon steel containing 1.3% carbon, and hence determine the
following properties at the points marked a, b, and c:
(i) the phases present,
(ii) the composition of the phases present, and,
(iii) the percentage of each phase present.
(b) For the alloy at point c determine:
(i) the percentage of micro-constituents present,
(ii) sketch, label, and describe the microstructure of the alloy, and,
(iii) suggest an application for this alloy based upon its mechanical properties, and
list these properties.

Figure 5-42

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Chapter 5: Phase Diagrams

A11.1
Refer to figure 2 to clarify the answers to this question.

(a) Point a
(i) Phases present are γ and liquid L.
(ii) Composition is: γ = 0.93% carbon, (point d)
L = 1.7% carbon, (point e)
𝑊𝑊 (1.7−1.3) 𝑥𝑥 100
(iii) Percentage of phases: % γ = 𝑉𝑉+𝑊𝑊 = 1.7−0.93
= 52

𝑉𝑉 (1.3−0.93) 𝑥𝑥 100
% L = 𝑉𝑉+𝑊𝑊 = 1.7−0.93
= 48

Point b
(i) Phase = γ, (austenite).
(ii) Composition of γ = 1.3% carbon.
(iii) Percentage of γ = 100%.

Point c
(i) Phases present are: α, (ferrite), and Fe3C, (cementite).
(ii) Composition of phases are: α = 0.022% carbon, Fe3C = 6.67% carbon.
(iii) Percentage of phases are:

𝑌𝑌 (6.67−1.3) 𝑥𝑥 100
%α = 𝑋𝑋+𝑌𝑌 = 6.67−0.022
= 81

𝑋𝑋 (1.3−0.022) 𝑥𝑥 100
% Fe3C = 𝑋𝑋+𝑌𝑌
= 6.67−0.022
= 19

(b) For alloy c

(i) Alloy c is hypereutectoid, and hence the microconstituents are pearlite,
(eutectoid), of composition 0.76% carbon, and cementite of composition
6.67% carbon.
The percentage of microconstituents are:
𝑌𝑌 (6.67−1.3) 𝑥𝑥 100
% pearlite = 𝑌𝑌+𝑍𝑍 = 6.67−0.76
= 91

𝑍𝑍 (1.3−0.76) 𝑥𝑥 100
% Fe3C = 𝑌𝑌+𝑍𝑍 = 6.67−0.76
=9
(ii) The microstructure of the alloy consists of equiaxed grains of pearlite with
grain boundaries of cementite as illustrated in Figure 5-43.

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Chapter 5: Phase Diagrams

Figure 5-43

(iii) A 1.3% plain carbon steel as illustrated is classified as a tool steel. It is very
hard, tough, and abrasion resistant. It has low ductility. Applications include
ball bearings, files, and boring tools.

Typical hardness is HB = 250, and tensile strength = 850 MPa.

Figure 5-44

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References

1 Bailey, A R. The Role of Microstructure in Metals. 3rd ed. Surrey, England: Metaserv,
1982.
2 Ball, Phillip. H2O: a Biography of Water. London, UK: Weidenfeld & Nicolson, 1999.
3 Callister, Jr., William D. Materials Science and Engineering an Introduction. 7th ed.
York, PA: Techbooks, 2007.
4 Moffat, William G., George W. Pearsall, and John Wulff. The Structure and Properties of
Materials. Vol. 1. New York, USA: John Wiley & Sons, 1964.
5 Schlenker, B R. Introduction to Materials Science. SI ed. Sydney, Australia: John Wiley
& Sons, 1974.

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Chapter 6: Heat Treatment

Heat Treatment

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Chapter 6: Heat Treatment

6.1 Introduction to Diffusion

The mechanical properties of steel and non-ferrous alloys depend upon three main factors:

i. Alloy composition.
ii. History of mechanical working.
iii. Thermal or heat treatment.

These factors are linked to changes in microstructure, which in turn are linked to phase
transformations brought about directly or indirectly by one or more of the factors listed above.

The production and modification of many important materials depends upon diffusion mechanisms
usually as a result of thermal or heat treatment. Examples include the manufacture of sintered carbide
cutting tools, permeable polymers, self-lubricating bearings, and components of intricate shape from
very high melting point alloys, to name a few. Heat treating processes for metals such as hardening,
tempering, annealing, and surface hardening by carburization depend upon the control of atomic
diffusion during processing.

Diffusion is defined as the motion of matter through matter. All diffusion depends upon the atoms
possessing sufficient thermal vibrational energy to move through groups of other atoms. Gases
because of their unrestricted molecular motion diffuse rapidly, liquids less rapidly, and solids very
slowly. In engineering materials it is usually the diffusion of solids that are most important,
particularly in the manufacture of ceramics and metals.

The two most important driving forces in diffusion are temperature and concentration gradient.

6.1.1 Thermodynamics of Diffusion

The two principles under-pinning the spontaneity of natural processes are the tendency towards
minimum energy, and the tendency towards maximum randomness or entropy. In any process there
is often a trade off between these two thermodynamic entities. The change in enthalpy and entropy
in reacting systems are combined into the single quantity, Gibbs free energy G. The change in Gibbs
free energy ∆G, thus becomes the criteria for spontaneity.

Consider two blocks of different metals, copper and nickel fixed together. A small number of atoms of
each metal, because of their thermal energies will diffuse into each other, and the concentration
gradient that existed between them will diminish. This “randomizing” effect is clearly a result of an
increase in entropy, and is non-reversible. The two blocks of metal will fuse together, and the joint or
bond will consist of an alloy of the two metals. This process will be accelerated as the temperature is
raised, but held below the individual melting points of the metals. This example of diffusion is
illustrated in Figure 6-1.

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Chapter 6: Heat Treatment

Figure 6-12

Figure 13.2 illustrates the diffusion of metal B through metal A from right to left. Note the
concentration gradient change, ∆C as the diffusion proceeds over a distance ∆x.

Figure 6-22

6.1.2 The Mechanisms of Diffusion

There are two major mechanisms by which diffusion proceeds in solids. Vacancy diffusion occurs in
substitutional solid solutions, where the vacant site is substituted by an atom of the same or similar
size. Interstitial diffusion occurs when small atoms like C, N, O or H move from one interstitial site to
another, a common example being carbon in iron, in steel manufacture. These mechanisms are
illustrated in Figure 6-3.

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Chapter 6: Heat Treatment

Figure 6-32

6.1.3 Mathematical Analysis of Diffusion

Fick’s first and second laws quantitatively define diffusion. Fick’s first law states that the flux of a
diffusing species is proportional to the concentration gradient. The flux J is defined as the number of
atoms passing through a given plane of unit area per unit time, and is illustrated in Figure 6-4.

Figure 6-46

In the above figure, J, the flux is positive from left to right as the diffusing species moves from the high
concentration Cs to the lower concentration Cx, a distance ∆x, under steady state conditions. The
𝑑𝑑𝑑𝑑
concentration gradient 𝑑𝑑𝑑𝑑 is negative from left to right.

𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑

The amount of material diffusing, J, is ∝ - = -D , where D = diffusion coefficient with
𝑚𝑚2 𝑠𝑠 𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑

𝑑𝑑𝑑𝑑
units of m2/s. The simple first order differential equation J = -D is therefore a mathematical
𝑑𝑑𝑑𝑑
statement of Fick’s first law for steady state diffusion.

Note that J is the diffusion flux (or, equivalently the number of atoms) M diffusing through, and
perpendicular to a unit cross-sectional area of solid per unit of time.
𝑀𝑀 𝑛𝑛𝑛𝑛.𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴
i.e. J = or , and its SI units are: kg / m2 · s or no. Atoms / m2 · s
𝐴𝐴𝐴𝐴 𝐴𝐴𝐴𝐴

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Chapter 6: Heat Treatment

Unfortunately most diffusion systems are not steady state, and are in fact represented by a second
order differential equation in which the rate of change of concentration gradient is proportional to
the second derivative, (Laplacian), of the concentration gradient. Thus the mathematical statement
𝑑𝑑𝑑𝑑 𝑑𝑑 2 𝐶𝐶
for Fick’s second law is: 𝑥𝑥 = D 2𝑥𝑥 . Solution to this equation and complex problems relating to the
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
kinetics of non-steady state diffusion are outside the scope of this subject. An example of a non-steady
state diffusion process is illustrated in Figure 6-5, where it can be seen that the change in
concentration of the diffusing species is not linear.

Figure 6-56

6.1.4 Diffusion Coefficient D, and its Temperature Dependence

In the study of kinetics, the Arrhenius equation was used to illustrate the inter-dependence of reaction
rate and temperature for a chemical reaction. Equivalent Arrhenius equations define the temperature
dependence of a range of natural phenomena, and there is an analogous relationship for diffusion,
namely;

D = D0 e-Ea/RT , where D0 = pre-exponential constant for a given diffusion system, Ea = activation energy,
R = universal gas constant, and T = absolute temperature.

Several values for the constant D0 and activation energy are given in the table below:

SYSTEM D0 , cm2/s Ea, k J/Mol.

C in FCC iron 0.23 138
C in BCC iron 0.011 88
Fe in FCC iron 0.65 280
Table 6-1

It may be observed from the above values that interstitial diffusion of carbon in FCC and BCC iron will
be more rapid than vacancy diffusion of iron in iron , due to the lower activation energies for the
carbon diffusions.

The activation energy barrier is illustrated for substitutional and interstitial diffusion mechanisms in
Figure 6-6, and confirms the lower energy requirements for interstitial diffusion as dicussed above.

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Chapter 6: Heat Treatment

Figure 6-62

Case hardening of steel components, (section 6.11), and the process of sintering metal and ceramic
powders, rely totally upon diffusion mechanisms for their production.

Carburization is a special case of diffusion, and of great practical use in engineering materials. For
some applications it is necessary to harden the surface of a steel component above that of its interior.
One method of achieving this goal is to increase the carbon content at the surface by a process known
as carburization. Here the steel component is exposed to an atmosphere potentially rich in carbon, at
an elevated temperature. Hydrocarbon gasses such as methane CH4 are commonly used for this
purpose. The methane decomposes to carbon on the surface of the steel, and is slowly absorbed into
the body of the steel, forming iron carbide. The depth of case and the speed of diffusion is time
dependent, and is a nonsteady-state diffusion. (See also section 6.15.2.1 .ii ).

6.2 Recrystallization and Grain Growth

As a crystalline material is deformed, its hardness increases as the dislocations become more
entangled. At the same time its ductility decreases. Typical property changes occur in the left hand
side of Figure 6-7 below.

Figure 6-74 Schematic cold-work and annealing cycle.

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Chapter 6: Heat Treatment

If the material is heated to a slightly elevated temperature the dislocations of opposite sign, (┴ and
┬), begin to cancel each other. The point defects disappear, and physical properties such as resistivity
approach the values of the undeformed alloy. This process is called recovery, and is illustrated in the
right hand side of Figure 6-7. The microstructure remains unchanged, until at higher temperatures
the elongated grains transform to fine equiaxed grains, as illustrated in Figure 6-8.

Figure 6-84 Recrystallization and grain growth in cold-worked nickel. All photomicrographs 170x. (a) Cold
worked. The direction of working is vertical. (b) Partly recrystallised. (c) Completely recrystallised. (d) After
grain growth has taken place.

At this point the hardness and ductility approach their original values. This nucleation of new, strain
free grains is called recrystallization. It proceeds until the entire sample consists of new grains as in
Figure 6-8 c. The name given to the type of heat treatment by which recrystallization and softening is
made to occur is annealing.

Deformation below the recrystallization temperature is called cold work, whereas deformation above
the recrystallization temperature is called hot work. A hot worked material does not strain harden
because recrystallization can keep pace with the mechanical distortion, and counteract its effects.

The recrystallization temperature of a material depends upon several variables; it decreases with
increased prior work, purity of the material, heating time, initial grain size, and with a decrease in the
cold working temperature. The grain size after recrystallization depends upon the degree of cold
work prior to recrystallization. This is illustrated in Figure 6-9.

Figure 6-94 Schematic representation of recrystallised grain size as a function of prior cold-work.

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Chapter 6: Heat Treatment

There is a critical minimum amount of cold work below which recrystallization does not occur. If the
degree of cold work is greater than the minimum, but still small, relatively few strain-free nuclei form
during recrystallization, and the new grain size is large. If the cold working is more severe, more
nuclei form, and the resultant recrystallised grains are much smaller, being associated with a much
larger area of grain boundaries. In a nut shell, recrystallization requires prior cold working or strain
hardening of the alloy, if it is to occur.

Grain growth, the final change is independent of prior cold work. Any fine grained aggregate of
crystals will increase in grain size when heated at an elevated temperature. The 'driving force' for this
grain growth is the reduction in surface energy by the reduction in grain boundary area. The higher
the temperature the more rapid the grains grow. Figure 6-8 d above shows the grain growth of the
cold worked nickel alloy. Excessive grain growth during heat treatment is to be avoided since it
greatly weakens the alloy.

Another important microstructural change that occurs during recrystallization and grain growth is
the development of annealing twins in face-centred cubic metals. Figure 6-10 below shows twinning
at the atomic level.

Figure 6-105 Diagrammatic representation of twinning.

Figure 6-11 illustrates twinning in an annealed brass.

Figure 6-11 A reflected light photomicrograph of the microstructure of 70-30 brass (70% Cu, 30% Zn),
showing many grains of different orientations and showing twins (the parallel-sided regions) within the
grains. 500x.

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Chapter 6: Heat Treatment

To further amplify the process of recrystallization and grain growth, see Figure 6-12 and Figure 6-13
below.

Figure 6-122 Photomicrographs showing several stages of the recrystallization and grain growth of brass. (a)
Cold worked (33%CW) grain structure. (b) Initial stage of recrystallization after heating 3 seconds at 580°C
(1065°F); the very small grains are those that have recrystallised. (c) Partial replacement of cold-worked
grains by recrystallised ones (4 seconds at 580°C). (d) Complete recrystallization (8 seconds at 580°C). (e)
Grain growth after 15 minutes at 580°C. (f) Grain growth after 10 minutes at 700°C (1290°F). All
photomicrographs 75x.

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Chapter 6: Heat Treatment

Figure 6-132 The influence of annealing temperature (for an annealing time of 1 hour) on the tensile strength
and ductility of a brass alloy. Grain size as a function of annealing temperature is indicated. Grain structures
during recovery, recrystallization and grain growth stages are shown schematically.

The relationship between percentage cold work and recrystallization temperature for iron is shown
in Figure 6-14.

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Chapter 6: Heat Treatment

Figure 6-142 Recrystallization temperature versus the percentage of cold work.

Hot working: When mechanical work is carried out on a metal or alloy at a temperature which is
above the recrystallization point, no deformations of the grains occur. Hence for this fabrication there
are:

i. Lower energy requirements, compared to cold working.

ii. No grain growth and recrystallization.
iii. No internal stresses.

6.3 Phase Transformations

When an alloy is subjected to heat treatment, i.e. heating or cooling processes, various structural
changes occur. These changes may be either microstructural, or Phase changes. Some of these changes
involve diffusion processes. There are three possible types of phase changes, namely:

i. Those where there is no change in the number or composition of the phases, such as
solidification, recrystallization, grain growth and allotropic change, for example, α to γ iron.

ii. Those where the number and composition of the phases change, for example, the eutectoid
reaction for the steel γ → α + Fe3C .
Both i. and ii. involve diffusion processes.

iii. Transformations which do not involve diffusion processes, for example, formation of
martensite during the rapid cooling of austenite.

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6.4 Microstructural Changes

6.4.1 Pearlite (Eutectoid)

𝛾𝛾(0.76%C)
������� ⇌ �������������������
𝛼𝛼(0.02%C) + 𝐹𝐹𝐹𝐹3 𝐶𝐶(6.7%C)
Austenite Pearlite

The isothermal diagram (TTT 2 plot) shows the phase transformations when a steel of 0.76% C
composition is cooled.

Figure 6-152 Isothermal transformation diagram for eutectoid iron-carbon alloy.

The cooling cycle is illustrated by the line ABCD, that is, rapid cooling AB ( γ region), and then
maintaining the temperature constant at about 620°C BCD, producing pearlite (coarse to medium). If
BD is lowered to 540°C, the pearlite is finer due to diffusion occurring more slowly.

Figure 6-162 Photomicrographs of (a) coarse pearlite and (b) fine pearlite. 3000x.

2 TTT = Temperature, time, transition where the temperature of the alloy is held constant throughout the

transformation.

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Chapter 6: Heat Treatment

Figure 6-17 summarises the effect of equilibrium cooling upon the microstructures of a range of plain
carbon steels, in the context of the Fe-C phase diagram.

Figure 6-17

6.4.2 Bainite

Like pearlite, bainite is a microconstituent, formed by the transformation of austenite. Bainite consists
of needle like particles of cementite in a matrix of ferrite, so fine that they can not be resolved using
optical microscopy. Its formation is at temperatures lower than for pearlite, but higher than for
martensite. Its hardness and strength are greater than fine pearlite. The TTT diagram showing the
formation of bainite in a eutectoid steel is shown in Figure 6-18 below.

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Chapter 6: Heat Treatment

Figure 6-182 Isothermal transformation diagram for an iron-carbon alloy of eutectoid composition, including
austenite-to-pearlite (A-P) and austenite-to-bainite (A-B) transformations.

6.4.3 Spheroidite

If either pearlite or bainite microconstituents are heated to a temperature of about 700°C for 18-24
hours, another microstructure called spheroidite forms. This is a dispersion of spheroidal particles of
cementite in a matrix of ferrite. This microconstituent forms from carbon diffusion, but neither the
number nor the composition of the phases change. The driving force for this reaction is the reduction
of the boundary areas separating α and Fe3C spheroids.

Figure 6-192 Photomicrograph of a steel having a spheroidite microstructure. The small particles are
cementite; the continuous phase is α ferrite. 1000x.

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6.4.4 Martensite

When a plain carbon steel with a carbon content of greater than 0.2 % is rapidly quenched from the
austenitic region, a very hard microconstituent known as martensite forms. This transformation
holds the key to the various techniques for hardening steel by heat treatment. Reference was made in
section 5.7 to the allotropy of iron. It is in fact this aspect of iron’s nature that enables the martensitic
transformation to occur.

Austenite or γ iron is face centred cubic, and has a much greater capacity to dissolve carbon than body
centred cubic iron, due to the larger unit cell opening illustrated in (a) of Figure 6-20.

FCC BCC BCT

Figure 6-2012

The smaller opening in the BCC is shown in (b). When the austenite phase is rapidly cooled, it does
not have sufficient time to revert to the body centred cubic form, and is forced to transform to an
elongated body centred tetragonal form, in which the carbon atom is trapped, figure (c). For this
accommodation to be made, considerable distortion of the crystal needs to occur, and it is this elastic
strain that causes the martensite to be hard and brittle. Some vital statistics will further clarify this
process; the diameter of the carbon atom is 0.154 nm, the largest interstitial hole in γ iron is 0.104
nm, and the largest in the α, or BCC is 0.072 nm.

Martensite appears as a needle-like or acicular microconstituent, as illustrated in Figure 6-21. See

also sections 6.7 and 6.8 for its mechanical properties and heat treatments.

Figure 6-212 Photomicrograph showing the martensitic microstructure. The needle-shaped grains are the
martensite phase, and the white regions are austenite that failed to transform during rapid quenching. 1220x.

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6.5 Temperature-Time-Transformation (TTT) Diagrams)

In section 6.4 the changes to the structure and properties of austenite upon slow and rapid cooling
have been discussed. This section will investigate the further changes that occur to the properties of
a plain carbon steel of eutectoid composition when it is rapidly cooled to temperatures below the
eutectoid temperature, and held at specific temperatures for specified times before being finally
water quenched. This process is known as isothermal transformation, and is a very useful heat
treatment for modifying steel properties.

The process consists of (1) austenitization in a furnace, (2) isothermal transformation in a salt bath, at
a specified temperature below 723 0C for a specified time, and (3) water quenching to room
temperature. This process is illustrated in Figure 6-22.

Figure 6-2212

If this process is repeated for steel samples of eutectoid composition, and each is isothermally
transformed at progressively lower temperatures, an isothermal, or TTT diagram can be constructed.
These diagrams enable metallurgists to determine how a steel may be heat treated to produce specific
mechanical properties. Figure 6-23 illustrates a TTT diagram for a eutectoid steel. It consists of two
“S” shaped curves. The left hand side curve represents the onset of isothermal transformation, and
the right hand curve the completion of that transformation of austenite. The regions are labelled A for
austenite, P for pearlite, B for bainite, and M for martensite. Each of these regions represent a phase
or a microconstituent with characteristic mechanical properties. In Figure 6-23, the microstructure
is pictured, and Brinell hardness is listed.

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Figure 6-23

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Figure 6-24 is similar to Figure 6-23, but can be used to calculate specific heat treatments.

Figure 6-242 The complete isothermal transformation diagram for an iron-carbon alloy of eutectoid
composition: A, austenite; B, bainite; M, martensite; P, pearlite.

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6.6 Continuous-Cooling-Transformation (CCT Diagrams)

In many industrial operations alloys are continuously cooled, rather than using arrested or
discontinuous cooling. A typical CCT curve is illustrated in Figure 6-25.

Figure 6-252 Moderately rapid and slow cooling curves superimposed on a continuous cooling
transformation diagram for a eutectoid iron-carbon alloy.

The diagram illustrates that there is a critical cooling rate to achieve any particular transition. Note
that for the region below the nose AB, there will be no further formation of pearlite. If a cooling curve
passes through AB, the transformation ceases at the point of intersection. With continued cooling the
unreacted austenite begins to transform to martensite, upon crossing the M line. The following figure
illustrates the critical cooling rate necessary to produce various structures.

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Figure 6-262 Continuous cooling transformation diagram for a eutectoid iron-carbon alloy and superimposed
cooling curves, demonstrating the dependence of the final microstructure on the transformations that occur
during cooling.

It should be noted that the shape of both TTT and CCT curves are profoundly altered when plain
carbon steels are alloyed.

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6.7 Mechanical Properties of Iron-Carbon Alloys Containing

Transformed Phases

6.7.1 Pearlite
Fine pearlite is stronger than coarse pearlite due to more α /Fe3C boundaries, which impede the
movement of dislocations. Various properties for fine pearlite are illustrated in Figure 6-27
specifically: yield strength, tensile strength, Brinell hardness, % elongation, % reduction in CSA, and
izod impact strength.

Figure 6-272 Fine pearlite.

Figure 6-28 a below illustrates Brinell hardness for fine and coarse pearlite and spheroidite.

Figure 6-28 Mechanical properties as a function of carbon content.

Figure 6-28 b illustrates ductility change as a function of carbon content for plain carbon steels having
microstructures of spheroidite, fine and coarse pearlite.

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6.7.2 Spheroidite

Mechanical properties of spheroidite are compared to fine and coarse pearlite in Figure 6-28.
Spheroidite is more ductile than pearlite, but is not as strong or as hard. However, spheroidite is
tougher than pearlite, because crack propagation is greatly restricted by the very large fraction of
ferrite compared to cementite in its structure.

6.7.3 Martensite

This is the hardest and most brittle of the microconstituents. Since austenite, FCC, is denser than
martensite, BCT, the small increase in volume due to the rapid quenching may lead to cracking,
particularly for carbon contents greater than 0.6%. The hardness of martensite and tempered
martensite are compared below.

Figure 6-292 Hardness (at room temperature) as a function of carbon concentration for plain carbon
martensitic, tempered martensitic, tempered at 371°C (700°F).

6.8 Tempered Martensite

In the 'as quenched' state, martensite is so hard and brittle that it finds little practical application.
However, the toughness and ductility can be greatly improved by tempering. This heat treatment also
accomplishes stress relieving. Tempering is achieved by soaking the martensitic structure at
temperatures between 250 and 650°C. The change is:

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martensite (BCT) → tempered martensite (α +Fe3C )

   
single phase fine phases

The tempering process allows the dissolved carbon in the martensite to diffuse out of the lattice. The
thermal energy allows the carbon atoms to aggregate in sufficient numbers to produce very small
particles of Fe3C, impossible to resolve using optical microscopy. The continued treatment at higher
temperatures ultimately leads to a fine unresolvable dispersion of Fe3C in α . The changes in
microstructure of tempered martensite at 600 and 660°C from two hours to four days is illustrated in
the following figures.

Figure 6-301 Typical martensitic structure of water quenched carbon steel.

Figure 6-311 Effect of tempering for 2 hours at 600°C on quenched steel shown in Figure 12.30.

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Figure 6-321 Tempering for 4 days at 600°C.

Figure 6-331 Tempering for 4 days at 660°C.

Figure 6-341 Heavily tempered steel (4 days at 660°C) – magnification 2000x.

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Figure 6-29 shows hardness at room temperature as a function of carbon content for plain carbon
martensitic, tempered martensitic and pearlite steels.

The Figure below, Figure 6-35, shows the mechanical properties of a quenched and tempered steel of
the following composition:

• 0.4% carbon
• 1.8% nickel
• 0.8% chromium
• 0.25% molybdenum
• 0.7% manganese

Figure 6-352 Tensile and yield strength versus tempering temperature.

Figure 6-36 summarises the quenching and tempering process as part of a TTT diagram, and
illustrates the microstructure and hardness of three possible products.

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Figure 6-36

6.8.1 Temper Embrittlement

The tempering of some steels may result in temper embrittlement. This occurs when some steels are
tempered at temperatures greater than 575°C, followed by slow cooling, or when tempered between
375 to 575°C. The presence of certain alloying metals Ni, Cr, Mn plus one or more of Sb, P, As and Sn
impurities will shift the ductile to brittle fracture to higher temperatures. Fracture is along grain
boundaries where the impurities have congregated. Body-centred cubic structures are more
susceptible than face-centred cubic structures (most steels).

Temper embrittlement can be avoided by:

i. Controlling the composition.
ii. Heating above 575°C or below 375°C, and quenching to room temperature.
The mechanical properties of hardened and tempered 0.54 C steel are tabulated in Table 6-2.

Tensile strength Elongation on Reduction Hardness

Condition
MPa 5.65√A% of area % Rockwell C HRC
Normalised 750 15 35 11
Oil quenched from 840°C 1725 1 0 47
Oil quenched 840°C,
1291 5 20 38
tempered at 300°C
Oil quenched at 840°C,
1160 9 36 28
tempered at 500°C
Oil quenched at 840°C,
1010 11 40 23
tempered at 550°C
Oil quenched at 840°C,
860 14 48 15
tempered at 600°C
Table 6-25 The mechanical properties of hardened and tempered 0.54% C steel compared with properties in
the normalised condition.

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6.9 Review of Phase Transformations and Mechanical Properties

Figure 6-372 Possible transformations involving the decomposition of austenite. Solid arrows,
transformations involving diffusion; dashed arrow, diffusionless transformation.

Mechanical properties
Microconstituent Phases present Arrangement of phases
(relative)
Relatively small Fe3C
Spheroidite α ferrite + Fe3C sphere-like particles in an Soft and ductile
α -matrix
Alternating layers of α Harder and stronger than
Coarse pearlite α ferrite + Fe3C ferrite and Fe3C that are spheroidite, but not as
relatively thick ductile as spheroidite
Alternating layers of α Harder and stronger than
Fine pearlite α ferrite + Fe3C ferrite and Fe3C that are coarse pearlite, but not as
relatively thin ductile as coarse pearlite
Hardness and strength
Very fine and elongated greater than fine pearlite;
Bainite α ferrite + Fe3C particles of Fe3C in an α - hardness less than
ferrite matrix martensite; ductility
greater than martensite
Strong; not as hard as
Very small Fe3C sphere-
Tempered
martensite
α ferrite + Fe3C like particles in an α -
martensite, but much
tougher and more ductile
ferrite matrix
than martensite
Body-centred
Martensite tetragonal, Needle-shaped grains Very hard and very brittle
single phase

Table 6-32 Summary of microstructures and mechanical properties for iron-carbon alloys.

Useful definitions:

i. Phase: a homogenous portion of a system that has uniform physical and chemical properties.
ii. Microconstituent: an element of the microstructure that has an identifiable and characteristic
structure. It may consist of more than one phase.
iii. Cementite (iron carbide Fe3C): an interstitial compound, not a chemical entity. It consists of C
and Fe atoms in the ratio of 1:3 in an orthorhombic crystal lattice. It is a phase in the iron-
carbon system, and contains 6.67% C. It is hard and brittle.

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iv. Austenite, γ : a face-centred cubic iron and also iron and steel alloys that have FCC crystal
structure. The maximum solubility of carbon is 1.7% at 1130°C. It is non magnetic, and is a
phase.
v. Bainite: a microconstituent forming from the transformation of γ at temperatures between
which pearlite and martensite form. The microstructure is a fine dispersion of cementite in
ferrite.
vi. Martensite: a metastable and stressed microconstituent. It is a supersaturated solution of
carbon in a metastable iron, body-centred tetragonal. Its microstructure is fine needles and it
is hard and brittle.
vii. Ferrite, α : Body-centred cubic crystal iron, and also steel alloys with body-centred cubic
structure. It is a phase, with a maximum solubility for carbon of 0.022% at 723°C. It is
magnetic, soft and ductile.
viii. Pearlite, eutectoid: a two phase microconstituent found in steels and irons. It results from the
eutectoid reaction, γ → α + Fe3C , consisting of alternating layers of ferrite and cementite.
Its bulk carbon content is 0.76%.

6.10 Reasons for Heat Treatment

i. To stress relieve.
ii. To modify 'as cast' structures such as to equiax columnar crystals.
iii. To refine grain structure.
iv. To soften for further working.
v. To improve mechanical properties.
vi. To impart hardness, and wear resistance.

Heat treatment involves heating and soaking to a particular temperature, and then cooling at a certain
rate.

6.11 Heat Treating Process

The term “heat treatment” usually refers to a suite of thermal treatments with the goal of preparing
the material for fabrication. Specific objectives may be the improvement of machining characteristics,
the reduction of forming forces, or the restoration of ductility to enable further processing. Thus the
same metal can be softened for ease of cold working, and then, by another heat treatment given a
totally different set of properties for actual service. The most commonly used heat treatments are
described in the section following.

6.11.1 Hardening

From the structural viewpoint, hardening steel requires a change in crystal structure from the face
centred cubic austenite to a body centred cubic structure at room temperature. The iron-carbon
diagram illustrated below gives the appropriate temperatures to heat steel of specified carbon
content to form austenite (γ).

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Figure 6-387

Quenching the austenitized steel in a suitable medium hardens the steel by “trapping” the carbon in
the metastable martensite as outlined in section 6.4.4.The rate of cooling is a critical factor in the
hardening process, and depends upon the composition of the steel. Depending on the rate of cooling
required, water, oil, or air may be used, water giving the most rapid cooling rate.
The ease with which a steel will transform to a hardened structure is known as the hardenability, and
this topic is dealt with in section 6.16.The quenching conditions required to produce a steel of specific
mechanical properties is determined by the actual microstructure that results from the quenching,
which in turn is a function of the type and proportion of phases and micro-constituents present in the
quenched steel. The relationship between quenching rate, composition, and final structure is obtained
from TTT, and CCT diagrams discussed previously in sections 6.7-.6.9
It will be obvious that the rate of cooling of a steel object will only be constant if the rate of heat
extraction is uniform. This will clearly not be the case for thick cross-sections, or for items with
variations in cross-section. The outer, and thinner sections will cool more rapidly, and may therefore
be harder and more “stressed” than the more slowly cooled thicker sections. This situation may be
used to advantage if a tough inner core is required, together with a hard , abrasion resistant surface.

6.11.2 Quenching

Quench media vary in their ability to extract heat. The first stage occurs when the hot metal
vapourizes the liquid, and a layer of slower conducting vapour is between the steel and the quench
medium. Stage 2 occurs when the metal cools somewhat, and vapour bubbles nucleate, allowing metal
and liquid quench to contact. This results in the fastest cooling rate. Stage 3 occurs when the metal is
below the boiling point of the quench medium, and heat is extracted more slowly than in stage 2, by
a combination of conduction and convection. It should be noted that agitation of the medium will
result in more rapid cooling. The most commonly used quenching media in decreasing order of
severity are salt water, pure water, oil, molten salts, and air.

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6.11.3 Tempering

Because martensite, the usual product of quench hardening in steels lacks toughness and ductility, or
in other words is brittle and stressed, it is not useful for engineering purposes. The microstructural
changes, and the mechanical properties of tempered martensite are outlined in section 6.8.

The proper tempering temperature for a particular steel will depend upon its composition, and the
desired properties. The diagram below illustrates the effect of tempering temperature on the
properties of the quench-hardened steel in a general sense. The process of tempering is used to
modify the properties of the hard, brittle martensite.

Figure 6-397

The usual procedure for tempering is to place the part after quenching into a furnace at the
appropriate temperature, soak at this temperature for about 2 hours, and then air cool. The following
heat treatments, and structural changes are a guide to assist in choosing the most suitable tempering
temperature:

100-2000C --Precipitation of intermediate iron carbide, and reversion of the

Matrix to BCC. At this temperature only minimal softening occurs.

200-4000C --Sub-microscopic precipitation of very fine cementite in ferrite,

with a retention of the original martensite boundaries is
accompanied by some softening, and an increase in ductility.

400-5500C --Martensite boundaries disappear, and new ferrite boundaries

appear .Cementite spheroids begin to grow in size.The
properties move in the direction of a weaker, tougher,and
more ductile material.

Above 5500C --Cementite particles continue to grow, in a soft matrix of

ferrite.This structure has the highest toughness and
ductility, and the lowest strength of all tempered martensite

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6.11.4 Processing Heat Treatments for Steel

The concepts underlying heat treatment have as their theoretical base the iron-carbon phase diagram,
a simplified version being reproduced in Figure 6-40.

Figure 6-405

The range of heat treating processes discussed may be employed to reduce hardness, to remove
residual stresses, to improve toughness, to refine grain size, to reduce segregation, or to alter the
mechanical, electrical, or magnetic properties of the steel.
The key transition lines are labelled in standard notation, specifically:
A1 is the eutectoid line,
A3 is the boundary between austenite, and austenite + ferrite,
Acm is the boundary between austenite, and austenite and cementite.
See also Figure 6-52.

6.11.4.1 Full annealing of hypoeutectoid steels

This heat treatment controls dispersion strengthening by controlling the amount, size, shape, and
distribution of cementite. These steels are heated to 30-600C above the A3 temperature to fully
austenitize the structure, and then slowly cooled to a temperature below A1.The slow cooling is often
carried out in the furnace, which is turned off. The resulting structure is coarse pearlite, and ferrite,
the proportions dependent upon the carbon content. The mechanical properties of these annealed
steels are tabulated below.

Figure 6-415

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6.11.4.2 Full annealing of hypereutectoid steels

The steel is heated to 30-600C above A1 into the austenite + cementite region, and slow cooled as for
hypoeutectoid steels. It should be noted that hypereutectoid steels are not fully austenitized by
heating above the Acm boundary as might be expected, because this treatment results in
embrittlement as a result of cementite forming at the grain boundaries. The final structure consists
of coarse pearlite, plus cementite, the proportion dependent upon the carbon content.

6.11.4.3 Normalizing

Full annealing is a time consuming and costly process, and when extreme softness is not required,
normalizing is the preferred treatment. Here the steel is heated to 30-600C above A3 (hypoeutectoid),
or Acm (hypereutectoid), soaked to austenitize fully, and removed from the furnace and air cooled. It
should also be noted that cooling in air as contrasted to furnace cooling will result in different rates
of cooling between the outside and the inside of the metal, and hence different mechanical properties.
The resultant structure will be finer pearlite, and smaller grain structure than for the equivalent
annealed structure. A table of typical mechanical properties for a normalized hypoeutectoid steel is
reproduced below. Photomicrographs of an annealed and normalized eutectoid steel illustrate the
differences described above.

Figure 6-425

Figure 6-431

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6.11.4.4 Process anneal

This heat treatment is used if dimensional distortion is to be avoided, and some softening is required.
It is a substitute for full annealing, which can result in distortion as a result of the recrystallization
that occurs. It is also a cheaper option if full softening is not required. It is only applicable to steels
with carbon contents up to about 0.25%. The table below lists the comparative mechanical properties
of a cold worked and process annealed steel.

Table 6-4

6.11.4.5 Spheroidize anneal

For higher carbon steels, (greater than 0.60% carbon), that must be prepared for machining or
working, the heat treatment known as spheroidization is used. For plain carbon steels the metal is
heated to just below A1 until all the cementite is in the form of finely dispersed spheroids in a matrix
of ferrite. The metal is air cooled. Steel in this condition is very easy to machine as it is soft, and the
structure of the hard, fine dispersion of cementite in the softer ferrite matrix promotes chip
formation. The photomicrographs below illustrate the increasing spheroidization of the cementite as
a function of time.

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Figure
6-441

A schematic summary of the simple heat treatments for (a) hypoeutectoid, and (b) hypereutectoid
steels is illustrated below.

Figure 6-458

6.11.4.6 Stress relieve

Complex machine parts often require stress relieving to achieve dimensional stability. Examples of
situations for which this type of heat treatment is used include the following:

*Parts that require weld deposits to be machined away,

*Machining of cold finished shapes,
*Castings that require significant machining,
*Parts with very close dimensional tolerances,
*Long, slender parts machined from heavier shapes.

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Parts for stress relieving are heated to temperatures below A1, between 550 and 6500C for about 1
hour after reaching temperature, and then air cooled.

During the stress releaving treatment the temperature is sufficiently high to allow the accumulated
dislocations resulting from the previous fabrication operations to move and disperse, and thus
remove internal strains. If the metal has been cold worked, recrystallization may occur. This process
will also result in stress relief and softening. The diagram below illustrates the change in yield
strength for a 0.20% carbon steel as a function of stress relieving temperature.

Figure 6-467

6.11.5 Summary of Heat treatments and Properties

Figure 6-47 summarises the regions of the Fe-C phase diagram that correspond to specific heat
treatments covered in section 6.11.

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Figure 6-477

Table 6-5 lists mechanical properties and applications of the most widely used plain carbon steels.

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Table 6-512

6.11.6 Heat treatment of welds

Heating and cooling are integral aspects of welding processes, particularly fusion welding procedures,
where both base metal and weld metal are heated above their melting points and then rapidly cooled.
In fusion welding a pool of molten weld metal is contained within a metal mould formed by the base
metal, some of which itself melts and mixes with the weld metal. The resultant structure and
properties can best be understood by referring to the figure below which shows the microstructure
of the weld.

Figure 6-483

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The diagram shows clearly the three major parts of the weld, specifically the weld metal, the base
metal, and the heat affected zone. It is in the heat affected zone that many problems may arise if the
process of welding and post weld heat treatment are not carefully carried out. The properties of the
weldment may be further appreciated by studying the diagram following, which illustrates the crystal
structure, and the strength at various positions within the welded structure.

Figure 6-498

Properties of the heat affected zone are very seriously reduced by the heating and cooling process,
and must be understood and taken into account if serious problems are to be avoided. The first
consideration is to attempt to match the properties of the weld metal in the “as cast condition “to the
base metal. This can be done by selecting appropriate weld rod or electrode material that possesses
equivalent strength to the base metal. The correct weld metal will show fine equiaxed grains rather
than columnar and directional grains, which are not as strong as the former. Additional defects may
occur in the weld metal such as appear in castings, namely gas porosity, inclusions, blow holes, cracks,
and shrinkage. The previous diagram shows a range of grain size in the heat affected zone from coarse
to fine, away from the weld metal. This structure is clearly different from the base metal, and certainly
weaker. The base metal as shown with elongated grains has been originally cold worked, and as such
will be subject to recrystallization and grain growth when heated. It is weakest in the area of grain
growth. It should be noted that welding procedures that minimize the time of welding will result in a
reduction of adverse effects in the heat affected zone. Processes such as plasma arc, electron beam,
laser, and spot welding are superior in this regard to oxyfuel and electric arc methods. In order to
carry out the correct heat treatment, it is important to understand the “after weld “structure of the
different combinations of welded alloys. The diagram below illustrates this point.

The diagram illustrates the microstructures at specified temperatures for,

(b) the structure at the maximum temperature,

(c) the structure after cooling in a steel of low hardenability,
(d) the structure after cooling in a steel of high hardenability.

It will be obvious from the structure of (c) that a stress relieving heat treatment will be necessary to
equalize the strain between adjacent grains of pearlite of varying size. For (d) the presence of the
brittle microconstituent martensite will be of particular concern. This weldment will require a
tempering heat treatment to transform the martensite into tougher tempered martensite. It should
be noted that if the carbon content of the steel is less than 0.30%, no martensite will form during the
cooling period.

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Figure 6-508

The final consideration in this brief discussion is the effect of internal stresses on the dimensional
stability of the weldment, and the likelihood of distortion and cracking. The diagram below illustrates
a simple example of residual stresses in a fusion weld, where T denotes a tension, and C denotes
compression forces.

Figure 6-51

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To minimize these types of defects the final weldment can be given a stress relieve heat treatment if
this is practicable. An alternative method is to minimize stress in the first place before welding.
Heating the base metal prior to welding will reduce the rate of cooling in the heat affected zone. There
are many other practical measures that can be used, but these require a clear understanding of the
metallurgy of the process so that optimal selection of methodology can be undertaken. These
procedures are beyond the scope of this discussion, but may be found in reputable texts on welding
practice.

6.12 Martensitic Transformation and Hardenability

The successful heat treatment of steels to produce martensite depends upon the uniform distribution
of this structure across the full cross-section of the metal. Three factors determine the total
conversion to martensite:

i. Composition of the alloy.

ii. Speed of quenching (previously discussed)
iii. The size of the specimen.

The ability of steel to harden by martensite formation is defined by its hardenability. This term is
quantitatively defined as a measure of the depth to which a specific ferrous alloy may be hardened by
the formation of martensite upon quenching from a temperature above the upper critical
temperature. The diagram in below is an Fe-C phase diagram and indicates heat treatment
temperatures for plain carbon steels.

Figure 6-522 Iron-carbon phase diagram.

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6.13 Jominy End-Quench Hardenability Test

The steel for hardenability testing is machined into a Jominy specimen, 4" long and 1" in diameter.
The sample is autenitized and end quenched with water, delivered at a specified flow rate. A flat
section is ground along the specimens length, and hardness checks carried out at specified intervals.
These processes are illustrated in Figure 6-53.

Figure 6-532 Schematic diagram of Jominy end-quench specimen.

Figure 6-542 Typical hardenability plot of Rockwell C hardness against distance from quenched end of the
specimen.

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6.14 Correlation of Hardenability and Cooling Curve Information

This is illustrated in Figure 6-55.

Figure 6-552

Hardenability curves can be prepared by using Jominy test pieces made from different alloy steels. A
typical curve is shown in Figure 6-56 for a series of alloy steels, each containing 0.4% C. The curves
relate hardness, cooling rate, distance from the quenched end and percentage of martensite formed.

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Figure 6-562 Hardenability curves for five different steel alloys, each containing 0.4 wt% C. Approximate alloy
compositions (wt%) are as follows: 4340-1.85 Ni, 0.80 Cr and 0.25 Mo; 4140-1.0 Cr and 0.20 Mo; 8640-0.55
Ni, 0.5 Cr and 0.20 Mo; 5140-0.85 Cr; and 1040 is an unalloyed steel.

For most alloys there is a range of acceptable hardenability, illustrated below in Figure 6-57.

Figure 6-572 The hardenability band for an 8640 steel indicating maximum and minimum limits.

Other factors affecting the hardenability of alloys are general shape and cross-sectional area of the
specimen, the quenching medium, and the degree of agitation of the medium. The three most common
quenching media are water, oil, and air in decreasing severity. Molten salt baths are also used when
certain isothermal processes are carried out.

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6.15 Surface Hardening of Steel

Many products require different properties at different locations within the component. Quite
frequently this requirement takes the form of a hard, wear resistant surface, coupled with a tough
resistant core. The methods developed to provide such properties can generally be classified into two
basic groups:

i. Selective heating of the surface

ii. Altered surface chemistry by the deposition of carbon or nitrogen.

The basis for all surface hardening using carbon is the formation of martensite or tempered
martensite as a hard surface skin. For this to occur the minimum carbon content must be 0.4%.

6.15.1 Selective Heating of the Surface

The maximum hardness will depend upon the carbon content, and the depth upon the hardenability.
Refer to section 6.13 Jominy End-Quench Hardenability Test.

6.15.1.1 Flame Hardening

Flame hardening uses an oxy-acetylene flame to raise the surface temperature into the austenitizing
range, 50°C above UCT. The component is then quenched and tempered. Heat input is rapid to the
surface, but slow to penetrate to the core, leaving the interior free from any significant changes. This
type of treatment with hand held heating equipment is flexible, particularly with very large
components. Depths of 6mm of case are obtained.

6.15.1.2 Induction Heating

The component is placed inside an induction coil through which an alternating current (AC) is passed.
Induced current in the component heats it up. Heating rates are very rapid. The process can be
adapted for special shapes, and quality control is high. The gear illustrated below has been surface
hardened but has retained its tough core. Quenching and tempering has been carried out.

Figure 6-583 Section of gear teeth showing induction hardened surfaces.

6.15.1.3 Laser Beam Hardening

Laser beam hardening is adaptable to uneven surfaces and automation. Zinc or manganese phosphate
is applied to the steel surface to improve the efficiency of light to heat conversion. The process is
rapid, and heat is largely confined to the surface, which is usually quenched and tempered.

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Other techniques for heating include an electron beam (in a vacuum), and immersion in a lead or
molten salt bath.

6.15.2 Changing the Surface Chemistry

This process is used when the component has insufficient carbon, (less than 0.4 %) to attain the
required surface properties by selective heating.

6.15.2.1 Pack and Gas Carburizing

This is the most common process, and involves the addition of carbon to the surface, and its
adsorption by diffusion at elevated temperatures. Two processes may achieve this carbon addition:
i. Pack carburization: the components are packed in an air-tight cast iron box with wood or bone
charcoal, together with BaCO3 for 6 to 72 hours at 900°C. During this time the heat produces
CO as follows:

i. BaCO3 → BaO+CO 2

heat

ii. CO2 + C ⇌ 2CO

𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚
iii. 2CO ⇌ C + CO2

The carbon released by iii. is readily absorbed into the austenite. At this point the components
are unpacked and given the appropriate heat treatment. The depth of case is a function of
time.
An advantage of pack carburization is the retention of a ductile, low carbon core, which
imparts toughness under stressed conditions. By this process carbon contents of 0.7 to 1.2%
are achieved, with depths of tenths of mm up to 1.5mm.
Draw backs to pack carburization are non-uniform heating, difficulty in handling the parts,
and difficulty in adapting the process to automation. These difficulties are overcome by using
gas carburization.
ii. Gas carburization: here the carburizing medium is a gas containing CO, generated by
catalytically cracking methane or other hydrocarbon gas mixtures. The underlying principles
of carburization are similar to pack carburization. The operation is carried out in a furnace
containing the carburization gas, and the components pass through on a conveyer. It is thus
readily automated and yields excellent quality control. The process is illustrated in Figure
6-60. For the surface diffusion of carbon see also section 6.1.

6.15.2.2 Nitriding

This process produces hardening by forming very hard nitrides with certain alloying constituents in
the steel, namely: Al, Cr, Mo and V. The components are heat treated and tempered before nitriding.
The nitriding process is carried out in a protective atmosphere of cracked ammonia.
catalyst
2NH3 ⇌ N2 + 3H2

The N2 forms hard carbides at the surface during the operation, 10 to 40 hours at 500 to 625°C. Cases
up to 0.65mm are formed, and distortion is very low. Nitrided surfaces are harder than carburized
surfaces. However, nitriding is expensive and is limited to high value components.

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6.16 Powder Metallurgy

This is a process where powdered materials are compressed and sintered together in a furnace in a
protective gas atmosphere. Sintering is the process by which fine particles become bonded together.
The process is usually accompanied by an increase in strength and ductility.

The following four groups illustrate the range of components produced by the pressing and sintering
of metal powders.

1. Porous products: porous self lubricated bearings, impregnated with up to 40% v/v oil, and
filters of specified porosity.
2. Products of complex shapes: small gears and machine parts of complex shapes required in large
numbers, that cannot easily be produced by machining.
3. Products difficult to machine: hard cemented carbides and nitrides used as cutting tools are
made by mixing the powdered ceramic with a binder metal such as cobalt or nickel. After
sintering the abrasive carbide is dispersed in a tough metallic matrix.
4. Composites : these materials may be made by mixing together the powders of metals or
nonmetals, usually difficult to alloy or mix. For example, graphite and copper are formed into
brushes for electric motors, and mutually insoluble aluminium and lead can be sintered into
bearings.
In all these processes the driving force for mass transfer is diffusion.

The process consists of the following stages:

1. Manufacture of the powder by various methods including the atomization of molten metal by
an inert gas.
2. Mixing the major powdered components, for example copper, tin and graphite for a bronze
bearing, together with a solid lubricant for ease of pressing and forming.
3. Pressing the powder into a carefully machined die to the correct green density.
4. Sintering in a furnace at the correct temperatures for each stage, in a protective gas
atmosphere.
5. Finishing operations, for example sizing for dimensional control, oil impregnation, or a range
of possible surface treatments .

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Chapter 6: Heat Treatment

Figure 6-59 illustrates the process schematically.

Figure 6-598

A typical sintering furnace is illustrated in Figure 6-60.

Figure 6-609

The sintering process takes place in the soaking and hot zones of the furnace in a non oxidizing
atmosphere. The end of the furnace,(shortened in the diagram), is a cooling zone, such that the
components exit at a sufficiently low temperature to avoid oxidation, and at the same time to permit
handling.

Figure 6-61 shows the sintering mechanism, illustrating the shrinkage of a powder compact. This
results from the diffusion of atoms away from the grain boundary of the metal to the pore, thereby
“filling in”the pore. This mechanism is yet another example of the thermodynamic principle of the
lowering of free energy for a spontaneous process. The grain boundary is a region of high energy, and
the sintering temperature permits the grain boundary energy to be lowered by promoting diffusion
away from the boundary. At the same time the pore volume is reduced, the particles sinter together,
and the strength of the compact increases.

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Chapter 6: Heat Treatment

Figure 6-6110

The sintered product results in a partial fusing of the metal powders due to the reduction in the
surface area of each particle by the diffusing and subsequent strengthening mechanism. Figure 6-62
illustrates these structural changes in the context of each stage of production.

Figure 6-6211

Figure 6-63 and Figure 6-64 illustrate the range of components that can be made by the powder
metallurgy process, namely a sintered carbide cutting tool and a range of complex shapes, difficult to
machine by conventional methods.

Figure 6-633

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Chapter 6: Heat Treatment

Figure 6-647

Figure 6-65 illustrates the advantages of powder metallurgy over forging and machining to produce
a gear.

Figure 6-653

Moving from left to right on the top row shows each stage of the forging process, specifically the
sheared stock, rough forging, forged blank, plus the scrap. The finished gear is then machined from
the forged blank. In contrast the powder metallurgy process involves only one pre-form to produce
the gear without a machining operation, and without scrap. Powder metallurgy would therefore be
the preferred process for manufacturing this. gear.

6.17 Questions and Answers – Heat Treatment

Q12.1 Two pieces of steel, each of eutectoid composition are heated to 300 C above the upper critical
temperature, and then quenched at a rate exceeding the critical cooling velocity for this grade of steel.

One piece is tempered at 4000 C, and the other at 6000 C, by soaking at these respective temperatures,
and then cooling to room temperature.

Describe the microstructural changes that occur, and outline the differences in mechanical properties
for the two samples by referring to Figure 6-66.

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Chapter 6: Heat Treatment

Figure 6-66 Effect of tempering temperature on the properties of eutectoid steel.

Q12.2 Briefly describe the following processes, and why they are carried out. In the answer describe
the microstructural changes that occur, and how these changes affect the properties of the steel
specimens on which they are performed.

(a) Annealing
(b) Nitriding.

Q12.3 Refer to Figure 6-67, a portion of the iron- carbon phase diagram to answer this question.
A steel containing 0.4% C is heated to 7400C and then quenched. Determine the amount and
composition of the martensite that forms.

Figure 6-67 The eutectoid portion of the iron- carbon phase diagram

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Chapter 6: Heat Treatment

Q12.4 a 1050 steel is held at 8000C for 1 hour, quenched to 7000C and held for 50s, quenched to
4000C and held for 20s, and finally quenched to room temperature. What is the final microstructure
of the steel? Use the TTT diagram in Figure 6-68.

Figure 6-68 The TTT isothermal diagram for a 1050 steel

Q12.5 A 1050 steel is isothermally heat treated to give a hardness of HRC = 23. Describe the heat
treatment and the amount of each microconstituent after each step of the heat treatment. Refer to
Figure 6-67 and Figure 6-68.

A12.1
The steel samples are heated and soaked in the austenite region of the iron-carbon phase diagram,
and rapidly quenched. The austenite is converted to martensite, a metastable microconstituent which
is hard and brittle.

Tempering is a heat treatment process whereby the sample is reheated to some temperature below
the eutectoid temperature in order to modify the properties of the martensite.

The decomposition of martensite in the tempering process causes the strength and hardness to
decrease, while the ductility and impact properties are improved.

At lower tempering temperatures transformation of martensite to stable ferrite and cementite is only
partial, and the steel will still be hard, and partially brittle, but stress relieved.

As the tempering temperature is increased the martensite transformation to ferrite and cementite
becomes more complete, and the softening and toughening continues to increase. During this process
the hard cementite gradually forms tiny spheroids in a matrix of soft ferrite, ultimately forming
spheroidite, the softest and most ductile of the tempered forms.

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Chapter 6: Heat Treatment

The microstructure gradually changes from fine tempered martensite to spheroidite, illustrated in
Figure 6-24 to Figure 6-28 of the lecture notes.

An estimate of the mechanical properties of the two tempered samples may be determined by
reference to Figure 6-66.

The properties are tabled below for comparison.

Tempering Temperature 0 C Tensile Strength MPa Yield Strength MPa Hardness HRC
400 1276 1000 44
600 1035 690 37
Table 6-6

The results clearly illustrate the reduction of the above mechanical properties as a function of
increasing tempering temperature.

Note:
The conversion factor from psi to MPa is:
1 psi = 0.0069 MPa

A12.2

(a) Annealing is a heat treatment designed to dispersion strengthen steels. Hypoeutectoid steels
are heated just above A3 , soaked, and furnace cooled. Hypereutectoid steels are heated just
above A1, soaked, and furnace cooled. In each case the very slow cooling allows diffusion of
primary ferrite and coarse pearlite in the case of the hypoeutectoid steels, and the diffusion
of discontinuous cementite, and coarse pearlite for hypereutectoid steels. In both cases the
steel has low strength, and high ductility.

(b) Nitriding, like carburizing, is a process by which a thin hard surface is produced on a ductile
steel component, thus providing a wear resistant surface on a low carbon ductile core.
Nitriding is performed in a furnace with an atmosphere of cracked ammonia. This consists of
some free nitrogen and hydrogen gases. The formation of hard iron nitrides, analogous to
iron carbide, forms on the surface, the depth of case depending upon the time and
temperature of exposure. The process is carried out at temperatures below A1. Compressive
residual stresses are introduced at the surface, providing excellent fatigue resistance, in
addition to improved hardness, strength, and toughness.

A12.3

When the steel is heated to 7400C , it is in the 2 phase region of α + γ as depicted in Figure 6-67. A tie
line is drawn as shown in Figure 6-69 below, and the lever rule is then applied to calculate the amount
of austenite, and then equate the austenite to the martensite.

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Chapter 6: Heat Treatment

Figure 6-69

Austenite composition = martensite composition = 0.68% C

𝐴𝐴 0.40−0.021
% austenite = % martensite = = x 100 = 58%
𝐴𝐴+𝐵𝐵 0.68−0.021

% primary ferrite = 42%

A12.4

(i) After 1 hour at 8000C 100% austenite forms, point (1) in Figure 6-70.
(ii) Ferrite begins to form after 20s at 7000C but, after 50s the steel contains only ferrite and unstable
austenite, points (2) and (3) in Figure 6-70.

(iii) After quenching to 4000C , the steel is still only ferrite and austenite. However after about 3s
bainite begins to form, and after 20s contains ferrite, bainite, and still some unstable austenite, points
(4) and (5) Figure 6-70.

(iv) After quenching to room temperature, the remaining austenite crosses the Ms and Mf
temperatures, and transforms to martensite. The final structure is ferrite, bainite, and martensite.

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Chapter 6: Heat Treatment

Figure 6-70 Isothermal transformation of a 0.5% carbon steel

A12.5

Refer to Figure 6-71 and Figure 6-72 to illustrate the following descriptive answers.
(i) From Figure 6-71 it can be seen that the A3 temperature is 7600C. Thus to austenitize, the steel
is soaked at 760 + (30 to 50) = 790 – 8100C for about 1 hour, at which time the steel is 100%
austenite.

Figure 6-71 Austenitization temperature for a 1050 steel

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Chapter 6: Heat Treatment

To obtain a Rockwell hardness of 23, the sample must transform to ferrite plus pearlite as illustrated
in Figure 6-72.

Figure 6-72 Isothermal TTT diagram for a 1050 steel

(ii) After about 1.5s the austenite begins to transform to ferrite, point (3) in figure 7. After about
2s pearlite begins to form, and after 7s pearlite formation is complete, point (4)
(iii)The steel is cooled to room temperature after about 10s, its final structure consisting of
primary ferrite plus pearlite with a hardness of HRC 23.
(iv) The final percentage of microconstituents are pearlite = 62%, and primary ferrite = 38%.
Figure 6-73 shows this calculation.

Figure 6-73 Iron- carbon phase diagram for a 0.50% C steel

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References

1 Bailey, A R. The Role of Microstructure in Metals. 3rd ed. Surrey, England: The Gatwick
P Ltd., 1982.
2 Callister, Jr, William D. Materials Science and Engineering an Introduction. 7th ed.
York, PA: John Wiley & Sons, 2007.
3 De Garmo, E P., J T. Black, and R A. Kohser. Materials and Processes in Manufacturing.
7th ed. Macmillan, 1984.
4 Moffatt, William G., George W. Pearsall, and John Wulff. The Structure and Properties
of Materials. Vol. 1. New York, USA: John Wiley & Sons, 1964.
5 Monks, H A., and D C. Rochester. Technician Structure & Properties of Metals. Vol. 2.
Southampton: The Camelot P Ltd, 1979.
6 Brophy, J.H., Rose, R.M., Wulff, John, The Structure and Properties of Materials, volume
II, 1964, Wiley, USA.
7 Budinski, K.G., Engineering Materials, Properties and Selection, 4th Ed., 1992 Prentice-
Hall, New Jersey, USA.
8 Askeland, Donald,R., The Science and Engineering of Materials, 2nd Ed., 1989, PWS-
KENT, USA.
9 Schlenker, B.R., Introduction to Materials Science, SI Edition, 1986, Jacaranda Wiley,
Singapore.
10 Shackelford, J.E., Material Science for Engineers, 3rd Ed., 1992, MACMILLAN, USA.
11 Ashby, M.,Shercliff, H., Cebon, D., Materials Engineering, Science, Processing and
Design, 2007, Butterworth-Heinemann, Oxford UK.
12 Smith, William, F., Hashemi, Javad, Foundations of Materials Science and Engineering,
5th ed., McGraw-Hill, 2010.

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Chapter 7: Electrochemistry

Electrochemistry

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Chapter 7: Electrochemistry

7.1 Introduction
Electrochemistry deals with the relationships between electricity and chemical reactions. It forms the
basis for the principles underlying voltaic cells or batteries, electrolysis, corrosion, and the important
developments in fuel cells, and more efficient battery devices.

7.2 Oxidation and Reduction

The corrosion of iron or other metals results in the conversion of the metal into a compound by its
interaction with one or more components of the environment, usually oxygen. When a metal corrodes
it loses electrons and forms a cation. It is said to be oxidized. The general reaction is:

M → Mn+ + n e (7-1)
Where, M represents the symbol for the metal
Mn+ represents the metal ion
ne represents the number of electrons

A typical example is rusting, the oxidation of iron:

Fe → Fe 2+ + 2 e (7-2)
We may define oxidation as a reaction where electrons are lost, or when there is an increase in
oxidation number. One of the compounds is rust or iron II oxide, which is formed when iron metal
reacts with oxygen.
2 Fe + O 2 → 2 Fe O (7-3)
In this reaction the iron loses its electrons to oxygen which is transformed from neutral O2 to oxide
ions O2-.

O 2 + 4 e → 2 O 2− (7-4)

Reduction may be defined as a reaction where electrons are gained, or where there is a decrease in
oxidation number. It will be obvious that when the half oxidation of equation (7-2) and the half
reduction of equation (7-4) are combined, we have the rusting process of equation (7-3).

Oxidation or reduction cannot occur separately, since electrons from one reactant are transferred to
another. Such reactions are called 'redox' processes.

7.3 Oxidation Numbers

Before oxidation-reduction reactions can be clearly identified, a method, by which a record of the
number of electrons is exchanged, must be devised. To do this we assign oxidation numbers to each
different type of atom undergoing reaction.

The oxidation number is defined as a positive or negative number assigned to an element in a

molecule or ion on the basis of a set of rules.

7.3.1 Rules

i. The oxidation number for elements is 0.

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Chapter 7: Electrochemistry

ii. The oxidation number for ions is the charge on the ion. For example:
K+ = +1 S2− = −2
iii. Non-metals usually have a negative oxidation number. For example:
Oxygen = −2 Halogens = −1
iv. Hydrogen is +1 when bonded to non-metals and -1 when bonded to metals.
v. The sum of the oxidation numbers in a neutral compound is zero.

7.4 Oxidation of Metals by Acid or Salt

The reaction of a metal with either an acid or a salt may be represented generally as:
A + BX → AX + B (7-5)
Some examples are:

Zn (s) + 2 HCl(aq) → ZnCl2(aq) + H 2(g) (7-6)

Zn (s) + CuSO 4(aq) → ZnSO 4(aq) + Cu (s) (7-7)

We will assign oxidation numbers to equation (7-6) to illustrate their use:

Zn (s) + 2 HCl(aq) → ZnCl2(aq) + H 2(g)

0 +1 +2 0

The oxidation number of Zn increases from 0 to +2, hence zinc is oxidized to Zn2+. The oxidation
number of H decreases from +1 to 0, hence H+ is reduced to H 2(g) . Cl remains constant at -1.

7.5 The Activity Series

Different metals vary in the ease with which they are oxidized. For example Zn is readily oxidized by
an aqueous solution of Cu2+, but Ag is not, as shown below:

Zn (s) + CuSO 4(aq) → ZnSO 4(aq) + Cu (s)

Ag (s) + CuSO 4(aq) → No Reaction

A list of metals arranged in order of decreasing ease of oxidation produces an activity series. This
series can be used to predict which combinations will react. Any metal in the series can be oxidized
by the ions of elements below it.

Thus Mn can be oxidized by aqueous Sn2+, but Hg cannot be oxidized by Zn2+. It will be observed that
the 'reactive' metals are at the top of the series, and the less reactive metals are below them.

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Chapter 7: Electrochemistry

Metal Oxidation Reaction

Lithium Li(s) → Li + (aq)
 +e−

Potassium K (s) → K + (aq)

 +e−

Barium Ba (s) → Ba 2+ (aq)

 +2e −

Calcium Ca (s) → Ca 2+ (aq)

 +2e −

Sodium Na (s) → Na + (aq)

 +e−

Magnesium Mg (s) → Mg 2+ (aq)

 +2e −

Ease of oxidation increases

Aluminium Al(s) → Al3+ (aq)
 +3e −

Manganese Mn (s) → Mn 2+ (aq)

 +2e −

Zinc Zn (s) → Zn 2+ (aq)

 +2e −

Chromium Cr(s) → Cr 3+ (aq)

 +3e −

Iron Fe(s) → Fe2+ (aq)

 +2e −

Cobalt Co(s) → Co 2+ (aq)

 +2e −

Nickel Ni(s) → Ni 2+ (aq)

 +2e −

Tin Sn (s) → Sn 2+ (aq)

 +2e −

Lead Pb(s) → Pb 2+ (aq)

 +2e −

Hydrogen H 2(g) → 2H + (aq)

 +2e −

Copper Cu (s) → Cu 2+ (aq)

 +2e −

Silver Ag (s) → Ag + (aq)

 +e−

Mercury Hg (l) → Hg 2+ (aq)

 +2e −

Platinum Pt (s) → Pt 2+ (aq)

 +2e −

Gold Au (s) → Au 3+ (aq)

 +3e −

Figure 7-11 Activity series of metals in aqueous solution

An activity series is a list of metals arranged in order of decreasing ease of oxidation. The activity
series for most common metals is included, as well as hydrogen. The metals at the top of the table,
such as the alkali metals and the alkaline earth metals, are most easily oxidized, that is, they react
most readily to form compounds.

7.6 Voltaic or Galvanic Cells

The energy released in a spontaneous reaction, for example, a redox reaction can be harnessed to
perform useful work, accomplished by the transfer of electrons. A schematic diagram of a voltaic cell
using a salt bridge to connect the two half cells is illustrated in Figure 7-2.

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Chapter 7: Electrochemistry

Figure 7-21 A voltaic cell that uses a salt bridge to complete the electrical circuit

Note the following details:

i. Oxidation occurs at the anode.

ii. Reduction occurs at the cathode.
iii. Electrons flow from anode to cathode through the connecting wire.
iv. To maintain electrical balance in the cell, positive ions (cations), migrate to the Cu cathode,
and negative ion (anions), migrate to the anode (Zn). The anions derive from the salt bridge
(NO3− ) , and the electrolyte. In this case since Zn ( NO3 )2 and Cu ( NO3 )2 were used, NO3−
ions are the migrating ions.
v. Ions transfer via the salt bridge.

7.7 Cell EMF under Standard Conditions

Reactions in a voltaic cell are spontaneous. Electrons at the anode have a higher potential than at the
cathode, and hence flow from anode to cathode. The difference in potential energy per electrical
charge (potential difference) between the two electrodes is measured in volts.

One volt is the potential difference required to impart 1 Joule of energy to a charge of 1 Coulomb (C).
That is:
Joule J
1 Volt = 1 =1
Coulomb C

Recall that one electron has a charge of 1.602×10-19 C.

The potential difference acts as a driving force, pushing the electrons through the external circuit, and
is known as EMF, or electro-motive force. Ecell is known as the cell potential, or cell voltage.

For spontaneous cell reactions, Ecell is positive.

Ecell depends upon several factors:

i. The specific cell reaction

ii. The concentration of products and reactants
iii. The temperature

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Chapter 7: Electrochemistry

For STANDARD CONDITIONS, temperature is equal to 25°C or 298°K, electrolyte concentration is

equal to 1.0 molar, and pressure is equal to 1.0 atmosphere.

Under standard conditions Ecell becomes E°cell, the standard cell potential.

7.8 Standard Reduction Half Cell Potentials

By convention half-cell potentials, are expressed as half reduction reactions. Thus,

= 
Ecell 
Ered ( cathode ) − Ered ( anode ) (7-8)

Potential
Reduction Half-Reaction
(E° Volts)
F2(g) + 2e −  −
→ 2F(aq) +2.87
MnO −4(aq) + 8H (aq)
+
+ 5e −  2+
→ Mn (aq) + 4H 2O(l) +1.51
Cl2(g) + 2e −  −
→ 2Cl(aq) +1.36
2− +
Cr2O7(aq) + 14H (aq) + 6e−  3+
→ 2Cr(aq) + 7H 2O(l) +1.33
+
O 2(g) + 4H (aq) + 4e − 
→ 2H 2O(l) +1.23
Br2(l) + 2e −  −
→ 2Br(aq) +1.06
− +
NO3(aq) + 4H (aq) + 3e− 
→ NO(g) + 2H 2O(l) +0.96
+
Ag (aq) + e− 
→ Ag (s) +0.80
+
Fe3(aq) + e −  2+
→ Fe(aq) +0.77
+
O 2(g) + 2H (aq) + 2e − 
→ H 2O 2(aq) +0.68
MnO −4(aq) + 2H 2O(l) + 3e −  −
→ MnO 2(s) + 4OH (aq) +0.59
I 2(s) + 2e −  −
→ 2I(aq) +0.54
O 2(g) + 2H 2O(l) + 4e−  −
→ 4OH (aq) +0.40
Cu 2+
(aq) + 2e −

→ Cu (s) +0.34
+
2H (aq) + 2e− 
→ H 2(g) 0 [defined]
2+
Ni (aq) + 2e − 
→ Ni (s) -0.28
2+
Fe(aq) + 2e − 
→ Fe(s) -0.44
2+
Zn (aq) + 2e− 
→ Zn (s) -0.76
2H 2O(l) + 2e−  −
→ H 2(g) + 2OH (aq) -0.83
+
Al3(aq) + 3e − 
→ Al(s) -1.66
+
Na (aq) + e− 
→ Na (s) -2.71
+
Li (aq) + e − 
→ Li(s) -3.05

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Table 7-11 Standard reduction potentials in water at 25°C

It is convenient to adopt a standard for the cathode half-cell reaction (cathode). The standard adopted
is that for the hydrogen electrode (SHE or NHE), assigned a value of 0.00V at 25°C and 1 atmosphere
of pressure. The reaction is given by:
+
2H (aq −
1M)
+ 2e 
→ H 2(g,1atm) 
Ered = 0.00V
The standard hydrogen electrode (SHE) is illustrated below in Figure 7-3.

Figure 7-31 The standard hydrogen electrode (SHE) used as a reference electrode

An SHE consists of platinum electrode coated with finely divided Pt in contact with H 2(g) at 1 atm
pressure, and an acidic solution with  H +  = 1M .

The cell using a hydrogen electrode and the Zn2+/Zn electrode is illustrated in Figure 7-4.

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Chapter 7: Electrochemistry

Figure 7-41 A voltaic cell using a standard hydrogen electrode

The reaction is
+
Zn (s) + 2H (aq) → Zn 2+ + H 2(g)

for which the voltmeter reads +0.76V. Substituting into equation (7-7) gives:

= 
Ecell 
Ered ( cathode ) − Ered

( anode )
= 0V − Ered
0.76V 
( anode )

Ered ( anode ) = −0.76V
Thus the standard reduction potential for Zn2+/Zn is -0.76V.

The table of standard reduction potentials in water at 25°C has been compiled by comparing the half
cell potentials for a range of metals, with the standard hydrogen electrode as illustrated above for Zn.

The standard hydrogen electrode, (SHE), is the reference electrode used to compile the table of
standard reduction potentials in Appendix G. Because the use of this electrode outside the laboratory
is not practicable, other reference electrodes have been devised, and these are more useful for
corrosion monitoring as discussed in chapter 8.

7.8.1 Rules

There are several useful rules which must be known before the table of standard reduction potentials
can be applied, namely:

i. Each half reaction is written as a half reduction. This is a convention, and the half reduction
may be converted to a half oxidation simply by reversing the equation, and changing the sign
of the E° value.

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Chapter 7: Electrochemistry

ii. Changing the stoichiometric quantity in front of the half reaction does not affect the value of
the standard reduction potential. This is because the ratio of energy (Joules), per unit of
electrical charge (Coulombs), remains constant, and hence the cell voltage V = J C is a
constant.
iii. A positive half potential indicates a spontaneous reaction, and a negative value a non-
spontaneous reaction. The same applies to cells, and hence all voltaic cells have positive E°’s.

7.8.2 Example Problem

Example 2.1 Using the standard reduction potentials, calculate the standard EMF for
+ 2+
2Al3(aq) + 3Ca (s) → 2Al(s) + 3Ca (aq)
.

Solution

From the tables:

+
Al3(aq) + 3e → Al(s) E =
−1.66V 
2+
Ca (aq) + 2e → Ca (s) E =
−2.87V



Reverse :
2+
Ca (s) → Ca (aq) + 2e E =
2.87V 

 × 3:
2+
3Ca (s) → 3Ca (aq) + 6e E  =
2.87V 
 × 2:
+
2Al3(aq) + 6e → 2Al(s) E  =
−1.66V 

 + :
3Ca (s) + 2Al3+ → 3Ca 2+ + 2Al E =
1.21V

Note that since the EMF of the cell must be positive for a voltaic cell, this procedure will lead to the
correct value. Also, there is no gain or loss of electrons.

7.9 Strengths of Oxidizing and Reducing Agents


We have seen that the more positive is the Ered , the more likely is the reactant in the half reaction to
be reduced, and hence to oxidize the other species by accepting its electrons. By referring to the table
of standard reduction potentials it can be seen that the strongest oxidizing agents are:

Fluorine F2

Permanganate ion MnO −4

Chlorine Cl 2

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2−
Dichromate ion Cr2O7
Oxygen O 2 , and so on …

Conversely lithium ion Li+ with the most negative E red will be the least likely to be reduced, and hence,
is most likely to be readily oxidized. Alternatively we can say that Li(s) will be a strong reducing agent.
This should be obvious since if we reverse the half reduction for Li+ we have:
+
Li (s) 
→ Li (aq) +e E = +3.05V , which is a spontaneous reaction.

Commonly used reducing agents are hydrogen, H2, and the reactive metals such as Na and Al. Figure
7-5 summarizes the ability of substances to act as oxidizing or reducing agents, and is derived from
the table of standard reduction potentials.

Figure 7-51 Relative strengths of oxidizing agents


The standard reduction potentials, Ered , listed in Table 7-1, are related to the ability of substances to
serve as oxidizing or reducing agents. Species on the left side of the half-reactions can act as oxidizing

agents, and those on the right side can act as reducing agents. As Ered becomes more positive, the

species on the left become stronger and stronger oxidizing agents. As Ered becomes more negative, the
species on the right become stronger and stronger reducing agents.

7.10 Free Energy (G), and Redox Reactions

The criteria for spontaneity of a process may be stated qualitatively as the tendency towards
minimum energy, and the tendency towards maximum randomness or dispersion. The tendency
towards minimum energy is expressed as a release of heat, or enthalpy change at constant pressure (
−∆H ).
The tendency towards maximum randomness is expressed as a change or increase in entropy at
constant temperature ( −∆S ).

Spontaneous processes satisfy one or both of these criteria, for example, expanding gases, cooling
bodies, the dissolution of a solid in a liquid or oxidation of a fuel. The thermodynamic quantity that

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connects enthalpy and entropy together is the Gibbs free energy, G, proposed by Willard Gibbs in the
19th Century. This relationship may be expressed in the form:

G= H − TS (7-9)
where T is the absolute temperature
∆G = ∆H − T ∆S
Enthalpy Entropy (7-10)
term term

It can be shown that if:

i. ΔG is negative, the reaction is spontaneous

ii. ΔG is zero, the reaction is at equilibrium
iii. ΔG is positive, the reaction is not spontaneous

7.10.1 Standard Free Energy ∆G°

As for the E° values, standard conditions are also defined for free energy. This is shown below.

State of Matter Standard State

Solid Pure solid
Liquid Pure liquid
Gas 1 atm pressure
Solution 1 M concentration
Standard free energy of formation of an element
Elements
in its standard state is defined as zero.
Table 7-21 Conventions used in establishing standard free energies

Most chemical reactions occur under non-standard conditions. The relationship for ΔG under non-
standard conditions is given by:

∆G =∆G  + RT ln Q (7-11)
Where Q is the reaction quotient, which is identical to the equilibrium constant K, when the
concentrations of reactants and products are not at equilibrium.

At equilibrium ∆G = 0 and equation (7-11) simplifies to:

∆G  =
− RT ln K (7-12)
Where R = universal gas constant = 8.314 J·K-1·mol-1

7.11 EMF and Change in Free Energy ∆G

Both ∆G and the EMF E of a reaction are measures of spontaneity, and we may connect the two by:

∆G = -nFE (7-13)
Where n = number of moles of electrons transferred in the reaction
F = Faraday constant = 96 485 C·mol-1

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E = EMF in volts

The Faraday constant, F, is the charge on one mole of electrons, that is:

1 F = 6.022 × 1023 mol-1 × 1.602 × 10−19 C

= 96 485Cmol-1
For reactants and products in their standard states:

∆G  = -nFE  (7-14)
Note the dimensional consistency of the left and right hand side of equation (7-14).

∆𝐺𝐺° (𝐽𝐽/𝑚𝑚𝑚𝑚𝑚𝑚) = −𝑛𝑛(𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐) × 𝐹𝐹(𝐶𝐶 ⁄𝑚𝑚𝑚𝑚𝑚𝑚 ) × 𝐸𝐸°(𝐽𝐽⁄𝐶𝐶 )

= −𝑛𝑛𝑛𝑛𝑛𝑛°(𝐽𝐽⁄𝑚𝑚𝑚𝑚𝑚𝑚)

7.12 Cell EMF under Non-standard Conditions

Substituting equation (7-13) and equation (7-14) into equation (7-11) gives:

−nFE = −nFE  + RT ln Q
RT
∴ E = E − ln Q
nF
Using 2.303 to convert from natural to common logarithms, using T = 298K and R = 8.314 J/K.mol.

0.0592
= E −
E log Q (7-15)
n
Equation (7-15) is termed the Nernst equation and it can be used to calculate the cell EMF under non-
standard conditions.

The general equation for a typical reaction in aqueous solution encountered in a galvanic cell at
equilibrium is :
aA + bB ↔ dD + eE (7-16)
A and B represent the reactants and D and E the products.

a, b, c and d represent the molar quantities of A,B,C and D.

Equation (7-17) represents a system at equilibrium. For a galvanic cell at equilibrium Ecell = 0 volts
and ∆G = 0. Its equilibrium constant
d e
D E 
K=  a  b (7-17)
 A  B

where the term in brackets eg [A] represents the molar concentration of the reactant/products at
equilibrium. A cell at equilibrium corresponds to a “flat battery”, and is no longer able to produce
electrical energy.

In contrast, an active cell is not at equilibrium, and electrical energy is produced from the spontaneous
cell reaction. In this situation the reaction quotient Q is analogous with the expression for K, namely,

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d e
D E 
=Q  a  b (7-18)
 A  B
For equation (7-18) the bracketed terms refer to the specified molar concentrations of the electrolytes
at a nominated time for the active cell, usually the initial cell conditions. In this form Q may be
substituted into the Nernst equation, (7-15).

7.13 Concentration Cells

The voltaic cells studied this far have involved different metals and their salt solutions. However, a
type of voltaic cell involving only one metal/electrolyte can generate a cell EMF if the concentration
of the electrolytes in each half cell is different. This leads to a concentration gradient, which can
generate a cell potential.

Consider the two Ni half cells illustrated below, with different nickel ion concentrations in the two
half cells. The cell will generate an EMF until  Ni 2+  =  Ni 2+  .
LH cell RH cell

Figure 7-61 Concentration cell based on the Ni2+-Ni cell reaction. In (a) the concentrations of Ni2+(aq) in the two
compartments are unequal, and the cell generates an electrical current. The cell operates until the
concentrations on Ni2+(aq) in the two compartments become equal, (b) at which point the cell has
reached equilibrium and is 'dead'.

Hence the half cell with the weaker  Ni 2+  will need to generate more Ni2+ until such time as the
concentrations in each cell are equal. The most dilute half cell reaction is:

→ Ni 2+ (aq) + 2 e
Ni (s) 
and will be the anode. The overall reaction will be:
2+ 2+
Cathode Ni (aq,concentrated) 
→ Ni (aq,dilute) Anode

Now using the Nernst equation:

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0.0592
= E −
Ecell log Q
n
0.0592 1× 10−3 

= 0− log
2 [1.0]
= +0.0888V

Note that concentration cells form the basis for the operation of a pH meter, due to differences in
 H +  across a glass membrane, and also in processes involving brain and heart tissue.

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7.13.1 Example Problem

Example 2.2 Given the following reduction half reactions:

+ 2+
Fe3(aq) + e 
→ Fe(aq) E  = 0.77V 
2− +
S2O6(aq) + 4H (aq) + 2e 
→ 2H 2SO3(aq) E  = 0.60V 
2+ 2−
(a) Write a balanced equation for the oxidation of Fe(aq) by S2O6(aq) .
(b) Calculate ∆G ° for the reaction at 298°K.
(c) Calculate the equilibrium constant at 298°K.
(d) Is the cell reactions spontaneous or non-spontaneous? Explain.

Solution

(a) Reverse  and × 2:

2+ +
2Fe (aq) 
→ 2Fe3(aq) + 2e E = −0.77V 

2− +
S2O6(aq) + 4H (aq) + 2e → 2H 2SO3(aq) E =
0.60V 

 + :
2+ 2− + +
2Fe(aq) + S2 O6(aq) + 4H (aq) 
→ 2Fe3(aq) + 2H 2SO3(aq) 
= −0.17V
Ecell
Note that the cell reaction is not spontaneous because of a negative E°.

(b) Using equation (7-14):

(c)
∆G  = −nFE 
= −2 × 96485 × −0.17
= 32804.9J / mol

A positive ∆G ° further confirms a non-spontaneous reaction.

(d) Using equation (7-12):

∆𝐺𝐺° = −𝑅𝑅𝑅𝑅 ln 𝐾𝐾
32804.9 = 8.31 × 298 ln 𝐾𝐾
= −2476.38 ln 𝐾𝐾
32804.9 𝐽𝐽𝐽𝐽𝐽𝐽𝐽𝐽
∴ ln 𝐾𝐾 = −
2476.38 𝐽𝐽/𝑀𝑀𝑀𝑀𝑀𝑀

= −13.25
∴ 𝐾𝐾 = 𝑒𝑒 −13.25
= 1.81 × 10−6

Since K << 1, this verifies a non-spontaneous reaction.

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Example 2.3 A voltaic cell is constructed that uses the following reaction, and operates at 298K:

2+ 2+
Zn (s) + Ni (aq) 
→ Zn (aq) + Ni (s) 

(a) What is the EMF of the cell under standard conditions?

cell when  Ni 2+  3.0M
(b) What is the EMF of the = = and  Zn 2+  0.1M ?
cell when  Ni 2+  0.2M
(c) What is the EMF of the = = and  Zn 2+  0.9M ?

Solution

(a) Writing the half reactions and their half reduction potentials (from tables).

2+
Zn (aq) + 2e 
→ Zn (s) E = −0.763V 
2+
Ni (aq) + 2e 
→ Ni (s) E = −0.28V 

Reverse :
2+
Zn (s) 
→ Zn (aq) + 2e E  = 0.763V 

 + :
2+ 2+
Zn (s) + Ni (aq) 
→ Zn (aq) Ni (s) 
Ecell = 0.483V

(b) Using the Nernst equation (7-15):

0.0592 [Zn2+ ]
E𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 = E ° − log
2 [Ni2+ ]
0.0592 0.1
= 0.483 − log
2 3
0.0592
= 0.483 − × −1.477
2
= 0.527V

(c)
0.0592 [Zn2+ ]
E𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 = E ° − log
2 [Ni2+ ]
0.0592 0.9
= 0.483 − log
2 0.2
0.0592
= 0.483 − × 0.653
2
= 0.464V

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7.14 Batteries
Batteries continue to fill a vital need as power sources for a wide range of technologies, from space
exploration to flash lights, and from solar powered cars to computers and digital cameras.

A great deal of research has been expended in developing the 'perfect' battery, and even today this
goal seems elusive. However, vast strides have been taken, and research continues on several fronts,
all of which draw upon a highly sophisticated understanding of materials science. We will discuss
here only three examples which will give an overview of the technology as it stands today.

7.14.1 The Lead-Acid Battery

The lead-acid battery is one of the oldest, but one of the most reliable and widely used of all batteries.
The 12 volt battery consists of 6 unit cells each of 2 volt capacity connected in series.

Figure 7-75 (a) A motor vehicle battery. (b) A lead-acid storage cell. (c) A simplified cross-section of a lead-
acid battery

A summary of the major features of the lead-acid battery:

i. Anode: lead - spongy lead packed into a lead grid.

ii. Cathode: lead dioxide PbO2 pressed into a lead grid.
iii. Electrolyte: sulphuric acid H2SO4.
iv. The half cell reactions are as follows:

Cathode: PbO 2(s) + HSO −4(aq) + 3H (aq)

+
+ 2e → PbSO 4(s) + 2H 2O(l) E =
1.685V
− +
Anode: Pb(s) + HSO 4(aq) → PbSO 4(s) + H (aq) + 2e E =
0.356V
− +
Cell reaction: PbO 2(s) + Pb(s) + 2HSO 4(aq) + 2H (aq) → 2PbSO 4(s) + 2H 2 O(l) E  =
2.041V

v. Electrode spacers: glass fibre

vi. Characteristics:
• Reversible
• H2SO4 is consumed during discharge, the reverse of the cell reaction equation.
• Used where a steady operating EMF is of importance

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• Low internal resistance approximately equal to 0.005 Ω which permits large current
drains, for example an automobile starter motor.
• Low energy density, that is, ratio of output to mass is low relative to more modern
batteries.

7.14.2 The Lithium-ion Battery

This is one of the newest and most promising of modern cells. It is found in cell phones, laptops and
digital cameras. These batteries are based on the ability of Li+ to be inserted into and removed from
certain solids, such as graphite, layered oxide or phosphate, or a spinel. In this case lithium-ion
batteries differ from conventional batteries. The specifications are as follows:

i. Anode: graphite
ii. Cathode: usually one of three possible solids
• Lithium cobalt oxide LiCoO2
• Lithium iron phosphate
• Lithium manganese oxide (a spinel)

iii. Electrolyte: a liquid electrolyte is used containing ether as solvent with soluble electrolyte salt
containing lithium such as LiPF6, LiBF4 or LiClO4.
iv. Cell reaction: LiCoO 2 + C6 ⇌ Li1− x C6 → Li x CoO 2 It is important to note that Li+ are not
reduced, but spontaneously migrate from the graphite anode to the cathode, allowing
electrons to flow through the external circuit, thus producing electrical energy. During this
process the transition metal Co is reduced from Co4+ to Co3+ during discharge.
v. Cell voltage: 3.7V average
vi. Energy to mass ratio: currently the highest.

Figure 7-86 Lithium-ion rechargeable battery. Discharge mechanism

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Figure 7-96 Lithium-ion rechargeable battery. Charge mechanism

7.14.3 Fuel Cells

When conventional hydrogen fuels such as methane, propane and butane, or hydrogen are combusted
the thermal efficiency is no better than 40%. The direct production of electricity from fuels using a
voltaic cell offers the potential for much greater efficiency. Fuel cells are voltaic cells that utilize the
oxidation of fuels such as methane, methanol CH3OH and H2 in a cell reaction.

i. The Proton Exchange Membrane Cell (PEM)

The overall cell reaction for a fuel cell based on O2 and H2 is:

2H 2(g) + O 2(g) 
→ 2H 2O(l) E cell = 1.23V

Figure 7-101 A low-temperature H2-O2 fuel cell. The porous membrane allows the H+ ions generated by the
oxidation of H2 at the anode to migrate to the cathode, where H2O is formed

The cell consists of graphite electrodes with a thin layer of platinum catalyst on their surface.
Under alkaline conditions the half cell reactions are:

Cathode: → 4OH −
4e + O 2 + 2H 2O  E  = 0.40V
Anode: 2H 2 + 4OH − 
→ 4H 2O + 4e E  = 0.83V

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Chapter 7: Electrochemistry

Cell reaction: 2H 2(g) + O 2(g) 

→ 2H 2 O(l) 
Ecell = 1.23V

The anode and cathode are separated by a thin polymer membrane which is permeable to
protons (H+), but not electrons, and therefore acts as a salt bridge. The operating temperature
is 80°C. NASA has used this fuel cell in space craft.

ii. The Solid Oxide Ceramic Fuel Cell (SOFC)

These SOFC systems use natural gas as a fuel. SOFCs can also use other fuels such as LPG and
ethanol. Unlike other fuel cells SOFCs do not need pure hydrogen. The natural gas is treated
to remove sulphur, and then combined with steam to remove other gases, leaving a methane-
rich gas.

The fuel passes over the anode side which breaks down the methane gas under high
temperature, releasing hydrogen. On the cathode side high-temperature oxygen is blown
across the cathode. The oxygen ions then travel through the electrolyte membrane and
combine with hydrogen on the anode side and create an electric current, water and heat.

Figure 7-114

When a load (i.e. light globe) is connected between the anode and cathode, the circuit is completed
allowing the electrons to flow from the anode back to the cathode and produce electricity, much the
same as connecting a light globe to a battery. Most individual fuel cells produce less than one volt of
electricity, so they are assembled in layers called 'stacks' to provide a useful voltage. Today, fuel cells
can silently produce clean, efficient heat and electricity from natural gas.

Key points of the solid oxide ceramic fuel cell:

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a. A solid oxide electrolyte of ZrO2 and Yt2O3. Ratio of oxide ions/metal ion is: 2:1 for
ZrO2 and 1.5:1 for Yt2O3. Gaps in lattice promote transfer of oxide ions O2-. High melting
point of the ceramic permits high temperature operation at 800°C.

b. Raw materials: air (O2) to cathode and fuel such as hydrocarbon gas to anode.

c. Fuel purification
• Remove H2S and SO2 – oxidize H2S to SO2 and absorb in alkali.
• Remove C3H8, C2H6 and C4H10 by catalytic cracking or ultra filtration.
• React the pure methane fuel with steam at 850°C:

CH 4(g) + H 2O(g) →

Cat
3H 2(g) + CO(g)
2−
d. Cathode reaction: O 2 + 4e  → 2O . Oxide ions diffuse through solid ceramic
electrolyte to the anode where they combine with H2 and CO.

e. Anode reaction: → 4H + + 4e
2H 2 
Net reaction: O 2 + 2H 2 
→ 2H 2O E  = 1.23V

f. Products: electric current, heat, nitrogen, CO2 and H2O.

iii. Other Types Of Fuel Cells

Different types of fuel cells are categorised by the type of electrolyte. Within each fuel cell type
different companies are using different designs to tailor a fuel cell’s performance for a given
application. The main groups of fuel cells are listed below:

a) Polymer electrolyte fuel cell (PEFC) or proton exchange membrane fuel cell (PEMFC).
Here, the electrolyte is a polymer ion exchange membrane that is very good at
conducting protons often combined with an expensive platinum catalyst. These fuel
cells are a good option for automotive and portable applications as they are best suited
for fast start up and shut down situations.
b) Phosphoric acid fuel cells (PAFC). In this fuel cell, concentrated phosphoric acid is
used as the electrolyte. The design and power outputs make them suitable for buses
and large stationary applications.
c) Alkaline fuel cells (AFC). The electrolyte is essentially a potassium hydroxide solution.
These fuel cells are often used for expensive missions and critical applications such as
the USA space programme.
d) Molten carbonate fuel cells (MCFC). These highly specialised fuel cells use a
combination of high temperature alkali carbonate (sodium or potassium) as an
electrolyte and can use a wide range of fuel types. MCFC are best suited to large
stationary power applications.
e) Solid oxide fuel cells (SOFC). With SOFCs, the electrolyte is a solid non-porous ceramic
based metal oxide often Yttria doped Zirconia material. Because SOFCs operate at high
temperature, a wide range of fuels can be used without having to specially pre-treat
the fuel.

Fuel cell Operating Electrical

Fuel type Applications
type temperature efficiency
Most hydrocarbon Large (100’s of kW to mW)
MCFC ~ 550 – 700°C ~ 50 to <70%
based fuels stationary power generation

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Fuel cell Operating Electrical

Fuel type Applications
type temperature efficiency
Most hydrocarbon Small (<1kW) to large (mW)
SOFC ~ 450 – 1000°C ~ 45 to <70%
based fuels stationary power generation
AFC ~ 150 – 200°C ~ 40% Pure hydrogen Space exploration
Buses, trucks & large
PAFC ~ 100 – 220°C ~ 35 to 40% Pure hydrogen
stationary applications
PEFC/ Passenger cars & mobile
~ 80°C ~ 30 to 35% Pure hydrogen
PEMFC applications
Table 7-34 Tabulated data of various fuel cells

7.15 The Electrolytic Cell

In this type of cell electrical energy is required to bring about an otherwise non-spontaneous chemical
reaction. Typical applications include the extraction of metals from their ores, where the electrolyte
may be molten, for example, sodium, aluminium, or aqueous for copper or zinc. Another widely
encountered use is for electroplating, for decoration, or improving the resistance to corrosion. For
example, the chromium plating of automobile bumper bars.

In all cases the energy source is a battery or a generated supply of direct current (DC). The
electrochemistry is the same as for voltaic or galvanic cells, with half reduction reactions occurring at
the cathode, and half oxidation reactions at the anode. Figure 7-12 and Figure 7-13 illustrate the
extraction of sodium metal from molten NaCl, and the electroplating of nickel.

Figure 7-121 Electrolysis of molten sodium chloride. Cl- ions are oxidized to Cl2(g) at the anode, and Na+ ions
are reduced to Na(l) at the cathode.

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Figure 7-131 Electrolytic cell with an active metal electrode. Nickel dissolves from the anode to form Ni (aq
2+ .
)

At the cathode Ni (aq

2+
)
is reduced and forms a nickel "plate" on the cathode.

In the above cell nickel is electroplated on to the article (the cathode). The electrolyte is aqueous
NiSO4, and the anode pure nickel, which dissolves and replenishes the supply of Ni2+ to the
electrolyte.
2+
Cathode reaction (reduction): Ni (aq) + 2e 
→ Ni (s)

2+
Anode reaction (oxidation): Ni (s) 
→ Ni (aq) + 2e

7.16 Quantitative Aspects of Electrolysis

Consider the following half reduction reactions:

i. Na + + e  → Na
ii. Cu 2+ + 2e → Cu
3+
iii. Al + 3e  → Al

The stoichiometry of these reactions shows how many electrons are needed to bring about the
reduction.
One mole electrons ≡ 1 mole Na
Two moles electrons ≡ 1 mole Cu
Three moles electrons ≡ 1 mole Al

The quantity of charge Q is measured in Coulombs, which is the quantity of charge passing a point in
a circuit in one second, when the current is 1.0 ampere. Thus:

Q = It (7-19)
Where Q = quantity of charge in Coulombs
I = the current in amperes
t = the time in seconds

At this point it is useful to define certain electrical quantities in order to verify the units.

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i. The volt: is the potential difference required to impart 1 Joule (J) of energy to a charge of 1
Joule J
Coulomb (C). Thus, 1 Volt = 1 =1 .
Coulomb C
ii. Electric current is formed by electric charges in motion; it is equal to the quantity of electric
charge passing a given point per unit time.
iii. Ampere: is that steady current, which flowing in two infinitely long, straight, parallel
conductors of negligible cross sectional area (CSA) placed 1 metre apart in a vacuum produces
a force between them of 2 × 107 N / m 2 length of conductor.
iv. The Faraday, F is the charge on 1 mole of electrons.
𝐹𝐹 = 𝑁𝑁𝑁𝑁
= 6.022 × 1023 × 1.6 × 10−19
= 96485 𝐶𝐶. 𝑚𝑚𝑚𝑚𝑚𝑚 −1
= 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐

The relationship between charge, the amount of reactant, and the amount of product produced by
electrolysis is illustrated by the schematic in Figure 7-14.

Figure 7-141 Relationship between charge and amount of reactant and product in electrolysis reactions. This
flowchart shows the steps relating the quantity of electrical charge used in electrolysis to the amounts of
substances oxidized or reduced.

7.16.1 Faraday’s Laws

In a galvanic cell, a typical example being a battery or a corrosion cell, the anode will spontaneously
dissolve according to the half oxidation equation:
X → X n + + ne (7-20)
where X is the metal, X n + is the product of oxidation of the metal, that is the cation and n is the valency
or charge on the cation.

Conversely in an electrolytic cell, the anode will not dissolve spontaneously, and an external source of
energy will be required to bring about this reaction. The resulting cations will be reduced to the metal
at the cathode as illustrated in the half reduction equation (7-21):
X n + + ne → X (7-21)
It will be observed that equation (7-21) is the reverse of (7-20); however in each case a metal is
oxidised or a cation is reduced.

Faraday observed that the mass of metal dissolved or deposited in a galvanic or an electrolytic cell
respectively, was proportional to the quantity of charge transferred in the cell. This will be evident by
inspecting equations (7-20) and (7-21), where the quantity of charge ne is the number of moles of
electrons, the total charge being measured in coulombs. This observation forms the basis of Faraday’s
law.

Thus the mass of metal w ∝ the quantity of charge Q transferred, namely ne,
and thus w ∝ It, since from (7-19), Q = It

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Since 1 mole of electrons has a charge of 1 Faraday, from equations (7-20) and (7-21) it can be seen
that:

n moles of electrons → 1 mole of metal X

ie nF coulombs of charge → 1 mole of metal X → M g of metal X

M
∴ 1 coulomb of charge → g of metal X,
nF
and since Q = It, Q coulombs of charge → ItM/nF g of metal X.

Hence the weight of metal deposited or corroded,

ItM
W= (7-22)
nF
where,

w = weight in grams
I = current in amperes
t = time in seconds
n = moles of electrons = valency of metal ion
F = Faraday = 96,485 coulombs/mole
M = molar mass in g/mole
Equation (7-22) is a quantitative statement of Faraday’s law, which is useful for determining weight
losses due to corrosion, as well as the mass of metal obtained from electro-refining processes as
outlined in section 7.17.

Equation (7-22) may be expressed using current density i instead of current I,

current I
where i=
area of corroding surface A

Thus
iAtM
w= (7-23)
nF
The SI units of current density are amperes/m2. It should be noted that current density i is more
representative of corrosion rate than current I, and discussed in more detail in section 8.11.

Example 2.4 Calculate the number of grams of aluminium produced in 1.0 hour by the electrolysis of
molten AlCl3 if I = 10.0A.

Solution
3+
The half-cell reaction is: Al(l) + 3e 
→ Al(l) 

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Chapter 7: Electrochemistry

I = 10.0 A
Q = It
= 10.0 × 60 × 60
= 36000C

3 Faradays of Charge → 1 Mole Aluminium

i.e. 3 x 96488C → 27g Aluminium

27 × 36000
∴ 36000𝐶𝐶 → 𝑔𝑔 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴
3 × 96488
→ 3.36 𝑔𝑔 𝑜𝑜𝑜𝑜 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴

7.16.2 Electrical Work

Faraday discovered the relationship between the free energy change ∆G, the cell potential difference
E, and the charge transported, nF. Under standard conditions, the galvanic cell potential is E°, and
therefore
∆G ˚ = -nFE (7-24)
Under non-standard conditions,

∆G = -nFE (7-25)
Note the minus sign in equations (7-24) and (7-25), which indicates the spontaneous nature of the
reaction. Note also the dimensional consistency of these equations illustrated below.

∆G (J/mol) = F (C/mol) x E (J/C).

The maximum useful work that can be obtained from a voltaic cell is:

wmax = −nFE
For an electrolytic cell,
wmax = nFEexternal
Note that E for a non-spontaneous reaction is negative, and hence the wmax is positive for an
electrolytic cell.

To force the process to occur, Eexternal > Ecell , that is, the external electrical source is doing work on the
cell. Electrical work is expressed in Joules, where 1 J = 1 Watt ×1 second. The widely used unit of
electrical work in industry is the kilowatt hour (kWh).

= 1000Watts × 60s × 60s

1kWh
= 3.6 ×106 J

Example 2.5 Calculate the number of kWh of electricity to produce 1000kg of aluminium by
3+
electrolysis of Al(l) if the applied voltage is 4.5V.

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Solution
3+
The half cell reaction is: Al(l) + 3e 
→ Al(l) 
From, 1 mole Aluminium requires 3 Faradays of Charge
i.e. 27g of Aluminium requires 3 x 96499C = 289464C
289464
Thus, 1g of Aluminium requires C
27
289464 × 1000 × 1000
∴ 1000kg of Aluminium requires C = 1.07 × 1010 𝐶𝐶
27
But 𝑤𝑤 = 𝑛𝑛𝑛𝑛𝑛𝑛𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒
where n F = Total number Coulombs = 1.07 × 1010 C
∴ 𝑤𝑤 = 1.07 × 1010 C × 4.5 J/C = 4.82 × 1010 J
4.82 × 1010 J
∴ kWh = = 1.34 × 104
3.6 × 106 J/kWh

7.17 Aluminium Production

The three main stages are:

i. Mining the bauxite ore

ii. Refining the bauxite to pure alumina
iii. Smelting alumina to aluminium metal

The flow sheet for refining and smelting is attached.

Figure 7-153 Integrated process flow diagram. Relative amounts of raw materials shown are typical ranges
and refer to the requirements for the production of one tonne of aluminium.

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7.17.1 The Ore

Bauxite is mined at Weipa in north Queensland. It consists of hydrated alumina Al2O3·3H2O with large
quantities of iron oxides, and smaller quantities of silica SiO2 and titanium dioxide TiO2. After mining,
the ore is crushed ready for refining.

7.17.2 The Hydrometallurgy of Refining

The bayer process consists of digesting the crushed bauxite with caustic soda solution, which
dissolves the alumina, leaving all the impurities in the solid state. The liquor is filtered, and the soluble
aluminium component is separated from the impure residue. It is the amphoteric nature of the
alumina which makes separation possible, alumina being readily soluble in NaOH:
→ 2Al ( OH )4(aq) + 2H 2(g) .
− −
Al2O3 ⋅ 3H 2O (s) + 2H 2O (l) + 2OH (aq) 
Typical operating conditions are with caustic soda solution concentrations from 100-300g/L,
operating temperatures 150-250°C, and operating pressures from 10-40 atmospheres. After filtration
the soluble aluminium in the form of sodium aluminate NaAl ( OH )4 is precipitated as pure hydrated
alumina with the alumina crystals. These act as nuclei for Al2O3 precipitation. The purified Al2O3·3H2O
is filtered off, and the NaOH reclaimed.

7.17.3 Calcining the Alumina

This is the term used to describe the process where the hydrated alumina is heated to high
temperatures to remove all the water of hydration and produce anhydrous Al2O3.

  
Al2O3 ⋅ 3H 2O 
150 C
→ Al2O3 ⋅ H 2O + 2H 2O 
450 C
→α Al2O3 + H 2O 
1250 C
→ γ Al2O3

7.17.4 Electrolytic Reduction

This operation is carried out by the Hall-Hérault process, because the melting point of Al2O3 is very
high at 2045°C, which is too high for efficient operation. The principle of the Hall-Hérault process is
to dissolve the alumina in inert molten solvent with a lower melting point. The mineral cryolite
Na3AlF6 with a melting point of 1012°C was chosen.

The cell operates at about 950°C using an electrolyte or cryolite with 6-8% Al2O3, at a voltage of 4.5V.
The decomposition of the alumina accounts for 1.6 volts, another 1.6 volts to maintain the
temperature of the bath, the remainder for voltage drops due to inefficient contacts, and over
voltages.

The cell anode and cathode is carbon, manufactured in-situ.

Cathode reaction: Al3+ + 3e 

→ Al
Anode reaction: 3C + 6O 2− 
→ 3CO 2 + 12e
Cell reaction: 3C + 2Al2O3 
→ 4Al + 3CO2

This is the net cell reaction. The electrolytic cell is illustrated.

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Figure 7-167 Aluminium reduction process.

7.17.5 Energy Requirements

These are very high, and add greatly to the cost of production. The major contributing factors are:

i. The extremely high stability of Al2O3 as reflected in the high melting point of 2045°C.
ii. The high temperatures and pressures required to purify the bauxite, and manufacture the
carbon electrodes.
iii. The high electro-chemical equivalent, and low density of Al, relative to other metals illustrated
below in Table 7-4. The electrochemical equivalent is the mass of substance liberated by the
passage of a unit quantity of electricity-units kilogram/Coulomb.

Atomic weight Valency Density Electrochemical

Metal
amu g·cm-3 equivalent
Aluminium 27 3 2.7 9.32 × 10−8
Copper 63.5 2 9.0 32.9 × 10−8
Nickel 58.7 2 8.9 30.4 × 10−8
Silver 107.9 1 10.5 111.8 × 10−8
Zinc 65.4 2 7.1 33.9 × 10−8
Table 7-41 Electrochemical equivalents of some common metals

iv. Low electrolytic cell efficiency in the order of 40%.

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7.17.6 Recycling

About 22% of all aluminium produced is used as packaging. Bearing in mind the high energy cost/kg
of aluminium there is a compelling case for recycling.

Figure 7-171 What it takes to produce 1000kg of aluminium.

7.18 Questions and Answers – Electrochemistry and Cells

Q2.1 A voltaic cell utilizes the following reaction, and operates at 298 K:

3 Ce4+(aq) + Cr(s) → 3 Ce3+(aq) + Cr3+(aq)

(a) What is the emf of the cell under standard conditions?

(b) What is the emf of the cell when [Ce4+] = 2.0 M, [Ce3+] = 0.010 M, and [Cr3+] = 0.010 M?
(c) Sketch a schematic diagram for the cell, marking in the following features:
• the electrode materials,
• the direction of electron flow,
• the anode and cathode,
• the ions present, and their migration direction,
• the charge on the anode.

Q2.2 An aqueous Chromium chloride solution is electrolysed using chromium electrodes. A current
of 0.2 A flows for 1447 s. The increase in mass of the cathode is 0.052 g.

(a) How many coulombs of electricity are used?

(b) How many moles of electrons are transferred?
(c) How many moles of chromium are liberated?
(d) What is the charge on the chromium ion?

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Chapter 7: Electrochemistry

(e) Write a balanced equation for the half reduction reaction.

A2.1

(a) From the table of standard reduction potentials, the two half cell reactions may be written as:

3 Ce4+(aq) + 3e → 3 Ce3+(aq) E0 = 1.61 V --------------(1)

Cr(s) → Cr3+(aq) + 3e E0 = 0.74 V --------------(2)

Adding (1) and (2) gives:

3 Ce4+(aq) + Cr(s) → 3 Ce3+(aq) + Cr3+(aq) E0cell = 2.35 V

(b) Using the Nernst equation:

Ecell = E0cell - 0.0592/3 log {[Ce3+]3 [Cr3+]/[Ce4+]3}, and

Given [Ce4+] = 2.0 M

[Ce3+] = 0.01 M
[Cr3+] = 0.01 M

∴ Ecell = 2.35 – 0.0592/3 log {[0.01]3 [0.01]/[2.0]³}

= 2.35 – 0.0197 log 1.25 x 10-7
= 2.49 V

(c) The anode material will be chromium, since it must supply the source of chromium ions. The
cathode will be platinum, since it is unlikely that cerium would be available. Reduction of
cerium (iv) to cerium (iii) will readily occur at an inert platinum electrode.

• The direction of the electron flow is from anode to cathode.

• The diagram of the cell below shows the position of the anode and the cathode.
• The cations present will be attracted to the platinum cathode. Details of the anions
present are not given, but they are likely to be nitrate or sulphate, since these salts of
chromium and cerium are water soluble. The anions will migrate to the chromium anode.
• The charge on the anode will be positive (+).

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A2.2

(a) The number of coulombs Q = It

= 0.2 A x 1447 s = 289.4 C

(b) One faraday is the charge on 1 mole of electrons = 96485 C

∴ 289.4 C = 289.4 C/96485 C/mol

= 0.003 mol of electrons

(c) The mass of chromium deposited was 0.052g

∴ number of moles, nCr = 0.052g/52g/mol

= 0.001

(d)From the data above, 3 moles of electrons are required to deposit 1 mole of chromium.
Hence the charge on the chromium ion is 3+. The half reduction is therefore:

Cr3+ + 3e → Cr

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References
1 Brown, Theodore L., H E. Lemay, Jr, and Bruce E. Bursten. Chemistry the Central
Science. 10th ed. Upper Saddle River, NJ: Pearson, Prentice Hall, 2006.
2 Callister, Jr., William D. Materials Science and Engineering an Introduction. 7th ed.
York, PA: Techbooks, 2007.
3 Integrated Process Flow Diagram. Comalco.
4 "How Does a Fuel Cell Work." Ceramic Fuel Cells Limited. 2007. 28 Jan. 2006
<www.cfcl.com.au>.
5 James, Maria, Robert Stokes, Wan Ng, and Jennifer Moloney. Chemical Connections.
2nd ed. Vol. 2. Milton, Queensland: John Wiley & Sons, 2000.
6 "Lithium-Ion Batteries Image Gallery." How Stuff Works. Discovery Communications
Inc. 26 June 2008 <http://www.howstuffworks.com>.
7 Aluminium Reduction Process. Rio Tinto.

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Chapter 8: Corrosion

Corrosion

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Chapter 8: Corrosion

8.1 Introduction
Corrosion is defined as the oxidation of a metal in its environment. All metals except the noble metals
will oxidize in air. The corrosion of iron and steel is of the greatest economic importance. It has been
estimated that 20% of all steel manufactured is used to replace corroded steel.

The oxidation of metals is spontaneous and irreversible, thermodynamically speaking. Whilst some
metals, for example, certain stainless steels, titanium and aluminium oxidize, producing adherent and
coherent oxide coatings on their surface, which prevent further oxidation, rust on steel is not coherent
and simply causes further attack to occur.

8.2 The Galvantic Series

The table of standard reduction potentials, as discussed in 2.8 Standard Reduction Half Cell Potentials,
lists half cell potentials of pure metals in 1.0M solutions of their ions at 25°C. When dealing with the
corrosion of alloys in a range of aqueous environments, this table is of little use. Consequently
galvanic series have been developed for metals and alloys in sea water. It’s theoretical basis, however
is the same as for the table of standard reduction potentials. Such a table ranks alloys in order of their
ease of oxidation in sea water, and is thus a useful guide for alloy selection in a marine environment.

A typical galvanic series is illustrated in Figure 8-1.

8.3 Rusting of Steel

Moisture and air are necessary if iron is to corrode. We will consider the half reactions involved in
this process.

i. Oxidation of Fe to Fe2+:
: Fe → Fe 2+ + 2e E =
0.44V (8-1)

: Fe 2+ → Fe3+ + e E =
−0.771V (8-2)

+,: Fe → Fe3+ + 3e E =
−0.331V (8-3)
ii. The reduction of O2 in acidic and basic media

: O 2 + 4H + + 4e → 2H 2O E =
1.23V (8-4)

: O 2 + 2H 2O + 4e → 4OH − E =
0.40V (8-5)

The common process of oxidation involves 2×+:

2Fe + O 2 + 4H + → 2Fe2+ + 2H 2O E =
1.67V (8-6)

The Fe2+ undergoes further oxidation in the presence of moisture to form rust:

2+ +
4Fe(aq) + O 2(g) + 4H 2O(l) + 2 xH 2O(l) → 2Fe2O3 ⋅ xH 2O(s) + 8H (aq)
 (8-7)
Rust

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Figure 8-11 Potential of metals in sea water. Corrosion potentials of various materials in flowing sea water
(2.5-4m/s) at temperatures in the range 10-26°C. The hatched symbols indicate potentials exhibited by
stainless steels in acidic water such as exists in crevices.

Figure 8-2 illustrates the mechanism for the corrosion of steel under a drop of water.

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Chapter 8: Corrosion

Figure 8-23 Corrosion of iron in contact with water.

Figure 8-3 illustrates how the presence of a metal more reactive than steel offers cathodic protection
to the steel. This topic is discussed further in section 8.11.6.

Figure 8-33 Cathodic protection of iron in contact with zinc.

Fig. 3.4 illustrates how the presence of a break in mill scale on a steel plate allows corrosion to occur
in the damaged site.

Figure 8-41 Corrosion cell. Steel with broken mill scale in sea water.

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8.4 Passivity
Some metals are naturally passive towards corrosion, for example, Cr, Al, Ni, Ti, stainless steels and
Al due to the formation of coherent oxide films on their surfaces. However, under certain conditions
the protective coating can be damaged, and corrosion rates can then be catastrophic.

8.5 Factors Increasing the Rate of Corrosion

i. The velocity of the liquid corroding medium.
ii. Increase in temperature.
iii. The composition of the corrosive medium, in particular with respect to H+ and Cl-.
iv. The presence of residual stresses in the metal.
v. The presence of stress points, which can be anodic.

8.6 Types of Corrosion

8.6.1 Uniform Corrosion

Uniform corrosion corresponds to that type of corrosion involving the greatest weight loss. This type
of corrosion is a common sight where steel structures exposed to the environment rust over their
entire surface. The weathered surface appearance may be encouraged for aesthetic reasons, and is
common where copper or steel is employed as a building material or for architectural decoration.
Corrosion will be more rapid in a marine environment, either in salt laden air or from direct contact
with seawater. Pipes buried in soil are also particularly vulnerable to uniform attack. Alternatively
uniform corrosion may occur on the inside of pipes carrying fluids, where it is not visible, but where
its detection and monitoring is relatively simple, for example by measuring thickness change
ultrasonically as discussed in section 8.12.

Exposed surfaces may be painted or cathodically protected. Uniform corrosion results from the
existence of small anodic and cathodic regions that occur naturally on the surface of metals as a result
of localized stresses and minor differences in composition. These irregularities arise as a
consequences of manufacturing methods. Figure 3-55 illustrates these surface defects, with cathodes
marked positive and anodes negative. Corrosion occurs at the anodic sites, from which electrons flow
to the cathode, providing cathodic protection in these small areas.

Figure 8-55 An impression of local anodes and cathodes of corrosion cells occurring on the same metal
surface.

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8.6.2 Galvanic or Bimetallic Corrosion

8.6.2.1 Introduction

This type of corrosion occurs when two metals with different susceptibilities to oxidation are coupled
together. These differences can be quantified by reference to the table of standard reduction
potentials in Appendix G. Those metals with the largest negative reduction half potential will corrode
more readily than those metals with a more positive reduction potential.

The galvanic series for metals and alloys in seawater is a more useful practical guide than the table of
standard reduction potentials for predicting the tendency of metals to corrode. The galvanic series
illustrated in Figure 8-1. (See also section 8.2)

8.6.2.2 Electrochemistry

Before considering examples of galvanic corrosion it would be useful to review briefly the nature and
mechanisms associated with this type of corrosion. Figure 8-6 illustrates the electrochemical
reactions that occur when zinc is exposed to an aqueous solution.

Figure 8-617. Corrosion of zinc in aqueous solution

We will now consider the corrosion products of zinc in (i) neutral aerated water and (ii) in acidified
water.

i. The anode half reaction is:

2 Zn (s) → 2 Zn 2+ (aq) + 4 e (8-8)

The cathode half reaction is:

Ο 2(g) + 2 H 2 O + 4 e → 4 ΟΗ − (aq) (8-9)

Adding the two half reactions gives:

2 Zn + Ο 2 + 2 H 2 O → 2 Zn 2+ + 4 ΟΗ − → 2 Zn (OH) 2 (s) (8-10)

The net reaction indicates that zinc dissolves as illustrated by the corroded regions near the
top of the metal, forming an insoluble hydroxide of zinc on the surface.

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Chapter 8: Corrosion

ii. The anode half reaction is the same as (8.8) above, that is zinc will dissolve forming zinc ions.

There are two possible cathode half reactions in this situation, the first being the reduction of
oxygen to form hydroxide ions as in (8.9) above. The second cathode half reaction is the
reduction of hydrogen ions from the acid, to gaseous hydrogen, and given by:

2 Η + (aq) + 2 e → H 2 (aq) (8-11)

By adding this reaction to the half oxidation, the overall reaction is:

Zn + 2 H + → Zn 2+ + Η 2 (8-12)

The fact that two overall reactions are possible for this combination, confirms that in acid
environments metals will generally corrode more rapidly than in neutral media.

Some further general deductions can be made by further reference to Figure 8-6, namely:

• Electrons drift away from the anode to the cathode.

• The cathode, being negative, will attract cations, in this case H+, which then react with
dissolved O2 forming OH− , or with each other, forming hydrogen gas,

Η + + H+ → H2 (8-13)
• The anodic regions corrode.

• The cathodic regions are protected from corrosion.

• The corrosion products may form a loosely adherent layer if solid, on the surface, or
be evolved as bubbles, if gaseous.

Figure 8-7 illustrates a piece of mild steel immersed in a mildly acidic solution. Note that
hydrogen gas is liberated as bubbles from the cathodic regions and the steel corrodes rapidly
2+
from the anodic areas, where Fe(s) → Fe (aq) +2e
Note that if the environment was seawater, with pH approximately 8, the cathodic corrosion
product would be insoluble iron hydroxide Fe(OH)2 and not hydrogen. This reaction product
is analogous to the zinc hydroxide discussed above in connection with the rusting of steel, and
detailed in section 8.3.

Figure 8-717: Corrosion of steel in acidic media

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8.6.2.3 Prevention Techniques

In dealing with galvanic corrosion there are a range of preventative actions that may be taken to
minimize its occurrence, and these are listed below:

(a) Select metals that are close together in the galvanic series.

(b) Electrically insulate the contact surfaces between the metals.

(c) Paint or coat the metals to exclude air and moisture.

(d) Cathodically protect the structure.

(e) Make the area of the anode as large as possible. The following discussion elaborates on the
relevance of surface area A in this context.

The surface area effect can be a significant consideration when designing systems that will minimize
corrosion.

In any system, the anodic current must equal the cathodic current, that is: Ianodic = Icathodic

When the above equality is expressed in terms of current density i, given that
current
i= , Ianodic = i a × A a = Ianodic = i c × A c
area
Ac
ia = ic (8-14)
Aa
Equation (8-14), implies that the anode current density increases when the denominator in the ratio
𝐴𝐴𝑐𝑐
is small. Since the rate of corrosion increases when the anode current density is high, making the
𝐴𝐴𝑎𝑎
anode surface large relative to the cathode surface area, will minimize the severity of corrosion.

The situation may therefore be summarized as the ratio of cathodic to anodic surfaces is an amplifying
𝐴𝐴
factor for corrosion when 𝑐𝑐 ≫ 1 and a retarding factor when ≪ 1.
𝐴𝐴𝑎𝑎

The implications of surface area ratio are particularly important in various forms of corrosion such
as pitting and stress corrosion cracking, where a large ratio is a serious aggravating factor.

The deleterious effect of a particular anodic current concentrated over a small area will be obvious
when this effect is considered for a combination of steel and copper employed as plate or rivets,
illustrated in Figure 8-8.

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Figure 8-817: (a) Corrosion of steel rivets in copper plate, (b) Corrosion of steel plate with copper rivets

It will be obvious that the combination in (a) with the more readily corroding anodic steel rivet with
the smaller surface area, will corrode rapidly, causing premature failure of the joint.

The effect illustrated by the schematic diagram in Figure 8-8 is further illustrated in the photographs
of the same combination shown in Figure 8-9 and Figure 8-10.

Figure 8-92 Galvanic couples of iron and copper showing that when copper rivets (small cathodes) are
inserted into mild steel (large anode) the copper does not corrode, while the corrosion of the mild steel is
evenly distributed.

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Chapter 8: Corrosion

Figure 8-102 When iron rivets are inserted into copper sheet the iron rivets are badly corroded.

8.6.3 Differential Aeration, and Crevice Corrosion

This type of corrosion occurs in small crevices and in 'stagnant' areas, which give rise to regions of
depleted O2 levels. As a result, concentration cells develop, and corrosion is exacerbated. The
mechanism is complex, but it is known that Cl- in particular speeds up the process, in the presence of
depleted O2 levels.

As the process develops there is a build up of metal ions, usually Fe2+ and H+. pH differences can vary
greatly, the low pH values being particularly deleterious. Further-more the process is self sustaining,
and can lead to exponential increases of corrosion. Stainless steels can be particularly susceptible.

Examples of crevice corrosion are illustrated in Figure 8-11, Figure 8-12 and Figure 8-13.

Prevention can be maximized by:

i. Using welds rather than bolts or rivets, thus avoiding crevices.

ii. Removing accumulated deposits (areas of low O2).
iii. Modify design to avoid stagnant areas.

Electrochemical corrosion can occur as a result of concentration differences in electrolyte or oxygen,

which give rise to concentration cells. This type of corrosion occurs in crevices and recesses, and
under deposits of dirt or corrosion products. The stagnant region becomes depleted of oxygen, at
which point corrosion occurs, with the region being anodic.

The crevice must be wide enough for the solution or the air to penetrate. The electrons generated in
the crevice region will be conducted through the metal to participate in cathodic reactions. In many
aqueous environments, and particularly marine environments, the solution within the crevice has
been found to contain high levels of hydrogen ions and chloride ions, leading to a serious build up of
acid. Under these conditions corrosion can be very rapid indeed due to high current densities. Many
alloys that passivate like aluminium and stainless steel are particularly vulnerable to these conditions.
Figure 8-11 illustrates the mechanism of crevice corrosion.

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The mechanism of crevice corrosion may be explained in the following steps for stainless steel in
seawater. Refer also to Figure 8-11,

1. Assume the usual anodic and cathodic reactions,

Anodic M → M+ + e (1) usually : Fe → Fe2+ + 2e
Cathodic O2 + 2H2O + 4e → 4OH- (2)
2. The solution in the crevice is stagnant, and is therefore depleted of oxygen. Thus the cathodic
reaction is suppressed, but the anodic reaction continues, and as a consequence a high
concentration of metal ions build up. These are commonly Fe2+, and Cr3+.
3. To balance the increase in positive charge, negatively charged chloride ions, Cl- will migrate
into the crevice to restore the electrical charge equilibrium.
4. The cations and anions form salts FeCl2 and CrCl3, which then hydrolyse, liberating hydrogen
ions.
A typical reaction is, Cr3+ + 3H2O → Cr (OH)3 + 3H+
5. The build up of acid can be quite dramatic, and as a result the inside of the crevice will be
eaten away.
Many alloys that form a passivating film like 304 stainless steel are particularly susceptible to crevice
corrosion.

Crevice corrosion can be avoided by welding rather than riveting or bolting joints, by using non
absorbent gaskets, and by the regular removal of deposits. In addition it is possible to eliminate
crevice corrosion by designing vessels so that stagnant areas are avoided.

Figure 8-114

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Figure 8-125 An impression of crevice corrosion. An oxidation-concentration cell is set up as a result of the
difference between the level of oxygen under and outside the washer.

Figure 8-138 Stainless steel universal joint showing crevice corrosion and pitting in the region where the
rubber grommet fitted.

A very common example of crevice corrosion occurs in car door bottoms, where blocked drainage
holes cause the build up of residues and detritus. The tell-tale signs are lines of corrosion near the
bottom panel. This is illustrated in the figure below.

Figure 8-14

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8.6.4 Pitting Corrosion

This is a very localized type of corrosion, producing small pits and holes. This type of corrosion is also
caused by differential aeration. Note that protection can be achieved by using a sacrificial anode of
zinc or aluminium.

The mechanism of pitting corrosion is illustrated in Figure 8-15. This section should also be read in
conjunction with Figure 8-2, Figure 8-3 and Figure 8-4, which will further illustrate pitting corrosion
and cathodic protection.

Figure 8-158 The mechanism of pitting because of differential-aeration beneath a water droplet. (a) General
corrosion over the whole of the wetted metal surface depletes the oxygen levels in the adjacent electrolyte. (b)
Longer diffusion path for oxygen to reach the central area makes this the anode. Metal dissolution occurs in
the centre of the droplet and reaction of metal ions with hydroxyl ions formed at the edge generates a ring of
rust around the corrosion pit.

8.6.5 Intergranular Corrosion

The grain boundaries of metals have higher surface energy levels than regions inside the grains.
Further-more grain boundaries are regions where impurities accumulate, and hence become areas of
electrochemical activity. Stainless steels are susceptible to grain boundary activation when heat
treated in the range 500-800°C. For stainless steels with carbon content, chromium carbides Cr23C6
precipitate at the grain boundaries under these heat treatment conditions.

Protection can be achieved by:

i. Heat treating to higher temperatures to dissolve the carbides.

ii. Lowering the carbon content to <0.03%.
iii. Alloying the stainless steel with Nb or Ti which scavenge carbon.

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Figure 8-167 Intergranular cracks in 80/20 brass caused by exposure to ammoniacal solution.

Figure 8-177 Transgranular cracks in a Mg-7% Al alloy exposed to a chromate-chloride solution (x500).

Figure 8-184 Schematic illustration of chromium carbide particles that have precipitated along grain
boundaries in stainless steel, and attendant zones of chromium depletion.

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8.6.6 Selective Leaching

The most common form is the dezincification of α brass in the presence of corrosive chemicals. This
phenomena also occurs in certain alloys of Al, Fe, Co and Cr. The problem can be reduced by a careful
choice of alloy, matched to the particular environment.

This problem is exacerbated by high temperatures and chloride irons as well as differential aeration
and the zinc in the beta phase is attached first.

Figure 8-198 A dezincified leaded brass bolt, 12mm diameter. The corrosion penetrated to a depth of 3mm
and caused severe porosity and embrittlement.

Figure 8-208 Microstructure of a laboratory-prepared dezincified specimen of 60/40 leaded brass (x200,
ammonia/peroxide etch).

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Figure 8-218 A schematic illustration of the dezincified layers of the specimen shown in Figure 8-20.

8.6.7 Impingement and Erosion Corrosion

Fluids, or fluids with fine solid particles cause erosion corrosion when droplets impinge onto a metal
surface. Continuous impingement can lead to the production of cracks, which over time increase in
size and result in material failure. Surface asperities can lead to erosion of the surface, which over
time can result in accelerated corrosion. These events are illustrated in Figure 8-22.

Figure 8-223

In (a) impingement makes a crater with possible crack initiation. In (b) asperities form, which may
flake off. In (c) continuing impingement will further erode the damaged surface, and lead to crack
enlargement and pit formation.

Other scenarios for erosion corrosion are encountered when gaskets are poorly located in pipe
sections leading to impingement and erosion, as illustrated in Figure 8-23.

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Figure 8-233

Poorly designed joints in pipes can lead to premature onset of turbulent flow of fluid in the pipe,
followed by impingement, and then to erosion corrosion. If the fluid entrains solid abrasive particles,
corrosion will be more rapid. This is illustrated in Figure 8-24.

Figure 8-243

Figure 8-254 Impingement failure of an elbow that was part of a steam condensate line.

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8.6.8 Cavitation Corrosion

8.6.8.1 Introduction

Hydrodynamic cavitation is a phenomenon that accompanies the turbulent flow of fluids. There are
many examples in nature and in engineering, where the rapid change in hydrodynamic pressure gives
rise to the formation of bubbles under low pressure conditions. The subsequent collapse of the
bubbles under high pressure conditions releases large amounts of energy, and as a result the surface
upon which the collapse occurs may experience severe stress and erosion. A typical example in
marine engineering is associated with ship’s rudders and propellers, where this problem has serious
implications, both from an engineering and an economic standpoint.

8.6.8.2 Bubble Formation

When a liquid like water is confined in a closed vessel, evaporation of liquid molecules to form
gaseous molecules will occur, until the space above the liquid becomes saturated with vapour. At this
point equilibrium occurs, where the rate of evaporation equals the rate of condensation. This process
is illustrated for water in the equation, H2O(l) ↔ H2O(g) . The saturated vapour pressure of a liquid
depends upon three factors, (1) the temperature, (2) the liquid pressure, and (3) the value of the
molar enthalpy of vapourization of the liquid, which is a function of the strength of the intermolecular
bonding.

If the pressure on the liquid is reduced, the saturated vapour pressure is reduced, and the boiling
point is lowered as a consequence, since a liquid boils when its saturated vapour pressure equals the
pressure exerted on the liquid. For water the boiling point is 1000 C when the saturated vapour
pressure equals the external pressure, specifically the air pressure of 1 atmosphere or 101 kPa. The
saturated vapour pressure of water at selected temperatures is shown in the table below.

Temperature, 0 C Saturated vapour pressure, atm.

0 0.0060
5 0.0086
10 0.0121
15 0.0168
20 0.0231
25 0.0313
50 0.1217
100 1.000
Table 8-1

The relationship between svp, saturated vapour pressure and temperature is shown graphically in
Figure 8-26.

Figure 8-269

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From the Table 8-1, data for water, it can be seen that when the external water pressure is reduced
from 1.0 atmospheres to 0.0086 atmospheres the boiling point is reduced from 1000 C to 50 C ! Bubble
formation and cavitation erosion is illustrated in Figure 8-27.

Figure 8-273 illustrates bubble formation when a fluid experiences changes in pressure, with cavitation
corrosion as a result.

8.6.8.3 Cavitation in a Ship

The rudder and the propeller in an ocean going vessel are very susceptible to cavitation corrosion.
Cavitation inception occurs behind the rotating blade of the propeller, where a partial void or vacuum
will be produced. A low pressure bubble will form, which will be partly filled with water vapour and
possibly also with entrained air. The transfer of this bubble to a site of higher hydrodynamic pressure
will cause the bubble to collapse to a minute fraction of its original size. The gas will dissipate into the
surrounding liquid, and release a significant amount of energy. At the point of total collapse the
temperature of the vapour within the bubble may be several thousand Kelvin, and the pressure
several hundred atmospheres. A suggested mechanism for bubble collapse is illustrated in Figure
8-28.

Figure 8-2810

Cavitation not only causes mechanical erosion and breakdown of the material, but can also result in
a serious loss of thrust between the water and the propeller. This is illustrated in Figure 8-29, where
the entrained air at the tips of the propeller blades is clearly shown.

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Figure 8-2910

A ship’s rudder, placed directly behind the propeller to give the ship maximum maneuverability, is
particularly susceptible to erosion followed by corrosion. The erosion may be due to the turbulent
flow of the water around the rudder, and from the bursting cavitation bubbles from the motion of the
propeller. The impact of the bursting bubbles on the rudder will erode protective coatings such as
paint or passivating oxides, leaving the metal vulnerable to electrochemical corrosion attack. Certain
types of rudder design are particularly prone to cavitation, particularly the semispade design, due to
the gap between the horn and blade. This situation is depicted in Figure 8-30 and Figure 8-31, where
A = cavitation damage, B = rudder plate, C = rudder horn.

Figure 8-3011

Figure 8-3112

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8.6.8.4 Methods of Prevention

There are two main approaches for the control of cavitation erosion, (1) prevention by design, and
(2), containment, after the erosion has set in.

(1) Cavitation can be reduced significantly at the initial design stage. This technique requires a
detailed theoretical understanding of the physics and hydrodynamics of fluid flow around
vulnerable sections of the ship’s structure. Modelling with scaled replicas under simulated
conditions is part of the proven methodology, but the results need to be carefully analysed in
order to be valid. Rudder design and its location with respect to the propeller are other key
factors to optimize at the design stage.
(2) The use of cathodic protection and the application of protective coatings are the two most
common practices for containment. Cathodic protection will only suppress corrosion after the
original surface coating has been eroded away, and therefore treats the symptom and not the
cause.
Various coatings have been used such as cladding the rudder with stainless steel. Problems
with galvanic corrosion between the iron or steel of the rudder and the more noble stainless
steel have limited this approach.
The most successful coating to date is a composite glassflake-vinyl ester combination, where
the glass flakes provide excellent toughness and resistance to impact. Furthermore the
coating is an electrical insulator, which successfully prevents electrochemical corrosion
taking place. This coating can be applied to new rudders as well as those previously damaged
by cavitation erosion. Current information indicates this type of coating can provide long term
protection.

In conclusion it can be said that prevention of cavitation is quite difficult to achieve in practice, and
requires a combination of approaches as outlined above in order to guarantee good success.

8.6.9 Stress Corrosion

A material under external or internal stress will always be more vulnerable to corrosion, particularly
if the environment is chemically aggressive. For example, stressed stainless steel is susceptible to
attack in the presence of Cl-, while brass will corrode in the presence of ammonia.

The best way to eliminate this type of corrosion is to remove stresses by appropriate heat treatment
prior to exposure to corrosive medium. If the stress is due to external loads, increasing the cross-
sectional area will reduce the stress.

Figure 8-326 Stress Corrosion fatigue.

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8.6.10 Stray Current Corrosion

Stray electric currents are readily carried by metal structures, and may leave the structure at a point
of least resistance. If this occurs severe corrosion will occur at the site where conventional current
leaves the structure. The flow of electrons is into the metal structure away from the anode site.
Conventional current passes in the opposite direction to electron flow. The anode is that site where
electrons flow into the metal. The site to which the electrons flow becomes a cathode. This is
illustrated in Figure 8-33.

Figure 8-332

Stray current sources can emanate from buried earth conductors, and from incorrectly connected
welding equipment.

For a steel ship being fitted out from a slip or wharf, stray currents can be generated from welding
equipment if the welding equipment is not correctly connected. The stray currents will be much
greater than the cathodic protection current, and will therefore cause severe corrosion where the
conventional current leaves the ship’s hull. When the conventional current enters the ship’s hull, the
entry point will be a cathode. If the hull is coated with an oil based paint, the formation of alkaline
cathode products will saponify the paint, and cause blistering. The cathode reaction is: O2 + 2H2O +
4e → 4OH⁻. This reaction produces a localized concentration of OH⁻., resulting in an increase in
alkalinity. If the steel is coated with oil based paint, the alkalinity will attack the paint by a
saponification reaction, and the paint will blister. This will make the steel more susceptible to
corrosion. The saponification reaction is:

C17H35COOH + NaOH → C17H35COONa + H2O

oil water soluble soap

These areas will then become susceptible to corrosion. Figure 8-34 illustrates the incorrect ways to
connect welding equipment.

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Figure 8-341

If the welding is done with the positive electrode, and no return cable, the ship’s hull will become an
anode, and the stray current will cause corrosion where it leaves the ship’s hull. This is the situation
with the left hand connection.

In the right hand connection, the welding is done with a negative electrode, and without a return
cable. The ship’s hull becomes a cathode, with possible damage to the paint as referred to above.

Figure 8-35 represents a correct method for connecting off-shore welding equipment. This time the
equipment is not earthed, and a low resistance, large diameter return cable is used. This ensures that
the sea and the wharf do not act as a conductor, since the return current will be facilitated to pass
through the lower resistance return cable. With this configuration, no stray current corrosion will
occur.

Figure 8-351

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8.6.11 Bacterial Corrosion

8.6.11.1 Introduction

Research on oil rigs in the North Sea has indicated that the extent of corrosion observed on these
structures cannot be accounted for in its totality by electro-chemical mechanisms entirely. Sulphur
metabolizing bacteria, both anaerobic and aerobic produce hydrogen sulphide and sulphate ions
respectively. Further bacterial and chemical processes in natural waters produce a large range of
compounds including sulphuric acid, which will corrode steel structures.

Bacteria are commonly found in sea mud, crude oil and frequently occur at interfaces between liquids
and solids.In these processes the bacteria set up their own electro-chemical cell in which a portion of
the metal surface forms the anode of the cell, where oxidation occurs. Structures called tubercles form
in which bacteria pit and corrode the metal surface.

The Figure 8-36 illustrates the formation of the electro-chemical cell by Gallionella.

Figure 8-361

8.6.11.2 Bacteria

Some sulphate reducing bacteria produce hydrogen sulphide gas which can cause sulphide stress
cracking.

In the presence of oxygen, aerobic bacteria like Thiobacillus thiooxidans will utilize energy by
metabolizing the oxidation of sulphur compounds to sulphuric acid as,

2S + 2H2O + 3O2 → 4H+ + 2SO42-

, leaving the steel surface to corrode, ultimately forming rust and surface pits.

Layers of anaerobic bacteria can exist in the inner parts of the corrosion products, while the outer
parts are inhabited by aerobic bacteria. Bacterial colonies and deposits can form concentration cells,
causing and enhancing galvanic corrosion. It should also be noted that certain types of bacteria will
attack plastics and concrete, as well as metals and alloys.

The adaptability of bacteria, and their ubiquitous nature presents yet another hurdle for the corrosion
scientist, particularly for buried structures on land and at sea. One of many methods for controlling
bacterial corrosion is the use of biocides or inhibitors such as benzalkonium chloride, widely used in
the oilfield industries.

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The figure below illustrates the random nature of bacterial corrosion on the surface of a produced
water system flange, from an oil processing plant. The rate of growth of bacteria is a first order
process; that is the rate of growth is proportional to the quantity of bacteria initially present. This
relates to an exponential growth rate of the form N = N0ekt, where N = the quantity at time t, N0 = the
quantity at t = 0, and k = a constant. The mode of attack illustrated below indicates a possible colony
of bacteria, due to its circular cross-section, and would account for the aggressive nature of the
corrosion. The reported rate of 10 mm per year is an astronomically high rate by any standard.

Figure 8-3713

8.7 Hydrogen Embrittlement

Because H2 is a very small molecule it can form interstitial solid solutions in metals by diffusing into
the grains. The presence of H atoms at interstitial sites can impede the motions of dislocations which
pile up, leading to brittle fracture. Thus, certain otherwise ductile materials become embrittled as in
stress corrosion.

Hydrogen embrittlement is particularly problematic in steel tanks which store acids. In such cases
atomic (nascent) H is often part of the environment. Other examples occur in heat treatment furnaces
and welding, when even very low concentration of H in the atmospheres can produce serious
mechanical weakening. Martensitic steels are very vulnerable, whilst the more ductile face-centred-
cubic metals are more tolerant.

Effects may be reduced by:

i. Replacing the alloy with one of lower tensile strength, and higher ductility, to increase the
safety margin.
ii. Eliminate the source of H.
iii. 'Bake' the alloy to out gas H2(g).

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8.8 Corrosive Environments

i. Atmosphere O 2 , H 2O
ii. Acids H + , Cl− , SO 24−

iii. Bases NaOH, Ca ( OH )2 , NH3

iv. Molten salts
v. Aqueous salts sea water

vi. Soils O2 , H 2O, salts, bacteria

8.9 Types of Surface Oxides on Metals

The formation of oxide films on metal surfaces under wet or dry conditions will generally reduce the
rate of corrosion by reducing the area of metal exposed to the oxidising environment.
The Pilling-Bedworth ratio determines the type of oxide coating on the metal substrates, and whether
it will passivate the surface. (See Figure 8-38)
𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑝𝑝𝑝𝑝𝑝𝑝 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎
P-B ratio = 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑝𝑝𝑝𝑝𝑝𝑝 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎
= Moxide x ρmetal/n x Mmetal x ρoxide
Where M = atomic or molecular mass,
ρ = density, and,
n = number of metal atoms in the oxide.

If the P-B ratio is less than 1, the oxide will experience tensile stresses, and will crack and become
porous.

If more than 2, compressive stresses will develop as the thickness of the film increases, and the film
will flake off, thus offering no protection.

If the ratio is equal to, or close to 1, the film is adherent, and non-porous, and will offer protection.
Good examples of protective oxide films are those on aluminium, titanium, and stainless steels. Values
of P-B ratios for magnesium, aluminium, and iron are 0.8, 1.3, and 2.1 respectively.

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Figure 8-383

8.10 Anodic Corrosion Sites

Stressed materials, for example metals that have been cold worked and deformed, possess a higher
free energy than unstressed materials, and will corrode more rapidly relative to unstressed locations
within the same sample. Another source of stress in a polycrystalline metal are the grain boundaries.
Grain boundaries, like metal surfaces have free unbonded electrons, which will contribute to
reactivity, relative to the body of the crystal. Furthermore the random juxtaposition of crystals of
different orientations, in close proximity, leads to compressive and tensile forces at the crystal
interfaces. These examples are illustrated in Figure 8-39.

Figure 8-393

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8.11 Methods of Preventing Corrosion

8.11.1 Choice of Material

Material selection is an important component of corrosion protection. Most alloys require a coating
or the application of cathodic protection to reduce the rate of corrosion.

Of the ferrous metals plain carbon steels are commonly used because they are cheap and easy to
fabricate. However low carbon, low alloy steels are very susceptible to corrosion and need protection
in the long term. Providing that protection can be costly.

In certain situations where maintenance is difficult and a longer corrosion free life is required the
selection of a more costly high alloy or stainless steel may be justified.

8.11.1.1 Austenitic Stainless Steels

When chromium and nickel are added to low carbon steel, the corrosion resistance is greatly
improved. Additions of 17-19% chromium and 7-10% nickel produces a range of austenitic stainless
steels widely used in a variety of engineering applications including marine environments (see also
section 5.8.5).

To understand why this family of steels resist corrosion, the effect of adding nickel and chromium to
low carbon plain carbon steels needs to be considered.

The phase diagram below illustrates the effect of adding 18% Cr and 8% Ni, (FCC), to a low carbon
steel.

Figure 8-40

Comparing this phase diagram with that for a plain carbon steel, figure 12.29, reveals a greatly
enlarged austenitic γ phase region. The austenitic phase is FCC and carbon is soluble in this gamma
phase, compared to the alpha ferrite phase common at room temperature for plain carbon steels.
The presence of carbon in the form of Fe3C in plain carbon steels will exacerbate corrosion. The fact
that carbon is in solid solution in austenitic stainless steels reduces the susceptibility to corrosion
significantly. Furthermore the presence of chromium causes a coherent oxide film to form on the
surface, thus providing good protection against corrosion.

This passive film is very stable under oxidising conditions such as in the presence of oxidising acids
like sulphuric or nitric, or when anodic protection is applied. However, this protective film cannot be

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taken for granted as it is particularly vulnerable to reducing conditions and mineral acid
environments, such as encountered in crevice corrosion in a marine environment.
The microstructure of type 304 stainless steel in the annealed condition consists of equiaxed grains
of austenite, illustrated below.

Figure 8-41
It should be noted that stainless steels can be ferritic, martensitic, austenitic or precipitation
hardenable. These alloys have a wide range of properties and are employed widely in engineering.
However the most corrosion resistant alloys are the austenitic types. Their compositions and
properties are tabled below.

Table 8-2

8.11.2 Change the Nature of the Environment

The nature of the environment can be changed by:

i. Lowering temperature and concentration of corrosive fluids.

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ii. Reducing the velocity of corrosive liquids.

iii. Using inhibitors which can act upon either the surface of the metal, or react with the corrosive
medium, reducing corrosion rates.

8.11.3 Design

Use sensible design to minimize residual or external stress, avoid galvanic couples and stagnant areas.
Figure 8-42 (a)-(i) show some geometric design faults which favour corrosion, and how these faults
may be overcome by good design.

Figure 8-42-a5 Storage tanks should be designed to allow complete drainage.

Figure 3-39-b5 Crevices should be filled to prevent retention of liquid.

Figure 3-39-c5 Access for maintenance should be 'designed in'. For example, the space 't' should be adequate
to allow the metal to be painted.

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Figure 3-39-d5 Unless steel columns are protected at ground level with, say, a concrete coating, corrosion will
occur. A paint coating may break down prematurely at ground level.

Figure 3-39-e5 Overlap joints should be made as shown, to ensure that water cannot enter the joint.

Figure 3-39-f 5 The importance of adequate insulation. i Inadequate insulation of a pipe carrying hot gases
leads to condensation, the formation of a corrosive liquid, and corrosion of the pipe. ii Adequate insulation
prevents condensation.

Figure 3-39-g5 Methods of avoiding corrosion at interfaces.

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Figure 3-39-h5 Collection of water in structural members should be prevented by incorporating drainage
holes or by reversing the member.

Figure 3-39-i5 Good and bad joining by welding.

8.11.4 Inhibition and Environmental Control

Usually is only feasible in 'confined' environments. For example, packages, closed circuit or
recirculating systems.

Inhibition can take several forms:

i. Inhibiting the atmosphere, for example, dehumidification of the air and lowering the air
temperature will reduce the corrosion rates.
ii. Vapour phase inhibitors are volatile organic compounds, which deposit a hydrophobic film on
metal surfaces thus, excluding air, O2 and H2O.
iii. A chemical that can interfere with the anodic half or the cathodic half of the cell reaction. For
example the cathode reaction which is,
−
2 H 2O + O 2 + 4e → 4OH
, can be impeded by adding Zn2+ or Mg2+ which deposit insoluble hydroxides on the cathode.
The anode reaction,
Fe → Fe2+ + 2e
will be impeded by adding phosphate ion, which precipitates the Fe2+ as insoluble phosphate.

8.11.5 Protective Coatings

These may be an oxide coating, paint, enamel, plastic or metal applied by electrolysis, hot dipping or
spraying. Coatings must adhere to the surface, and be non permeable and chemically and physically
resistant to radiation, gases and aggressive environments.

8.11.6 Cathodic Protection

8.11.6.1 Theoretical Basis; the Potential-pH Diagram

The susceptibility of a metal to corrode when exposed to the environment will depend upon many
factors. These environmental parameters will vary greatly, but the two most important ones are the
pH and the reducing or oxidizing power of the corroding environment. A useful concept to represent
the effects of aqueous environments on metals became known as the E-pH or Pourbaix diagram.
E-pH diagrams have been developed for most metals and some alloys, and enable certain predictions
to be made about the interaction between the metal and a specified environment. They are useful in
the following ways:

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• To predict whether or not corrosion is likely to occur,

• To estimate the nature of corrosion products formed,

• To predict how a changed environment may contribute to the prevention or reduction

of corrosion.

Figure 8-43 illustrates the E-pH diagram for iron, (plain carbon steels), at 250 C in a humid
environment.

Figure 8-4317: Pourbaix diagram for steel in a moist environment

This diagram was compiled by considering all possible reactions between iron and the aqueous
environment. At potentials more positive than -0.6 and at pH values less than 9, the ferrous ion is
stable. This implies that under these conditions iron will corrode, (oxidize), by the reaction
Fe → Fe 2+ + 2 e . This zone is known as passive, and here iron will oxidize to form insoluble
hydroxides, either Fe(OH)2 or Fe(OH)3. These insoluble deposits may or may not offer partial
protection, but this cannot be relied upon. Further inspection of Figure 3-40 will indicate that there
is a large immunity zone where iron exists in its metallic form. It may be expected that in this zone
little or no corrosion would occur, that is the iron is protected. This portion of the diagram indicates
that if the iron’s potential is made negative or shifted cathodically to values below approximately -0.6
volts vs SHE in the pH range from -2 to 16, it will be protected. This cathodic protection zone is marked
clearly in Figure 8-43.

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Figure 8-4417: Pourbaix diagram for steel showing the zone of protection

The region below -0.6 V vs SHE is known as the immune zone, and the region above as the passive zone.
It should be noted that seawater has a pH of about 8.5.

Figure 8-45 is another form of the Pourbaix diagram, similar to the above, but clearly marking the
passive, corrosion and immune zones.

In industrial corrosion control the generally accepted cathodic protection criterion of -0.85 V vs the
saturated silver-silver chloride electrode, (SSC) is commonly used. This is the reference used in Figure
8-45. Other reference electrodes used are copper-copper sulphate reference electrode,(CCS) and
saturated calomel electrode, (SCE). For further details on reference electrodes see section 8.12 under
Monitoring Corrosion.

Figure 8-458: A Pourbaix diagram for steel showing active and passive zones

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A metal is deemed to be in a corroding condition if the concentration of its ions are ≥ 10-6 M. If the
concentration of the ions are ≤ 10-6 M the metal is deemed to be in the immune zone.

Figure 8-46 illustrates the relationship between the cathodic potential Ecorr, the current density i and
the corrosion rate r.

Figure 8-468: An Evans diagram for steel, relating Ecorr, i and r

Note that for the recommended cathodic protection potential of -850 mV vs SCE (saturated calomel
electrode) there is a corresponding current density and corrosion rate. As the corrosion protection
potential becomes more negative the current density requirements increase and the corrosion rate
decreases. It can be seen that once the corrosion protection zone is entered, (as illustrated in the
Pourbaix diagram), there is no advantage to be gained by using potentials significantly more negative
than of -850 mV, due to increased energy costs. Finally, it is worth repeating that corrosion rate is a
function of current density and not current.

8.11.6.2 Sacrificial Anode Cathodic Protection

In this process, an electrochemically active metal, usually zinc, but sometimes aluminium or
magnesium is used for the protection of steel. The principle underlying this type of protection is that
of bimetallic or galvanic corrosion covered in sections 8.3 and 8.6.2. For this method of protection the
correct number of anodes and their correct spacing on the structure is determined to achieve a
uniform potential gradient across the entire structure by electrical connection. Control is maintained
by electrical monitoring and regular inspection of anodes for weight loss.

This type of protection is commonly employed on smaller vessels and marine structures, and may be
used in conjunction with painting and impressed current cathodic protection. Figure 8-47 and Figure
8-48 illustrate cathodic protection of a ships hull by sacrificial anodes.

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Figure 8-47

Figure 8-48

Buried pipelines are often protected using sacrificial magnesium or zinc anodes which are buried with
the pipe as illustrated in Figure 8-49.

Figure 8-49

The structure is shown in elevation along its length in section (a). Section (b) illustrates the
distribution of potential along the pipeline, and the effect of a defect causing that region of the pipe to
be unprotected.

Figure 8-50 illustrates the cathodic protection of a pipe buried in moist soil with a sacrificial zinc
anode.

Figure 8-50 18: Cathodic protection of a buried pipe using a sacrificial zinc anode

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When determining the number of sacrificial anodes for SACP or calculating current densities for ICCP
in seawater, the composition of the seawater is relevant, particularly with respect to the
concentration of calcium and magnesium ions. This is because these ions will form insoluble
carbonates on the cathode, and thus significantly reduce the number of sacrificial anodes, or the
magnitude of the protection current density required if ICCP is used. The cost savings under these
circumstances will therefore be considerably reduced.

The natural presence of Mg2+ and Ca2+ in seawater will coat the walls of structures by reacting with
carbonate ion derived from dissolved carbon dioxide to form insoluble calcium carbonate. The
relevant reactions are given below:

i. Reaction of CO2 with water CO2 + H2O ↔ H2CO3

ii. Dissociation of carbonic acid H2CO3 ↔ H+ + HCO32-
iii. Dissociation of the bicarbonate ion HCO32- ↔ H+ + CO32-
iv. Cathodic half reaction as a result of the polarization of the cathode 2H2O + O2 + 4e → 4OH-
v. Formation of insoluble calcium carbonate Ca2+ + CO32- ↔ CaCO3(s)

Figure 8-51 illustrates the formation of the insoluble calcareous deposit on the surface of a steel
member immersed in seawater as a result of the series of reactions illustrated in (i) – (v) above.

Figure 8-5117:The effect of calcium in seawater on cathodic protection

The deposit is seen on the left hand side of the steel. C is the concentration of ions at the surface. This
concentration depends upon the rate of diffusion of the carbonate ion through the water to the metal
surface. Reactions (i), (ii), (iii) and (v) are promoted by the presence of alkali in the form of OH-
produced by the cathodic half reaction (iv) in seawater at a pH of 8.5.

δ is the width of the diffusion layer, and the concentration gradient diminishes across this space,
reaching an equilibrium concentration of C0. The production of a pH profile across this layer results
in the beneficial deposit inside the space, and quite different reactions outside in the bulk seawater.
The following conclusions can be deduced from observing the data in the Table 8-3below:

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Table 8-317: Corrosion rates of metals in seawater as a function of water velocity

1. Ferrous metals are much more susceptible to corrosion than non-ferrous metals and stainless
steel.

2. The formation of the calcareous deposit is retarded as the relative motion between the
structure and seawater increases. Thus the corrosion protection diminishes with higher
velocities.

8.11.6.3 Impressed Current Cathodic Protection

In this type of protection, an external source of direct current is applied, and the structure is made the
cathode. Under these conditions the electron flow is into the structure. Inert anodes need to be
correctly placed at regular intervals along the length for a uniform potential to be produced.
ICCP is commonly used for the protection of ships hulls and marine structures. It has the advantage
of being easily monitored, and does not require the replacement of anodes. It is widely used for the
extra protection of steel reinforcing in concrete structures, particularly those exposed to de-icing salt
or seawater, (see section 9.4).

Figure 8-52 illustrates the ICCP of a ships hull.

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Potentiostat

Figure 8-52

ICCP monitoring of a subsea pipeline is illustrated in Figure 8-53. It shows the survey vessel with a
multi-electrode probe attached to a remotely operated under water vehicle by an umbilical. A remote
reference electrode is also attached by an umbilical to the vessel.

Figure 8-53

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Chapter 8: Corrosion

Figure 8-54 illustrates the plot of potential along the length of the pipeline, which enables the process
to be monitored and controlled.

Figure 8-54

8.11.7 Anodic Protection

The Evans diagram reproduced in Figure 8-55 illustrates the principle of anodic protection using a
potentiometric scan for steel in seawater. This plot of applied potential against log current density
highlights the changing surface characteristics as the applied voltage is varied.

Figure 8-55

Point O represents the free corrosion of steel. The curve at more negative potentials than Ecorr
represents the metal under cathodic protection as discussed above. If the applied potential is made
more positive, the current density increases initially quite rapidly to a maximum value of imax, but then
suddenly falls to a very low value of ipass. At this stage the metal has achieved the desired passive state
where it is well protected by a film of inert corrosion product.

The principle of anodic protection is now evident, being that zone of passivity achieved by the
maintenance of a positive potential at low current density. The passive film will remain stable and
protective if the electrical parameters are not changed.

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Certain metals like stainless steels and aluminium alloys are easily passivated, forming cohesive and
adherent oxide films. Plain carbon steels are not easily passivated in seawater, but can be easily
passivated in oxidising acids like concentrated nitric and sulphuric. Thus plain carbon steel can be
used as storge tanks for these acids when anodically protected.

Figure 8-56 illustrates the anodic protection of a steel storage tank for acid.

Figure 8-56

The control circuitry is the same as for cathodic protection, using a potentiostat to maintain the
required potential. Advantages of anodic protection are several, including low operating costs and
controlled conditions, together with the ability to use cheaper alloys in lieu of expensive alloy steels
for storing corrosive chemicals. Circuitry must be fail safe as power failures will lead to rapid loss of
passivation, with possibly catastrophic effects.

8.11.8 Electropolishing Stainless Steel

8.11.8.1 Introduction

There is an expectation that stainless steels will not corrode due to their chromium and nickel content.
This is usually not the case, and all too often “tea stains”, or rust deposits are observed on the surface,
particularly in a marine environment.

The successful passivation of stainless steel depends upon several factors, specifically the surface
finishing history of the alloy, and the method of passivation. The process known as electropolishing
not only achieves the most durable form of passivation, but in addition will smooth and polish the
surface to a high degree of finish.

8.11.8.2 Metal Surfaces

A metal surface exposed to the air is a two phase interface, and will possess excess energy due to
several factors. One important reason is that the metal surface is in a constantly changing
environment, which results in changing equilibrium reactions between the metal atoms and oxygen
and water vapour in the atmosphere. Another factor that results in high surface energy is the presence
of impurity atoms, and defects or discontinuities in the crystal structure of the metal itself. All the
factors that contribute to high surface energy will result in an increased tendency for the metal
surface to corrode. Finally mechanical or thermal finishing operations such as cold working, polishing,
abrading, welding, and hardening by quenching, will also contribute to high surface energy and

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increased reactivity. There is therefore a natural tendency to lower the surface energy by chemical
interaction with the air, a common product being an oxide coating.

Figure 8-57illustrates the presence of a step in a metal surface due to movement along slip planes as
a result of an applied tensile force. The slip step on the surface of the passivated metal creates an
active site for pitting corrosion to occur.

Figure 8-57

8.11.8.3 Electropolishing

The process involves making the object the anode in a system very similar to electroplating. The
cathode is stainless steel, and the electrolyte is a mixture of sulphuric and phosphoric acids. To
achieve optimal conditions current density and temperature are controlled, as well as time. The
spacing between, and orientation of the anode relative to the cathode are also important. A typical set
up is illustrated in Figure 8-58.

Figure 8-58

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During the process the surface irregularities are levelled to produce a very smooth or polished
surface. This occurs because the tips of the irregularities have very small surface areas, and therefore
the current density at these points is high. This leads to rapid dissolution at these features, and
consequently a smoothing of the surface contours. The surface simultaneously attains
electrochemical stability as a result of its equipotential status and lower surface energy.

In stainless steels the iron and nickel will dissolve preferentially to the chromium, leaving an excess
of chromium atoms on the surface. Since it is the presence of chromium oxide on the surface that
provides the corrosion protection for stainless steels, the process not only polishes but optimizes
passivation and corrosion protection.

The reactions are: Fe → Fe2+ + 2e, and Ni → Ni2+ + 2e, at the anode surface, leaving an excess of
chromium ions Cr3+. The chromium ions react with the oxygen liberated at the anode: 2H2O → O2 +
4H+ + 4e, forming passive chromium oxide.

The cations liberated at the anode will either form a sludge, or deposit as insoluble sulphates or
phosphates on the cathode, from which they must be removed from time to time.

8.11.8.4 Applications

Electropolishing produces a smooth shiny finish on the surface of the stainless steel. Microscopic
examination confirms that electropolishing is quite superior to mechanical methods of polishing,
optimizing surface finish, and surface passivation at the same time. The almost complete absence of
surface flaws not only offers long term corrosion protection, but also significantly reduces the
retention of bacteria and micro-organisms. For these reasons electopolished stainless steel finds
application in medical prostheses, and the food and pharmaceutical industries, as well as a wide range
of engineering applications.

Electropolishing is also used for de-burring and cleaning metal surfaces. The following figures
illustrate the de-burring of a part which is difficult to treat mechanically, and a group of surgical
prostheses and instruments.

Figure 8-59

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Chapter 8: Corrosion

Figure 8-60

OPERATING CONDITIONS:

• Current density = 5-25 A/dm2

• Temperature = 40-750C
• Time = 2-20 min.
• Electrolyte = Equal volumes of concentrated sulphuric and phosphoric acids.
• The complete process involves degreasing, and decontamination in a mineral acid, (if weld or
metal comtaninants are suspected). These operations are carried out prior to the
electropolishing operation.
• Rinsing thoroughly to remove electrolyte and soluble surface residues is essential.
• A post treatment may also employ a further passivation in dilute nitric acid.

8.12 Corrosion Monitoring

To control corrosion in engineering structures requires a detailed understanding of the
electrochemical mechanisms under-pinning this process. Knowledge of the kinetics and
thermodynamics of the corrosion reactions enable preventative strategies to be employed. A vital
part of this process involves measuring the rate of the corrosion process, which will be discussed in
the next section. The three most practical methods of monitoring corrosion are by measuring:

• Free corrosion potential Ecorr

• Weight loss
• Thickness loss

8.12.1 Corrosion Rates

The table of standard reduction potentials as well as the galvanic series are thermodynamic
parameters that relate to systems in equilibrium. Real corroding systems are not at equilibrium, that
is there is a flow of electrons from anode to cathode. This means that half cell potential parameters
cannot be used to determine reaction rates. They do however represent the driving force behind the

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Chapter 8: Corrosion

reaction and indicate the tendency for it to occur, but give no information of the rate at which it
proceeds.

For non-equilibrium processes encountered in corrosion reactions, polarization occurs. Polarization

is defined as the displacement of an electrode potential from its equilibrium value as a result of
current flow. The magnitude of this displacement is known as overvoltage 𝜂𝜂. Overvoltage is expressed
as plus or minus voltage relative to the equilibrium potential. For example if the free corrosion
potential Ecorr of a corroding system involving steel is measured as -0.5 V,

𝜂𝜂 = -0.5 V – (- 0.44 V) = - 0.06 V,

2+
where -0.44 V represents the standard half reduction potential for iron, Fe(s) → Fe (aq) + 2e.
Polarization is due to activation and concentration effects on the electrochemical reactions. Details of
these processes may be obtained from standard texts on corrosion.

8.12.2 Corrosion Potential

The corrosion potential Ecorr is the potential of a freely corroding surface which arises from the mutual
polarization of the anodic and cathodic half reactions that drive the overall corrosion reaction. This
parameter is easily measured, and is amongst the most important indicators of the thermodynamic
state of the process. As such it is of great value in monitoring corrosion. Figure 8-61 illustrates the
set-up to measure Ecorr.

Figure 8-6117: Apparatus to measure the free corrosion potential Ecorr, of a metal

The left hand electrode is the freely corroding metal and the right hand electrode is the reference
electrode. The electrodes are immersed in an electrolyte and the potential measurement is recorded
using a high impedence voltmeter.

Earlier reference was made to the standard hydrogen electrode SHE, in section 7.8. Because this
electrode is not practical to be used outside the laboratory, several more robust reference electrodes
have been devised for field use. For marine corrosion the silver-silver chloride electrode SSCRE is
widely used. Other common types are the saturated calomel electrode SCRE, the copper-copper
sulphate electrode CCSRE and the zinc electrode.

It is often necessary to be able to convert potential readings obtained from one type of reference
electrode to that of another reference electrode, and this commonly arises when using the Pourbaix
diagram discussed in section 8.11.6.1. Table 8-4 compares the potential of selected reference
electrodes with respect to the SHE.

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Table 8-417 Conversion chart for Reference electrodes

The following problem will illustrate how this conversion table may be used. The free corrosion
potential of a steel pipe relative to the SSCRE was measured as -0.600 V. To covert this potential to a
value on the scale in which the hydrogen electrode has a potential of zero, it is necessary to add 0.210
V to the potential that was measured, making it -0.390 V.

Alternatively if the potential reading of -0.390 V were to be expressed with respect to the CCSRE, it
would be necessary to add -0.320 V to the potential reading, making it -0.710 V.

Section 8.11.6.3 discussed the principle of impressed current cathodic protection. In this context the
control and monitoring of this system of protection involves the correct placement of inert anodes
and reference electodes on the structure to be protected. This layout is illustrated in Figure 8-62 on
an oil tanker.

Figure 8-6217: The layout of electrodes for ICCP on an oil tanker

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The circuity to control the applied current and resulting protection potential is a potentiostat
illustrated in Figure 8-63.

Figure 8-638: Potentiostat circuitry for potential control for ICCP

In this system if the protection potential varies say from -850 mV vs SCE to a more positive value,
possibly entering the corrosion zone, the reference electrode will detect the potential shift on the
steel. The potentiostat will then adjust the applied current to restore the required protection
potential, thus maintaining cathodic protection.

8.12.3 Weight loss and Corrosion Penetration Rate, CPR

The corrosion penetration rate CPR equation (8-15) is defined as the thickness loss of material per
unit of time, as a result of corrosion. Its mathematical expression is given by:
Kw
CPR = (8-15)
ρAt
where:
CPR is measured in mm/yr
w = Weight loss in mg
ρ = density of the metal in g/cm3
A = area of corroding surface in cm2
t = time in hours
K = a constant to compensate for unit conversion = 87.6 for the above system.
𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
It has been shown in section 7.16.1 equation (7-22), that weight loss due to corrosion w = 𝑛𝑛𝑛𝑛 .
The rate of corrosion r is another useful parameter in monitoring corrosion and is expressed in units
mol/m2.s. An expression for the rate r may be derived from equation (7-22)as follows:
𝑤𝑤 𝑖𝑖𝑖𝑖𝑖𝑖
Moles of metal = =
𝑀𝑀 𝑛𝑛𝑛𝑛

𝑤𝑤 𝑖𝑖𝑖𝑖
Moles of metal/m2 = =
𝑀𝑀𝑀𝑀 𝑛𝑛𝑛𝑛
i
= = Moles of metal / m 2=
r rate .s (8-16)
nF
where
i = corrosion current in A/m2

Equation (8-16) verifies that the rate of corrosion r is ∝ current density i.

It has been illustrated in the above section that there is a relationship between the corrosion
penetration rate CPR and corrosion current density i. It can be shown that for steel when CPR is 1
mm/yr the equivalent corrosion current density i is 0.086 mA/cm2.

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8.12.4 Thickness Measurement

Corrosion may also be monitored by measuring the loss in wall thickness of a metallic structure. This
is readily accomplished by using an array of transducers attached to the surface of the metal,
commonly employed to measure the rate of uniform corrosion in pipelines.

The transducer consists of a piezoelectric crystal that emits a high frequency or ultrasonic sound
wave. The time taken for the wave travelling at a known velocity through the metal is proportional to
its thickness. The signal is processed by a computer to convert directly to thickness. Figure 8-64
illustrates the principle involved, and shows the ultrasonic wave being reflected from the inner
corroded surface of the pipe.

Figure 8-6417: Thickness monitoring using ultrasonic waves

8.12.5 Other monitoring Methods

Zero resistance ammetry is a system useful for monitoring bacterial corrosion in pipelines carrying
oil, since free oxygen produced during the corrosion process can be readily detected using this
technique.

Another technique used employs the measurement of the impedance of the corroding surface and is
known as electrochemical impedance spectroscopy. These industrial monitoring procedures are
employed in industry and further details may be obtained from consulting the literature.

8.13 Corrosion Case Histories

8.13.1 Introduction

For many people the serious effects of corrosion are only fully appreciated after the event occurs,
when the tell-tale signs are only too evident. When you actually see the physical signs of corrosion,
most of the damage is already done, and usually irreversible.

Tackling the problem of corrosion requires a pro-active approach, and a clear understanding of the
underlying causes. Prevention is the key to controlling corrosion, and this must be the mind set at the
engineering design stage. At this point the environment and the environmental effects on the material
must be taken into account.

Controlling corrosion in practice requires a good grasp of the theoretical principles under-pinning
corrosion. However, in addition, a study of case histories, over a wide range of materials and

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Chapter 8: Corrosion

environments is an invaluable aid to a more in-depth appreciation of the many facets of corrosion.
This is the aim of this brief study.

Details may be found on MYLO under Corrosion Case Histories.

8.14 Question and Answers – Corrosion

Q3.1Magnesium metal is used as a sacrificial anode to protect underground pipes from corrosion.

a) Why is magnesium referred to as a sacrificial anode?

b) How does magnesium provide protection for buried steel pipes?
c) How does galvanic protection in part (a) differ from impressed current cathodic protection?
d) What are the environmental factors encountered underground that will exacerbate corrosion
of steel?

Q3.2
a) Explain how under normal conditions steel reinforcing in concrete will be immune from
corrosion.
b) Outline the environments under which the protection referred to above may fail.
c) What practical measures may be taken to minimize adverse environmental conditions?

A3.1

(a) The term sacrificial anode refers to any metal that is part of a corrosion or galvanic cell, that
loses electrons to the other half cell. Magnesium is a reactive metal, that is it is high in the
activity series, and is readily oxidized as shown in the half reaction:
Mg → Mg2+ + 2e E0 = 2.39 V
The high positive standard oxidation potential indicates that magnesium oxidizes
spontaneously, yielding a flow of electrons into the cathode. The cathode is the structure or
object requiring protection, and is usually steel. It is the flow of electrons into the steel from
the sacrificial anode that provides cathodic protection.
(b) If the buried steel pipe is electrically connected to the magnesium anode, cathodic protection
will be accomplished. Over time the magnesium will eventually dissolve, and will need to be
replaced.
(c) Cathodic protection may be achieved either by the use of a sacrificial anode, as discussed
above, or by impressing a direct cathodic current into the structure requiring protection.
The circuit for such protection consists of an inert anode, and a controlled source of DC.
(d) Harmful environmental factors encountered may include moisture, acidic clay soils,
bacteria, and stray currents from electrical machines in the vicinity. Soils containing
dissolved salts will exacerbate the electrical conductivity, and be especially problematic.

A3.2

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(a) When cement is mixed with water, the hydration reaction which takes a very long period to
reach equilibrium, produces as a product calcium hydroxide, which is strongly alkaline. The
presence of this alkali produces a pH of 12.5 in the concrete. At this pH, a passive iron oxide,(
Fe2O3), is produced and maintained on the steel reinforcing surface, providing corrosion
protection.
(b) If the alkaline environment of the concrete can be maintained, no corrosion of the steel
reinforcing will occur. Problems arise when the concrete loses its alkalinity, which can occur
due to two main environmental contaminants. The first is the ingress of acidic gases like
sulphur dioxide, or acids, in liquid form. In each case the calcium hydroxide will be attacked
and reduced. If sufficient acid is absorbed the protective oxide will no longer be sustained.
Under these conditions rust will form and cause spalling, due to the increased volume
occupied by the hydrated rust oxide.
A second cause of reduced alkalinity is the presence of salt. This can be a real problem in
marine environments. The chloride ion severely attacks the passive oxide film on the steel,
producing pits. The freshly exposed steel is then subject to rusting and spalling.
(c) There are several ways to reduce the adverse effects of these environmental contaminants.
They are:

i. Minimize the porosity of the concrete to reduce its permeability, and the ingress of corrosive
elements. This can be achieved by attention to quality control when the concrete is being
placed, with particular care during the vibration phase.
ii. Coat the surface of the concrete with a barrier coating.
iii. Galvanize the steel reinforcing.
iv. Cathodically protect the reinforcing.

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References
1 Berendsen, A M. Marine Painting Manual. Glasgow, Great Britain: Kluwer Academic,
1989.
2 Bimetallic Corrosion. London, UK: Department of Industry and the Central Office of
Information, 1982.
3 Brown, Theodore L., H E. Lemay, Jr, and Bruce E. Bursten. Chemistry the Central
Science. 10th ed. Upper Saddle River, NJ: Pearson, Prentice Hall, 2006.
4 Callister, Jr., William D. Materials Science and Engineering an Introduction. 7th ed.
York, PA: Techbooks, 2007.
5 Controlling Corrosion 1. London, UK: Department of Industry and the Central Office of
Information, 1980.
6 Corrosion Factors in Pumps and Valves. London, UK: Department of Industry and the
Central Office of Information, 1981.
7 Stress Corrosion. London, UK: Department of Industry and the Central Office of
Information, 1980.
8 Trethewey, Kenneth R., and John Chamberlain. Corrosion for Students of Science and
Engineering. New York, USA: John Wiley & Sons, 1988.
9 www. chemguide.co.uk/physical/phaseequia/vapourpress.html
10 en.wikipedia.org/wiki/Cavitation
11 mailchimp.com/d3c2d740deb178cffaa9a7c21/files/WP
12 [email protected]
13 Manahan, Stanley,E., Environmental Chemistry, 7th Ed., Lewis, 2000
14 Brophy, J.H., Rose, R.M., Wulff, J, The Structure and Properties of Materials, volume 2,
John Wiley & Sons, 1967.
15 Euro inox Electropolishing Stainless Steels, Materials and Applications Series, Volume
11
16 http://www.corrosion-doctors.org/Corrosion-Thermodynamics/Potential-pH-
diagram-iron
17 Roberge, Pierre, R., Corrosion Engineering, Principles and Practice, McGraw-Hill, 2008
18 Ashby, M., Shercliff, H., Cebon, D., Materials, Engineering, Science, Processing and
Design, Elsevier, Butterworth-Heinemann, 2007.

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Chapter 9: Concrete

Concrete

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9.1 Introduction
Concrete is widely used as a material of construction. It is one of the most versatile of materials,
permitting of being cast into almost any shape whilst in the form of slurry at ambient temperatures.
Roads, bridges, jetties and ornamental features are just a few of the many applications of this material.

Concrete like brick, glass, stone, cement, mortar, porcelain, pottery and sintered carbides, oxides and
nitrides is a member of a broad class of materials known as ceramics. We may define a ceramic as a
solid inorganic material, either crystalline or amorphous. Most ceramics have high melting points and
are strong in compression but weak in tension. Typical crystalline ceramics are oxides, carbides and
silicates. Amorphous ceramics are known as glasses.

Concrete consists of a mixture of cement, sand, and an aggregate of small stones. A very common mix
consists of four parts aggregate, two parts sand and one part cement (by volume). For full hydration
and the development of maximum strength, a water/cement ratio of about 0.4:1 is necessary. If the
water/cement ratio is much in excess of this value the strength of the hardened cement will be
reduced.

9.2 Cement
Since it is the cement that binds the aggregate together, thus providing the cohesive strength of the
concrete components, we need to look more closely at the nature of cement and its function. Ordinary
Portland cement is formed by heating to over 2000°C a mixture of limestone and clay to form a series
of glassy cementitious compounds.

CaCO3(s) 
Heat
→ CaO(s) + CO 2(g)
 (9-1)
Limestone

Clay 
Heat
→ SiO 2(s) + Al2O3(s) + Fe2O3(s) + H 2O(g) (9-2)

The main reaction products, oxides of calcium, silicon, aluminium, iron, sodium, potassium et cetera
fuse together at the high temperatures involved, and form a glassy mass. The finely ground clinker
contains four principle compounds.

Compound Formula
Tricalcium Silicate 3CaO ⋅ SiO 2 ( C3S)
Dicalcium Silicate 2CaO ⋅ SiO 2 ( C 2S)
Tricalcium Aluminate 3CaO ⋅ Al2 O3 ( C3 A )
Tetracalcium Aluminoferrite 4CaO ⋅ Al2 O3 ⋅ Fe2 O3 ( C4 AF )

Table 9-17 The four principle compounds.

Percentage Composition (%)

Type C3S C2S C3A C4AF
Normal Portland 48-65 10-30 2-11 7-17
High early strength Portland 50-65 7-25 6-13 7-13

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Percentage Composition (%)

Type C3S C2S C3A C4AF
Low heat Portland 25-30 40-45 3-6 12-17
Sulphate resisting Portland 50-60 15-25 2-5 10-15

Table 9-27 Typical compound composition of Portland Cement.

Mineral Formula Percent

Lime CaO 62.0
Silica SiO2 22.0
Alumina Al2O3 7.5
Magnesia MgO 2.5
Iron oxide Fe2O3 2.5
Sulphur dioxide SO3 1.5
Other — 2.0

Table 9-37 Typical composition of high quality Portland cement.

It should be emphasised that when water and cement are mixed, a chemical reaction occurs. The
process by which cement hardens is not one of drying but one of hydration, in which water actually
participates in a chemical bonding process. This process of hydration and hardening, a relatively slow
process may continue for up to several years.

It is the hydrated cement or solid gel that binds the other particles in the aggregate into a stiff mass,
which 'sets'. The mass then hardens further as hydration progresses to the core of each particle. It
should be noted that a gel is a solid framework of colloidal particles linked together, and containing a
fluid in its interstices. Depending upon the linking and the geometry of the interstices the gel may be
either rigid or elastic.

When the cement is mixed with water, the adsorption of the water produces a gel composed
principally of hydrated calcium silicates. A typical hydration reaction is:

2 ( 3CaO ⋅ SiO 2 ) + 6H 2O → 3CaO ⋅ 2SiO 2 ⋅ 3H 2O + 3Ca ( OH )2 (9-3)

During the process of hydration the fine cement particles dissolve at the surface, and then precipitate
out as a fine mesh and then aggregate together. Water is trapped by capillary action between the
particles, which gives rise to the structure pictured.

Figure 9-12 Structure of cement gel.

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Pores are left within the cement paste. These gel pores are in the order of 1.5-2.0nm and trap or bind
the water. Capillary pores, marked 'C' in Figure 9-1, are much larger in the order of 1000nm or more,
and they may be interconnected. Thus concrete is said to be porous.

9.3 Concrete
Concrete is a multiphase material. The number and nature of the phases together with their
distribution can give rise to a wide range of properties. The most common multiphase material is rock
which is composed of two or more minerals, for example, granite comprises of feldspar, quartz and
mica.

Concrete is a mixture of sized gravel, and sand, and is bonded together with a hydrated Portland
cement gel. The gel is really a two phase mixture on a sub microscopic level (solid and liquid), but
behaves as a single, non-crystalline phase.

To achieve the optimum strength and workability of a concrete mixture the ingredients must be
added in the correct proportions. Dense packing of the aggregate and good interfacial contact are
achieved by having particles of different sizes; the fine particles of sand should fill the spaces between
the coarser particles of gravel. Aggregates normally constitute between 60-80% by volume of the
cement: water paste to coat all particles. Complete mixing is essential if concrete of optimum strength
is to be obtained.

Another very important factor is the cement to water ratio. Too little water leads to incomplete
bonding, and too much water leads to excessive porosity.

9.3.1 The Strength of Concrete

The final properties of concrete will be dependent upon quite a few variables including:

i. Proportion of water and cement, sand and aggregate.

ii. Average size and shape of aggregate.
iii. The surface texture of the aggregate.
iv. Finishing techniques after the concrete is poured.
v. Type and placement of reinforcing.

Compressive strengths of plain concrete may be as high as 65 MPa, but the tensile strength is only
about one-tenth of the compressive strength.

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Figure 9-27 Compressive strength versus water/cement ratio for various cement types. Note the graphs are
valid when these cements are combined with quality aggregates in a mix without chemical admixtures and
cured under controlled laboratory conditions.

Figure 9-37 Strength of various mixes of concrete versus water-cementitious ratio.

9.3.2 Reinforced Concrete

When a concrete member is subjected to stress, failure usually occurs at the interface between
aggregate and cement. The tensile strength of non-reinforced concrete is low (up to 5MPa). To
overcome this disadvantage concrete fabrications are reinforced most usually with steel. This
reinforcing consists of a network of rods or bars, and the concrete is allowed to set around this
framework. The reinforcements are located in that section of the concrete which is to be subjected to
tensile stresses.

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Figure 9-4 and Figure 9-5 illustrate the use of a simple beam, and a series of bars. In each case a
mechanical bond occurs between the concrete and the steel, enhanced by incorporating a textured
surface onto the steel, for example, patterns or projections. The extra surface area increases the
bonding.

Figure 9-45 Plain reinforced concrete beam. The upper layers of the beam are in compression and the lower
layers are in tension. Steel bars help to sustain the tensile stress.

Figure 9-55 Pre-stressed concrete beam. Steel wires in tension exert a compressive force on the concrete.

Another form of reinforced concrete is known as pre-stressed concrete where the concrete is put into
a state of compression by means of highly stressed steel wires. When a pre-stressed concrete beam is
in service the initial compressive stress must be overcome before tensile stresses can be developed
within the material. Thus the engineer can design a safety margin into a structural member by pre or
post stressing. The effects of reinforcement of various types are illustrated in Figure 9-6.

Figure 9-68 The effects of steel reinforcement in concrete structures. (A) A suspended concrete beam or slab
fails in tension when loaded. (B) When the steel reinforcement is places as shown, it takes the tensile load and
failure does not occur. (C) In a concrete slab lying on the ground and loaded as shown, the uniform ground
reaction places the top portion of the slab in tension, and thus the reinforcing steel is placed in the top portion
of the concrete slab. (D) Pre-tensioned steel reinforcement prevents deflection when a load is applied to a
suspended beam or slab. This is one form of prestressed concrete.

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9.3.3 Compression Testing of Concrete

Australian Standard AS1012 describes the current methods for testing concrete. Of the many types of
testing available the most common strength test is the compression test. Table 9-4 lists the
subsections of AS 1012.

Part Year
Part 1 1981 Method for sampling fresh concrete (Amdt 1, March 1987)
Part 2 1983 Method for preparation of concrete mixes in the laboratory
Part 3 1983 Methods for the determination of properties related to the consistency of
concrete
Part 4 1983 Methods for the determination of air content of freshly mixed concrete
Part 5 1983 Method for determination of mass per unit volume of freshly mixed
concrete
Part 6 1983 Method for the determination of bleeding of concrete
Part 8 1986 Method for making and curing concrete compression, indirect tensile and
flexure test specimens in the laboratory or in the field (Amdt 1, July 1989)
Part 9 1986 Method for the determination of the compressive strength of concrete
specimens
Part 10 1985 Method for the determination of indirect tensile strength of concrete
cylinders ('Brazil' or splitting test) (Amdt 1, March 1987)
Part 11 1985 Method for the determination of the flexural strength of concrete
specimens
Part 12 1986 Methods for the determination of mass per unit volume of hardened
concrete
Part 13 1970 Determination of drying shrinkage of concrete (Amdt 1, Dec 1986)
Part 14 1973 Method for securing and testing cores from hardened concrete for
compressive strength or indirect tensile strength (Incorporating Amdts 1
and 2)
Part 15 1979 Method for the estimation of portland cement content of hardened
concrete.
Part 16 1974 Determination of creep of concrete cylinders in compression
Part 17 1976 Methods for the determination of the static chord modulus of elasticity and
Poisson’s ratio of concrete specimens
Part 18 1975 Determination of setting time of fresh concrete, mortar and grout by
penetration resistance
Part 19 1988 Accelerated curing of concrete compression test specimens (laboratory or
field) – Hot water and warm water methods

Table 9-47 Methods of testing concrete, Australian Standard AS 1012.

Further reference to the quantitative aspects of the compression test will be found in 11.0 Mechanical
Properties of Metals.

It is sufficient to say, at this point, that representave concrete test cylinders are prepared from the
exact formulation of concrete to be used. Alternately if on-site testing is to be carried out a
representative sample is taken.

Factors which must be controlled are curing time, storage environment, capping and rate of loading.
Brittle materials like concrete will fail in certain ways when subjected to compressive forces. The
modes of failure are illustrated in Figure 9-7.

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Figure 9-78 Types of compression failures in brittle materials. θ equals 45° for metals.

9.4 Corrosion of Reinforced Concrete

9.4.1 Introduction

The corrosion of concrete can be discussed under there major headings, namely:

i. The corrosion of steel reinforcing in concrete.

ii. The corrosion of non-ferrous metals in concrete.
iii. The corrosion or chemical attack on concrete in an aggressive environment.

9.4.2 Concrete as an Environment for Steel

If bright steel is left unprotected in the environment it will rust. Thermodynamics dictates that iron
must rust and eventually revert to iron oxide. Corrosion cannot be permanently stopped, it is
inevitable. The difference in energy level between the higher energy state of the pure metal and its
oxide is about 6 MJ/kg. It is the capacity to lose this energy that renders iron so susceptible to
corrosion.

It has been shown in equation (9-3) that calcium hydroxide is produced during the hydration reaction
of the cement. The presence of this alkali gives concrete a pH of about 12.5. The presence of such high
alkali content allows a passive film of Fe2O3 to exist on the steel surface. If this passive film can be
maintained the structure will remain sound. Thus, the concrete cover provides protection for
chemical as well as a physical protection for the steel.

However, circumstances do occur when this level of protection breaks down, and corrosion of the
reinforcement will occur. Since rust has a larger volume than steel from which it is formed, the result
can be cracking, rust staining and spalling as illustrated in Figure 9-8, Figure 9-9 and Figure 9-10.

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Figure 9-89 Cracking and rust-staining of concrete.

Figure 9-99 Spalling of the concrete cover following severe corrosion of the reinforcement.

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Figure 9-104 Localised corrosion (right) as a consequence of impact damage during construction.

The effects of cracking and corrosion were major factors in the collapse of the Minneapolis Bridge in
the USA, which killed at lease five people.

Figure 9-112 The Minneapolis Bridge that took at least five lives.

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9.4.3 Loss of Alkalinity by Carbonation

Alkalinity, and thus protection of the reinforcing steel can be lost as a result of:

i. The ingress of acidic gases such as carbon dioxide or sulphur dioxide. These acids react with
the calcium hydroxide and reduce the alkalinity.

Ca ( OH )2(aq) + CO 2(g) + H 2O(l) → CaCO3(s) + 2H 2O(l)


H 2CO3( aq )

ii. Leaching by water from the surface: In practice both these factors lead to a loss of alkalinity
and ultimately to corrosion of the steel reinforcement. Figure 9-12 and Figure 9-13 illustrate
the effects of mild and severe carbonation.

Figure 9-129 Slight carbonation of concrete.

Figure 9-139 Severe carbonation of concrete leading to corrosion of the reinforcement.

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If the permeability of the concrete can be reduced by optimizing the concrete formulation,
carbonation will be reduced. Coating the concrete with one of the proprietary paints will also reduce
the effects of carbonation.

9.4.4 Attack by Chloride Ions

While the passive film remains intact the structure is protected and safe. Apart from pH, the stability
of the oxide film is also affected by the presence of chloride ion. This factor may become a problem,
particularly for structures in a marine environment. Chloride ions can diffuse through the concrete
cover where they will attack the protective film:

Fe2O3 + 6NaCl + 3H 2O → 2Fe3+ + 6Cl− + 6NaOH (9-4)

This reaction causes pitting in the protective film, and allows the bare iron to be oxidized:

Anodic Reaction: Fe → Fe 2+ + 2e (9-5)

If the passivation reaction can be written as

2Fe2+ + 6OH − → Fe2O3 + 3H 2O + 2e (9-6)

it can be seen that by inspecting equation (9-4) and equation (9-6) the onset of pitting is governed by
the ratio of the chloride ion concentration to the hydroxide ion concentration. This is illustrated in
Figure 9-14 below.

Figure 9-142 Effect of chloride and pH on corrosion of steel.

9.4.5 Protecting the Passive Film on Steel Reinforcing

i. Concrete mix design

The durability of the concrete structure will depend upon the rate of diffusion of Cl- through
the concrete and also the hydroxide ion concentration in the pore water. The latter is
dependent upon the cement concentration in the concrete mixture. The rate of deterioration
is thus a two stage process, specifically based on diffusion time and the more rapid initiation
of pitting. These factors are illustrated in Figure 9-15.

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Figure 9-152 The progress of deterioration.

Additional studies have shown that for a chloride concentration of 0.3% w/w of the cement
in the concrete, and a corrosion free life of 8 years, a concrete cover of 28mm is required.

Figure 9-162 Chloride penetration of reinforced concrete.

Figure 9-17shows the important relationship between porosity and compressive strength.

Figure 9-172 Strength and permeability.

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Carbonation and the ingress of chloride ion through the pores of the concrete are now
accepted as major causes leading to the corrosion of the steel reinforcement. It will be obvious
that if the porosity of concrete can be minimized, carbonation and chloride ion ingress can be
substantially reduced, with subsequent savings in terms of corrosion.
If excessive porosity is to be avoided careful quality control must be exercised at the time of
pouring. The wet pour must be adequately consolidated by vibration, to eliminate as much as
possible air pockets and honeycombing. Furthermore the vibration will ensure intimate
contact between cement slurry and aggregate and lead to the most effective curing
environment. The importance of proper 'on-site' practices at all stages of concrete
manufacture and placement cannot be over emphasized.

ii. Inhibitors
These are chemicals which can be added to the concrete to strengthen the passive film by
oxidizing ferrous ions. Examples of inhibitors are nitrites and ethanolamines.

iii. Galvanizing the steel reinforcing

If the reinforcing steel is galvanized, the zinc coating acts as a sacrificial anode, thus
prolonging the life of the steel. However, zinc is readily attacked in the presence of strong
alkali, and its use it not recommended at pH values greater than 12.

iv. Cathodic prevention and protection

For steel there will exist a range of impressed potentials which will ensure passivity, that is a
region where pitting cannot occur. If the passive film is completely intact the potential will be
lower and less costly to maintain than if the film has been damaged and where a higher
potential will be required. Figure 9-18 illustrates the variation of applied potential in
millivolts against a saturated calomel electrode, versus chloride content. Corrosive and
passive zones are shown. Cathodic protection may be represented by the path --.
Cathodic protection is represented by the path ---.

Figure 9-182 Cathodic protection and prevention.

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The application of impressed current cathodic protection (ICCP) as applied to reinforced

concrete is illustrated in Figure 9-19.

Figure 9-193 Cathodic protection schematic for steel concrete.

ICCP systems are widely used for the protection of reinforced concrete structures. The long
life titanium anodes are readily embedded in the concrete, and the application of voltage using
a transformer-rectifier units permits sufficient levels or current output to obtain protection
in a properly designed system.

9.5 The Corrosion of Non-Ferrous Metals in Concrete

9.5.1 Introduction

The crucial factor to bear in mind is the highly alkaline nature of concrete, which is desirable as an
environment for promoting a passive oxide film on steel. However, certain metals such as zinc,
aluminium and lead will react with alkalis and will be at risk. It should be realised that the
requirements for protection of concrete in some aggressive environment need not be identical to the
requirements for the protection of reinforcement in a similar environment.

9.5.2 Aluminium

Aluminium is corroded readily by alkali present in concrete, forming a soluble aluminate:

2Al + 2NaOH + 6H 2O → 2NaAl ( OH )4 + 3H 2

This chemical attack, after the initial reaction, is relatively minor. The aluminium is however
susceptible to galvanic currents within the concrete, particularly in the presence of moisture. Coatings
such as bitumen or resin often with the addition of zinc phosphate or chromate passifiers offer
protection.

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9.5.3 Lead

Lead like aluminium reacts with the Ca ( OH )2 present in concrete, but the reaction product formed
on the surface gives some protection. Like aluminium, lead is also susceptible to the action of galvanic
currents. Protective coatings similar to those used for aluminium may be applied to lead.

9.5.4 Zinc

Zinc will react with alkali producing soluble zincates in a manner similar to aluminium. Hydrogen gas
which is also produced may impair the bond between galvanized steel reinforcing, as an entrained
gas at the interface. Zinc is relatively unattacked at pH levels below 12.

9.6 Corrosion of Concrete in Aggressive Environments

9.6.1 Introduction

Concrete subjected to the attack of aggressive waters can be either completely submerged or exposed
to cycles of wetting and drying. As a general rule higher strength concretes being less permeable, are
less susceptible to many chemical agents compared to weaker more porous concrete. In addition to
the importance of the water: cement ratio, as a factor directly affecting permeability, the
incorporation of fly ash into the aggregate yields a concrete of lower permeability, due to the resulting
effect on the structure of the capillaries, which become more complex and more meandering.

Other factors such as particle size and shape, and mineralogical composition of the concrete
components will also affect porosity and pre structure of the mix. It should also be pointed out that
the relative proportions of the main components in portland cement may significantly affect strength
and resistance to certain types of chemical attack.

For example the C3S and C2S components contribute most to the ultimate strength of the cement. The
C3A contributes to the early strength, and promotes the hydration of the C3S and C2S. Refer to Table
9-1 and Table 9-2.

9.6.2 Acidic and Softwaters and Aggressive Soils

Because concrete is alkaline, it will be attacked to a greater or lesser extent by acidic water. Waters
with pH values as high as 10 have been shown to be aggressive. As the pH drops, the attack becomes
more rapid.

Common acid attacks are often due to lactic acid and acetic acids in food processing plants, or to
calcium bicarbonate levels in water. Concrete is particularly vulnerable when subjected to aggressive
solutions under pressure on one side of a structural member only. These conditions would require
special protective coatings or linings on the concrete surface.

9.6.3 Sulphate Attack on Concrete

Sulphates of magnesium and sodium present in soil water are aggressive agents towards tricalcium
aluminate, C3A, in cement, forming calcium sulphoaluminates. This product expands on formation and
causes disintegration of the cement matrix. In such cases choosing a cement level with a lower C3A
content will greatly improve resistance.

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9.6.4 Sewage Attack

Sewage and waste waters are usually nearly neutral, around pH7. Sewage may contain hydrogen
sulphide, an acidic gas formed by anaerobic bacterial action. When H2S dissolves in water it forms
acidic products which attack the concrete. In such cases attack is reduced by combining a low
permeability concrete with a protective coating.

9.6.5 Seawater Attack on Concrete

Concrete in continuously submerged structures is less likely to deteriorate than identical concrete in
the tidal or splash zones. In such environments high strength, low permeability concretes are most
resistant. Concrete which is continuously in contact with seawater (3.5% NaCl) is susceptible to
attack, due to one or more of three possible factors:

i. Sulphate ions (previously discussed in 4.6.3 Sulphate Attack on Concrete)

ii. Ingress of chloride ion
iii. The rate of steel corrosion accelerated by oxygen diffusion.

Concrete in the tidal or splash zone is more exposed to aggressive attack due to the repeated
crystallization and dissolving of salts in the concrete by the cyclic drying and wetting actions.
Battering by waves and tide, temperature variation, and an increased rate of oxygen diffusion, as well
as more rapid carbonation place great stress on the structure, relative to continuously submerged
structures.

Interestingly the presence of C3A in the cement increases resistance to chloride ion attack on
reinforcement, but increases attack by sulphate. Hence C3A levels in cement are restricted to the range
of 5-8%. Incorporation of fly ash or silica fume as a substitute for a portion of aggregate and sand
further improves the durability, and can be of significant benefit.

Finally, improvements in wharf design to reduce the severity of splash have further improved the
durability of concrete structures. Figure 9-20 illustrates recent wharf design.

Figure 9-204 Recent wharf design. The thickened integral deck slab increases the clearance above water level
compared to discrete decks and beams. Round/octagonal piles generate less splash than piles of square
section.

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9.7 Ceramics
Ceramics are compounds of metallic and non-metallic elements, for which the inter-atomic bonding
is predominantly ionic, with some covalent. The word ceramic derrives from the Greek meaning
“burnt stuff”.

Common examples of widely used ceramics are oxides such as Al2O3, SiO2, MgO, CaO, tungsten carbide
WC, silicon carbide SiC, boron nitride BN, diamond, carbon, graphite, clay, and rock. Clay and rock are
actually composites made up of two or more ceramic constituents.

Ceramics are usually hard and brittle, have high melting and boiling points, and are strong in
compression, but weak in tension.

9.7.1 Atomic structures

The simplest structures consist of crystals in which metal atoms and oxygen combine, with their
crystal geometry determined by the relative size and charge of the atoms. These crystal structures
build up in such a way as to maintain electrical neutrality.

Structures may be crystalline or partly amorphous. Slow cooling from the molten state optimizes
conditions for the formation of crystalline structures. Rapid cooling does not allow sufficient time to
enable atoms time to take up their equilibrium positions in the crystal lattice, and hence a proportion
of amorphous structure occurs. Amorphous ceramics are known as glasses.

Impurity compounds in silicate ceramics such as the oxides of sodium, potassium, and calcium known
as fluxes, encourage the formation of glasses by opening out the structured network into a more
disordered amorphous or glassy form as shown below.

Figure 9-21

The above figure illustrates the tetrahedral structure of Si and O atoms on the left.

Figure 9-22

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The right hand side diagram shows a typical silicate ceramic, partly crystalline, but also showing
random opennings in the structure, associated with a glassy character.

The diagram above shows how the addition of a flux will open up the tetrahedral ring structure and
form a glass.

9.7.2 Silicate ceramics

As discussed earlier silicates consist of tetrahedral units of Si and O atoms. The actual unit can occur
as SiO44- in differing arrangements.

Figure 9-23

The SiO44- unit is illustrated above. The Si-O bonds are only 51% ionic.

Silica can exist in several structural forms or polymorphs such as β quartz and cristobalite which are
pictured below.

Note the comparative openness of the structures pictured. This results in silica having quite a low
density of 2.65g/cm3. Furthermore the strength of the Si-O bond is reflected in the very high melting
point of 17100C.

9.7.3 The ceramic bond

When a silicate ceramic is heated with a flux such as CaO or Na2O, usually in the form of Na2CO3,these
fluxes diffuse into the surface of the ceramic network, forming a low melting point glass phase which
cements the ceramic particles together as illustrated below:

Figure 9-24

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9.7.4 Simple Silicates

The five common structures formed from the SiO44- tetrahedra are shown below.

Figure 9-25

Silicon atoms can be replaced by metal atoms if they are of the correct size and do not result in lattice
strain. In addition electrical neutrality must be maintained in foreign element substitution. This
process gives rise to a large number of silicate rock forming minerals such as:

Fosterite Mg2SiO4 , by substituting Mg2+ , and

Potassium feldspar KAlSi3O8 , by substituting K+ and Al3+

Feldspars are commonly found in many rocks such as granite,basalt and dolerite.

9.7.5 Layered silicates

Figure 9-26

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A 2-dimensional structure can be made when 3 oxygen ions are shared per tetrahedra as illustrated
above.

The repeating unit is (Si2O5)2-, and electrical neutrality is maintained by a second planar sheet having
an excess of cations which bond to the unbonded oxygen anions projecting below the page in the
above diagram.

Common ceramics with a layered structure are the clay kaolinite, and mica. Structures for these
minerals are reproduced below.

Figure 9-27

A simple schematic diagram for kaolinite is given in Figure 8-31 to simplify the more detailed
molecular structure above.

Al2(OH)42- kaolinite(clay)
---------------------------------
Si2O52- Al2O3.2SiO2.2H2O

In mica, the alkali metal ions K+,Na+ etc fit into the holes in the silicate sheet.

The plates or sheets in these layered silicates are weakly bonded together with van der Waals forces,
and hence slip past each other readily. In clay the additional presence of water assists this slip, thus
making clays geologically unstable materials.

Asbestos unlike clay and mica is a fibrous silicate with a complex double chain structure.

Finally it should be noted that clays are widely used in pottery, as filter aids in water treatment, in
brick making, and in refractories. Clay is also the vital raw material for the manufacture of cement,
which in concrete is the most commonly used material of construction.

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Figure 9-28 (a) The arrangement of silicate tetahedra in a sheet silicate. (b) The arrangement of silicate in a
mica crystal, viewed on end. The alakali ions actually fit in the large holes shown in the view of (a). In tale and
kaolinite the silicate tetrahedral are arranged similarly in a sheet, but there are no alakali ions holding the
sheets together.

It can be readily seen from the discussion thus far that ceramics are structurally amongst the most
complex inorganic materials on earth. Their properties like so many materials are a direct function of
their structure.

9.7.6 Properties of Ceramics

A detailed discussion of the diverse range of properties is beyond the scope of this modest article,
however the most important of the properties is outlined briefly below.

1. Ceramics generally have low densities, somewhere between 2.3 and 3.9 g/cm3 ..When low
density is coupled with high levels of strength and hardness it can be seen that this will result
in high strength to weight ratios.
2. High melting points are another characteristic property, thus making ceramics very useful as
refractories. Carbon and graphite are also useful refractories in addition to clays. It should be
remembered that ceramic furnace linings are often made from either acidic or basic oxides,
where they become a vital component in the smelting and refining process for manufacturing
metals like copper and steel.
3. Chemical inertness is another useful property on account of the strong bonding found in
ceramics. They are also often highly resistant to oxidation and attack by acids and bases.
4. They possess high electrical resistivity and low thermal conductivity because they are
network solids, in which all the valence electrons are used in bond formation.
5. Ceramics are brittle materials, and exhibit little or no deformation under load.

It is useful to compare the behaviour of a ceramic to steel under load. This is illustrated in the diagram
below.

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Figure 9-29

Acknowledgements

1. Moffatt,W.G, Pearsall,G.W, Wulff,John, Structure and properties of materials, volume 1,

Wiley,1964.

2. Callister,W.D, Materials science and engineering An introduction, 7th edition, Wiley 2007.

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References
1 Callister, Jr, William D. Materials Science and Engineering an Introduction. 7th ed.
York, PA: John Wiley & Sons, 2007.
2 Cherry, B W. "How to Make It Last a Little Bit Longer." Editorial. Corrosion and
Materials Oct. 2007: 16-22.
3 Freitag, S. "Concrete CP Tutorial Part 1: Methods of Cathodic Protection." Editorial.
Corrosion and Materials Aug. 2006.
4 Freitag, S., Bruce, S. "Durability of Reinforced Concrete Wharves in New Zealand."
Editorial. Corrosion and Materials Aug. 2006: 10-14.
5 John, V B. Introduction to Engineering Materials. Bath, Great Britain: The Macmillan P
Ltd., 1972.
6 Moffat, William G., George W. Pearsall, and John Wulff. The Structure and Properties of
Materials. Vol. 1. New York, USA: John Wiley & Sons, 1964.
7 Ryan, W G., and A Samarin, eds. Australian Concrete Technology. Melbourne, Australia:
Longman Cheshire, 1992.
8 Schlenker, B R. Introduction to Materials Science. SI ed. Sydney, Australia: John Wiley
& Sons, 1974.
9 Treadaway, K W., and P. R W. Vassie. Guides to Practice in Corrosion Control: the
Corrosion of Steel, and Its Monitoring, in Concrete. Vol. 7. London, UK: Maybank P Ltd.,
1981.

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Appendix A Decimal Fractions and Multiples1

Fraction Prefix Symbol

10-1 deci d
10-2 centi c
10-3 milli m
10-6 micro µ
10-9 nano n
10-12 pico p
10-15 femto f
10-18 atto a
10-21 zepto z
10-24 yocto y

Fraction Prefix Symbol

10 deca da
102 hecto h
103 kilo k
106 mega M
109 giga G
1012 tera T
1015 peta P
1018 exa E
1021 zeta Z
1024 yotta Y

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Appendix B Greek Alphabet1

Greek letter Greek name English equivalent

Α α alpha a
Β β beta b
Γ γ gamma g
∆ δ delta d
Ε ε epsilon e
Ζ ζ zeta z
Η η eta e
Θ θ theta th
Ι ι iota i
Κ κ kappa k
Λ λ lambda l
Μ µ mu m
Ν ν nu n
Ξ ξ xi x
Ο ο omicron o
Π π pi p
Ρ ρ rho r
Σ σ sigma s
Τ τ tau t
ϒ υ upsilon u
Φ ϕ phi ph
Χ χ chi ch
Ψ ψ psi ps
Ω ω omega o

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Appendix C Fundamental Constants2

Quantity Symbol Value Unit

1.660 538 73×10–24 g
Atomic mass unit 1 amu
6.022 141 99×1023 amu
Avogadro’s number N 6.022 141 99×1023 mol-1
Boltzmann’s constant k 1.380 650 3×10–23 J · K-1
Electron charge e 1.602 176 464×10–19 C
Faraday’s constant F 9.648 534 15×104 C · mol-1
0.082 058 205 L · atm · mol-1 · K-1
Gas constant R 8.314 472 J · K-1 · mol-1
8.314 472 m3 · Pa · mol-1 · K-1
5.485 799×10–4 amu
Mass of electron me
9.109 381 88×10–28 g
1.008 664 9 amu
Mass of neutron mn
1.674 927 16×10–24 g
1.007 276 5 amu
Mass of proton mp
1.672 621 58×10–24 g
Pi π 3.141 592 653
Plank’s constant h 6.626 068 76×10–34 J·s
Speed of light c 2.997 924 58×108 m · s-1

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Appendix D List of Elements2

Atomic Atomic Atomic Atomic
Element Symbol Element Symbol
number weight number weight
Actinium Ac 89 227.03a Neptunium Np 93 237.05a
Aluminium Al 13 26.981 538 Nickel Ni 28 58.693 4
Americium Am 95 243.06a Niobium Nb 41 92.906 38
Antimony Sb 51 121.760 Nitrogen N 7 14.006 7
Argon Ar 18 39.948 Nobelium No 102 259.10a
Arsenic As 33 74.921 60 Osmium Os 76 190.23
Astatine At 85 209.99a Oxygen O 8 15.999 4
Barium Ba 56 137.327 Palladium Pd 46 106.42
Berkelium Bk 97 247.07a Phosphorous P 15 30.973 761
Beryllium Be 4 9.012 182 Platinum Pt 78 195.078
Bismuth Bi 83 208.980 38 Plutonium Pu 94 244.06a
Bohrium Bh 107 264.12a Polonium Po 84 208.98a
Boron B 5 10.811 Potassium K 19 39.0983
Bromine Br 35 79.904 Praseodymium Pr 59 140.907 65
Cadmium Cd 48 112.411 Promethium Pm 61 145a
Calcium Ca 20 40.078 Protactinium Pa 91 231.035 88
Californium Cf 98 251.08a Radium Ra 88 226.03a
Carbon C 6 12.010 7 Radon Rn 86 222.02a
Cerium Ce 58 140.116 Roentgenium Rg 111 272.15a
Cesium Cs 55 132.905 45 Rhenium Re 75 186.207
Chlorine Cl 17 35.453 Rhodium Rh 45 102.905 50
Chromium Cr 24 51.9961 Rubidium Rb 37 85.467 8
Cobalt Co 27 58.933 200 Ruthenium Ru 44 101.07
Copper Cu 29 63.546 Rutherfordium Rf 104 261.11a
Curium Cm 96 247.07a Samarium Sm 62 150.36
Darmstadtium Ds 110 271.15a Scandium Sc 21 44.955 910
Dubnium Db 105 262.11a Seaborgium Sg 106 266a
Dysprosium Dy 66 162.50 Selenium Se 34 78.96
Einsteinium Es 99 252.08a Silicon Si 14 28.085 5
Erbium Er 68 167.259 Silver Ag 47 107.868 2
Europium Eu 63 151.964 Sodium Na 11 22.989 770
Fermium Fm 100 257.10a Strontium Sr 38 87.62
Fluorine F 9 18.998 403 2 Sulfur S 16 32.065
Francium Fr 87 223.02a Tantalum Ta 73 180.947 9
Gadolinium Gd 64 157.25 Technetium Tc 43 98a
Gallium Ga 31 69.723 Tellurium Te 52 127.60
Germanium Ge 32 72.64 Terbium Tb 65 158.925 34
Gold Au 79 196.966 55 Thallium Tl 81 204.383 3
Hafnium Hf 72 178.49 Thorium Th 90 232.038 1
Hassium Hs 108 269.13a Thulium Tm 69 168.934 21
Helium He 2 4.002 602 Tin Sn 50 118.710
Holmium Ho 67 164.930 32 Titanium Ti 22 47.867
Hydrogen H 1 1.007 94 Tungsten W 74 183.84
Indium In 49 114.818 Ununbiumb Uubb 112 285a
Iodine I 53 126.904 47 Ununhexiumb Uuhb 116 293a
Iridium Ir 77 192.217 Ununoctiumb Uuob 118 294a
Iron Fe 26 55.845 Ununpentiumb Uupb 115 288a
Krypton Kr 36 83.80 Ununquadiumb Uuqb 114 289a
Lanthanum La 57 138.905 5 Ununseptium Uns 117
Lawrencium Lr 103 262.11a Ununtriumb Uutb 113 284a
Lead Pb 82 207.2 Uranium U 92 238.028 91
Lithium Li 3 6.941 Vanadium V 23 50.941 5
Lutetium Lu 71 174.967 Xenon Xe 54 131.293
Magnesium Mg 12 24.305 0 Ytterbium Yb 70 173.04
Manganese Mn 25 54.938 049 Yttrium Y 39 88.905 85
Meitnerium Mt 109 268.14a Zinc Zn 30 65.39
Mendevium Md 101 258.10a Zirconium Zr 40 91.224
Mercury Hg 80 200.59 aMass of longest-lived or most important isotope
Molybdenum Mo 42 95.94 b The names/symbols of elements 112-118 are under
Neodymium Nd 60 144.24 review
Neon Ne 10 20.179 7

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Appendix E Periodic Table2

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Appendix F Common Ions2

Positive Ions (Cations)
+1 +2 +3
+
Ammonium NH 4 Barium Ba 2+ Aluminium Al3+
Cesium Cs + Cadmium Cd 2+ Chromium (III) Cr 3+
Copper(I) Cu + Calcium Ca 2+ Iron (III) Fe3+
Hydrogen H+ Chromium (II) Cr 2+
Lithium Li + Cobalt Co 2+
Potassium K+ Copper (II) Cu 2+
Silver Ag + Iron (II) Fe 2+
Sodium Na + Lead (II) Pb 2+
Magnesium Mg 2+
Manganese (II) Mn 2+
Mercury (I) Hg 22+
Mercury (II) Hg 2+
Strontium Sr 2+
Nickel Ni 2+
Tin (II) Sn 2+
Zinc Zn 2+

Negative Ions (Anions)

-1 -2 -3
− 2−
Acetate C2 H 3O 2 Carbonate CO 3 Arsenate AsO34−
Bromide Br − Chromate CrO24− Phosphate PO34−
Chlorate ClO3− Dichromate Cr2O72−
Chloride Cl − Hydrogen phosphate HPO 24−
Cyanide CN − Oxide O 2−
Dihydrogen phosphate H 2PO 4− Peroxide O 22−
Fluoride F− Sulfate SO 24−
Hydride H− Sulfide S2−
Hydrogen carbonate HCO3− Sulfite SO32−
Hydrogen sulfite HSO3−
Hydroxide OH −
Iodide I−
Nitrate NO3−
Nitrite NO −2
Perchlorate ClO −4
Permanganate MnO −4
Thiocyanate SCN −
Appendix G Standard Reduction Potentials at 25°C2
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Half-Reaction E° (V)
+ −
Ag (aq) + e → Ag (s) +0.799
AgBr(s) + e − → Ag (s) + Br(aq)
−
+0.095
− −
AgCl(s) + e → Ag (s) + Cl (aq) +0.222
Ag ( CN )2(aq) + e − → Ag (s) + 2CN (aq)
− −
−0.31
Ag 2 CrO 4(s) + 2e − → 2Ag (s) + CrO 24(aq)
−
+0.446
AgI(s) + e − → Ag (s) + I(aq)
−
−0.151
Ag ( S2 O3 )2(aq) + e − → Ag (s) + 2S2 O3(aq)
3− 2−
+0.01
+
Al3(aq) + 3e − → Al(s) −1.66
+
H 3 AsO 4(aq) + 2H (aq) + 2e − → H 3 AsO3(aq) + H 2 O(l) +0.559
2+
Ba (aq) + 2e − → Ba (s) −2.90
+ +
BiO(aq) + 2H (aq) + 3e − → Bi (s) + H 2 O(l) +0.32
Br2(l) + 2e − → 2Br(aq)
−
+1.065
− +
BrO3(aq) + 6H (aq) + 5e − → Br2 (l) + 3H 2 O(l) +1.52
+
2CO 2(g) + 2H (aq) + 2e − → H 2 C2 O 4(aq) −0.49
2+
Ca (aq) + 2e − → Ca (s) −2.87
2+
Cd (aq) + 2e − → Cd (s) −0.403
4+
Ce(aq) + e − → Ce3(aq)
+
+1.61
Cl2(g) + 2e − → 2Cl(aq)
−
+1.359
+
HClO(aq) + H (aq) + e − → Cl2(g) + H 2 O(l) +1.63
−
ClO(aq) + H 2 O(l) + 2e − → Cl(aq)
− −
+ 2OH (aq) +0.89
− +
ClO3(aq) + 6H (aq) + 5e − → Cl2(g) + 3H 2 O(l) +1.47
2+
Co (aq) + 2e − → Co (s) −0.277
+
Co3(aq) + e − → Co (aq)
2+
+1.842
3+
Cr(aq) + 3e − → Cr(s) −0.74
3+
Cr(aq) + e − → Cr(aq)
2+
−0.41
2− +
Cr2 O7(aq) + 14H (aq) + 6e − → 2Cr(aq)
3+
+ 7H 2 O(l) +1.33
−
CrO 24(aq) + 4H 2 O(l) + 3e − → Cr ( OH )3(s) + 5OH (aq)
−
−0.13
2+
Cu (aq) + 2e − → Cu (s) +0.337
2+
Cu (aq) + e − → Cu (aq)
+
+0.153
+
Cu (aq) + e − → Cu (s) +0.521

Half-Reaction E° (V)

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CuI (s) + e − → Cu (s) + I (aq)

−
−0.185
F2(g) + 2e − → 2F(aq)
−
+2.87
2+
Fe(aq) + 2e − → Fe(s) −0.440
+
Fe3(aq) + e − → Fe(aq)
2+
+0.771
Fe ( CN )6(aq) + e − → Fe ( CN )6(aq)
3− 4−
+0.36
+
2H (aq) + 2e − → H 2(g) +0.000
2H 2O(l) + 2e − → H 2(g) + 2OH (aq)
−
−0.83
−
HO 2(aq) + H 2O(l) + 2e − → 3OH (aq)
−
+0.88
+
H 2O 2(aq) + 2H (aq) + 2e − → 2H 2O(l) +1.776
+
Hg 22(aq) + 2e − → 2Hg (l) +0.789
2+
2Hg (aq) + 2e − → Hg 2(aq)
2+
+0.920
2+
Hg(aq) + 2e − → Hg(l) +0.854
I 2(s) + 2e − → 2I (aq)
−
+0.536
− +
IO3(aq) + 6H (aq) + 5e − → I 2(s) + 3H 2O(l) +1.195
+
K (aq) + e − → K (s) +2.925
+
Li(aq) + e − → Li(s) −3.05
2+
Mg (aq) + 2e − → Mg (s) −2.37
2+
Mn (aq) + 2e − → Mn (s) −1.18
+
MnO 2(s) + 4H (aq) + 2e − → Mn (aq)
2+
+ 2H 2O(l) +1.23
− +
MnO 4(aq) + 8H (aq) + 5e − → Mn (aq)
2+
+ 4H 2O(l) +1.51
−
MnO 4(aq) + 2H 2O(l) + 3e − → MnO 2(s) + 4OH (a− q) +0.59
+
HNO 2(aq) + H (aq) + e − → NO(g) + H 2O(l) +1.00
N 2(g) + 4H 2O(l) + 4e − → 4OH (aq)
−
+ N 2 H 4(aq) −1.16
+
N 2(g) + 5H (aq) + 4e − → N 2 H 5(aq)
+
−0.23
− + −
NO 3(aq) + 4H (aq) + 3e → NO(g) + 2H 2O(l) +0.96
+
Na (aq) + e − → Na (s) −2.71
2+
Ni(aq) + 2e − → Ni(s) −0.28
+
O 2(g) + 4H (aq) + 4e − → 2H 2O(l) +1.23
O 2(g) + 2H 2O(l) + 4e − → 4OH (aq)
−
+0.40
+
O 2(g) + 2H (aq) + 2e − → H 2O 2(aq) +0.68
+
O3(g) 2H (aq) + 2e − → O 2(g) + H 2O(l) +2.07
2+
Pb(aq) + 2e − → Pb(s) −0.126
Half-Reaction E° (V)
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− +
PbO 2(s) + HSO 4(aq) + 3H (aq) + 2e − → PbSO 4(s) + 2H 2O(l) +1.685
+
PbSO 4(s) + H (aq) + 2e − → Pb (s) + HSO 4(aq)
−
−0.356
−
PtCl24(aq) + 2e − → Pt (s) + 4Cl(aq)
−
+0.73
+
S(s) + 2H (aq) + 2e − → H 2S(g) +0.141
+
H 2SO3(aq) + 4H (aq) + 4e − → S(s) + 3H 2O(l) +0.45
HSO 4−(aq) + 3H (aq)
+
+ 2e − → H 2SO3(aq) + H 2O(l) +0.17
2+
Sn (aq) + 2e − → Sn (s) −0.136
4+
Sn (aq) + 2e − → Sn (aq)
2+
+0.154
+ +
VO 2(aq) + 2H (aq) + e − → VO(aq)
2+
+ H 2O(l) +1.00
2+
Zn (aq) + 2e − → Zn (s) −0.763

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Appendix H Aqueous Equilibrium Constants2

Appendix H1 Dissociation constants for acids at 25°C

Name Formula Ka1 Ka2 Ka3
Acetic HC2H3O2 1.8×10–5
Arsenic H3AsO4 5.6×10–3 1.0×10–7 3.0×10–12
Arsenous H3AsO3 5.1×10–10
Ascorbic HC6H7O6 8.0×10–5 1.6×10–12
Benzoic HC7H5O2 6.3×10–5
Boric H3BO3 5.8×10–10
Butanoic HC4H7O2 1.5×10–5
Carbonic H2CO3 4.3×10–7 5.6×10–11
Chloroacetic HC2H2O2Cl 1.4×10–3
Chlorous HClO2 1.1×10–2
Citric H3C6H5O7 7.4×10–4 1.7×10–5 4.0×10–7
Cyanic HCNO 3.5×10–4
Formic HCHO2 1.8×10–4
Hydroazoic HN3 1.9×10–5
Hydrocyanic HCN 4.9×10–10
Hydrofluoric HF 6.8×10–4
Hydrogen chromate ion HCrO4– 3.0×10–7
Hydrogen peroxide H2O2 2.4×10–12
Hydrogen selenate ion HSeO4 2.2×10–2
Hydrosulfuric acid H2S 9.5×10–8 1×10–19
Hypobromous HBrO 2.5×10–9
Hypochlorous HClO 3.0×10–8
Hypoiodous HIO 2.3×10–11
Iodic HIO3 1.7×10–1
Lactic HC3H5O3 1.4×10–4
Malonic H2C3H2O4 1.5×10–3 2.0×10–6
Nitrous HNO2 4.5×10–4
Oxalic H2C2O4 5.9×10–2 6.4×10–5
Paraperiodic H5IO6 2.8×10–2 5.3×10–9
Phenol HC6H5O 1.3 ×10–10
Phosphoric H3PO4 7.5×10–3 6.2×10–8 4.2×10–13
Propionic HC3H5O2 1.3×10–5
Pyrophosphoric H4P2O7 3.0×10–2 4.4×10–3
Selenous H2SeO3 2.3×10–3 5.3×10–9
Sulfuric H2SO4 Strong acid 1.2×10–2
Sulfurous H2SO3 1.7×10–2 6.4×10–8
Tartaric H2C4H4O6 1.0×10–3 4.6×10–5

Appendix H-2 Dissociation constants for bases at 25°C

Name Formula Kb
Ammonia NH3 1.8×10–5
Aniline C6H5NH2 4.3×10–10
Dimethylamine (CH3)2NH 5.4×10–4
Ethylamine C2H5NH2 6.4×10–4
Hydrazine H2NNH2 1.3×10–6
Hydroxylamine HONH2 1.1×10–8
Methylamine CH3NH2 4.4×10–4
Pyridine C5H5N 1.7×10–9
Trimethylamine (CH3)3N 6.4×10–5

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APPENDIX I
Thermodynamic Quantities for Selected Substances
At 298.15 K (250C)

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