viii Contents

Summary 384
Problems 385
Multiple Choice Questions 387
Sources for Experimental Data 392
Suggestions for Further Reading 392

16 Magnetic Materials 393–411

16.1 Terminology and Classification 394
16.2 Magnetic Moments due to Electron Spin 395
16.3 Ferromagnetism and Related Phenomena 397
16.4 The Domain Structure 399
16.5 The Hysteresis Loop 400
16.6 Soft Magnetic Materials 402
16.7 Hard Magnetic Materials 405
Summary 407
Problems 407
Multiple Choice Questions 409
Sources for Experimental Data 411
Suggestions for Further Reading 411

17 Dielectric Materials 412–426

17.1 Polarization 413
17.2 Temperature and Frequency Effects 416
17.3 Electric Breakdown 419
17.4 Ferroelectric Materials 420
Summary 423
Problems 424
Multiple Choice Questions 424
Sources for Experimental Data 426
Suggestions for Further Reading 426

Appendix I—Properties of Elements 427–429

Appendix II—Properties of Engineering Materials 430

Index 431–439
 Preface

Since the first edition was published, many new features have been added to this
book. They include new chapters and new sections on recent topics such as the
oxide superconductors, fabrication techniques used in manufacturing integrated
circuits, fullerenes, and fracture mechanism maps. In this edition, the text has
been updated and rewritten for greater clarity. The diagrams have been improved
and drawn using a computer software.
The author is thankful to Mr. Narendra Babu for his assistance in preparing
the diagrams. Thanks are also due to the editorial and production team of the
Publishers, PHI Learning, in particular, to Mr. K.C. Devasia, for their assistance.
The author is grateful to his colleagues at IIT Delhi—Dr. R.K. Pandey,
Dr. S.K. Gupta, Dr. A.N. Kumar and Dr. R. Prasad—for their valuable suggestions.

V. RAGHAVAN

ix
 Preface to the First Edition

In keeping with modern trends, the courses in engineering materials or

engineering metals and alloys have been replaced by a course in Materials Science
in many institutions in India and abroad. Most of the curricula in metallurgy,
ceramics and other materials-oriented disciplines have also incorporated a first
general course in materials science. This book is intended for use in such courses
as well as by the students of applied sciences. Postgraduates who have had no
previous exposure to the subject should also find this book useful.
In deciding the level at which this material is to be covered, it has been
assumed that the reader has a background in college level physics, chemistry and
mathematics. Though not essential, an elementary knowledge of physical
chemistry and thermodynamics would be an added advantage.
A reasonably wide coverage in sufficient depth has been attempted, giving
the necessary importance to the physical, mechanical, chemical, electrical and
magnetic properties. Consistent with the moderate size of the book, the author
has tried to emphasize the properties that are more structure-sensitive. Keeping
in view the engineering applications, numerous examples of real materials of
technological importance have been discussed.
A number of colleagues of the author and over 1500 students who studied
this first course during the last 10 years have contributed significantly in class
testing and greatly improving this work. In particular, mention must be made of
Drs. E.C. Subbarao, D. Chakravorty, L.A. Shepard, M.F. Merriam, C.V. Seshadri,
R.K. Mittal and Shri V.M. Kumar and M.L. Gandhi. The author is grateful to
Professor N.M. Swani for his encouragement and interest. Special mention must
be made of Professor Morris Cohen for providing the author an opportunity to
teach materials science courses at the Massachusetts Institute of Technology.

January 1974 V. RAGHAVAN

x
 SI UNITS

Base Units

Quantity Unit Symbol

Length l metre m
Mass m kilogram kg
Time t second s
Electric current I ampere A
Temperature T kelvin K
*Amount of substance n mole mol
Luminous intensity candela cd
*
The mole is the amount of substance that contains as many elementary entities as
there are atoms in 0.012 kg of carbon-12. The elementary entities may be atoms, ions,
electrons, other particles or groups of particles.

Supplementary Units

Plane angle radian rad

Solid angle steradian sr

Derived Units with Special Names

Equivalence in
Quantity Special Symbol
name other derived base units
units
Frequency hertz Hz — s–1
Force, weight newton N — kg m s–2
123 123

–2
Stress, strength, pascal Pa Nm kg m–1 s–2
pressure
Energy, work, joule J Nm kg m2 s–2
quantity of heat
Power watt W J s–1 kg m2 s–3
Electric charge coulomb C — As
Electric potential volt V W A–1 kg m2 s–3 A–1
Resistance ohm W V A–1 kg m2 s–3 A–2
Capacitance farad F C V –1 kg–1 m–2 s4 A2
Magnetic flux weber Wb Vs kg m2 s–2 A–1
Wb m–2 kg s–2 A–1
123

Magnetic flux tesla T

density
Inductance henry H Wb A–1 kg m2 s–2 A–2
xi
xii SI Units

Prefix Names of Multiples and Submultiples

Factor by which
unit is multiplied Name Symbol
12
10 tera T
109 giga G
106 mega M
103 kilo k
102 hecto h
101 deka da
10–1 deci d
10–2 centi c
10–3 milli m
10–6 micro m
10–9 nano n
10–12 pico p
10–15 femto f
10–18 atto a
Note: All multiple prefix symbols (except kilo, hecto and deka) are written in capitals
and all submultiple symbols are written in lower case letters.

Have a feel for SI units !

Sir Issac Newton, the Apple and SI units

Length unit: 1 metre ~ distance the apple travelled

Time unit: 1 second ~ time of fall of the apple
Force unit: 1 newton ~ weight of the apple
 SI Units xiii

Conventions to be followed when using SI units

1. When writing unit symbols, do not use full stops, plurals, dots or dashes.
2. No degree symbol for kelvin, write as K and not as °K.
3. No kgm (kilogram mass) or kgf (kilogram force). The mass unit is
kilogram (kg) and the force unit is newton (N).
4. No space between the prefix symbol and the unit symbol, e.g.,
meganewton should be written as MN and not as M N.
5. One space between two symbols for clarity, e.g., metre second should be
written as m s and not as ms, which means millisecond.
6. All symbols associated with proper names are written with a capital, e.g.,
A, K, N, etc. When they are written as a word, the lower case is used
throughout: ampere, kelvin and newton.
7. Prefix symbols for multiples and submultiples are preferred in steps of 103.
Thus, tera (T), giga (G), mega (M), kilo (k), milli (m), micro (m), nano (n)
and pico (p) are preferred prefix symbols.
8. Attach prefix to numerator and not to denominator, e.g., use MN m–2
instead of N mm–2, even though both are identical.
9. Three digits are grouped together on either side of the decimal point, e.g.,
1.256 637 83
60 023
Four digit number need not be so grouped, e.g.,
7386
0.6921

Some non-SI units generally accepted

1. degree (celsius), °C.

2. minutes, hours, days, months and years.
3. Angstrom Å for 10–10 m.
4. Electronvolt, eV for energy equal to 1.602 ´ 10–19 J. (1 electronvolt is the
kinetic energy acquired by an electron when falling through a potential of
1 volt.)
 PHYSICAL CONSTANTS

Avogadro’s number N = 6.023 ´ 1023 mol–1

Boltzmann’s constant k = 1.380 ´ 10–23 J K–1
= 8.614 ´ 10–5 eV K–1
Gas constant R = 8.314 J mol–1 K–1
Planck’s constant h = 6.626 ´ 10–34 J s
Electronic charge e = 1.602 ´ 10–19 C
Electron rest mass m0 = 9.109 ´ 10–31 kg
Velocity of light c = 2.998 ´ 108 m s–1
Bohr magneton (magnetic moment) mB = 9.273 ´ 10–24 A m2
Permittivity of free space e0 = 8.854 ´ 10–12 F m–1
Permeability of free space m0 = 4p ´ 10–7 H m–1
= 1.257 ´ 10–6 H m–1
Faraday’s constant F = 96.49 kC mol–1 (of electrons)
Atomic mass unit (amu) 1/(103N) = 1.660 ´ 10–27 kg
Acceleration due to gravity g = 9.81 m s–2

xiv
 CONVERSION FACTORS

1 inch = 25.4 mm
1 nm = 10–9 m
1Å = 10–10 m = 0.1 nm
1° = 1/57.3 rad

T °C = (T + 273.15) K
T °F = 5/9(T + 459.67) K
1 per °F = 9/5 K–1

1 kgf = 9.81 N
1 lb = 4.45 N
1 dyne = 10–5 N
1 dyne/cm = 10–3 N m–1
1 atmosphere = 0.101 325 MN m–2
1 bar = 10–1 MPa
1 psi = 6.89 kN m–2
1 ksi (103 psi) = 6.89 MN m–2
1 ton/sq.in. = 15.46 MN m–2
1 kgf/cm2 = 98.1 kN m–2
1 kgf/mm2 = 9.81 MN m–2
1 dyne/cm2 = 0.1 N m–2
1 torr (mm of Hg) = 133.3 N m–2
1 kgf/mm3/2 = 0.310 MN m–3/2
1 ksi Öin = 1.10 MN m–3/2

1 eV = 1.602 ´ 10–19 J
1 erg = 10–7 J
1 calorie = 4.18 J
1 eV/entity = 96.49 kJ mol–1
1 erg/cm = 10–5 J m–1
1 erg/cm2 = 10–3 J m–2
1 erg/cm3 = 0.1 J m–3
1 lb-in/in2 = 175 J m–2

1 lb/cu.in = 27 680 kg m–3

1 cm/cm3 = 104 m m–3
1 mole/cm2/sec = 104 mol m–2 s–1
1 mole/cm3 = 106 mol m–3
1 cm2/sec = 10–4 m2 s–1
xv
xvi Conversion Factors

1 poise = 0.1 Pa s
1 debye = 3.33 ´ 10–30 C m
1 mA/cm2 = 10 A m–2
1 A hr = 3.6 kC
1 ohm cm = 10–2 ohm m
1 mho/cm = 102 ohm–1 m–1
1 volt/mil = 39 370 V m–1
1 cm2/volt sec = 10–4 m2 V–1s–1

1 gauss = 10–4 Wb m–2

1 oersted = 79.6 A m–1
 GREEK ALPHABETS

Name Forms Sound Name Forms Sound

alpha a a nu n n
beta b b xi x, X x
gamma g, G g omicron o o
delta d, D d pi p, P p
epsilon e e rho r r
zeta z z sigma s, S s
eta h e tau t t
theta q, Q th upsilon u u
iota i i phi f, F ph
kappa k k khi c kh
lambda l, L l psi j, y ps
mu m m omega w, W o

xvii
1
CHAPTER

Introduction

In this introductory chapter, we briefly discuss the nature of Materials Science

and Engineering. After defining or explaining what Materials Science and
Engineering is, we classify engineering materials according to their nature and
the various categories of applications. Then we discuss the different levels of the
internal structure of materials. Finally, we emphasize the importance of the
structure–property relationships in materials, outlining the general approach of
the ensuing chapters.

1.1 Materials Science and Engineering

The phrase ‘Materials Science and Engineering’ needs some elucidation for the
beginner. The word ‘materials’ here does not refer to all matter in the Universe.
If this were so, it would include all the physical sciences and the life sciences—
from astronomy to zoology! By including the word ‘inanimate’ in the definition,
we can exclude the life sciences from our purview. Further, we can restrict the
definition only to matter useful to mankind. Even here, the range is too broad for
the purposes of the engineer. For example, we can list a large number of things
useful to man, such as food, medicines, explosives, chemicals, water, steel,
plastics and concrete, only some of which qualify as engineering materials. We
then have to be more specific and define materials as that part of inanimate
matter, which is useful to the engineer in the practice of his profession. In the
currently understood sense of the term, materials refer only to solid materials,
even though it is possible to quote a number of examples of liquid and gaseous
materials such as sulphuric acid and steam, which are useful to the engineer.
The word ‘science’ in the phrase refers to the physical sciences, in particular
to chemistry and physics. As we confine ourselves mainly to solids in materials
science, the subject is related to solid state chemistry and solid state physics.
The word ‘engineering’ indicates that the engineering usefulness of the matter
under study is always kept in mind, irrespective of whether the basic laws of
science can be applied rigorously or not. Where the basic laws cannot be
applied, the materials engineer does not give up what is important to him from a
practical point of view. He uses the best possible approximation, develops
1
2 Introduction

empirical rules, and extrapolates available information to unknown situations. In

this respect, materials science and engineering draws heavily from the
engineering sciences such as metallurgy, ceramics and polymer science. These,
in their own time, have grown out of their interaction with the basic sciences of
chemistry and physics.

1.2 Classification of Engineering Materials

Having defined the limits of materials that come under our purview, we can
classify them in three broad groups according to their nature:
(i) Metals and alloys
(ii) Ceramics and glasses
(iii) Organic polymers.
Metals are familiar objects with a characteristic appearance; they are capable
of changing their shape permanently, and have good thermal and electrical
conductivity. An alloy is a combination of more than one metal. Ceramics and
glasses are nonmetallic inorganic substances, which are brittle and have good
thermal and electrical insulating properties. Organic polymers are relatively inert
and light, and generally have a high degree of plasticity. Figure 1.1 lists typical
examples from each of these three groups of materials. In addition, examples of
materials which lie between two groups are also shown.

Metals and Alloys

Me
l

Steels, aluminium, copper,

e

tal-
ste

silver, gold
ced s
ein , GaA

rei

Brasses, bronzes, manganin,

nfo
for

invar
rid i, Ge

rce

Superalloys
dp
e-r

Boron rare earth

S

las

magnetic alloys
tics
Bo

Ceramics and Glasses Organic Polymers

MgO, CdS, Al2O3, SiC, Plastics: PVC, PTFE,
BaTiO3 polyethylene
Silica, soda-lime-glass, Fibres: terylene, nylon,
concrete, cement cotton
Ferrites and garnets Natural and synthetic
Ceramic rubbers
superconductors Leather

Glass fibre-reinforced
plastics

Fig. 1.1 The three major groups of engineering materials.

 Levels of Structure 3

An alternative way of classifying materials is according to the three major

areas in which they are used:
(i) Structures
(ii) Machines
(iii) Devices.
Structures (not to be confused with the internal structure of a material) refer to
the objects without moving parts erected by engineers, such as a concrete dam, a
steel melting furnace, a suspension bridge and an oil refinery tower. Machines
include lathes, steam and gas turbines, engines, electric motors and generators.
Devices are the most recent addition to engineering materials and refer to such
innovations as a transistor, a photoelectric cell, piezoelectric pressure gauges,
ceramic magnets and lasers.
Invariably, in each category of applications, we find materials from all the
three groups described above. To give some examples, an aircraft structure is built
of aluminium alloys and plastics; a steel melting furnace is built of refractory
oxides and structural steel; safety helmets are made of glass-reinforced plastics.
Similarly, we have metal-oxide semiconductors. The block diagram in Fig. 1.2
depicts this interplay between material groups and categories of applications.

Metals and Alloys Ceramics and Glasses Polymers

Engineering Materials

Applications

Structures Machines Devices

Fig. 1.2 Each category of engineering application requires materials from any or
all of the three groups of materials.

1.3 Levels of Structure

The internal structure of a material, simply called the structure, can be studied
at various levels of observation. The magnification and resolution of the physical
aid used are a measure of the level of observation. The higher the magnification,
the finer is the level. The details that are disclosed at a certain level of
observation are generally different from the details disclosed at some other level.
Henry Sorby was one of the first to realize this, when he wrote in 1886:
4 Introduction

Though I had studied the microscopical structure of iron and steel for many
years, it was not until last autumn that I employed what may be called high
powers. This was partly because I did not see how this could be satisfactorily
done and partly because it seemed to me unnecessary. I had found that in
almost every case a power (magnification) of 50 linear showed on a smaller
scale as much as one of 200, and this led me to conclude that I had seen the
ultimate structure. Now that the results are known, it is easy to see that my
reasoning was false, since a power of 650 linear enables us to see a structure of
an almost entirely new order.
We have now come a long way since Sorby’s time. Magnifications with
matching resolutions of a million times linear are now common.
Depending on the level, we can classify the structure of materials as:
Macrostructure
Microstructure
Substructure
Crystal structure
Electronic structure
Nuclear structure.
Macrostructure of a material is examined with naked eye or under a low
magnification. The internal symmetry of the atomic arrangements in a crystalline
material may reflect in the external form of a crystal such as quartz. Large
individual crystals of a crystalline material may be visible to the naked eye, as in
a brass doorknob by the constant polishing and etching action of the human
hand and sweat.
Microstructure generally refers to the structure as observed under the optical
microscope, see Fig. 1.3. This microscope can magnify a structure up to about
1500 times linear, without loss of resolution of details of the structure. The limit

Fig. 1.3 Crystal boundaries in nickel ferrite, Fe2NiO4, magnified 900 times linear.
(W.D. Kingery, Introduction to Ceramics, with permission from John Wiley,
New York)
 Levels of Structure 5

of resolution of the human eye is about 0.1 mm (10–4 m), that is, the eye can
distinguish two lines as separate lines, only when their distance of separation is
more than 0.1 mm. The optical microscope can resolve details down to a limit of
about 0.1 mm (10–7 m).
Substructure refers to the structure obtained by using a microscope with a
much higher magnification and resolution than the optical microscope. In an
electron microscope, a magnification of 1 000 000 times linear is possible. By
virtue of the smaller wavelength of electrons as compared to visible light, the
resolving power also increases correspondingly so that much finer details show
up in the electron microscope. We can obtain a wealth of additional information
on very fine particles or on crystal imperfections such as dislocations. Figure 1.4

Fig. 1.4 Substructure of a Ni–Fe–Cr alloy showing curved dislocation lines,

magnified 30 000 times in an electron microscope.
(R.B. Nicholson, Strengthening Methods in Crystals, with permission from Applied
Science Publishers Ltd., Barking, UK)

shows dislocations imaged in a transmission electron microscope. Here, electrons

pass through a thin foil of the specimen and the associated diffraction effects
produce the image. The electron diffraction patterns obtained along with the
photograph of the substructure greatly aid in understanding the processes taking
place in materials on such a minute scale.
In a scanning electron microscope, an electron beam is scanned across the
surface of the specimen, which must be conducting. Back scattered electrons at
6 Introduction

each point are collected and displayed at the same scanning rate on a cathode
ray tube. The result is an image, much like a television image, of the surface
features of the specimen. This image has a very great depth of field so that even
a fractured surface without any polishing can be imaged (refer Fig. 12.1e).
Magnifications range from 10 ´ to 50 000 ´.
In the electron probe microanalyzer, a beam of electrons bombards the
specimen surface. X-rays that have wavelengths characteristic of the elements in
the specimen are emitted. Using suitable standards, elements present in the
specimen can be identified and their concentration determined from the X-ray
intensity. Thus this technique allows microchemical analysis on spots as small as
1 mm.
Another modern microscope is the field ion microscope. It produces images
of individual atoms (Fig. 1.5) and imperfections in atomic arrangements.

Fig. 1.5 Field–ion micrograph of a hemispherical tip of platinum. The white dots
arranged in circles are images of individual atoms.
(Courtesy: E.W. Mueller)