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University of Cambridge
Department of
Materials Science and Metallurgy
NATURAL SCIENCES TRIPOS
Part IB
MATERIALS SCIENCE & METALLURGY
Course A
Phase Transformations
Dr E. R. Wallach
Michaelmas Term 2009

AH1 Course A: Phase Transformations AH1
INTRODUCTION
Improving metallic materials is a vital activity at the leading edge of science and technology.
Metals have offered unrivalled combinations of properties and reliability over many centuries,
generally at affordable costs. They are versatile because subtle changes in their
microstructure can cause significant variations in their properties, e.g. the strengths of
commercial steels range from as low as 50 MPa to up to 5500 MPa. It is possible to specify
and obtain metals with very specific properties and so metals continue to be used in many
different applications despite the increased competition from other classes of material such as
polymers, ceramics and composites.
Hence an understanding of the development of microstructure in metals is essential for the
materials scientist.
Course B builds on the coverage of metals and alloys in Part IA. Whereas Part IA dealt mainly
with the thermodynamic aspects, kinetics will be emphasised when treating phenomena such
as diffusion, solidification and solid-state transformations.
Objectives
At the end of this course you should understand:
- kinetics of transformations in materials by considering diffusion in terms of mechanisms,
rate equations and the effects of microstructure and alloy composition;
- how grain structures in cast materials arise, how the distribution of solute in liquids affects
the microstructures and concentration profiles in solidified products, simple analysis of
heat-flow in castings, the relative advantages of different commercial casting processes,
microstructural evolution in cast irons and aluminium cast alloys;
- nature of grain boundaries, the processes of recovery, recrystallisation and grain growth
in cold-worked metals, the effects of alloy additions on the kinetics of these processes;
- mechanisms by which precipitation occurs in two-phase systems including the
importance of metastable phases, precipitate free zones, precipitate coarsening, real
alloy systems based on aluminium alloys and nickel-base superalloys;
- combination of diffusion controlled and diffusional transformations in steels leading to the
wide range of commercial steels and different mechanisms by which properties can be
optimised;
- sustainability issues based on life cycle analyses.
Dendrites in water (left) and in a Cu-P cast alloy (right).
[email protected] 2009-10
CONTENTS
Introduction 1
Contents 2
Resources 3
Guide to Symbols 5
1. Diffusion 7
1.1 Introduction 7
1.2 Fick’s First Law of Diffusion 9
1.3 Fick’s Second Law of Diffusion 10
1.4 Diffusion in Real Materials 14
1.5 Diffusion and Microstructure 17
1.6 Thermodynamics of Diffusion 21
2. Solidification 25
2.1 Introduction 25
2.2 Solidification Microstructures of Pure Metals 28
2.3 Solidification Microstructures of Metallic Alloys 30
2.4 Heat Flow in Solidification 40
2.5 Solidification Processing 44
2.6 Peritectic Transformations 48
3. Microstructure and Properties 49

3.1 Dislocations 49
3.2 Grains and Grain Boundaries 53
3.3 Precipitates 64
4. Alloy systems 75
4.1 Ternary Phase Diagrams 75
4.2 Cast Irons 78
4.3 Steels 81
4.4 Aluminium Alloys 88
4.5 Titanium Alloys 92
4.6 Nickel-base Superalloys 95
5. Sustainability of Metals 97
5.1 Life-Cycle Analysis 97
5.2 Lifetime: Degradation of Metals 100
5.3 Notes on using Cambridge Engineering Selector software 101
Glossary 102
ADDITIONAL RESOURCES
Web and computer resources
Specific course material is available from the website of the Department of Materials Science:
www.msm.cam.ac.uk/Teaching/mat1b/index.html
Additional information to assist with understanding of the course is as follows.
1. DoITPoMS Micrograph Library has many images of microstructures, together with

descriptions and explanations:
www.msm.cam.ac.uk/doitpoms/miclib/index.php
2. DoITPoMS Teaching & Learning Packages www.msm.cam.ac.uk/doitpoms/tlplib/index.php

include the following packates which are directly relevant:
Casting
Diffusion
Electromigration
Optical Microscopy & Specimen Preparation
Phase Diagrams and Solidification
Solidification of Alloys
The Jominy End Quench Test
3. MATTER software on CD-ROM has a number of chapters that provide good introductions to:
“Atomic Diffusion in Metals and Alloys”;
“Aluminium Alloys: Strengthening” and
“Aluminium Alloys: Processing”)
[Available on the department computers in Lab 201, etc. and in many colleges.]
4. MATTER software www.matter.org.uk/solidification has two relevant sections called:

“Redistribution” and
“Cell, dendrite and grain structure”
5. aluMATTER http://aluminium.matter.org.uk has considerable information on aluminium

alloys, including strengthening and softening mechanisms, as well as processing:
6. SteelMATTER and also SteelUniversity have information on steels, including processing

and hardness testing
www.matter.org.uk/steelmatter
www.steeluniversity.org/
7. Some other resources related to this course are available on the department website at
www.msm.cam.ac.uk/phase-trans/teaching.html
Books
D.A. Porter and K. E. Easterling, Phase Transformations in Metals and Alloys,

2nd edition, (Chapman and Hall, 1992) OR 3rd edition, (CRC Press, 2009)
This is a key book for the course.
P.G. Shewmon, Transformations in Metals, (McGraw-Hill, 1969).

Another excellent text, unfortunately out of print, but in several libraries.
Newey and Weaver, Materials Principles & Practice (Butterworths, 1990).

A good book, originally commissioned for the Open University materials courses.
Weidmann, Lewis and Reid, Structural Materials (Butterworths, 1990).

Lots of information on steels and microstructures.
R.E. Reed-Hill & R. Abbaschian, Physical Metallurgy Principles, 3rd edition, (PWS-Kent
Publishing Co., Boston, Mass., 1994).
R.E. Smallman & R.J. Bishop Modern Physical Metallurgy and Materials Engineering Science,
6th edition, (Butterworth-Heinemann, 1999).
Honeycombe R. W. K. and Bhadeshia H. K. D. H., Steels: Microstructure and Properties, 2nd

edition, (Arnold 1995).
I. J. Polmear, Light Alloys - Metallurgy of the Light Metals, 3rd edition, (Arnold 1995).
Metallographic samples
Metallographic samples are an integral part of this course, and are fully described in the
separate IB Metallography booklet, see
www.msm.cam.ac.uk/Teaching/mat1b/index.html
Questions pertinent to the various samples labelled M1 to M34 are given in the IB
Metallographic booklet, and there are additional references to these on the questions sheets
for the course. The phase diagrams in the IB Data Book provide additional information and
need to be consulted in conjunction with viewing and interpreting the microstructures.
Use the microscopes in the second floor Teaching Laboratory 201 during 9.00 am and 5.00 pm
on weekdays.
Choose a variety of magnifications to examine the prepared mounted and polished samples,
and record your observations in the IB Metallographic booklet provided.
GUIDE TO SYMBOLS
The following is a guide to symbols used in the handout. An attempt has been made to use
each symbol to represent just one quantity where possible. However there are some instances
in which a particular symbol is so commonly used for different quantities (i.e. G for Gibbs free
energy and shear modulus) that it would be more confusing to use something else. In these
cases, it should be clear which interpretation is intended from the context.
A Area (m2)
b Burgers vector (m)
Bi The Biot number
cV volumetric heat capacity (J m -3 K-1)
C concentration (composition) (at%, wt% or fraction)
C0 overall composition (m-3)
C composition of phase (m-3)
C composition of phase in equilibrium with phase (m-3)

D diffusion coefficient (diffusivity) (m2 s-1)
EV energy per unit volume (J m -3)
d diameter (m)
F force (N)
f fraction
fS fraction solidified
G Gibbs free energy (J mol-1) OR shear modulus (J m -3)
h interfacial heat transfer coefficient (W m -2 K-1)
H enthalpy (J mol-1)
J flux (m-2 s-1)
k partition coefficient
kB Boltzmann constant (J K-1)
K thermal conductivity (W m-1 K-1)
L length (m)
m gradient of the liquidus line on the phase diagram (at.% K-1 or wt.% K-1)
N number
n number per unit volume (m -3)
P Drag pressure (force per unit area on a grain boundary) (N m -2)
q heat flux (J m-2 s-1)
Q activation energy (J mol-1) OR rate of heat generation (J m -3 s-1)
Qf activation energy for vacancy formation (J mol-1)
r radius (m)
r* critical radius (m)
S entropy (J mol-1 K-1)
T temperature (K)
TL liquidus temperature (K)
Tm melting temperature (K)
t time (s)
U stored energy per unit volume (J m -3) OR strain energy per unit volume (J m -3)
v velocity (m s-1)
W work per unit volume (J m -3)
Wn work of nucleation per unit volume (J m -3)
x distance (m)
X concentration (composition) (at.%, wt.% or fraction)
z atomic spacing (m)
thermal diffusivity (m2 s-1)
grain boundary width (m)
strain
surface energy (J m-2)
jump distance (m)

jump frequency (s-1)
stress (N m-2)
misorientation angle (°)
μ chemical potential (J mol-1)
dislocation density (m-2)
1. DIFFUSION
1.1 Introduction
Diffusion is a transport phenomenon caused by the physical motion of chemical species

(molecules, atoms or ions), heat or similar properties of a medium (gas, liquid or solid).
Diffusion is a consequence of concentration differences (or, strictly, chemical potential

differences – see section 1.6.1). In general, species move from high concentration areas to
low concentrations areas until uniform concentration is achieved.
Mass transport can generally involve:
• fluid flow – dominant in gases or liquids (e.g. convection currents);
• viscous flow – flow of a viscous material, generally amorphous or semi-crystalline (e.g.

glasses and polymers) due to the forces acting on it at that moment;
• atomic diffusion – principal mechanism in solids and in static liquids (as occurs in
solidification).
Atomic diffusion occurs during important processes such as:
• solidification of materials [section 2];
• precipitation strengthening, e.g. Al-Cu alloys [MMS IA and section 3];
• annealing of metals to reduce excess vacancies & dislocations formed during working
[section 3];
• manufacture of doped silicon, e.g. as used in many electronic devices [IB : course E].
Atomic diffusion in crystalline solids is:
• jumping of atoms on a fixed network of sites within a crystalline lattice;
• generally the consequence of a thermodynamic driving force, i.e. chemical potential

gradient (often, but not exclusively, a concentration gradient).
Diffusion can be regarded and analysed on a macroscopic (continuum) scale or atomistically.
1.1.1 Random walk approach
Let atomic jumps, each jump having a magnitude or average distance , occur with a
frequency (number of jumps per sec) where
= 0 exp (–Q/RT)
For a number of random jumps, n, the mean distance x after time t is given is given by:
x= n = t
Hence the diffusion distance is proportional to .
1.1.2 Mechanisms of diffusion in crystalline solids
Atoms in the solid-state migrate by jumping into either interstitial or substitutional vacant lattice
sites.
Interstitial diffusion
Substitutional
diffusion
direct exchange ring vacancy
Distortion of the lattice during an atomic movement results in a barrier to motion. The
magnitudes of these “activation energies” will be quite different for all of the above mechanisms.
1.2 Fick’s First Law of diffusion – diffusion in a uniform concentration gradient

Consider two adjacent planes of atoms in a crystalline solid: assume cubic with lattice
parameter a.
1 2 3 4 5
Concentration C
of impurity
atoms (dark)
distance x
The concentration is the number of atoms per unit volume. Hence the number of impurity
atoms contained in a plane (per unit area in the y-z plane) is the impurity concentration
multiplied by a, i.e. number of impurity atoms per m 2
Consider the atomic flux, J of impurity atoms crossing in each direction JL R and JR L
where the atomic flux is the number of atoms passing through a square metre per second):
1 1
JLR = C a and JR L = C + C a
6 6
hence net flux from left to right (down the concentration gradient) is the difference JLR JR L
1 1 C C
J = C a = a2 OR J = D
6 6 x x
This is Fick’s first law of diffusion where D is the diffusion coefficient with units of m2 s-1.
It applies to steady state diffusion, when the concentration gradient does not vary with time.
From the random walk approach (page 8):

mean diffusion distance, x= t (as the atomic spacing, a replaces )
and from the above derivation of Fick’s 1st law D= 1

6
a2
Hence x = 6Dt , x 2 Dt , or simply x Dt
These expressions are useful for estimating diffusion distances.
1.3 Fick’s Second Law of diffusion
Consider two nearby planes of atoms, denoted by A and B and the movement of atoms across
the element between them due to an imposed concentration gradient:
A B
concentration C
distance x
C
Flux into element JA = D
x A
C C
2C

Flux out of element JB = D = D + x 2
x B
x A x
Hence the numbers of atoms entering and leaving the element in a time increment t are:
Nin = J A At and Nout = JB At
The change in concentration C in this time is given by
C =
Nin Nout
=
(J A
JB ) A t
volume A x
C J C
= = D
t x x x
C 2C
Fick’s second law is: = D 2
t x
1.3.1 Solutions to Fick’s Second Law
For general cases, numerical solutions are used (e.g. see Crank 1 – for reference only).
Consider now two special cases for which analytical solutions are possible.
1.3.1.1 Fixed quantity of solute and a semi-infinite bar
Let there be a total number of atoms (per square metre of cross section), B, at one end of the
bar
C time t0
distance x
Fick’s 2nd law can be solved using the following two boundary conditions
i. initially, the solute concentration away from the end of the bar is zero
C{ x,t = 0} = 0
ii. as time increases, the total amount of solute is fixed, hence the area under the curve
remains constant
C{ x,t} dx = B
The solution, which satisfies both Fick’s 2nd law and also the above boundary conditions, is
given by:
C
x2
C{ x,t} =
B
exp t1
Dt 4Dt
t2
t3
x distance x
1 nd
Crank J.C., “The Mathematics of Diffusion”, Oxford University Press, 2 edition 1979.
(ISBN 0198534116, 9780198534112)
1.3.1.2 Constant surface concentration at end of a semi-infinite bar
The solute concentration at the surface (Cs) remains constant. The initial concentration in the
bar is C0.
C
Cs
C0
distance x
The profile that develops is slightly less straightforward than previously.

As the source of solute at x = 0 is constantly replenished, the result is the equivalent of adding
together lots of exponential functions with different widths. i.e. the solution is the result of
integrating the exponential function, and this is called the “error function”.
The error function is a mathematical function (like sine or cosine) and has the form
{ exp { - }
x
erf x} =
2
u 2 du
0
with properties as shown graphically and numerically:
+1
at x = – erf (x) = –1
erf 0 at x = 0 erf (x) = 0
at x = + erf (x) = +1
1
- x=0
After time, the profile develops according to the “error function”
CS
t2
t1
C0
distance x
In order to solve Fick’s 2nd law, the following boundary conditions need to be met:
i. C{ x,t = 0} = C0
ii. C{ x = ,t} = C0
iii. C{ x = 0,t} = CS
and the solution to Fick’s 2nd law is then given by:
x
C{ x,t} = A + B erf
2 Dt
x
i.e. ( )
C{ x,t} = CS CS C0 erf
2 Dt
This solution applies when the surface concentration Co is kept constant and the concentration
inside changes with time, e.g. diffusing from a fixed partial pressure of gas into a metal.
It also is applicable to heat flow into a bar when one end is maintained at a constant
temperature (see Practical AP2).
The solution also ia used for two semi-infinite bars which are joined together. In this case, the
“surface” where the concentration remains constant is the interface between the two bars.
C
CA at time t0
CB
distance x
t0 t1 t2
CB
distance x
1.4 Diffusion in real materials
1.4.1 The Kirkendall experiment
The vacancy mechanism for diffusion was confirmed in an experiment by Smigelsklas &
Kirkendall in 1947. Two different alloys (copper and brass) were joined together with inert
markers (fine molybdenum wires) at the interface to form a diffusion couple.
This is shown more simply (schematically) below as a diffusion couple comprising just A atoms
on the left and B atoms on the right.
A B
JAJA
JJB
B
In the frame of the sample, A atoms move to the right faster than B atoms move to the left.
Hence there is a net flux of atoms to the right (whilst the inert marker atoms remain stationary).
Alternatively, the situation can be viewed in terms of vacancies. The equilibrium number of
vacancies in A is low and in B it is high. Hence vacancies tend to be created in B and then
diffuse from B across to A where they are destroyed; hence there is a net vacancy flux to the
left.
Observations are, in reality, made from outside the block (i.e. the block remains stationary from
an external perspective and does not move as shown pictorially above) with the result that the
inert marker wires appear to have moved to the left. This experiment confirms that diffusion
occurs via vacancies - other mechanisms such as the “ring” (introduced on page AH8) could
not generate a net movement of the markers in either direction.
1.4.2 Interdiffusion
~
The net effect can be described using Fick’s laws and the interdiffusion coefficient, D, is used.
It is the weighted average of the diffusion coefficients of the individual components DA and DB
with respect to an alloy’s composition defined in terms of the mole fractions of the two elements
Xi. The relationship is called the Darken equation and is:
~
D = X BDA + X A DB
In a system where there is complete solubility across the composition range (such as Cu-Ni
alloys), the diffusivities of the various species are as indicated below.
1.4.3 Temperature Dependence of Diffusion
If an atom in a potential well of height G* vibrates with a frequency 0, the frequency with which
it will make a successful jump into an adjacent position is given by:
G S H
= 0 exp = 0 exp exp given that G = H – T S
kBT kB kBT
It was shown in section 1.2 that , where a is the interplanar distance and, in practice,
is the smallest lattice vector, hence the Burger’s vector, b, in many crystalline materials.
S H H
Hence D = 61 0 b 2 exp exp or D = D0 exp
kB kBT kBT
Thus an Arrhenius graph, i.e. plot of log (D) versus 1/T, will give a straight line, as is shown on
the next page.
Arrhenius plot of ln (D) versus 1/T for the self-diffusion coefficients of various metals
and including the diffusion coefficient for interstitial diffusion of carbon in ferritic iron.
The gradient of the lines are –H/kB. The enthalpy term, H, is the activation energy for diffusion
in each metal and is frequently denoted by Q.
This activation energy can be separated into two components:

enthalpy of migration (due to lattice distortions), Qm
enthalpy of formation of vacancy in adjacent lattice site, Qf
Q Q
Hence D = D0 exp m exp f
kBT kBT
Since the formation of a vacant site is not needed for interstitial diffusion (such sites are always
available to a diffusing atom), the latter term is not needed for interstitial diffusion, hence
Qinterstitial << Qsubstitutional and so Dinterstitial >> Dsubstitutional.
D is similar for many metals at their melting points (around 10 -12 m2s-1).
For other materials, D will depend on the bonding in the material, e.g. D for silicon is much
lower due to its directional covalent bonding and hence there is a much higher activation
energy term.
1.5 Diffusion and Microstructure

If a lattice is locally disrupted, it will have a more open structure. The activation energy for
diffusion Q will be lower and so diffusion will be faster.
In metals, lattice disruption occurs in the vicinity of vacancies, dislocations and grain
boundaries, all of which provide easier diffusion paths.
1.5.1 Effect of Grain Boundaries

A grain can be represented by a cylinder of diameter d with grain boundary width .
grain grain
2
d
Area of grain = and area of half grain boundary = 2 r (shared by 2 grains)
2 2
area of grain boundary 2

Hence ratio of areas = =
area of grain d
Consider the total number of atoms per second that can diffuse through a grain (denoted now
by the term lattice) and its associated boundary.
It is given by the sum of the flux through each area of each = Jlattice Alattice + Jgb Agb
Since Alattice >> Agb can denote Alattice A
Then flux (number of atoms per unit area per second) is
2
J = Jlattice + Jgb
d
C C
Using Fick’s first law J = D and assuming a constant concentration gradient
x x
2
Dmeasured = Dlattice + Dgb
d
Grain boundaries have more open structures than the corresponding lattice, so Qgb < Qlattice and
the different Q values result in faster diffusion in polycrystalline samples than in single crystals.
In many polycrystalline alloys, the grain boundary area is just a small fraction of the total area.
Hence the contribution of grain boundary diffusion to the total diffusion is significant only at low
temperatures, when Dlattice << Dgb. This can be seen on an Arrhenius plot.
ln D
Dgb
D measured
2
Dgb
Dlattice d
1/T
The effect is clearly dependent on grain size. For smaller grains, the lower line will move
upwards so the significant contribution from grain boundary diffusion is seen over a greater
temperature range.
1.5.2 Effect of Dislocations

Dislocations, which are line defects, can also provide fast diffusion paths. Thinking of an edge
dislocation, there is a more open structure where the extra half-plane terminates.
By a similar analysis to that for grain boundaries, it can be shown that
(
Dmeasured = Dlattice + Ddisl Adisl ) (as for gb diffusion, assuming Alattice >> Adisl)
where Adisl – dislocation core area (typically ~1 nm)2

– dislocation density (typically 1012-1015 m/m3)
Since Adisl 10-5-10-8 m2, the effect of dislocations (like grain boundaries) is significant only at
low temperatures, when the rate of diffusion within the lattice itself is very small.
1.5.3 Effect of vacancies
The greater the number of vacancies in a sample, the faster substitutional diffusion will occur.
Q
The equilibrium vacancy concentration is given by n = n0 exp f

kBT
Dislocations can act as vacancy sources or sinks:
Vacancy source Vacancy sink

[Note that the white arrows show the directions in which the vacancies diffuse.]
An excess of vacancies can arise in a sample if it is quenched rapidly from a high temperature.
The equilibrium number of vacancies will be high at the high temperature and, if the sample is
cooled rapidly enough, there will not be time for the vacancies to diffuse to sinks in order to
reach the lower equilibrium number of vacancies. Hence, they become “frozen-in” at low
temperature, increasing the overall diffusivity so that it is greater than would be expected.
The number of vacancies also increases significantly during mechanical deformation, e.g.
when dislocation jogs are dragged through a lattice.
1.5.4 Diffusion in polymers: non-Fickian behaviour
Diffusion in polymers can be complex due to possible interactions between the polymer matrix
and the diffusing species, as well as the structure of the polymer itself (glassy or varying
amounts of crystallinity).
This means that there may be departures from Fick’s laws since, for cases considered
previously, it has been assumed that there is no interaction between the matrix and diffusing
species.
When a polymer is immersed in a liquid, the liquid may:
- not penetrate at all;
- dissolve the polymer;
- swell the polymer as it enters (a sharp interface forms at swollen and unreacted polymer).
In the last case, the diffusion coefficient in the swollen layer is significantly higher due to the
more open polymer structure there. Hence penetration of the liquid is governed by the kinetics
of the liquid-polymer interaction at the interface. This can result in linear migration of the sharp
interface and an almost linear weight gain with time, rather than parabolic (as seen in metals).
This property can be exploited for controlled drug delivery in medical applications.
When a drug is taken in the form of a tablet, the drug release can be:
- instantaneous, assuming the tablet dissolves almost immediately;
- time dependent, in which case a constant rate or sustained release is beneficial as the
same dose is available over a long period without being either excessive or too low.
Concentration of drug in the body as a function of time after administration in various ways.
1.6 Thermodynamics of diffusion
The ideas developed so far are insufficient for systems which favour the formation of multiple
phases. Consider a 2-phase alloy of A and B atoms, which exists as and phases.
If these two phases are in equilibrium, the A atoms in the phase have the same energy as
the A atoms in the phase. Hence, there is no tendency for either the A or B atoms to diffuse
even though the two phases have quite different compositions.
1.6.1 Chemical potential
To explain the above, it is necessary to use the concept of the chemical potential, μ.
If a small amount dXA of species A is added to a system, the change in the overall free energy
of the system dG is:
dG = μA dXA
Hence the chemical potential of a species A is defined as:

G
μA =
X A
For a single phase: G = μA XA + μB XB
and dG = μA dXA + μB dXB (see Porter & Easterling p.16 for a proof)
Using these 2 expressions, it can be shown that the chemical potential of each species in the
alloy (for some overall composition, X) can be found by drawing a tangent to the free energy
curve as shown on the next page.
μ A (X)
μ B (X)
A X B
Two phases in equilibrium: requires the A atoms in the phase to have the same energy (or
chemical potential) as the A atoms in the phase (and similarly for B atoms in the two phases).
This can be achieved only if the tangent to the two free energy curves is the same. Hence the
common tangent construction introduced in Part IA determines the equilibrium compositions
because it ensures that the chemical potential of each species is the same in both phases.

μB

μA
A X B
1.6.2 Diffusion in a chemical potential gradient
1.6.2.1 Down a concentration gradient
Q
P
A X B
In this case, a material in which initially there are two regions with different compositions P and
Q, diffusion down a concentration gradient will occur, leading to a single uniform,
homogeneous phase with composition R.
1.6.2.2 Up a concentration gradient
U
V
A X B
In this system, a material which initially has a single region of composition S will “unmix” to
form discrete regions with compositions U and V. Hence diffusion occurs up the concentration
gradient. Note that this can be called “spinodal decomposition” or “uphill” diffusion.
In each of the two examples, diffusion occurs down chemical potential gradients in order to
lower the overall free energy. Note that in case (b), diffusion is not down a concentration
gradient, but rather creates a concentration gradient by the formation of discrete regions
(phases) of different compositions but in which a given element has the same chemical
potential.
1.6.3 Diffusion in chemical potential gradient other than concentration
1.6.3.1 Diffusion in an elastically bent bar
If a bar is bent elastically, a strain gradient develops.
If the bar is made from a uniform solid solution of A and B atoms, where B atoms are larger
than A atoms, the B atoms will diffuse to where there is more space in the A-lattice (i.e. the
tensile region) in order to reduce the overall strain energy.
In this case, the chemical potential gradient, down which diffusion of the larger atoms occurs, is
a result of the variation in elastic strain across the bar thickness. The consequence is that a
concentration gradient forms as the strain decreases.
1.6.3.2 Electromigration (see DoITPoMS Teaching & Learning package)
Electromigration is the transport of material in a conductor under the influence of an applied

electric field, and can result in the failure of integrated circuits.
The applied electric field results in a metal ion experiencing an electrostatic force, the extent of
which depends on the charge on the ion core, modified by screening effects. This results in a
net flux of metal ions towards either the positive or negative terminals. Note that the overall
flux is extremely small but, over time, can cause failure of an electronic device.
2. SOLIDIFICATION
2.1 Introduction
Solidification is a critical processing route for many materials – e.g. metals and alloys, polymers.
Use of liquid phase easy mixing of different elements and/or compounds (alloying)
shaping to give final product directly by casting into mould i.e. container
which typically is sand, metal or ceramic.
There are many different solidification and casting methods (see section 2.5) including:
continuous casting: around a billion tonnes of steel per annum and can form steel sheet
directly by including rolling mills as part of steel making plant;
sand casting: cheap and good for mass-producing items such as car engine cylinder blocks
in cast irons or aluminium-silicon alloys;
die casting: forcing of liquid metal into intricate moulds leads to high definition products
that can be used directly with no further machining;
single crystals: silicon single crystals grown for electronic devices, and also
turbine blades in Ni-base superalloys for aero engines since elimination of
grain boundaries enhances creep resistance;
welding: localised melting and solidification enables joining of materials;
zone refining: enables metal purification.
Problems can arise which lead to poor or variable properties, including:
poor initial microstructure
partitioning of solute during solidification
porosity (summary of casting defects given in section 2.6)
2.1.1 Driving Force for Solidification
Gibbs
energy G
liquid
G = H TS
solid
G = H TS
Tm temperature T
At Tm
G = 0 and so H = Tm S
S = H / Tm
At any other lower temperature T, i.e. T < Tm

G = H -T (H / Tm)
H (Tm T )
=
Tm
H
= T OR = S T where T is the undercooling
Tm
2.1.2 Review of Nucleation and Growth

On cooling, solidification does not happen instantaneously upon cooling below Tm, but takes
place via:
• nucleation homogeneous: rare and only if very large T
heterogeneous: on mould walls, impurities etc.
• growth which may be affected by temperature gradients and preferred crystal

growth directions
G
liquid solid
G
Atoms will be able to move in either direction across the energy barrier.
Q
Rate of transfer L S exp
kBT
Rate of transfer S L
(
Q + G
exp
)

kBT
Q G
Hence the growth velocity, v exp
1 exp

kBT kBT
If T is small, then G is small and as exp(x) 1 + x for small x,
Q G
v exp k T
kBT B
v G
v T
In practice, heterogeneous nucleation occurs with undercoolings of a few milli Kelvin.
Growth rates of 50 m s-1 are usually regarded as very fast (compare to martensitic
transformations in the solid state which advance at the speed of sound – around 1100 m s-1).
2.2 Solidification Microstructures of Pure Metals
2.2.1 Grain Structures in Castings
Consider the solidification sequence when molten metal is poured into a cold mould.
chill
columnar
equiaxed
Chill zone:
• fine grains heterogeneously nucleate on the mould surface, with random orientations;
• many nuclei form due to large initial undercooling on cold mould walls.
Columnar zone:
• growth of some chill crystals which have optimal crystallographic direction, <100> in
many metallic alloys, and also influenced by direction of maximum temperature gradient;
• may form either dendrites or cellular interface, depending on the casting conditions.
Equiaxed zone:
• formed by chill crystals, detached dendrite arms (swept by convection to centre of

casting) or deliberate addition to molten metal of grain refiners/inoculants;
• desirable because the small grain size reduces the extent of microsegregation and also
improves mechanical properties (both strength and toughness) of final product.
2.2.2 Pure Metals: Thermal Dendrites
Consider a molten metal poured into a mould:
solid liquid solid liquid
T T
dT
> 0 dT
dx <0
dx
distance distance
Dendrites can grow from small perturbations on the growing solid if the conditions in liquid
ahead of the interface are more favourable for solidification.
Tm
m dT
< 0
dx
2.3 Solidification Microstructures of Metallic Alloys
2.3.1 The partition coefficient, k
When a solid and liquid are in equilibrium in an alloy system, the amount of solute (or impurity)
atoms in each phase will not generally be the same. Consider the part of a phase diagram
shown below (which, for instance, might represent one end of a eutectic system).
temperature T
S S+L L
CSL C0 CLS composition (%B)
In the above figure, the nomenclature C represents the composition of phase when it is in
equilibrium with phase , i.e. CSL means solid of that composition in equilibrium with liquid of
composition CLS at the given temperature. The starting composition of the liquid is C0.
In the example above, as the alloy cools in equilibrium, there is always approximately six times,
say, more solute in the liquid than there is in the solid and the partition coefficient, k, is defined
as
C SL
k=
C LS
Hence the partition coefficient is constant if the solidus and liquidus are straight lines. Its value
then is given by the ratio of the gradients of these lines on the phase diagram. Whilst the lines
on the phase diagram generally are not strictly straight, this approximation is often reasonable.
2.3.2 Equilibrium solidification (assuming one dimensional heat flow)
Let a solidifying bar cool sufficiently slowly that there is plenty of time for diffusion in both the
liquid and solid. The concentrations of each phase will be those given by the phase diagram.
C C CLS
LS
C
C0 C0
SL
C
CSL
distance distance
The final solid bar has the same uniform composition, C0, as the initial liquid if there is sufficient
time for diffusion of solute in the solid bar.
2.3.3 Equilibrium only at the interface: diffusion in liquid and none in the solid
Complete equilibrium is unlikely. Diffusion in the solid phase relative to that in liquid is
incredibly slow and generally can be neglected completely.
Consider the situation when the profile is determined solely by diffusion in the liquid. When the
solid begins to form, solute is rejected into the liquid. Within the liquid, this solute is distributed
into the liquid only by diffusion; this results in a build-up of this solute ahead of the interface.
S S+L
kC0 C0 C0/k composition
The first solid to form from liquid originally with composition C0 has a composition given by kC0
(where k is the partition coefficient).
As the solute builds up ahead of the interface, the compositions of both liquid and solid at the
interface increase. As equilibrium is maintained at the interface, the ratio of compositions will
be maintained at k. A steady state scenario is reached when the composition of the solid at the
interface reaches the original (or average) composition C0.
C C C0/k
C0 C0
kC0 kC0
distance distance
When this point is reached the solute profile does not change (there is no further build-up), but
simply moves forward at a constant velocity.
Consider the frame of the advancing interface:
CLS (=C0/k)
CSL (=C0)
v
x=0 distance
The rate at which the interface advances is balanced by the rate at which solute can diffuse
away:
i.e. (C LS
)
C SL v = flux of solute away from interface
Using Fick’s 1st law of diffusion, the rate at which solute diffuses away from the interface can
be calculated, as is shown on the next page.
Fick’s 1st law of diffusion can be used to balance the flux of solute across the interface (x = 0)
dC
J = D
dx x=0
Hence (C LS
)
C SL v = D
dC
dx
(i)
x=0
dC d2C
Fick’s 2nd law: = D 2
dt dx
dC dx dC dC
and also = = v
dt dt dx dx
Combining these gives an equation for the flux across the interface of the form (a rigorous
approach requires consideration of the reference frame moving with the interface):
dC 2C
v + D = 0 (ii)
dx x 2
Using (i) and (ii), the integration coefficients can be evaluated to give the result for the
composition at a distance x ahead of the interface:
C

Cx = C SL
(
+ C LS
C SL
)
exp
x
D
v

C0 (1 k) x
or Cx = C0 + exp
k D
v
distance
In the above, D/v is a measure of the width of the zone which is significantly enriched by solute.
The diffusivity of a liquid is typically around 10–9 m2 s-1 and so:
- at slow solidification rates (v 10 μm s-1) D/v 0.1 mm
- at fast solidification rates (v 1 mm s-1) D/v 1 μm
2.3.4 Equilibrium only at the interface: perfect mixing in the liquid and no mixing in solid
Now assume that solute that is ejected from the growing solid does not build up at the interface
but instead is mixed uniformly in the liquid, e.g. by convectional mixing/stirring of the liquid.
C C
C0 C0
kC0 kC0
distance distance
The crucial aspect here is that the solute profile in the liquid is always uniform due to the mixing.
To determine the profile, consider what happens as the interface advances a small amount, df.
C
df
dCL
CL
kCL
kC0
0 fraction solidified f 1
Equating the shaded areas to conserve solute gives:

fs
df
CL
dC
(CL ) ( )
kCL df = 1 f dCL which can be rewritten as 1 f =
(
L

)
0 C0 CL 1 k
( )( )
( )( )
k 1 k 1
and hence CL = C0 1 fs or CS = kC0 1 fs
This relationship is known as the Scheil Equation.
It suggests that as fs tends to 1, the composition would tend to infinity.
In practice, there has to be some limit on how much solute can be ejected into the liquid. It is
reached when the composition of the remaining liquid attains the eutectic composition since
this liquid will then solidify to form eutectic solid.
2.3.5 Solute profiles within solidified bars
Case A: equilibrium C
(see section 2.3.2)
C0
Case B: diffusion control C

(see section 2.3.3)
C0
kC0
Case C: perfect mixing in the liquid C

(see section 2.3.4)
C0
kC0
It is clear that it is possible to purify a material by producing the profile shown in case C, where
the solute is swept to the right hand end of the bar. If the last part of the bar to freeze is cut off,
then the overall impurity concentration in the remaining material is lowered. The whole process
can be repeated as many times as is wanted to significantly purify the bar.
This principle is called zone refining, i.e. a hot small (liquid) zone is passed along a bar,
causing the impurities to concentrate in the small liquid zone which is carried to the end of the
bar. The sequence then is repeated to enable purification of the bar to the level required.
2.3.5 Constitutional undercooling
Return now to the case of limited mixing in the liquid (Section 2.3.3), i.e. where the solute
ejected into the liquid is carried away only by diffusion (no convection leading to complete
mixing in the liquid) and thus will build up near to the interface over some distance given
approximately by D/v.
solid liquid
T
C
T2 CLS A
S S+L L B
SL
T1 C (=C0)
distance
SL LS
C = C0 C TL
composition
T2 Q
T1 P
distance
As the solute diffuses away gradually, the solute concentration in the liquid is non-uniform, i.e.
is high at the interface and decreases to the value C0, as shown by the curve A-B above.
Hence the liquidus temperature (the temperature at which can solidification begin) in the liquid
will also be non-uniform (lower at the interface, increasing to some constant value, curve P-Q).
If the actual temperature locally is below the equilibrium freezing temperature, then that liquid is
described as being undercooled (note that this sometimes is referred to as “supercooled”).
In pure metals (when the liquidus temperature is constant), a negative temperature gradient will
also cause undercooling, as was shown in section 2.2.2. In the above case, however,
undercooling is achieved near the interface even when there is a positive temperature gradient.
This is illustrated on the next page.
Actual temperature of liquid

T
TL
undercooled
region
distance
This phenomenon is known as constitutional undercooling as it is undercooling caused by

the effect of composition (constitution). Perturbations on a planar interface next to undercooled
liquid grow faster into the liquid and develop into cells or dendrites.
From the above figure, dendrite formation will be avoided (and a planar growth front maintained)
only if the actual temperature gradient in the liquid is high enough that there is no undercooled
region. Conversely, there is a critical temperature gradient below which a stable planar
interface will break down into cells or dendrites.
dTL dT
Undercooling occurs if >
dx x=0
dx
Let the magnitude of the slope of the liquidus line on the phase diagram be denoted as m and
note that m will be equal to –dTL/dC in the region of the phase diagram being considered.
dC dT dT dC
Undercooling occurs if m > or < m
dx x=0
dx dx dx x=0
From equation (i) in 14.2.3: (C LS

)
C SL v = D
dC
dx x=0
Hence undercooling occurs if

dT m C C v
<
LS SL
( )
dx D
(
dT m C0 / k C0 v
<
)
dx D
dT mC0 (1 k)v

<
dx kD
To avoid undercooling, the temperature gradient must be greater than this value.
In practice, this is difficult to achieve during solidification, as is shown on the next page.
Typical values may be = 10 K mm-1
DL = 5 x 109 m2 s-1
k = 0.2
C0 = 0.2 wt.%
m = 10 K wt.%-1
then the maximum velocity for a planar interface is vmax = 6 x 10-6 m s-1 (i.e. 2 cm per hour).
2.3.6 Segregation in castings

a. Macrosegregation
If a planar solidification front moves along a bar, solute concentrated in the liquid will be swept
to one end of the bar (this is known as macrosegregation - solute is segregated on a
macroscopic scale). It also is important to consider what happens to this solute when dendritic
growth occurs.
a. Microsegregation
Solute is rejected at all solidification fronts and will be trapped between growing dendrite arms.
This leads to composition variations in the final solid on the scale of the dendrite arm spacing.
This is called microsegregation, and is shown below for a Cu-Ni alloy. The light areas which
have solidified first are Ni-rich, and Cu-rich liquid has been trapped between the dendrite arms
before solidifying. Note that there is complete solid solubility across the Cu-Ni phase diagram
and no discrete second phases can form; the below contrast arises from the etching procedure.
Cu 70, Ni 30 (wt%), cored dendrites (etched in NH 4OH, H2O2)
Microsegregation in solidified alloys can be a problem as variations in composition can lead to

variable properties (mechanical, electrical, chemical). The effects can be reduced by
homogenisation, which involves annealing at an elevated temperature for sufficient time to
allow diffusion to even out the solute levels. It may be difficult or uneconomic to achieve fully.
2.4 Heat Flow in Solidification
2.4.1 Heat extraction from a casting
The rate of heat extraction during casting is a critical factor that strongly affects the
microstructure of the final solid. The contributions to the heat that must be removed are:
• superheat Ts: due to the need to pour liquid metal at a temperature above its melting
point;
• latent heat Hs: heat released as the metal solidifies;
• heat capacity of the system as it cools.
Ignoring the superheat, the equation governing the heat flow has the form
dT d2T Q
= 2 + where is the thermal diffusivity (equal to K/cV)
dt dx cV
K is the thermal conductivity (W m -1 K-1)
cV is the volumetric heat capacity (J m -3 K-1)
Q is the rate of latent heat generation (J m -3 s-1)
Analytical solutions to this are generally not possible except in some very simple cases.
Heat transfer across the interface between the mould and the casting will affect significantly the
rate of cooling.
Heat transfer at the mould/casting interface can occur by:
• direct contact (initially)
moul
mould air casting
• conduction through the air gap gap
d
• convective air currents
• radiation
2.4.2 The Biot Number
Heat is extracted from a casting in two stages:
• thermal conduction through the casting as it cools;
• interfacial heat transfer at the interface.
heat flow
casting liquid
mould
L
T
distance
The heat flux (in W m-2) within the casting is
KTcast
qcast =
L
where K is the thermal conductivity and Tcast/L is the thermal gradient in the casting (in the
heat flow direction). Hence heat conduction in the casting is characterised by K/L.
The heat flux across the interface is
qint = h Tint
where h is the heat transfer coefficient (characterises heat conduction across an interface/air
gap).
The Biot number, the ratio of these heat fluxes at the interface, is an indication of whether
heat extraction is dominated by conduction through the casting or across the interface.
h hL
Bi = =
K /L K
2.4.3 Newtonian cooling
Newtonian cooling occurs when the limiting factor is the interfacial heat transfer, i.e. the
transfer of heat across the interface is much slower than heat conduction through the casting
and hence the Biot number is very small (<<1). This situation is most likely if the metal has a
very high thermal conductivity (Al, Cu) or the casting is very small (thin).
It leads to the temperature being approximately uniform within the casting itself and the
temperature drop takes place at the interface between the casting and the mould.
mould metal liquid
distance
When Newtonian cooling occurs, the analysis of heat flow is relatively simple to analyse. The
rate of heat removal from the mould is balanced with the rate at which heat flows across the
interface:
qint = hTint
When molten metal is poured into the mould, its temperature is usually significantly higher than
the melting point - this is called superheat. Thus some time is required for the liquid to cool
before solidification can begin.
The rate of heat extraction for a material is given by the product of its heat capacity and cooling
rate. Hence the heat flux (heat removed per unit area per second) out of the liquid as it cools is:
dT
q= cV L
dt
which is balanced by the heat flow across the casting/mould interface:
dT dT hT
q= cV L = hTint or =
dt dt LcV
Obviously, in this case, T will change (decrease) as the liquid cools and so the rate of cooling
of the liquid actually slows down.
When the liquid reaches the melting temperature it still cannot solidify instantly as any latent
heat which is produced also has to be removed. If the solidification front moves forward at
velocity v, the rate at which heat is generated per unit area of casting is given by:
q = vHF
where HF is the latent heat per unit volume (or enthalpy of fusion)
balancing this with the heat flow across the casting/mould interface:
q = vHF = hT
hT
v=
HF
In practice, all castings are made using liquid which has been superheated since the
temperature of the liquid metal has to be significantly greater than the melting temperature of
the metal in order to ensure a mould is fully filled.
The effect of this superheat on the above equation is that more heat needs to be removed, and
so HF is replaced by the expression (HF + cv Ts) where Ts is the temperature difference
between the liquid metal at the time of pouring and its solidification temperature, and cv is the
specific heat of the liquid metal (taken generally to be the same value as for the solid).
2.5 Solidification processing

2.5.1 Sand casting
• Sand is packed around a wooden pattern in 2 half-moulds.
• Pattern is removed and the two half-moulds are placed together.
• A “runner” is required to pour in the molten metal and one or more “risers” to ensure the
liquid fills the mould.
Alternatively, a polystyrene pattern may be used and the sand packed around it using a full
mould. When the molten metal is poured, the polystyrene pattern is “burned-out”. This allows
far more complex shapes to be cast - re-entrant shapes are possible as the pattern does not
have to be removed prior to pouring.
Problems associated with sand-casting include:
• poor surface finish;
• inability to produce thin sections;
• often significant porosity due to water which is present to bind sand.
2.5.2 Die- casting
In die-casting, the mould is permanent and reusable. There are two common forms:
Gravity
Pressure
Advantages of die-casting include:

• fast cycle time;
• high definition and good surface finish arising from metal mould;
• fast solidification (due to metal mould) results in fine grain size;
• thin sections are possible.
Disadvantages of die-casting include:

• moulds are expensive as they must be precision-machined so use for mass production;
• it is difficult for metals with high melting points – mainly used with Al and Zn alloys;
• complex shapes cannot be ejected from the mould.
2.5.3 Investment casting
• A wax pattern is made with precise dimensions.
• Slurry is used to make a ceramic mould around the wax pattern.
• The mould is heated to remove the wax and a hollow ceramic mould remains.
The main advantage of this technique is that by producing a ceramic mould, metals with a high
melting temperature can be cast, such as Ni-based superalloys for aircraft turbine blades.
Hollow blades can be produced by including a ceramic liner in the original wax pattern in such
a way that its position is fixed even when the wax melts. After casting, the ceramic can be
chemically etched out of the turbine blade to leave air-cooling channels.
2.5.4 Continuous casting
This is the method used for large-scale steel production. The metal is cast and rolled
continuously in one process. The mould may oscillate in order to improve surface quality.
ladle
tundish to ensure constant head (pressure) of liquid metal
water cooled mould, lubricated to prevent sticking
rollers prior to flame cutting into billets which

then are rolled, extruded to final
products
2.5.5 Melt spinning
Cooling rates (Newtonian) of up to 107 K s-1 can be achieved in thin ribbons by casting onto a
water-cooled, rotating Cu wheel. Heat extraction is very rapid and metallic glasses can be
produced, i.e. no time for crystallisation. Ribbon can be produced at a rate of up to 40 m s-1.
2.5.6 Single crystal growth
2.5.6.1 Turbine blades: using investment casting
Achieved by addiing a “pig tail” to the bottom of the cast turbine blade mould.
Chill grains initially nucleate in the rectangular section below the pig tail and
only a few survive to grow as columar grains, as a consequence of their
preferred orientation (Section 2.1.1) and the imposed temperature gradient.
Competitive growth through the pig tail ensures just one grain enters the main
part of the mould. In this way, a single crystal turbine blade is fabricated.
2.5.6.2 Silicon single crystals: Czochralski process
Silicon single crystals underpin electronic devices, as will be covered in IB Course E, and are
fabricated by pulling a single crystal seed from very pure silicon melt at slow speed. In this
way, nucleation is avoided and a very large defect-free single crystal can be fabricated: up to
400 mm in diameter and up to 2 m in length.
2.6 The peritectic transformation
Similar to the eutectic and eutectoid reactions, the peritectic happens at a well-defined
temperature and composition. It is the formation of a single solid phase () by interdiffusion
between an original different solid phase () plus a liquid phase (L), i.e.
+L
Sn -21 wt.%Cu
An important aspect of solidification in a peritectic system in real systems is that the new solid
phase nucleates and grows heterogeneously on the original solid phase. Given the
relatively fast rate of cooling of a melt and the time that would be needed for diffusion in the
solid state to attain full equilibrium, not all the original phase transforms to . As full
equilibrium is not reached, a peritectic sample generally shows some residual original which
is surrounded by .
This is shown clearly for a Sn - 21 wt.%Cu alloy, as shown above (metallographic sample M5
and also see phase diagram in the Data Book).
The peritectic reaction is utilised commercially in grain refining aluminium cast products since a
smaller grain size results in improved toughness and strength:
- TiAl3 first nucleates at ~1300°C, well above the melting point of Al alloys (~600 - 660°C);
- the small TiAl3 nuclei provide heterogeneous nucleation sites for subsequent Al
solidification;
- result is a more extensive fine grain, equiaxed structure in the final casting with improved
properties.
3. MICROSTRUCTURE AND PROPERTIES
3.1 Dislocations
3.1.1 Review of dislocation types
Edge
Screw
Mixed In practice, virtually all dislocations lines in materials are mixed, i.e. can be
described as having a combination of edge and screw components.
A dislocation is a line defect around which there is a region of high energy (due to disruption of the
regular crystalline packing).
From Part IA Course D, the energy per unit dislocation line length is approximately Gb2 J m-1.
3.1.2 Order strengthening and superdislocations
Various strengthening mechanisms in metallic alloys were introduced in Part IA.

Some metallic alloys also can have ordered structures – see Part IA.
Consider an edge dislocation moving through an ordered alloy under a shear stress.
Before passage of dislocation After passage of one dislocation
Movement of one dislocation through the structure forces similar atoms to become neighbours
and results the formation of an Anti-Phase Boundary (APB) with a consequent increase in energy
of the structure. Hence dislocation motion is more difficult than in a disordered structure.
To minimise the energy increase associated with the APB, two dislocations generally will travel
together, one behind the other. This pair of dislocations, called a super-dislocation, leaves the
lattice in its preferred ordered (and lower energy) state. As a higher stress is required to move the
dislocation pair (super-dislocation), the ordered alloy is stronger than if the alloy was disordered.
Consider the passage of dislocations on a (001) plane of Cu3Au:
The Burgers vector of the super-dislocation is no longer associated with the shortest lattice vector
due to the change in lattice type.
A cubic close packed (fcc) metal will slip on {111} planes and the packing of these {111} planes
can be described as A, B and C. Consider again an ordered A3B alloy, of which two {111} planes
of the perfect lattice are shown below. Let atoms in the bottom plane be described as being in A
positions and those in the top plane as occupying B positions.
If an edge dislocation is introduced into the structure, it effectively introduces a missing half-plane
of atoms in the centre of the structure. Atoms in the top plane remain in B positions (rather than C
sites), even those that have undergone slip (which are shown below on the RHS). However
because this is an ordered alloy, those that have slipped are no longer in the perfectly ordered
positions but now have similar neighbours, and another edge dislocation will have to pass to leave
the structure in its lowest energy ordered configuration.
Hence the structure, due to the passage of a super-dislocation can be described by:
In fact, the situation is more complex because a single dislocation in an fcc alloy often will
dissociate into two partial dislocations as the overall energy of the two partials is lower than the
original perfect dislocation:
This means that some atoms in B sites move into C sites. This is known as a stacking fault.
Hence the dislocation in the ordered A3B alloy now appears as follows
So overall, the ordered material, which contains a pair of dislocations, can be described by:
Hence for slip to occur on the slip plane by dislocation motion in an ordered alloy:
- anti-phase domain boundaries must move and anti-phase domains are created and destroyed;
- domain boundaries also can interact with other microstructural features, on which they may
become pinned;
To overcome this requires additional work (analogous to the motion of ferroelectric domains as in
Part IA Course B). This leads to enhanced mechanical strength which is order strengthening.
This is exploited to optimise the strength of nickel-base superalloys used in gas turbine engines.
3.2 Grains and Grain Boundaries
Grain size and grain boundaries are important microstructural features. Small grains will generally
strengthen an alloy, as discussed in Part IA (the Hall-Petch relationship) and also simultaneously
improve toughness, although will have an adverse effect on high temperature creep behaviour.
3.2.1 The Nature of Grain Boundaries
The description of grain boundaries on an atomic scale is generally complex, but the simple case
of a low-angle symmetrical tilt boundary can be represented as shown below.
d = b/
From Part IA Course D and also as given on page AH49, the energy of a dislocation is Gb2 per
unit length (where G is the shear modulus).
The energy per unit area of the grain boundary () is given by the energy per unit length of each of
the edge dislocations multiplied by the number of dislocations per metre,1/d and hence
1
Gb2
= 2
d
= 21 G b
i.e. the energy associated with the grain boundary increases linearly with the misorientation
angle, , due to the fact that the spacing between dislocation cores decreases.
3.2.2 Grain Boundary Energy and the Coincidence Site Lattice
Initially the grain boundary energy increases approximately linearly with misorientation angle ,
but this then saturates at around 15°. At this angle, the edge dislocations become so close
together that the strain fields surrounding them begin to overlap and the simple analysis of adding
together the energies is no longer valid. This is illustrated by the dotted line in the figure below;
the energy of a grain boundary plateaus at misorientations higher than ~15º.
grain
boundary
energy
misorientation
However, it is found experimentally that there are several misorientation angles for which the
energy decreases sharply, and this is shown by the solid line in the above figure. This means that
there are some high-angle grain boundaries which have reduced energies.
This can be explained by a coincidence site lattice (CSL) model, where a significant fraction of
atomic sites in the two adjacent grains coincide or match at the interface. This is illustrated below
where one lattice has been rotated by an angle of 36.9° (equal to cos-1 0.8). As one in five lattice
points coincide exactly, this is known as a 5 boundary.
A 5 boundary:
3.2.3 The Effect of Cold-Work
Plastic deformation at room temperature, such as rolling, forging or extrusion, is known as cold-
work (see Part IA Course D). It results in:
• changes in the shape of grains;
• increased defect density - dislocations from 1015 to 1010 m m-3 (or m-2) and vacancies.
Annealed state
Cold-worked state
The increase in defect density results in an increase in the stored energy, which can be estimated
as follows:
stress
)
y
strain
Ignoring work-hardening:
W = y
Consider a steel with y = 300 MPa which has been subjected to a strain = 0.1
Most (~95%) of this work is released as heat and only around 5% (in this case ~1.5 x 106 J m-3) is
stored as internal defects due to work hardening.
This stored energy U (per unit volume) can be related the increase in dislocation density
Deformation twins or mechanical twins may be seen in an alloy which has a crystal structure
that does not have sufficient independent slip systems to be able to deform by slip (e.g. hcp. at
lower temperatures). Under an imposed stress, the strain is taken up by twinning rather than by
dislocation movement. Mechanical twins are shown below for a cold-rolled Zn sample.
μm
400 μm m
80 μm
Pure zinc – deformed (from DoITPoMS micrograph library)
Note that deformation twins have a “lenticular” (lens-like) shape, tapering towards the edges of the
grain boundary. This is to minimise the overall strain energy associated with the edges of the
mechanically twinned regions where they link to grain boundaries.
3.2.4 Recovery
If a cold-worked sample is annealed by raising its temperature to ~ 0.3 Tm, dislocations reduce the
internal strain energy by gliding and climbing to form networks of sub-grains within the original
elongated deformed grains (also, some dislocations of opposite sign may annihilate each other).
As the
overall dislocation density is not changed markedly, the strain energy U is not reduced
substantially and so the mechanical properties are not significantly altered.
However, electrical conductivity is “recovered”. This resistivity decrease is due to a reduction in

point scattering sites and the formation of “defect-free channels” between the dislocation arrays
within each grain.
3.2.5 Recrystallisation
The process of recrystallisation occurs at a temperature above ~ 0.6 - 0.7 Tm. Favourably oriented
sub-grains grow, sweeping out both the polygonised sub-grain structure and also the elongated
grain boundaries in order to form new, equiaxed grains.
The driving force for the transformation is the reduction in internal energy U as the dislocation
density decreases from around 1015 m m-3 to 1010 m m-3. The mechanical properties change as
the effects of work hardening are eliminated, e.g. yield strength decreases.
The final recrystallised grain size is determined by:
a) the extent of the original cold-work, as this determines the dislocation density. The strain prior
to annealing affects the driving force for recrystallisation and also the size of the sub-grains
formed during recovery.
From http://aluminium.matter.org.uk/content/html/eng/default.asp?catid=68&pageid=1238100209
b) the effect of alloying additions. This is due to the fact that they will either be present in solid
solution (leading to solute drag) or will form second-phase precipitates (leading to Zener drag).
Either of the two mechanisms (covered further in section 3.2.7) will act to inhibit recrystallisation.
Annealing twins form during recrystallisation of some fcc alloys, i.e. within a single grain, one or
more regions commonly grow in “twinned” orientations, where one twin is a mirror image of the
other. These annealing twins are characterised by their straight or facetted edges, and so are
distinct from the lenticular shapes observed as a result of mechanical twinning of hcp alloys (page
AH 56). This is illustrated in the micrographs below.
400 μm m
100 μm
Cu-30wt.%Zn alloy - single phase -brass (from DoITPoMS Micrograph library)
Annealing twins arise in fcc alloys as sub-grains grow by atoms diffusing across sub-grain
boundaries during recrystallisation. It is a consequence of the atoms joining {111} close packed
planes in the recrystallised regions incorrectly, i.e. ABA atomic packing can occur in the <111>
direction rather than the expected ABC. This is termed a stacking fault.
Note that the probability of forming annealing twins depends on the extra energy introduced by the
incorrect local ABA packing. Hence in aluminium alloys, which have an intrinsically high stacking
fault energy, annealing twins are not seen. However, they are readily observed in alloys with low
stacking fault energies such as -brass, as is shown above, and austenitic stainless steels.
3.2.6 Grain growth
The major driving force for recrystallisation is the reduction in excess stored energy associated
with the defect density arising from prior cold-work (i.e. it is determined by the amount of strain
present in the alloy before annealing).
Prolonged further heating can result in further reductions in energy by decreasing the
recrystallised grain boundary area by grain growth. This process is controlled solely by diffusion
and so depends on temperature and time only.
The driving force for grain growth is addressed in section 3.2.8 and also is compared with the
forces acting to restrict grain boundary motion.
3.2.7 Mechanisms for restricting grain growth
There are 2 major ways in which grain growth can be restricted in alloys:
• by solute atoms;
• by precipitates.
3.2.7.1 Solute drag
In a solid solution, the sizes of solute atoms differ from those of the matrix atom which causes:
• local lattice distortion and so a region of higher local strain energy around a solute atom;
• preferentially solute segregation to sub-grain and grain boundaries to reduce strain energy.
This in turn results in less mobility of the boundaries (since more energy is needed to move the
boundaries or the boundaries move but more slowly as the solute atoms are dragged along).
Hence pure metals are easier to recrystallise than alloys, and do so at lower temperatures.
Trecrystallisation (ºC)
40
30
20
99.9 99.9 99.9 10

% Al
3.2.7.2 Zener drag
Zener drag is the term used to describe the pinning of grain boundaries by precipitates or particles
embedded in the matrix, rather than atoms as in solid solution strengthening. A grain boundary
has a certain amount of surface energy associated with it. If part overlaps with a particle that bit
of grain boundary no longer exists in the matrix and this will lower the total energy of the system .
Assuming spherical particles, the largest reduction in energy occurs when the grain boundaries
intersect the equators of the particles and so there will be a force which attracts the boundary to
the centre of such particles.
The surface energy associated with the grain boundary (J m-2) is equivalent to a force per unit
length (N m-1) which acts where it intersects the particles. This surface energy is denoted by .
sin sin

r
particle
The boundary is moving upwards, but experiences an attractive force (a drag force) back towards
the centre of the particle. The site where the drag force acts is a line where the grain boundary
and particle intersect. This is a circle with circumference 2 (r cos).
The force per unit length exerted by the boundary on the particle resolved in the direction of
movement of the boundary is sin.
Hence the total force, F, which acts to pull the boundary back is
F = 2r cos sin
Differentiating with respect to dF = –2r sin cos d
= –r cos2 d
This is a maximum when =45° : Fmax = r
(There is no net force in either direction for =0° as the boundary is located at the lowest energy
position and no force for =90° as the area of contact is zero.)
A grain boundary will intersect many particles, as shown below.
2r
Consider n particles per unit volume, each of radius r, then the volume fraction of particles is:
4
f = r 3n
3
Particles whose centre lies within ±r of the grain boundary will intersect it.
Considering a boundary of unit area, the number of particles which will intersect it (nA) is simply
the number of particles per unit volume (n) multiplied by the volume lying within 2r of the boundary.
Hence the number of particles intersecting unit area of boundary:
3f
nA = 2r n =
2 r 2
and so the total force per unit area exerted on the grain boundary (the drag pressure P) is :
3 f f
P = Fmax nA = r nA =
2r r
This shows that the drag pressure P increases as r decreases and as f increases, that is P will be
large if there is a fine scale dispersion of small particles.
Note that the net pressure P = 0 if the boundary is planar, since statistically, equal numbers of
particles will be pushing and pulling. In practice, the boundary curves such that there are a larger
number pulling it back than pushing it forward.
3.2.8 Effectiveness of particles in restricting grain growth
3.2.8.1 The driving force for grain growth
A grain can be represented as a sphere of radius r, in which case its surface area A = 4r2 and its
volume V = 4/3r3. The energy associated with a grain due to the energy of the grain boundary is
4r2 and so the energy per unit volume:
2 r 2 3 3
EV = = = (where D is the grain diameter)
4
3
r 3 2r D
Hence the energy associated with grain boundaries can be reduced further after recrystallisation
by grain growth. This is the driving force (or grain growth pressure) for that process.
For a material in which the grain diameter is 10 μm and the grain boundary energy is 0.3 J m -2:
3 3 0.3
PG = = 0.1 MJ m-3
D 10 10 6
3.2.8.2 The Zener pinning force
Consider an alloy with grain boundary energy = 0.3 J m-2:
small spherical precipitates r = 30 nm
which make up 1 volume % f = 0.01
f 0.3 0.01
From the previous page, PZ = = 0.1 MJ m-3
r 30 10 9
As this is similar to the driving force for grain growth, this fine dispersion of precipitates will inhibit
grain growth.
In section 3.2.3, the driving force for recrystallisation was estimated as 1.5 MJ m-3. Hence in most
alloys which contain fine particles or precipitates:
- recrystallisation occurs readily (as long as the temperature is high enough to enable diffusion);
- grain growth beyond around 10 μm will, however, be restricted by Zener pinning.
3.2.9 Effect on properties
property
0.3 0.6 Tannealing / Tm
Resistivity falls dramatically upon recovery, whilst yield strength and toughness change when
recrystallisation occurs.
The graph below shows microhardness data for a variety of aluminium alloys, where the reduction
in hardness is indicative of the onset of recrystallisation. There is a general trend to higher
recrystallisation temperatures with increasing alloying additions due to solute drag.
microhardness
temperature ºC (30 minute soak)
3.3 Precipitates
3.3.1 Importance of precipitates
The presence of precipitates in an alloy can inhibit grain growth via the mechanism of Zener drag,
see section 3.2.8. Precipitates also are important in raising yield strengths of materials by pinning
dislocations (see Part IA Course D). This mechanism also requires the precipitates to be finely
dispersed. If they are able to grow, or coarsen (by a mechanism known as Ostwald ripening, see
section 3.3.7), dislocations can easily move past them (a mechanism known as Orowan bowing)
and the strength of the alloy will decrease.
A system where precipitation hardening is useful is that of Al-Cu (used in aircraft alloys). This was
introduced in Part IA Course C and will be looked at again in more detail in section 4.4.
3.3.2 Precipitate formation - revision of thermodynamics.
T
liquid
+ L

+
Co composition %B
Sequence to optimise formation of fine precipitates:
- hold at temperature (1) to attain complete solid solution;
- quench to room temperature (2) to maintain solid solution;
- age at slightly elevated temperature (3) which is below the solvus temperature
The temperatures in practice for an Al-4 wt.% Cu alloy areTage~160°C and Tsolvus~550°C.
3.3.3 Precipitate formation - revision of kinetics.
Wn r x surface energy
4area
r r radius of precipitate r
volume x (G
4/ vr 3– U)
3
Gv
Thermal fluctuations create embryos of the new phase, which only become stable nuclei on
exceeding the critical radius r*.
There is a driving force GV which depends on the undercooling. This driving force is opposed by:
- strain energy, U, (if the nucleating solid phase has different volume to the matrix), and
- surface energy, , (which depends on the coherency of the interface).
For a spherical nucleus, the work of nucleation Gn is:
4 3
Gn = r (Gv U) 4 r 2
3
and by differentiating this with respect to r, we can show that critical values for a stable spherical
nucleus are:
2
r* =
Gv
16 3
Gn * =
3 Gv2
Because the surface energy, , opposes the transformation to the new phase, more coherent
metastable precipitates may form more readily as an intermediate stage because Gn* will be
lower for these. This occurs in the Al-Cu system.
3.3.4 Nucleation of metastable precipitates
When considering the thermodynamics of non-equilibrium phase growth, free energy curves and
the common-tangent construction, as Part IA Course C, are still the approach for determining the
solvus for metastable precipitates.
G
metastable phase ”
solid
solution
stable phase
composition
T stable phase
solvus
solid metastable
solution phase solvus
% solute composition
*
On quenching from a solid solution to T , the free energy of the supersaturated solid solution is G1.
This can be lowered to G2 if the supersaturated solution decomposes to form and metastable '.
Subsequently the free energy can be lowered to G3 when final decomposition occurs, forming
and the stable phase .
3.3.5 Diffusion-controlled precipitate growth
Precipitates ( phase) will generally have a different chemical composition to that of the matrix ()
and hence their growth is usually by a diffusion-controlled mechanism.
As an individual precipitate grows, the extent of the associated diffusion field increases. This
slows down the rate of growth as the solute diffusion necessary for the growth has to occur over a
longer distance.
Consider the isothermal formation of a precipitate in a binary system:
+
C Co C %B
concentration
C
(%B)
C x
Co
Css
C
x distance
A number of assumptions are involved:
• concentrations at the interface between and are those given by the phase diagram;
• concentration gradient in the matrix is constant and linear;
• far-field concentration, C0, is constant.
The extra solute required in the precipitate comes from the depleted region, hence by equating
areas in the diagram on the previous page:
(C )
C0 x = 21 x C0 C ( ) [A]
Now, if the precipitate is growing, the interface is advancing at velocity dx/dt, hence in time dt it
advances by distance dx.
concentration
(%B) C
C x
Co
Css
C
x distance
The rate at which solute is incorporated into the precipitate is equal to the diffusive flux of solute
down the concentration gradient towards the interface :
(C C )
(C

C ) dxdt = D 0
x
[B]
Eliminate x using the two equations [A] and [B] gives:
dx
=
(C0
C ) 2
D
dt (C )(
C C C0 ) 2x
If C >> C then (C - C) (C - Co) which can be denoted by C .
Similarly, let Css represent (C0 - C) and so the above equation can be rewritten as:
2
dx C D
= ss

dt C 2x
2
C
Rearranging this gives 2x dx = ss
D dt
C
2
C
and integrating 2 x dx = ss
D
C
dt
2
C
x 2
= ss
Dt
C
C
Hence the precipitate thickness x = ss
Dt
C
dx 1 Css D
and growth velocity is given by v = =
dt 2 C t
In practice, the precipitate initially grows faster than this analysis predicts, due to the fact that
the diffusion profile is non-linear as shown below.
concentration
(%B)
distance
Due to this, more accurate expressions turn out to be:
C dx C D
x = 2 ss
Dt and v = = ss

C
dt C
t
3.3.6 Nucleation of Precipitates
When precipitates form in a solid matrix, heterogeneous (rather than homogeneous) nucleation is
much more likely because of the introduction of strain energy and surface energy. Thus
precipitation tends to occur preferentially at:
• grain boundaries;
• dislocations;
• vacancies;
• near impurities (or other precipitates) due to their local strain fields.
Consider the role of vacancies in an alloy. Under equilibrium, the number of vacancies n is given
by:
Q
n = n0 exp f
kT
where Qf is the activation energy for vacancy formation. Excess vacancies are trapped when an
alloy is quenched from high temperature and this leads to enhanced diffusion at the lower
temperature.
These excess vacancies will diffuse to sinks, e.g. grain boundaries, in order to return to the
equilibrium number at the given temperature. This will lead to a variation in vacancy concentration,
especially near to the grain boundary.
vacancy
concentration
distance
Precipitate free zone (PFZ) formation: vacancy depletion
Since precipitation is less probable for a lower vacancy concentration, this vacancy distribution at
grain boundaries results in precipitate-free zones adjacent to grain boundaries.
Precipitate free zone (PFZ) formation: solute depletion
Note that this effect may be seen or enhanced due to solute depletion near the grain boundary as
a consequence of precipitates heterogeneously nucleating and growing on the boundary itself.
Effects of precipitate-free zones:
• softer, weaker zone in which any subsequent deformation may be localised (can lead to
failure adjacent to grain boundaries);
• composition variation adjacent to grain boundaries (can cause localised corrosion as an

electrochemical cell is set up).
The widths of precipitate-free zones can be minimised by optimising precipitation heat-treatments:
• quench to retain supersaturated solution with excess vacancies;
• heat at low ageing temperature to promote initial metastable precipitates as formation of

these is less dependent on number of vacancies because precipitates are coherent (and
so have smaller nucleation barrier);
• raise ageing temperature slightly to grow more stable precipitates and to optimise strength
by control of precipitate size, coherence and spacing.
3.3.7 Stability of precipitates – Ostwald ripening
For high yield strength, it is advantageous to have an array of fine-scale precipitates so that they
are effective in pinning dislocations. Hence it is important that they do not coarsen at the
temperatures at which the material is used.
Smaller precipitates have a greater ratio of surface area to volume, hence have higher free energy.
This provides a driving force for the diffusion of solute from the small precipitates to larger ones.
solute
diffusion
small larger
radius r2 radius r1
Consider a precipitate of radius r, containing n atoms of solute.

If v is the volume of the precipitate phase per solute atom, then:
nv = 4 /3 r3 (A)
The free energy of formation of the precipitate Gn (see section 3.3.3)
4 3
Gn = r (Gv U) 4 r 2 (B)
3
Differentiating (A) and (B)
Gn Gn r v
= = 4 r 2 (Gv U) + 8 r 2
n r n 4 r 2
2
= v (Gv U)
r
Let one atom be transferred from particle of radius r2 to particle of radius r1. The net change in the
free energy of the system is:
If r1 > r2, G is negative, i.e. there is a thermodynamic driving force for transfer of atoms from
small to large particles (r2 to r1).
2
Hence driving force for coarsening is proportional to where r is precipitate radius and is
r
surface energy. This shows clearly that coherent precipitates, which have a low surface energy
with respect to the matrix, are stable and they do not coarsen.
The rate of coarsening will depend on:
• surface energy, (which depends on the precipitate coherence);
• temperature (which governs the rate of diffusion);
• solubility of solute in the matrix.
Coarsening can thus be controlled by:
• the nature of the precipitates (hence the use of coherent ’ precipitates Ni3(Ti,Al) in nickel-
based superalloys (see section 4.6);
• strict control of temperature (hence the need to monitor temperatures of aircraft engines)
The overall alloy strength is determined by
• precipitate density, size and coherency
3.3.8 Dispersion strengthening to avoid coarsening
To avoid the problems associated with precipitate coarsening, it is possible to introduce fine,
insoluble particles into an alloy by a different fabrication method. These particles will inhibit
dislocation movement if they are fine enough and uniformly distributed. This is the basis of
dispersion strengthening.
The approach involves:
• use of insoluble particles in the matrix (i.e. Al2O3 in Al, Y2O3 in Ni or Fe-based alloys);
• fabrication of powders from complex alloys by rapid solidification;
• manufacture by consolidation of a mixture of powders;
• sintering of powders to consolidate the material (involves diffusion, so requires high

temperature and pressure and a long time).
The high temperature stability of such alloys is better than the equivalent precipitation-hardened
alloys although the oxide distribution may not be as fine or the particles as small.
strength
temperature T
4. ALLOY SYSTEMS
4.1 Ternary phase diagrams
4.1.1 Representing three components and temperature
To date in Parts IA and IB, only phase diagrams for binary systems (those in which there are only
two components) have been considered. Many alloys of practical importance have a greater
number of alloying additions and it often helpful to use a phase diagram in which there are three
components. In order to represent three components plus the temperature, it is convenient to
construct a triangular-based prism.
In this 3-dimensional space, volume elements represent phase regions.
A vertical section is the same as a binary phase diagram; for example if A-C is a eutectic system,
the phase boundaries on the front face would be shown as:
4.1.2 Constant temperature sections in ternary phase diagrams
A useful representation of ternary phase diagrams is a horizontal section which shows the effect
of composition at a single temperature, an isothermal section. This produces an equilateral
triangle with the 3 components at the corners, and each point within the triangle represents a
unique combination of the components.
B
A C
Clearly the lower left corner represents 100% A, whilst the line BC represents 0% A. Each line
parallel to BC is a constant composition of A, which simply increases linearly across the triangle.
Hence, compositions can easily be read from the grid.
There is also another way to find the compositions. If lines are drawn, parallel to the axes, through
the constitution point, these lines will split the axes into parts which are proportional to the
compositions of each component. Clearly the operation of working out the composition can be
done by drawing just two lines.
B
A C
30% 20% 50%

C B A
A good example of a simple ternary diagram is that for Fe,Ni,Cr shown below representing a
temperature of 900ºC. It is evident that Fe and Ni (both f.c.c.) form a complete solid solution and
that a reasonable amount of Cr can be dissolved into this structure. Meanwhile b.c.c. Cr can
dissolve a large amount of Fe, but any significant amount of Ni results in 2 phases.
4.2 Cast Irons
4.2.1 Introduction to Cast Irons
The phase diagram for the Fe-C system, which was introduced in Part IA, is usually depicted for
iron-cementite (Fe-Fe3C). In fact, iron-graphite is the thermodynamically stable system and Fe3C,
a metastable phase, is usually shown rather than graphite simply because kinetic considerations
mean that Fe3C generally predominates in steels.
Cast irons, however, which have carbon contents in the range of 2-4 wt.% often are formed with
the stable graphite phase. The dotted line in the phase diagram on the following page denotes
the phase boundaries for iron-graphite.
Cast irons usually contain Si as well as other alloying additions. These alloying additions have a
significant effect on the phases which are found in the final alloy (often causing graphite to be
formed even for alloys which contain less than 4.3 wt% C). There are many different types of cast
iron with characteristic microstructures and properties. Two common families of cast iron are grey
cast iron and white cast iron.
4.2.2 Grey cast irons
Grey cast irons are favoured by high C or Si content, and if the cooling rate is slow
If the alloy is hyper-eutectic, i.e. C > 4.3 wt% or lower if significant Si > 1 wt.% is present:
- graphite flakes form when the temperature falls below the liquidus line;
- at the eutectic temperature, a graphite – eutectic forms from the remaining liquid phase;
- on cooling further below the eutectic temperature, C is rejected from the solid-solution to
grow on to existing pro-eutectoid flakes and also may nucleate new graphite flakes.
- at the eutectoid temperature (~723°C), the matrix normally transforms to pearlite.
There can be exceptions to the above, influenced by the presence of additional alloying elements.
For instance, sufficient Ni stabilises the phase and hence the final alloy can be graphite flakes in
a matrix. This is due to the thermodynamic effect of the Ni in the Fe (see section 4.3.2).
Fe – 3.6 wt.% C – 2.1 wt.% Si (from DoITPoMS Micrograph library)
The graphite flakes are desirable because they have a low density leading to volume expansion
on solidification (good for the surface definition of castings). In addition, such alloys have good
machinability as the graphite acts as a lubricant for the cutting tools as well as being intrinsically
brittle. However a negative aspect is that the flakes act as stress concentrators, leading to poor
toughness in service applications. In addition, the graphite flakes are interconnected so that any
cracks can propagate readily.
Common applications of grey cast irons include car cylinder heads and the bases of machining
tools such as lathes.
4.2.3 Spheroidal graphite cast irons
One variant of the grey cast irons is formed by Mg or Ce additions (~0.1 wt.%) to the melt which
cause spherical graphite nodules to form rather than the interconnected flakes.
Two theories have been proposed to account for the effect of these elemental additions. The Mg
or Ce impurities “poison” the preferred growth sites by attaching to the edges of the graphite
planes, slowing growth in that direction. Hence the graphite grows in a more isotropic manner,
leading to the development of approximately spherical particles. Alternatively, the surface
energies of the graphite and the liquid melt are altered such that the surface area of the graphite
is minimised when growing in the melt.
Fe – 3.6 wt.% C – 2.1 wt.% Si – 0.07 wt.% Mg (from DoITPoMS Micrograph library)
The absence of the graphite flakes leads to increased toughness. This effect is similar to that of
sodium in Al-Si casting alloys. Brittle interconnected Si plates are prevented from forming if small
amounts of the Na modifier are added to the melt (see question sheet AQ2).
Applications of spheroidal graphitic cast irons are generally those in which the increased
toughness/ductility is important and include car crankshafts, ductile iron pipes, fittings, valves and
manhole covers.
4.2.4 White cast irons
This family of cast irons are favoured by low C or Si contents and if the cooling rate is fast, so that
the non-equilibrium cementite,Fe3C, forms rather than graphite.
If the alloy is hypo-eutectic (C < 4.3 wt%):
- dendrites form as the primary phase, followed by the and Fe3C eutectic intergrowth;
- on further cooling below the eutectic temperature, C is rejected from the phase to form
more Fe3C;
- at the eutectoid temperature (~723°C), any remaining (both the primary dendrites plus that
in the eutectic) transforms to pearlite.
Fe – ~3 wt.% C (from DoITPoMS Micrograph library)
White cast irons are harder and more wear-resistant than grey cast irons. Applications include
rolls for crushing minerals.
Note.
The names “grey” and “white” used to describe cast irons are not associated with the etched
microstructures, but come from the appearance of the fracture surfaces.
White cast irons are brittle and so form smooth fracture surfaces, whereas grey cast irons, which
are more ductile, have less reflective surfaces when fractured.
4.3 Steels
4.3.1 Overview of steels
Steels are crucially important due to their widespread use in construction and other applications.
The extent to which steel dominates the metals market in terms of annual production
(approximately 1.4 billion tonnes) is associated both with the low cost (typically around 0.3 £/kg)
and also with the excellent mechanical properties (yield strengths often in excess of 1 GPa).
Additionally, the properties can often be tailored to suit a particular requirement by careful choice
of alloying additions together with appropriate themomechanical processing.
Steels are iron-based alloys with C content up to 1.5 wt.%, but almost all steels produced and
used commercially have C << 0.5 wt.% and so are hypo-eutectoid. Many modern high-strength
steels have C contents < 0.1 wt.% and suitable other alloying additions.
Categories of steel include :
Plain carbon steels low carbon C < 0.1 wt.%
medium carbon C < 0.25 wt.%
high carbon C > 0.25 wt.%
Alloy steels containing Cr, Mo, Ni, V, Nb, Ti, Al in varying amounts
Stainless steels, which contain Cr additions to give corrosion resistance and can be:
ferritic (Cr with low Ni)
austenitic (Cr with higher Ni, e.g. 18 wt.%, Cr, 8% Ni wt.%)
martensitic (as ferritic, but higher C, 0.1 < C < 0.6 wt.%)
4.3.2 Thermodynamics
Different alloying additions alter the nature of the Fe-C equilibrium:
Cr and Si stabilise the ferrite phase (hence can exist stably at high temperatures), whilst
C, Ni and Mn stabilise the austenite phase (hence can exist stably at low temperatures).
T T

Concentration of -stabilisers Concentration of -stabilisers
4.3.3 Kinetics
Alloying additions also causes shifts in the lines on TTT curves. Different additions will prefer to
exist in one phase rather than the other and so will partition during transformation from the
austenite phase. For this to occur, diffusion will have to occur at the growing interface.
Fe3C

Fe3C

Fe3C
Carbon occupies interstitial sites in both and phases and therefore can diffuse very rapidly.
Other alloying additions are substitutional on sites in the Fe lattice and will therefore diffuse much
more slowly. This makes transformations happen more slowly and hence displaces the TTT
curves to the right.
4.3.4 Martensite
If a steel is cooled moderately quickly from the austenite () phase, Widmanstätten ferrite () may
form (see Part IA Course C).
If quenched more rapidly from the austenite phase to a temperature typically less than around
250°C, a phase called martensite forms by a displacive (diffusionless) transformation (see Part IA).
Martensite is a non-equilibrium (metastable) phase and forms because there is no time for the C
to diffuse to form Fe3C. Hence the C remains in a supersaturated solid solution in a body-centred
tetragonal lattice. It has a high internal strain energy, which makes the material hard and brittle.
The hardness and brittle nature of martensite increases with the carbon content.
To restore some ductility and toughness, and to return to the equilibrium phases, martensite can
be tempered by heating to a temperature less than the eutectoid temperature. As with any other
supersaturated solution, e.g.. Al-Cu which will be covered in section 4.2.2, this results in
precipitate formation via a series of metastable phases.
Precipitation from a supersaturated solid-solution generally is associated with strengthening, as

occurs in the Al-Cu system, due to increased interaction of dislocations with the small precipitates.
However, when tempering martensite, there is a reduction in strength even though Fe 3C
precipitates are formed. This is because the significant reduction in the internal strain energy,
present in the original martensite, has a greater effect than the formation of the Fe3C precipitates.
Tempering a martensitic steel, therefore, allows control of yield strength, ductility and toughness.
Hardness or
yield strength
10 70
Tempering temperature (ºC)
Secondary hardening can occur in some alloy steels which show an increase in yield strength
when tempering around 550ºC to 600ºC – see dotted line in above figure.
Secondary hardening is due to the formation at ~550ºC to 600ºC of stable carbides of Cr, Mo, W,
Nb or V. These steels have a better wear-resistance than plain-carbon steels and may be used
as cutting tools which need to retain their strength when dull red hot.
4.3.5 Bainite
The (reconstructive diffusional) transformation to ferrite and pearlite during slow cooling and the
(displacive shear) transformation to martensite when quenching have been described. However,
it also is possible to produce different steel microstructures at intermediate cooling rates.
Bainites form by combined shear and diffusional transformations at temperatures above that at
which martensite forms. The resulting microstructures are extremely fine and can be resolved
only at high magnification using transmission electron microscopy (TEM).
Upper bainite:
• ferrite forms at austenite grain boundaries on cooling and grows into the by a shear
mechanism;
• the is plate-like in form, but on a very fine scale;
• C diffuses to the / interface where fine Fe3C precipitates nucleate and grow.
C
Lower bainite:
• forms at slightly lower temperatures where there is insufficient time for C to diffuse to the
/ interface;
• fine Fe3C precipitates nucleate and grow with an orientation relationship with the ferrite in
which they are growing.
4.3.6 TTT diagrams
As was seen in section 4.3.2, different alloying additions in steels alter the thermodynamics of
phase stability in the Fe-C system. Not only are the presence of the equilibrium phases affected
but also the kinetics of their formation. Kinetics of phase formation can be illustrated using TTT
diagrams (see Part IA Course C).
For steels, there are three principal effects of alloying additions on TTT diagrams:
- temperatures at which phases first nucleate will change;
- rates of nucleation and growth will be affected and phase growth is very dependent on the
relative diffusion coefficients of the elements present;
- relative stabilities of the various phases change, depending on the alloying additions present.
T T
time (log scale) time (log scale)
plain C steel alloy steel (e.g. 3 wt.% Ni, 1 wt.% Cr)
4.3.7 Steels: summary of transformations
Cooling rate:
slow ferrite and then pearlite form by equilibrium diffusional transformations
nucleates at grain boundaries and this leads to grain refinement
pearlite forms by eutectoid reaction (coupled growth of and cementite Fe3C)
moderate Widmanstätten (strain energy minimised) grows from grain boundaries,

pearlite grows as for slow cooling rate above.
fast upper bainite forms - as shear increases (at lower transformation temperatures)
then changes to
lower bainite formation instead (both types form with coupled shear and diffusion)
pearlite does not form
quench martensite forms by non-equilibrium displacive shear transformation (no diffusion)
Tempering:
martensite/bainites: spheroidal Fe3C) nucleates and grows in matrix – no pearlite possible
alloy steels: as above but possibility of secondary hardening (see section 4.3.4).
Normalise:
Heat a steel above A3 temperature (see section 4.2.1), i.e. just into the region, hold and then
cool but do not quench. Resulting nucleation and growth, firstly of grains when heating and
then of grains when cooling, leads to significant grain refinement and consequent
improvements in both yield strength and toughness.
4.4 Aluminium alloys

4.4.1 Introduction
Al alloys are used in either the as-cast condition or in the wrought state.
For cast products:

• cooling rate and the use of grain refiners ( see section 2.6.2) are important;
• many alloys are based on Al-12 wt% Si (eutectic), and Al-Zn particularly for die-casting;
• Si has the diamond cubic structure which is low density and therefore compensates for
shrinkage, reducing porosity in the casting;
• modification of silicon is achieved by small additions of Na (~0.2 wt%) to the melt, resulting
in the coarse Si plates becoming fine needles.
For wrought products (rolled, extruded, forged):

• final properties rely on appropriate heat treatment/working;
• alloys are either precipitation-hardened or work-hardened;
• precipitation-hardened alloys get strength by controlling precipitate distribution, size and
coherency;
• worked alloys get strength from small final grain size and high defect density.
Al alloys can be classified according to the US system:
Main additions Strengthening Applications
1xxx pure Al work-harden Foil and electrical conductors
2xxx Cu CuAl2 pptes Al-Cu-Mg for aircraft wing sheet
3xxx Mn work-harden General purpose – cookware
4xxx Si Si needles Casting alloy
5xxx Mg work-harden Very common, corrosion resistant, structural, boats
6xxx Mg & Si Mg2Si pptes Extruded products, construction, golf clubs
7xxx Mg & Zn MgZn2 pptes High strength alloy
8xxx Li (also others) Li3Al pptes Low density, increased stiffness - aircraft
Possible strengthening mechanisms include:

solid solution hardening;
grain size control;
two-phase alloys;
precipitates of optimised size and coherency;
oxide-dispersion strengthening.
4.4.2 Precipitation in Al-Cu alloys
This was introduced in Part IA and the relevant part of the phase diagram is shown below
T 700
L
600
+L
500
+
400 '
''
300
GP1
200
100
0
0 2 4 6 wt.% Cu
The solid lines show the equilibrium phase diagram, with an f.c.c. solid solution () based on Al
and an intermetallic Al2Cu phase, . A solvus is also shown for each of the metastable phases
free
energy
C
Co composition
0
A supersaturated solid solution is obtained by annealing the Al-4 wt% Cu alloy just below the
eutectic temperature of 548ºC, then quenching to room temperature. During subsequent heat-
treatment (ageing), a sequence of precipitates is observed: in order, they are
GP1 zones, '', ' and .
The stable (equilibrium) phase precipitate is shown on the equilibrium phase diagram. These
precipitation reactions progressively lower the free energy of the system; the metastable
precipitates form preferentially due to lower activation energies.
GG
+ ( (direct precipitation)
G
G
Go0

G
G11
+ GPZ
GG22
+ "
G
G33
+ ’
G
G44
+
composition, wt.% Cu
4.4.3 Structures of metastable precipitates
The first metastable precipitate to form is the Guinier-Preston (GP1) zone. This takes the form of
a Cu plate fully coherent with the Al matrix. There is a high degree of strain due to the differences
in lattice parameter: aCu = 0.9 aAl. The plates are ~10 nm in diameter and ~0.5 nm thick
Next is '' (also known as GP2). This is a tetragonal precipitate as shown below, fully coherent
with the Al matrix on the {001} plane. These form plates ~15 nm in diameter and 0.8 nm thick
which create some local strain.
Al atoms
0.768 nm
Cu atoms
0.404 nm
0.404 nm
' is also tetragonal and also coherent on the {001} plane, but fits less well on the other interfaces,
leading to greater strain.
0.580 nm
0.404 nm
0.404 nm
the final precipitate to form is the equilibrium phase. It is incoherent with the Al matrix and has a
body centred tetragonal unit cell.
0.487 nm
0.607 nm
0.607 nm
4.4.4 Optimisation of metastable precipitates for highest yield strength
For the highest yield strength, it is necessary to inhibit dislocation motion.
yield
stress
cutting bowing
stress stress
annealing time
When the precipitate dispersion is fine and the precipitates are coherent, they can easily be cut by
dislocations. Such an alloy is underaged. If the dispersion is too coarse, the dislocations can bow
between the precipitates (as they will be widely spaced). Such an alloy is overaged. In practice,
alloys are usually used in a slightly overaged condition, i.e. heat-treated to just past the peak
hardness.
4.5 Titanium alloys
4.5.1 Overview
Titanium and its alloys have:
• extremely high strength to weight ratios;
• excellent mechanical properties;
• very good corrosion resistance.
Hence there are extensive applications including:
• aerospace: compressor blades and other parts in gas turbine engines, airframes;
• energy generation: nuclear fuel plants, heat exchangers;
• chemical: food processing plants;
• medical: prostheses such as hip implants.
Titanium can exist as a number of phases. T < 882ºC: phase
T > 882ºC: phase
Fast-cooled: martensitic phases
Alloying additions can stabilise these phases to different temperature regimes (just as for steel
phases in section 4.2.2).
Interstitial elements include O, N, C, which have a high solubility and are mainly stabilisers.
They provide good solid-solution strengthening.
Substitutional additions will usually be -stabilisers if they have <4 bonding electrons (i.e. Al, Ga)
whereas if they have >4 bonding electrons, they are likely to stabilise and may even form a
eutectoid.
T T T
+
+

+ +
solute content solute content solute content
4.5.2 Titanium 6:4 (Ti- 6 wt.% Al, 4 wt.% V)
This is one of the most important commercially used Ti alloys. The final microstructure and grain
size depend on the amount of hot-working and the heat-treatment cycle. The microstructures can
be predicted using a similar approach to TTT diagrams for steels.
time (log scale)
In Ti - 6 Al - 4 V, both the and phases are stable at room temperature. Slow cooling from the
phase results in Widmanstätten laths inside the matrix. This is a “basket-weave” structure
with good strength, toughness and fatigue resistance.
Ti – 6 wt.% Al – 4 wt.% V (from DoITPoMS Micrograph library)
This alloy also shows superplasticity: the ability to deform up to ~800% at temperatures ~0.6 T/Tm
4.6 Nickel-base superalloys
4.6.1 Introduction
Ni-base alloys are useful at high temperature due to the fact that fcc metals tend to be more
stable than bcc metals and also Ni has a reasonably high melting point (1455°C). Such alloys are
used extensively for turbine blades which can be used at gas temperatures up to ~1700°C. This is
important because the efficiency of an engine increases with its operating temperature (Carnot
cycle). Principal concerns at such high temperatures are oxidation resistance and creep.
4.6.2 Ni – (Al, Ti)
The major solutes in Ni-based superalloys are Al and Ti, which are usually present in
concentrations of less than 10%.
Ti Ti
Ni Ni
For the above isothermal sections of the Ni-Ti-Al ternary phase diagram, consider the composition
marked by the red dot, which is approximately 90% Ni and equal amounts of Al and Ti. At low
temperatures, this composition produces 2 phases in equilibrium butthe single phase is favoured
at higher temperatures. Hence, annealing at high temperatures produces the single phase from
which, by aging at a lower temperature, a fine dispersion of ' precipitates can be formed.
The phase is based on Ni and therefore has the fcc. structure, with Al and Ti in solid solution
(occupying random substitutional sites on the lattice). The ' phase is approximately 75% Ni and
is an ordered phase of Ni3(Al,Ti) - i.e. Ni atoms occupy the “face centre positions” of the cell with
Al or Ti atoms at the corners). This structure is therefore no longer cubic F, but cubic P – as is
shown on the next page.
Both phases are cubic and have similar lattice parameters so the ' precipitates grow coherently
within the matrix with a simple cube-to-cube orientation relationship. Because the -' interfacial
energy is low, there is only a minimal driving force for coarsening of the ' precipitates and so the
precipitates are stable even when used at high temperatures (>1000°C).
The strengthening mechanism comes from the fact that the precipitates are ordered. Dislocations
in the phase find it difficult to penetrate into the ordered ' phase as that would upset the
ordering (see order hardening and superdislocations, section 3.1.2).
Modern Ni-based superalloys are, in practice, far more complex than this 3 component system.
The micrograph below is of an alloy containing Ni 53, Fe 19, Cr 18, Nb 5 (wt.% approximately)
plus small amounts of Ti, Mo, Co, Al. It contains three different precipitate phases which
strengthen the matrix.
Nickel-based superalloy IN718 held for 72 hours at 850°C

(from DoITPoMS Micrograph library)
5. SUSTAINABILITY OF METALS
5.1 Life Cycle Analysis (LCA)
5.1.1 Stages of life
There are 4 stages in the life cycle of a manufactured product, as shown in the diagram below.
Each of these stages may involve stresses on the environment, to different extents, including:
• energy consumption;
• water consumption;
• gas emissions;
• particulates;
• toxic residues.
It can be difficult to assess the levels of each of these stresses and to judge accurately the relative
importance of each, or to combine them to come up with a single overall index of sustainability.
Currently, single measures of environmental impact are widely used, e.g. based on energy
consumption or gas emissions (especially CO2). Manufacturers increasingly are required to
provide numeric data on energy usage and CO2emissions for making and using their products.
In practice, life cycle analysis, LCA, can produces similar results using one or both indices.
When selecting and using materials, the four main phases of the product life cycle considered to
be important are:
production, manufacture, usage, disposal
In practice, one phase often predominates over the others, as shown for some examples below.
5.1.2 Applications to manufactured products
As an example of how such life-cycle analysis can be carried out, consider the case of drinks
containers, which could easily be made using metals (either Al or steel), plastics (PET or PE) or
glass. Different comparison criteria might be used, but the amount of material required to hold a
litre of liquid (as is tabulated overleaf) clearly is one of the more appropriate for this application.
Production of raw material
Manufacture
Use
Disposal
Material Mass required Energy (MJ)
Aluminium 45
Steel 102
Glass 433
PET 62
PE 38
This approach allows identification of the material, from those considered, with the lowest impact.
5.1.3 Energy Inputs for Metallic Products
This course has dealt with how metals are turned into useful products, by solidification processing
and also by deformation processing. A necessary prior stage, however, usually is the extraction
of the metal from its ore. An introduction to the thermodynamics underlying materials extraction
will be included in Part IB Course B (i.e. the Ellingham diagram).
Consider aluminium as an example. It is the most abundant metal on earth, found as the oxide
bauxite, but is relatively expensive due to the fact that it takes a large amount of energy to extract
the aluminium from bauxite. This involves removal of the ore from the ground followed by further
processing in order to achieve the pure oxide alumina (Al2O3). Thermodynamic calculations show
that the free energy change for the reaction:
is -1576 kJ mol-1 (at 298 K).
As also will be evident from the Ellingham diagram, this confirms that Al2O3 is one of the most
stable metallic oxides and hence a large amount of energy is required to extract metallic Al.
Processing of metals also requires a significant amount of energy. Casting clearly involves taking
the alloy into its molten state – a typical value of energy usage in casting processes is around
3 MJ kg-1. Furthermore, deformation processing such as rolling or forging requires an energy
input of around 6 MJ kg-1. (Typical values for steel and Al from Cambridge Engineering Selector).
See notes in section 5.3 on how to use Cambridge Engineering Selector software.
5.1.4 Reuse and recycling
Metals have a large advantage over other materials when it comes to reuse and recycling. Due to
their good mechanical properties (strong and ductile), products are generally durable and suitable
for reuse. Furthermore, even when used in disposable products, recycling is usually relatively
straightforward because metals (unlike polymers, currently) are generally easy to separate.
The ability to recycle has a clear impact on the life-cycle analysis that was carried out earlier.
Using an energy sustainability index, the dominant factor for both steel and aluminium in drink
cans turns out to be production of the raw material. Hence, if a significant fraction of aluminium
cans are recycled, the impact in terms of energy use is reduced significantly. This is the reason
that aluminium is able to compete with steel for this application.
5.2 Lifetime: degradation of metals
Most metals react chemically in their environments, as will be covered in Part IB Course B. Many
metals in service form oxide layers and their individual nature will dictate the extent to which they
can protect the metal from continued degradation. As will be seen in Course B, aluminium oxide
often acts to protect underlying alloy from further reaction, whereas the different nature of the
oxides on steels can lead to the familiar problems associated with continual oxidation and rusting.
Finally, note that the degradation of metals is not always problematic and can also be beneficial.
When a metal oxidises, some of the energy used in its initial production can be recovered. This is
the basis of many batteries.
5.3 Notes on using Cambridge Engineering Selector software
Cambridge Engineering Selector (CES) software is available on the computers in the department.
It also can be downloaded for your own computer from:
www.msm.cam.ac.uk/Teaching/ces/index.html
Instructions for use.

1. Open CES Edupack 2008.
2. The Configuration box appears; choose Level 2.
3. From the pull-down File menu, choose New Project.
4. Under 1. Selection Data “Pick a selection template” on the left-hand side of your screen, use
the pull-down menu and choose “Edu level 2: Materials with Eco properties”.
5. You then have several options, including plotting a graph, see (a) below, obtaining data on
individual materials as in (b) below, or finding out about fabrication processes as in (c) below .
a. Under 2. Selection Stages, you can choose Graph. This will bring up a dialogue box which
allows you to specify the data to be plotted on both x and y axes of your graph. If you are
not familiar with this, select the Help option at the left-hand bottom corner of the dialogue
box and information on the Graph Stage wizard will be shown. An example is provided over
the page. For the data needed for the answer on question sheet BQ4, the graph stage is
not strictly required.
b. On the left-hand side of the screen is a list of 97 different materials. Scroll down and then
double click on a material of interest to show the full data stored on that material.
c. To find out about different fabrication processes (also useful for the Artefact Project next
term), change the selection template (showing “Edu level 2: Materials with Eco properties”)
in Selection Data to “Edu level 2: Processes – Shaping” and then choose individual
processes of interest from the 60 shown on the left-hand side of the screen.
6. The CES Help menu (top line) also provides full information on the software.
Background information on Eco Selection.
A full and helpful paper:

'The CES Eco Audit tool – a white paper', Ashby M.F., Ball N., and Bream C.
on choosing materials on the basis of eco considerations can be downloaded by selecting the
CES Help menu. The Welcome page of CES Help has Contents displayed and the second bullet
point is “White Papers”. Choose this option and then Download the above paper (the PDF option
does not work in all situations). The paper will download in a new browser window.
[Note that the above paper provides information on transportation costs.]
Plotting a graph using CES – see next page
Plotting a graph using CES
1. Follow the instructions in 5(a) on the previous page.
2. In the pull-down menu “Category”, there are twelve distinct groups plus “All - alphabetically”,
and each “Attribute” has been put into one of these to aid their identification and selection.
Hence select a “Category” and then, using the pull-down list below, select the particular
“Attribute” that you wish to plot on the x-axis. Note that you can name the axis by entering
data into the “Axis Title” box.
3. Repeat this for the y-axis by selecting the y-axis tab at the top of the selection box.
4. To plot the graph, choose “OK” at the bottom of the dialogue box
5. Additional options.
a. It is possible to combine Attributes by using the “Advanced” button. Select the first Attribute
and one of the various operators listed, followed by the second Attribute.
b. In addition, the selection of all materials in one or more of four main classes can be made
using the “Advanced” button. This allows the relative properties of the “Attribute” selected
for the y-axis to be compared for the material class/es selected. This is most conveniently
done by displaying the family along the x-axis. Hence select the “x-axis” tab followed by
“Advanced” and then the “Trees” tab. Select one or more of the four families in turn by
either highlighting the family and using “Insert”, or by double-clicking on the family. Choose
the “Attribute” for the y-axis as in 3 above and then plot the graph as in 4 above.
GLOSSARY
Activity Chemical activity generally is proportional to the concentration of a substance taking part
in a reaction and the activity is a measure of this, often linearly proportional to concentration.
Ageing The heat-treatment of a supersaturated alloy to promote precipitation, hence at a

temperature below the solvus on the relevant equilibrium phase diagram.
Anneal Heat a work-hardened alloy to induce recovery and recrystallisation.
Annealing Twins Those which arise as a result of a growth accident during the recrystallisation
of cubic close-packed materials such as -brass, copper or nickel. They have flat edges.
Anti-Phase Boundary The boundary between anti-phase domains.
Anti-Phase Domain In an ordered alloy, a region where the ordering is in a different sequence.
Atomic Flux The number of atoms crossing unit area in unit time.
Bainite A phase produced in steels by a combination of shear and diffusional transformations.
Binary alloy One consisting of 2 components or phases.
Biot Number A dimensionless quantity which indicates whether heat extraction from a casting is
dominated by conduction across the mould/casting interface or by conduction through the casting.
Chemical Potential The amount by which the free energy of a system is altered by a change in
the concentration of a species, the temperature, pressure, etc.
Constitutional undercooling Undercooling (or supercooling) arising due to variations in

composition near a solidifying interface.
Deformation Twins (also Mechanical Twins) These arise within a single grain in a material in
which there are insufficient slip systems to allow plastic deformation by dislocation movement.
The need to minimise the strain energy at grain boundaries results in the twins having a lenticular
shape.
Error Function A mathematical function which describes the solution to the diffusion equation,
Fick’s second law, when one end of a semi-infinite bar is maintained at a constant concentration.
Eutectic A phase transformation at a given temperature in which liquid solid1 + solid2
Fick’s 1st Law describes diffusion when concentration is independent of time, i.e. a constant
concentration gradient.
Fick’s 2nd Law describes diffusion when the concentration changes with time.
Grain Growth Following recrystallisation, a mechanism by which the overall energy of a material
can be decreased by the reduction in grain boundary area.
GP Zones The first metastable precipitates that form when ageing an Al-Cu alloy.
Interdiffusion Diffusion of an atomic species into a material comprising different atomic species.
Kirkendall Experiment An experiment which shows that diffusion in solids happens by a

vacancy mechanism.
Mechanical Twins see Deformation Twins.
Martensite. A metastable supersaturated solid-solution phase in steels formed by a displacive

(shear) transformation when quenching austenite.
Microsegregation Segregation of solute on a microscopic scale.
Normalise Heat a steel above A3 temperature i.e. just into the region, hold and then cool but
do not quench. Leads to significant grain refinement and improvements in mechanical properties.
Ostwald Ripening The growth of large precipitates at the expense of smaller ones to reduce
total precipitate surface area and hence lower the overall energy of a material.
Oxide Dispersion Strengthening The introduction of very fine, stable oxide powders into the
microstructure to prevent or minimise Ostwald ripening.
Partition Coefficient The ratio (at equilibrium) of the composition of solute in a solid to that in the
liquid with which it coexists at a given temperature.
Partitioning The preferential distribution of solute (impurities) into one phase rather than another.
Peritectic A phase transformation at a given temperature in which solid1 + liquid solid2
Precipitate Free Zones Regions surrounding grain boundaries which often contain many fewer
precipitates than the remainder of the material.
Quench Rapid cooling from higher temperatures by immersion of an alloy in a light oil or water so
that there is insufficient time for equilibrium phase transformations.
Recovery The process by which a cold-worked metal rearranges its dislocation structure at
around 0.3 Tm to form new sub-grains (the overall dislocation density is virtually unchanged).
Recrystallisation Following recovery, the formation of new, strain-free, equiaxed grains at a

temperature of ~ 0.6-0.7 Tm (the driving force is a substantial reduction in dislocation density).
Scheil Equation describes the composition profile that forms in the solid if there is no diffusion in
the solid but perfect mixing in the liquid during solidification.
Secondary Hardening is the formation of stable carbides in a martensitic steel containing

carbide-forming alloying elements when tempering at around 600°C.
Segregation The non-uniform distribution of solute in a material which arises via partitioning.
Self Diffusion Diffusion of an atomic species within a material composed of that atomic species.
Solute Impurity atoms in solution in an alloy.
Solute Drag The mechanism by which grain boundary movement is restricted by solute atoms in
a solid solution.
Stacking Fault A region in which the atomic stacking sequence is disrupted.
Supercooling See undercooling.
Superdislocation A combination of two dislocations which travel together to minimise lattice

disorder.
Superheating is the amount by which the temperature of a liquid (usually in a casting) is above
the equilibrium melting/fusion temperature.
Supersaturated solid solution is formed by cooling a binary alloy below its solvus at a rate fast
that enough there is insufficient time for the second phase to precipitate out from the matrix.
Ternary Alloy One consisting of three components.
Temper Heat a steel which has been quenched in order to form equilibrium phase.
Undercooling of a liquid is when its actual temperature is below the equilibrium melting/fusion
temperature (also called supercooling). Can promote formation of dendrites.
Zener Drag (or Zener Pinning) The mechanism by which grain boundary movement is restricted
by particles or precipitates embedded in the matrix.
Lecture 1
Lecture 2
Lecture 3
Lecture 4
Lecture 5
Lecture 6
Lecture 7
Lecture 8
Lecture 9
Lecture 10
Lecture 11
Lecture 12

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What are some of the main topics covered in the course?

What are some of the main topics covered in the course?

What are some examples of how microstructure affects material properties?

What are some examples of how microstructure affects material properties?

University of Cambridge

NATURAL SCIENCES TRIPOS

MATERIALS SCIENCE & METALLURGY

Michaelmas Term 2009

Dendrites in water (left) and in a Cu-P cast alloy (right).

3. Microstructure and Properties 49

Additional information to assist with understanding of the course is as follows.

1. DoITPoMS Micrograph Library has many images of microstructures, together with

2. DoITPoMS Teaching & Learning Packages www.msm.cam.ac.uk/doitpoms/tlplib/index.php

4. MATTER software www.matter.org.uk/solidification has two relevant sections called:

5. aluMATTER http://aluminium.matter.org.uk has considerable information on aluminium

6. SteelMATTER and also SteelUniversity have information on steels, including processing

D.A. Porter and K. E. Easterling, Phase Transformations in Metals and Alloys,

P.G. Shewmon, Transformations in Metals, (McGraw-Hill, 1969).

Newey and Weaver, Materials Principles & Practice (Butterworths, 1990).

Weidmann, Lewis and Reid, Structural Materials (Butterworths, 1990).

Honeycombe R. W. K. and Bhadeshia H. K. D. H., Steels: Microstructure and Properties, 2nd

C composition of phase in equilibrium with phase (m-3)

grain boundary width (m)

 jump distance (m)

μ chemical potential (J mol-1)

 dislocation density (m-2)

Diffusion is a transport phenomenon caused by the physical motion of chemical species

Diffusion is a consequence of concentration differences (or, strictly, chemical potential

Mass transport can generally involve:

• fluid flow – dominant in gases or liquids (e.g. convection currents);

• viscous flow – flow of a viscous material, generally amorphous or semi-crystalline (e.g.

Atomic diffusion occurs during important processes such as:

• solidification of materials [section 2];

• precipitation strengthening, e.g. Al-Cu alloys [MMS IA and section 3];

Atomic diffusion in crystalline solids is:

• jumping of atoms on a fixed network of sites within a crystalline lattice;

• generally the consequence of a thermodynamic driving force, i.e. chemical potential

Diffusion can be regarded and analysed on a macroscopic (continuum) scale or atomistically.

1.1.1 Random walk approach

Hence the diffusion distance is proportional to .

1.1.2 Mechanisms of diffusion in crystalline solids

direct exchange ring vacancy

1.2 Fick’s First Law of diffusion – diffusion in a uniform concentration gradient

From the random walk approach (page 8):

and from the above derivation of Fick’s 1st law D= 1

Hence x = 6Dt , x 2 Dt , or simply x Dt

These expressions are useful for estimating diffusion distances.

1.3 Fick’s Second Law of diffusion

Nin = J A At and Nout = JB At

The change in concentration C in this time is given by

1.3.1 Solutions to Fick’s Second Law

1.3.1.1 Fixed quantity of solute and a semi-infinite bar

1.3.1.2 Constant surface concentration at end of a semi-infinite bar

The profile that develops is slightly less straightforward than previously.

with properties as shown graphically and numerically:

After time, the profile develops according to the “error function”

and the solution to Fick’s 2nd law is then given by:

1.4 Diffusion in real materials

jump distance (m)

dislocation density (m-2)