METALLURGY

 Defined as art and science of procuring and

adopting metals and alloys to satisfy human
wants.
Crystal Structures
Structure of the Atom
 Atomic number equals to the amount of all the
electrons in the atom
 Atomic number equals to the amount of all the
protons in the atom
 Valence equals to the amount of free spaces
available for the electrons on the outer shell
 Atom that lost/gained its electron is called ion
Atomic Arrangements
 In gases there is no order
 In liquids there is short range order
 In solids there is long range order
 The order is determined by the type of atomic
bonds
Bonding of Metals
 Primary Bonds
Ionic bond
Covalent bond
Metallic bond
 Secondary Bonds
Dispersion bond
Dipole bond
Hydrogen bond
Ionic Bonds

- Formed from electrostatic attractions of closely

packed, oppositely charged ions.
- Formed when an atom that easily loses
electrons reacts with one that has a high
electron affinity.
08_136
Li Be O F

(0.60) (0.31)
60 31 (1.40) (1.36)
140 136

S Cl
Na Mg Al

(0.95) (0.65) (0.50)

95 65 50 (1.84) (1.81)
184 181

K Ca Ga Se Br

(1.33) (0.99) (0.62) (1.98) (1.95)

133 99 62 198 195

Te I
Rb Sr In Sn Sb

(1.48) (1.13) (0.81) (0.71) (0.62)

148 113 81 71 62 (2.21) (2.16)
221 216
Ionic bond
 Sodium Chloride Structure
Covalent Bonding – sharing valence
electrons
Scanning Tunneling Microscope Image of Iron
in the (110) plane
Metallic Bonding
Space Lattices
 A grid like pattern
 Composed of unit cells
 Unit cells are stacked together endlessly to form
the lattice (with no empty spaces between cells)
 Unit Cells
 The smallest volume of crystal which charecterizes the
arrangement and position of atoms in crystal structure
called unit cell.
There are six basic shapes of the unit cells

 Cubic (Simplest to understand)

 Body Centered (BCC)

 Face Centered (FCC)

 Hexagonal close-packed (HCP)
 Body-centered tetragonal (BCT)
 Rhombohedral
Why Does Anything Solidify?
 The energy of the crystal structure is less than
that of the liquid
 The difference is the volume free energy
 As the solid grows in size, the magnitude of the
total volume free energy increases…
Formation of Nucleii
 Molecules are always bumping into each other –
sometimes they stick
 At lower kinetic energies more stick
Solidification
 When the liquid solidifies,
energy must be removed.
 In planar growth the energy
is conducted into the solid
and out through the walls of
the container.
Grain Boundary

When the crystals (grains) meet they form a grain boundary

Dendrites
 Dendrites form as the metal solidifies out into the
melt, leaving molten metal behind, that has been
reheated from the heat evolved in the
solidification process.
Casting
 Most metals are poured into molds
 Produce ingots, that are later processed
 The structure of ingots is not homogeneous.
Solidification Imperfections
 Most atoms are in ideal locations. Small number
are out of place
 Point Defects
 Line Defects
 Surface Defects
 Types of Point Defects
a) Vacancy
b) Interstitial
a) Frenkel
defect
d) Impurity atom
Plastic Deformation
 Deformation of materials occurs when a line
defect (dislocation) moves through the material
 When a shear force is applied to a material, the
dislocations move
 Real materials have lots of dislocations,
therefore the strength of the material depends on
the force required to make the dislocation move,
not the bonding energy
Dislocations
 Line imperfections in a 3D lattice
 Edge
 Screw
 Mixed
Elastic and Plastic Deformation
Slip
Slip along the closely packed planes
Plastic deformation by twinning
 When a piece of metal is deformed, the
dislocations run into each other
 This traffic jam increases the material’s strength
 Deforming a piece of metal also actually
increases the number of dislocations
 This increases the strength too!!
Larger grains have more capacity to slip
What happens when a dislocation
runs into a flaw?
 Takes more energy to move “over the
imperfection”
 May stop moving all together
 Therefore, introducing imperfections into the
material, actually strengthens it!!
Edge dislocation
 ASTM Grain Size Numbers
N is the number of
grains per square
inch at a
magnification of 100

n is the ASTM grain

size
Affect of Grain Size on Strength
 In a small grain, a dislocation gets to the
boundary and stops – slip stops
 In a large grain, the dislocation can travel farther
 Small grain size equates to more strength
Phase Diagrams

Chapter 4
Why Alloys?
 The existence of two or more phases can
strengthen a material
 Usually pure metals are soft materials
 Alloying element – present in smaller amounts
(most steels contain less than 1% of carbon)
Let’s Start with a basic question..
What is a phase?
 Homogeneous in crystal structure and atomic
arrangement
 Same physical and chemical properties
 A definite interface with its surroundings
 Mechanically separable
 Solution and Solubility

Example: Solubility of salt in water

There exists a maximum amount of salt that
can be completely dissolved in water; excess
of salt stays as solid. This maximum amount
is the solubility of salt in water. The solution
containing the maximum concentration of salt
is a saturated solution.

Cooling of saturated solution results in the

formation of solid salt from the solution,
indicating that solubility decreases with Solid salt – the Salty water –
decreasing T. This process is called precipitate the solution
precipitation and the solid formed is a
precipitate. Heating the solution will lead to
the dissolving of the precipitate back into
solution.
 The same concepts apply to solids: solid solution,
saturation, solubility, precipitation

In this example there exist two phases in the

system and the two phases stay in equilibrium:

dissolving
Solution Solid
precipitation
For example
 A glass of ice water has two phases
Solid water phase
Liquid water phase
 A mixture of salt and pepper has two phases
Solid salt
Solid pepper
Solid, Liquid or Gas?
 We usually think of matter as having 3 phases,
but..
 It’s possible to have more than one solid phase.
 For example
when iron first freezes it is BCC
As it cools it changes to FCC
Upon further cooling it changes to BCC
Phase Diagram
 A visualization technique to help you see where different phases
exist, based on “state variables”

Pressure Liquid

Solid
Gas

Temperature
Mapping for a temperature-composition
equilibrium phase diagram
Allotropic Transformation
 Iron
 BCC at high temperatures 1538-1401 deg. C (d
 ferrite)
 FCC at moderate temperatures 1401-908 deg. C
(austenite)
 BCC at low temperatures up to 908 deg.C (a 
ferrite)
 Change in specific volume
Cooling Curve for a Pure Metal

Liquid
Temperature

solid
L + solid

Time
Forms in which Alloys Exist:
 Solid solutions
 Compounds
 Mixtures (e.g. bird feed)
Intermetallic Compounds
 Often alloying elements form with the host
intermetallic compounds – metals that are
chemically bonded to each other
 They are hard and brittle
 Give the alloy strength, wear resistance and
hardness
Solid Solutions
 Solubility of one metal in another occurs at the
atom-lattice level
 Can be substitutional or interstitital
Substitutional Solid Solution

Solute atoms displace the host atoms

Substitutional Solid Solution
 Possible only if the atoms have close atomic
diameters
Interstitial Solid Solution

Solute atoms are located between the atoms

of the host metal
Guidelines
 Host metal should be soft to provide ductility
 Alloying metal should be hard to provide strength
– more precipitate results in higher strength
 Precipitate should be discontinuous
Guidelines
 Smaller, more numerous precipitate particles
give higher strength because they interfere with
slip
 Round particles are better than sharp particles –
Sharp particles can initiate a crack
Type 1 solid solution alloys
 Completely soluble in each other in solid and
liquid states
 Difference in the atoms sizes should be less that
15%
 Similar chemical properties
 Similar crystal lattice
Cooling Curve of Pure Metal

Freezing takes place at

a constant temperature,
during freezing the
latent heat of
solidification is given
off.
 Cooling curves –determination of
phase diagrams
II
1455C
T
1085C Liquid Liquidus

(thermal arrest) T1
Solidus
T L+S
T2
Solid
I
T1 1085C
T II I III
T2

Cu % Ni

t
 liquid phase - 1455C
The simplest type of binary phase Solution of
Cu and Ni
diagrams is the Type I system, in
which the two metals form a
continuous solid solution over the T1 Co

Temperature
entire composition range. An CS1
T2 CL2
example is the Ni-Cu system.
CS2
T3 CL3
Solidification of alloy Co starts on Co
cooing at T1. The first solid formed a phase (FCC)
has a composition of Cs1 and the Solid solution
liquid Co. On further cooling the 1085C of Cu and Ni
solid particles grow larger in size
and change their composition to Cs2
and then Co, following the solidus
whereas the liquid decrease in Cu Composition Ni
volume and changes its composition
from Co to CL3 following the liquidus. L
The solidification completes at T3. a
How Does the Solid Form?

Liquid a

L+a ab
How Does the Eutectic Solid Form?

Liquid

L+ab
Eutectic Solids are strong
but generally have little
ductility
Type II – Eutectic Alloys

Partial equilibrium diagram for NaCl and H2O

derived from cooling-curve information
Cooling Curve for a Eutectic System
Plumber’s
solder is a
Liquid
eutectic
alloy of Pb
and Sn.
Temperature

ab Why?
L+ab

Low,
sharp
melting
Time point
Strength of Eutectic Alloys
 Each phase is solid solution strengthened
 Grain size affects the strength – well inoculated
melts have smaller grain size
 Interlamellar spacing
Iron-Carbon Phase Diagram
Solid State Transformations
(reactions)
 The change from one solid to another has a lot
in common with the solidification process
 It does not happen instantly
Need nucleation
Need time for growth
Nucleation
 Nucleation usually occurs at grain boundaries
 Unlike solidification, it isn’t too hard to get a
nucleus going
 However, the nucleation rate increases as the
temperature goes down
Growth
 The nucleus grows as material diffuses to the
site
 Diffusion is a function of temperature
 If you cool the material off immediately, it is hard
for diffusion to occur
 Supersaturated non-equilibrium structures can
occur
How Does the Solid Form?
This is
Liquid a what we
would like
to happen

L+a ab
How Does the Solid Form?

Liquid a This is what

typically
happens

L+a
a We want to
avoid this
structure,
b which is
caused by
slow cooling
Eutectoid and Eutectic Reactions
 One solid phase transforms to two different
solid phases S1→S2+S3 (eutectoid)
 One liquid phase transforms into two different
solid phases L1→S1+S2 (eutectic)
 The iron – carbon phase diagram both reaction
 This diagram is the basis for iron and steels
 peritectic
Iron-Iron Carbide Phase Diagram
1600
C
d, ferrite
1400
Liquid
C

Eutectic
L+g
g,
1200
C L + cementite
austenite
1000
C g  Cementite
Eutectoid
800
C

600 C a, ferrite Cementite

(Fe3C
400 C
Fe 1% C 2% C 3% C 4% C 5% C 6% C 6.70% C
 Invariant Reactions in Fe-C system
A horizontal line always indicates an invariant reaction in binary
phase diagrams

Peritectic Reaction

a (0.1 wt % C)  L (0.5 wt % C) d (0.18 wt % C)

1493o C

Eutectic Reaction

L (4.3 wt % C )  g (2.1 wt % C )  Fe3C (6.67 wt % C )

1150o C

Eutectoid Reaction

g (0.8 wt % C ) a (0.02 wt % C )  Fe3C (6.67 wt % C )

725o C
 Pure Iron
16
00
C  Solidifies first as d ferrite –
14
00
which is BCC
C
 Then, as it cools, it goes
12
00 through an allotropic phase
transformation to g austenite
C
10
00
C – which is FCC
80  Finally, it changes to a
0
C ferrite, which is BCC
60
0C

40
0 CF 1 2% 3 4% 5% 6% 6.70
e % C % C C C %C
C C
 Carbon is significantly
16
 00
C
more soluble in austenite 14
00
than in ferrite, because C

of the crystal structure

12
00
C

 As the austenite cools, 10

00

the carbon eventually C

8
comes out of solution as 0
0

cementite C
60
0
C
40
0 F 1 2% 3 4 5% 6% 6.70
C e % C % % C C %C
C C C
Dispersion Strengthened Iron
 In this region the iron is
dispersion
strengthened
 Solid a converts to a +
cementite

a a
Cementite
Hypoeutectoid Iron

Ductile
g
a Continuous
Phase

Pearlite
a
Hypereutectoid Iron
g

g Brittle
Fe3C Continuous
Phase
Used in
Ball
Fe3C Bearings

Pearlite
Is it Iron or Steel?
 Steel is an iron-carbon alloy – that may contain
other alloying elements
 Low , Medium and High Carbon Steel
Usually less than about 1%
 Alloy Steels such as Stainless contain other
elements such as Chromium
Steel & Cast Iron classifications
 On the basis of the Fe‐Fe3C phase diagram,
iron‐carbon alloys can be classified as:
Up to 0.8%C – Hypo‐eutectoid steels
0.8 – 2.0%C – Hyper‐eutectoid steels
2.0 – 4.3%C – Hypo‐eutectic Cast Irons
4.3 or more %C – Hyper‐eutectic Cast Irons
 plain carbon steels are classified as:
Low carbon or Mild Steels Up to 0.3%C)
Medium carbon or Mid carbon Steels (0.3 – 0.7%C)
High carbon or Tool Steels (0.7 – 1.4%C)
HRS vs. CRS
 HRS  HRS Characterized by:
AKA hot finishing – ingots or Extremely ductile (i.e. %
continuous cast shapes rolled elongation 20 to 30%)
in the “HOT” condition to a Moderate strength (Su approx
smaller shape. 60 – 75 ksi for 1020)
Since hot, grains recrystallize Rough surface finish – black
without material getting harder! scale left on surface.
Dislocations are annihilated
(recall dislocations impede slip
motion).
HRS vs. CRS
 CRS  CRS Characterized by:
AKA cold finishing – coil of Less ductlie – almost brittle
HRS rolled through a series of (i.e. % elongation 5 to 10%)
rolling mills AT ROOM High strength (Su approx 120
TEMPERATURE. ksi for 1020)
Since rolled at room
temperature, get crystal
defects called dislocations
which impede motion via slip!
AKA work hardening
Limit to how much you can
work harden before too brittle.
How reverse? Can
recrystallize by annealing.
 AISI - SAE Classification System

American Iron and Steel Institute (AISI)

 classifies alloys by chemistry
 4 digit number
1st number is the major alloying agent
2nd number designates the subgroup alloying agent
last two numbers approximate amount of carbon
(expresses in 0.01%)
 Plain Carbon Steel vs. Alloy
Steel

Plain Carbon Steel (10xx)

 Lowest cost
 Should be considered first in most application
 3 Classifications
Low Carbon Steel
Medium Carbon Steel
High Carbon Steel
 Plain Carbon Steel
1. Low Carbon (less than 0.3% carbon)
• Low strength, good formability
• If wear is a potential problem, can be carburized (diffusion
hardening)
• Most stampings made from these steels
• AISI 1008, 1010, 1015, 1018, 1020, 1022, 1025
2. Med Carbon (0.3% to 0.6%)
• Have moderate to high strength with fairly good ductility
• Can be used in most machine elements
• AISI 1030, 1040, 1050, 1060*
3. High Carbon (0.6% to 0.95%)
• Have high strength, lower elongation
• Can be quench hardened
• Used in applications where surface subject to abrasion – tools, knives,
chisels, ag implements.
• AISI 1080, 1095
Plain Carbon Steel (10xx)

 1018
Low carbon Yield strength 55ksi
 1045
Medium carbon Yield strength 70ksi
 ASTM A36 or A37 – aka structural steel
Low carbon Yield strength 36ksi
 12L14
Low carbon Yield strength 70ksi
 1144
Medium carbon Yield strength 95ksi
 Plain Carbon Steel vs.
Alloy Steel

Alloy Steel
 > 1.65%Mn, > 0.60% Si, or >0.60% Cu
 Most common alloy elements:
Chromium, nickel, molybdenum, vanadium, tungsten, cobalt,
boron, and copper.
 Added in small percents (<5%)
increase strength and hardenability
 Added in large percents (>20%)
improve corrosion resistance or stability at high or low temps
Alloying Elements used in
Steel

Sulfur (S) (11xx)

 Imparts brittleness
 Improves machining
 Okay if combined with Mn
 Some free-machining steels contain 0.08% to
0.15% S
 Alloying Elements used in Steel

Nickel (Ni) (2xxx)

 Increase toughness
 Increase impact resistance
 2% to 5%
 12% to 20% with low amounts of C possess great
corrosion resistance
 Invar
contains 36% Ni
virtually no thermal expansion
used for sensitive measuring devices
Alloying Elements used in Steel
Chromium (Cr) (5xxx)
 Usually < 2%
 increase hardenability and strength
 typically used in combination with Ni and Mo
 10.5% < Cr < 27% = stainless steel – used for corrosion
resistance
Molybdenum (Mo) (4xxx)
 Usually < 0.3%
 increase hardenability and strength
 Mo-carbides help increase creep resistance at elevated
temps
typical application is hot working tools
 Alloying Elements used in
Steel
Boron (B) (14xx)
 for low carbon steels, can drastically increase
hardenability
 improves machinablity and cold forming
capacity
Aluminum (Al)
 deoxidizer
 0.95% to 1.30%
 produce Al-nitrides during nitriding
Alloying Elements used in Steel

Manganese (Mn)
 combines with sulfur to prevent brittleness
 >1%
increases hardenability
 11% to 14%
increases hardness
good ductility
high strain hardening capacity
excellent wear resistance
 Ideal for impact resisting tools
Alloying Elements used in
Steel
Vanadium (V)
 Usually 0.03% to 0.25%
 increase strength
without loss of ductility
Tungsten (W)
 helps to form stable carbides
 increases hot hardness
used in tool steels
Alloying Elements used in
Steel

Copper (Cu)
 0.10% to 0.50%
 increase corrosion resistance
 Reduced surface quality and hot-working ability
 used in low carbon sheet steel and structural steels
Silicon (Si)
 About 2%
 increase strength without loss of ductility
 enhances magnetic properties
Corrosion Resistant Steel

 Stainless Steel
 10.5% < Cr < 27% = stainless steel – used for
corrosion resistance
 AISI assigns a 3 digit number
200 and 300 … Austenitic Stainless Steel
400 … Ferritic or Martensitic Stainless Steel
500 … Martensitic Stainless Steel
Stainless Steels

F-35 Joint Strike Fighter (JSF) Lightning II, built

by Lockheed Martin – airframe 17-7 PH – 600
series SS

Gateway Arch in St Louis – 304 series

 Key Points:
 Alloy steels containing at least 10% Cr are SS.
 Contain sufficient amount of Cr that they are NOT
considered low alloy.
 Corrosion resistance is imparted by the formation of a
passivation layer characterized by:
Insoluble chromium oxide film on the surface of the metal - (Cr2O3) .
Develops when exposed to oxygen and impervious to water and air.
Layer is too thin to be visible
Quickly reforms when damaged
Susceptible to sensitization, pitting, crevice corrosion and acidic environments.
Passivation can be improved by adding nickel, molybdenum and vanadium.
Tool Steel

 Wear Resistant, High Strength and Tough

 High Carbon steels
 Modified by alloy additions
 AISI-SAE Classification
Letter & Number Identification
 Tool Steel

Classification
 Letters pertain to significant characteristic
W,O,A,D,S,T,M,H,P,L,F
E.g. A is Air-Hardening medium alloy

 Numbers pertain to material type

1 thru 7
E.g. 2 is Cold-work
Time -Temperature
Transformation
 The rate of transformation depends on how
much you under cool the metal

Time for 50%

Transformation
Minimum Time required
for Transformation

Time
Iron
 The microstructure depends on how much you
undercool the iron
 If transformation occurs at a high temperature
(near the equilibrium phase change temperature)
the microstructure will be course
 At cooler temperatures, a finer microstructure is
formed
Other Microstructures of Iron
 If the transformation temperature of iron is kept
above about 550 C, a lamellar microstructure
results – which we call pearlite
 At temperatures below 550 C diffusion is very
slow. The resulting microstructure changes to
round particles of cementite in a ferrite matrix.
It’s called bainite
Pearlite

Iron Carbide (cementite) – dark, Ferrite – white

Why Does Bainite form?
 Extremely thin lamellar layers result in a lot of
surface area at the boundary between the
cementite and ferrite
 This results in high total surface energy – too
high
 The surface energy is reduced by switching to
more rounded particles
BAINITE

bainite (light), austenite (dark) interface

Affect of Temperature on Bainite
 Transformation temperature affects the bainite
microstructure, just like it affects pearlite
 Lower temperatures result in smaller cementite
particles in the ferrite matrix
What happens if you get REALLY
COLD
 At really low transformation temperatures
diffusion basically stops
 Neither bainite or pearlite can form
 The crystal trys to change from the FCC
austenite phase to the BCC ferrite phase, but it
traps the excess C in the matrix
 The result is a BCT crystal structure – called
Martensite
Martensite "needles" in a matrix of
austenite in a high carbon steel.
 There were great strides in optics
particularly in Germany, and in c. 1890,
a gifted German microscopist Adolf
Martens examined the microstructure,
and found, not visible to the naked eye,
many varieties of patterns at the
micron scale. In particular, hard steels
were found to have banded regions of
differently oriented, fascinating
microcrystalline phases, whereas
inferior steels had little coherent
patterning. The characteristic patterned
regions became known as Martensite.

Magnified 1000 times. Photo take by Osmund in 1901.

Martinsitic Reaction
 Diffusionless
 Not time dependant
 Not an equilibrium structure
 Steel Martinsite is very hard and brittle
Tempering Steel Martinsite
 If you warm martinsite back up diffusion can
occur
 At least some of the carbon forms cementite
 By controlling the tempering temperature and
time, a wide range of properties can be
produced
Lightly Tempered Martensitic
Structure
 The technique of quenching the iron into cold water is mentioned in this
gruesome description in Homer's Odyssey, describing the blinding of the giant
Cyclops (who had imprisoned Odysseus and his men in a cave). After getting
Cyclops drunk, they heat an olive stake and plunge it into his one eye: "The
blast and scorch of the burning ball singed all his eyebrows and eyelids, and
the fire made the roots of his eye crackle. As when a man who works as a
blacksmith plunges a screaming great axe blade or plane into cold water,
treating it for temper, since this is the way steel is made strong, even so
Cyclops' eye sizzles about the beam of the olive."
 (Translation after Richard Lattimore.) (Apparently the translation "treating it for temper"
is a translator's anachronism representing our modern viewpoint.)
Can you control the
microstructure that forms?
 Yes, by controlling the transformation
temperature and time
 You can get pearlite, bainite or martinsite
 Or.. Combinations of the different
microstructures
 Consider the following TTT diagram for a
eutectoid steel (0.77% C)
 Time-Temperature-Transformation for a Eutectiod
Steel

Equilibrium Phase Change Temperature

700 Ps
600 Pf Pearlite

500 Bs Bf Bainite
400 Start Time
Finish Time
300
Ms
200
Mf
100
Martinsite

0.1 1 10 100 1000 10,000 seconds