Phases

Phase: A phase is a microscopically homogeneous body of matter.

A phase is defined as a portion of a system whose properties and
composition are homogeneous and which is physically distinct from
other parts of the system.
Binary alloy: Mixture of two metallic elements.
Ternary alloy: Mixture of three metallic elements.
System: Is an isolated body of matter.
Component: Components of a system are metallic elements that make
up the system.
The study of phase transformation is concerned with how one or more
phases in an alloy (the system) change into a new phase or mixture of
phases. The transformation occurs due to the fact that initial state
of the system is unstable relative to the final state.1

Phase stability is measured by the Gibbs Free energy (G) for

a system relative to some other defined phase.
At constant temperature and pressure
G=H-TS
G= Molar Gibbs Free energy
H= Molar Enthalpy
T= Temperature
S= Molar Entropy
Enthalpy is the measure of heat content of a system given
by,
H= E +PV
E= Internal energy for a system
P= Pressure
V= Volume
2

PV takes into account the change in volume of the

system when the transformation occurs at constant
pressure. For condensed phases PV term is very small
for all practical purposes leading to the result,
HE,

for solid or liquid based transformations.

A system is said to be in equilibrium when dG=0.

Lowest possible value of Gibbs Free energy at
constant pressure, temperature for a closed system
defines the stability. Therefore, according to the
equation the state of highest stability will be the
one with best compromise between lowest
Enthalpy and highest Entropy.
At low temperatures, solid phases are more stable as they have
lowest internal energy (due to strong atomic bonding), and lowest
enthalpy.
At higher temperatures, however, -TS term dominates, and phases
with more freedom of atom movement, i.e. liquid & gas, become
more stable.
5

Any transformation that results in the

decrease in the Gibbs Free energy is
possible, namely If G= G2 - G1 < 0, then it is
possible.
Transformation
rate

Higher humps or energy barrier leads

to slower transformation rates

The mode of transformation is very much dependent on the effect of small

fluctuations from the initial condition and in particular on the criterion that any
particular fluctuation increases or decreases the free energy.
A metastable state is resistant to energetically small fluctuations as the
transformation path must pass through state(s) of higher energy. Conversely, if any
fluctuation is able to lower the free energy of the system, the initial condition is
then unstable, and there is no energetic barrier to transformation along the path
represented by this fluctuation.

Any transformation that results in a decrease in

Gibbs Free Energy is possible. Therefore, a
necessary criterion for any phase
transformation is:
G = G2-G1 < 0
Where G1 and G2 are the free energies of the
initial and the final states, respectively.
The transformation need not go directly to the
stable equilibrium state but can pass through a
whole series of intermediate metastable states.
8

Systems Free Energy

Intermediate microstructures
(transformation pathway)
Kinetics

Systems Free Energy

Intermediate microstructures
(transformation pathway)-structure
Interfaces, morphology..
Kinetics
10

11

Representative Ag-Ni Nanoparticle

Showing single phase solid solution

12

13

14

15

Single component system

Gibbs Free energy as a function of temperature at
constant pressure

Cp = (H/T)p
By definition, H=0 for pure elements in its most
stable state at 298K. The variation of H with T can
then be calculated as follows.

The variation of Entropy with T can also be

derived from the specific heat, Cp

Taking Entropy to be zero at 0 K,

16

Variation of Gibbs Free Energy with Temperature

17

The variation of G with T and P can be written as

At constant pressure, dP = 0 leading to
(G/T)p = -S.
G decreases with increasing T at a rate of -S

At all temperatures liquid has higher

enthalpy than solid, hence at low
temperatures GL>GS. However, liquid
has higher entropy than solid thus
making Gibbs Free energy of liquid
decrease more rapidly with T. For
temperatures up to Tm the solid phase
has the lowest free energy and is
therefore the stable equilibrium phase
while above Tm the liquid phase is the
stable equilibrium state of a system.

18

Effect of Pressure

Different trends

With change in Pressure the equilibrium temperature changes

19

If two phases in equilibrium are and , then for one mole of each
phase

If , and are in equilibrium

The above result gives the change in temperature

required to maintain the equilibrium between and
if pressure is increased by dP
20

At equilibrium

Clausius-Clapeyron equation
More generally the Clausius-Clapeyron equation pertains to the
relationship between the pressure and temperature for conditions
of equilibrium between two phases. The two phases could be vapor
and solid for sublimation or solid and liquid for melting.
21

22

Richards Rule
If a liquid metal is undercooled by T below
Tm before it solidifies, solidification will be
accompanied by a decrease in free energy G
(J/mol) as shown in Fig. This free energy
decrease provides
the driving force for
solidification. The magnitude of this change
can be obtained as follows.

At temperature T
Where,
At equilibrium melting temperature; G = 0

At Tm

Entropy of Fusion ~ R for most metals

23

Binary Solution
Gibbs Free energy of a binary solution can be calculated in the
following way

For Binary system, XA + XB = 1. One mole of

homogeneous solution is made by mixing together XA
moles of A and XB moles of B. XA, XB are called mole
fractions.

Step 1: Physical mixture of A & B- bring

together A & B atoms.
G1 = XAGA + XBGB (J/mol)
where
GA, GB are molar Gibbs Free energies of pure A and B respectively at the
24
temperature and pressure of the above experiment.

25

The Gibbs Free energy of the system will change during the
mixing by an amount equal to Gmix

G2 = G1 + Gmix
Gmix is the change in the Gibbs Free energy per mole
of the system caused by mixing.

26

G1 = H1-TS1
G2 = H2 TS2
Hmix =H2 H1
Smix = S2 S1

Gmix = Hmix - TSmix

Hmix is heat absorbed or evolved during mixing; ignoring
the volume change it involves only the internal energy
component before and after mixing.
Smix is the difference in entropy before and after mixing.
This difference in entropy between the unmixed and mixed
27
states is given by the Boltzmann equation

S = kBln, being a measure of randomness or

number of distinguishable microstates available,
kB the Boltzmann constant.

28

If there is no volume change or heat change during

mixing, then the only contribution to Smix is the change
in configurational entropy.
Assuming A & B atoms mix to form a substitutional solid solution and that all configurations
of A & B atoms are equally possible, then the number of distinguishable ways of arranging
the atoms on the lattice site is,

config =[ (NA + NB)!/NA!NB!]

NA, NB are number of A atoms and B atoms respectively. And also,
NA = XANa; NB = XBNa, Na being the Avogadros number related to
the Boltzmann constant as
NakB = R. The Stirlings approximation gives lnN! = NlnN N.
Smix = -R (XAlnXA + XBlnXB)
Smix >0 since mole fractions are less than unity, i.e. entropy
invariably increases up on mixing.29

Ideal solution
There is no change in the Enthalpy during mixing,
i.e. Hmix =0 leading to Gmix = TSmix.
for an ideal solution,
Gmix = RT(XAlnXA + XBlnXB)

30

Total Gibbs Free energy of an ideal solution is

thus given by
G = G2 = XAGA + XBGB + RT(XAlnXA + XBlnXB).

As the temperature increases GA

& GB decreases and the Gibbs
Free energy curve assumes a
greater curvature. The decrease
in GA & GB is due to thermal
entropy of both the components
and is given by
(G/T)P = -S

31

Chemical potential
dG = AdnA (T, P, nB constant)
If a small quantity of A, dnA is added to a large quantity of
a phase at a constant temperature and pressure, the size of
the system will increase by dnA, and therefore the total
Gibbs Free energy of the system will also change by a small
amount dG. If dnA is small enough, dG will be proportional
to the amount of A added.
A : chemical potential of A in the phase, and is function
of composition. Due to this, dnA should be small enough
so that the composition of the phase is not altered. Hence,
the chemical potential of A is defined as,
32

A = (G/nA)T,P,nB; G refers to the whole system.

For binary solution, at constant temperature and
pressure,
dG = AdnA + BdnB
If T & P changes are also allowed, then for a
system of n components,
dG = VdP SdT +AdnA + BdnB + ...... + ndnn.
If one mole of the original phase contains XA moles of A and XB moles
of B, then size of the system can be increased by 1 mole without
changing A and B if dnA:dnB = XB:XA. Gibbs Free energy of the
system will increase by the molar Gibbs Free energy, G given as
follows.
33

G = AXA + BXB (J/mol)

Now, XA + XB = 1; dXA = -dXB
dG/dXB = A(dXA/dXB) + B = B A
A and B can be obtained
by extrapolating the tangent
to the G curve to the sides
of the molar Gibbs Free
energy diagram

34

Comparing the first two equations below,

G = AXA + BXB,
G = XAGA + XBGB + RT(XAlnXA + XBlnXB),
A = GA + RTlnXA
B = GB + RTlnXB

35

Regular solution
For ideal solution (solid solution), so far it has been assumed that
Hmix = 0. However, this type of behaviour is exceptional in
practice, and usually mixing is either endothermic (heat
absorbed) or exothermic (heat evolved). The simple model used
for an ideal solution can however be extended to include the
Hmix term by using the so-called quasi-chemical approach.
Quasi-chemical approach assumes that the heat of mixing, Hmix is
only due to the bond energies between the adjacent atoms.
Assumption: Volumes of pure A and pure B are equal, and do not change during
mixing.
A-A bonds each with energy AA,
B-B bonds each with energy BB,
A-B bonds each with energy AB
Considering zero energy when atoms are at infinity,
Internal energy = E = PAA AA + PBB BB + PAB AB
36

Considering zero energy when atoms are at infinity,

Internal energy = E = PAA AA + PBB BB + PAB AB
PAA, PBB, and PAB refer to the number of bonds of corresponding type.

Before mixing pure A and pure B contain only A-A and B-B bonds respectively. Change
in the internal energy upon mixing is given by
Hmix = PAB, where = AB 0.5(AA + BB).
is the difference between the A-B bond energy and the average of the A-A and B-B
37
bond energies.

If = 0, Hmix = 0 giving rise to an ideal solution. In this case,

atoms are completely randomly arranged and the entropy of
mixing is given Smix = -R(XAlnXA + XBlnXB).
For such situation,
PAB = NazXAXB (bonds/mol)
z = the number of bonds per atom.
<0 leads to ordering, namely, atoms in the solution will
prefer to be surrounded by atoms of opposite type and this
increases PAB;
For >0, PAB tends to be smaller than in a random solution
leading to clustering of same type of atoms.
Hmix = XAXB and = Naz

38

Since Hmix = XAXB, dHmix/dXB = XA; Hence,

extrapolating the slope (dHmix/dX) at pure A or pure B
gives .
39

The Gibbs Free energy change on mixing for a regular solution is

given by the following equation,
Gmix = XAXB + RT(XAlnXA + XBlnXB).

40

Actual Gibbs Free energy of an alloy is given as

G = XAGA + XBGB + XAXB + RT(XAlnXA + XBlnXB)
Now, XA + XB = 1

41

Activity
Ideal Solution

Regular Solution

A = GA + RTlnXA
B = GB + RTlnXB

A = GA + RTlnaA
B = GB + RTlnaB

42

43

Activity and chemical potential are a measure

of the tendency of atoms to leave a solution
44

In its simplest formulation, the free energy G, of an alloy phase in a two component
A-B system may be expressed as
The thermodynamic approach associated with a
regular solution
GA, GB and XA, XB are the molar free energies and
mole fractions of the pure components, respectively.
The change in the Gibbs free energy caused by mixing
the components (Gmix) is illustrated by the graph.
The enthalpy of mixing (Hm), which is related to the
interaction parameter . Ignoring volume changes,
Hmi x represents the change in energy before and after
mixing of the two components and Smix is the
accompanying change in entropy.

The general condition for equilibrium in a system

containing several components (A, B, C . . . . ) and
phases is that the chemical potential of each
component must be the same in every phase.

45

Phase Diagrams
A phase diagram is a graphical representation of the loci of
thermodynamic variables when equilibrium among the phases of a
system is established under a given set of conditions.
A phase diagram depicts the interrelationship between the phases, the
temperature, and the composition in an alloy system only under
equilibrium conditions. These diagrams do not apply to metals/alloys
under an non-equilibrium condition.
A metal/alloy quenched from a higher temperature to a lower one may
posses phases that are more characteristic of the higher temperature than
they are of the quenched in temperature. In time, as a result of thermally
activated atomic movements the quenched specimen may approach
equilibrium low-temperature state. If this happens then the phase
relationship in the specimen will conform to the equilibrium diagram.
The phase diagram at any given temperature gives us the proper picture
only if sufficient time is allowed for the material to come
46 to equilibrium.

A binary alloy can take one of following forms

A single phase solid solution.
Two separated, approximately pure, components.
Two separated solid solutions.
A chemical compound, together with a solid solution.
The constitution of an alloy as described by a phase diagram is :
The phases present.
The weight percentage of each phase.
The composition of each phase.

47

Solid Solutions
A solid phase containing two or more kinds of atom, the relative proportions of which may
be varied within limits, is described as a solid solution.
Terminal solid solutions are based on the structures of the component metals. Intermediate
solid solutions may have structures which are different from any of those of the constituent
components.
Most solid solutions are of the substitutional type, in which the different atoms are
distributed over one or more sets of common sites, and may interchange positions on the
sites. In interstitial solutions, the solute atoms occupy sites in the spaces between the
positions of the atoms of the solvent metal; this can only happen when the solute atoms are
much smaller than the atoms of the solvent.
The definition of the unit cell, and the concept of the translational periodicity of the lattice,
lose their strict validity when applied to a disordered solid solution. The mean positions of
the atoms, will no longer be specified exactly, since there will be local distortions depending
on the details of the local atomic configurations. A knowledge of the type of atom at one end
of a given interatomic vector no longer implies knowledge of the atom at the other end, as it
does for a pure component or a fully ordered structure. In a solid solution, precise statements
of this nature have to be replaced by statements in terms of the probability of the atom being
of a certain type.
48

For many purposes, the strict non-periodicity of the structure is not important, since
most physical properties are averages over reasonably large numbers of atoms. Thus the
positions of X-ray diffraction maxima depend only on the average unit cell dimensions,
and their intensities depend only on the mean concentrations of atoms of different kinds
and the mean interatomic distances. An approximate description in which the structure
is regarded as having a unit cell of fixed size, with atomic positions occupied by
identical scattering centers of averaged atomic scattering factor.
A lattice vector of this structure may actually connect two unlike atoms, but is regarded
as connecting two average atoms.

If two metals have the same crystal structure, they may form a single
solid solution, and the lattice parameter then varies continuously with
composition from the value characteristic of one pure metal to that of
the other. The edge length of the unit cell, or the volume per atom, is
approximately linear with the atomic fraction of solute; this is
described as Vegard's law.

49

Gibbs Phase Rule

F = C P + 2
where
C is the number of components,
P the number of phases in equilibrium,
F the number of degrees of freedom or variance. F is the number of parameters which can and must be
specified in order to completely specify the state of the system. In the present context, the
thermodynamic parameters are temperature, total pressure, and compositions of the phases at
equilibrium. Number of variables that can be changed independently without changing the number of
phases in equilibrium.
Since binary temperature-composition phase diagrams are plotted at constant pressure, usually 1 bar,
one degree of freedom is already used up. In a binary system, C=2. Hence, for binary isobaric T-X
diagrams the phase rule reduces to

F=3-P
Binary T-X diagrams contain single-phase areas and two-phase areas. In the single phase areas, F= 3 - 1
= 2. That is, temperature and composition can be varied independently. These regions are thus called
bivarient. In two-phase regions, F = 3 - 2 = 1. If, say, T is chosen, then the compositions of both phases
are fixed by the ends of the tie-lines. Two-phase regions are thus termed univariant.
50

51

When three phases are at equilibrium in a binary system at constant pressure, F = 3 - 3 = 0. Hence, the
compositions of all three phases as well as T are fixed. There are two general types of three-phase
invariants in binary phase diagrams. These are the eutectic type and peritectic-type invariants
Eutectic type
Peritectic type
Some examples of eutectic-type invariants are:
(i) Eutectics in which = solid1, =liquid, = solid2. The eutectic reaction is l

s1 + s2

(ii) Monotectics in which =liquid1, = liquid2, = solid. The monotectic reaction is l2

(iii) Eutectoids in which =solid1, =solid2, =solid2. The eutectoid reaction is s2

11 + s

s1 + s3

(iv) Catatectics in which =liquid, = solid1, = solid2. The catatectic reaction is s1

1 + s2 .

Some examples of peritectic type invariants are:

(i) Peritectics in which =liquid, = solid1, =solid2. The peritectic reaction is 1 + s2

s1

(ii) Syntectics in which =liquid1, =solid, =liquid2. The syntectic reaction is 11 +12

(iii) Peritectoids in which = solid1, = solid2, = solid3. The peritectoid reaction is s1 + s3

52

s2 .

Isomorphus phase diagram: only a single type of crystal structure is observed for all
ratios of the components

Temperature of Fusion,
Melting point

At all compositions and temperatures in the area above the line labeled liquidus,
single-phase liquid alloys will be observed, while at all compositions and temperatures
below the line labeled solidus, alloys exist as single-phase solid solutions.

53

An alloy sample at equilibrium at a temperature and overall composition between the liquidus and the
solidus curves will consist of a mixture of solid and liquid phases. The compositions of the phases are
given by the liquidus and solidus compositions at that temperature.
For example, a BiSb sample of overall composition XSb=0.6 at T=700 K (at point R) will consist, at
equilibrium, of a mixture of liquid alloy of composition XSb = 0.37 (point P) and solid alloy of
composition XSb=0.82 (point Q). The line PQ is called a tie-line. As the overall composition is
varied at 700 K between points P and Q, the compositions of the liquid and solid phases remain fixed
at P and Q, and only the relative proportions of the two phases change. From a simple mass balance,
one can derive the lever rule for binary systems: (moles of liquid)/(moles of solid) = RQ/PR. Hence,
at 700 K a sample of BiSb alloy with overall composition XSb = 0.60 consists of liquid and solid
phases in the molar ratio (0.82 - 0.60)/(0.60 - 0.37) = 0.96. Were the composition axis expressed as
weight percent, then the lever rule would give the weight ratio of the two54
phases.

55

Under equilibrium cooling condition. At any temperature during equilibrium cooling the
solid phase has a uniform (homogeneous) composition.

In this example, the composition of the solid phase during cooling varies along the
line BQD. Hence, in order for the solid particles to have a uniform composition at
any temperature, diffusion of Sb from the center to the surface of the growing
particles must occur. Since solid state diffusion is a relatively slow process,
equilibrium cooling conditions are only approached if the temperature is decreased
very slowly. If a BiSb alloy of composition XSb=0.60 is cooled very rapidly from
the liquid, concentration gradients will be observed in the solid grains, with the
concentration of Sb decreasing towards the surface from a maximum of XSb = 0.93
56
(point B) at the center.

Thermodynamic origin of phase diagrams

gs varies with composition between

the standard molar Gibbs energies of
pure solid Ge and of pure solid Si ,
while gl varies between the standard
molar Gibbs energies of the pure
liquid components. The molar Gibbs
energies of mixing of the solid and
liquid phases are negative and are
equal to the difference between the
Gibbs energy of the solution and of
the Gibbs energies of the pure
unmixed components in each phase.

molar Gibbs energies of the solid and liquid phases,

three temperatures

57

Equilibrium in Heterogeneous Systems

The molar free energies of fcc A and bcc B
are shown as points a and b. The first step
in drawing the free energy curve of the
phase is to convert the stable bcc
arrangement of B atoms into an unstable
fcc arrangement. This requires an increase
in free energy bc. The free energy curve
for the a phase can now be constructed as
before by mixing fcc A and fcc B as
shown in the figure.
A similar procedure produces the molar free
energy curve for the phase. The distance
af is now the difference in free energy
between bcc A and fcc A

A rich alloy will have the lowest

free energy as a homogenous
phase and B rich alloy
as phase
58

59

Chemical
potential

60

61

the Gibbs energies of mixing, gs and gl, may each be expressed as the sum of an ideal term which
is purely entropic for a random substitutional solution of A and B particles, and an excess term, gE.

where XA and XB are the mole fractions of the components. An ideal solution is defined as one in
which gE=0.
If gE>O then the system is said to exhibit positive
deviations from ideality. If gE < 0 , then negative
deviations.
Curves of gs and gl for a hypothetical system A-B
are shown schematically in fig. at a constant
temperature below the melting points of pure A and
B such that the solid state is the stable state for both
pure components. In this system gE(l) < gE(s) so that
gs presents a flatter curve than does gl and there
exists a central composition region in which gl<gs.
Hence, there are two common tangent lines, P1Q1
and P2Q2. Such a situation gives rise to a phase
diagram with a minimum in the two-phase region
as observed in the Au-Cu system shown in figure.
At a composition and temperature corresponding to
the minimum point, liquid and solid of the same
composition exist in equilibrium.

62

gE(l) < gE(s)

gE(l) > gE(s)

When the boundaries of the two phase region intersect, they meet at a maximum or a minimum, and both
curves are tangent to each other and to the isothermal line at the point of intersection: congruent point.

63

Miscibility Gap
If gE >0 for a solution, then the solution is thermodynamically less stable than an ideal solution. In an alloy
system this can result from a large difference in atomic diameter of the components, which will lead to a
(positive) lattice strain energy.
Phase diagram and Gibbs energy curves of solid
solutions for the Au-Ni system

limiting slopes to the g ideal curve at XA= 1 and XB= 1 are both
infinite. Hence, g ideal will always be negative as XA
approaches 1 and XB approaches 1 no matter how low the
temperature. As a result, below a certain temperature the curves
of gm will exhibit two negative "humps".

64

65

When gE(s) is positive for the solid

phase in a system it is usually also
the case that gE(l) < gE(s) since the
unfavourable factors (such as a
difference in atomic dimensions)
which are causing gE(s)
to be
positive will have less of an
influence upon gE(l) in the liquid
phase
owing
to
the greater
flexibility of the liquid structure to
accommodate different atomic sizes,
valencies, etc. Hence, a solid-solid
miscibility gap is often associated
with a minimum in the two-phase
(solid + liquid) region.
Below the critical temperature the curve of gs
exhibits two inflection points indicated by the letter s
66spinodal points.
in fig. These are known as the

67

A necessary condition for the formation of the miscibility gap in the solid state is
that both components should crystallize in the same lattice form
A short range order is observed in the solid solution above the miscibility gap. This
is due to the strain contribution form the difference in sizes between the atoms.
When a random solid solution is formed the fit between the atoms with large
difference in the atomic sizes is rather poor and the lattice is strained. One way in
which the strain energy associated with the misfit can be relieved is by causing the
atoms of the component elements to assume an ordered arrangement just above the
critical miscibility gap temperature.
A still greater decrease in the strain energy is possible if the solid solution breaks
down to form crystals of the A-rich and B-rich phases (in a A-B binary system). In
this even it is postulated that separate crystals of two phases are formed with
conventional grain boundaries between and not coherent clusters of A atoms and B
atoms in the original solid solution crystals. Clustering in the coherent sense would
raise, not lower, the strain energy.
The nucleation of the segregated phases in a solid solution occurs at the grain
boundaries of the original matrix phase.
68

Eutectic
The more positive gE in a system is, the higher is
Tc, and the wider is the miscibility gap at any
temperature. Suppose that gE(s) is sufficiently
positive that Tc, is higher than the minimum in
the (solid-liquid) region. The result will be a
phase diagram such as that of the Ag-Cu system
Shown the Gibbs energy curves at 1100 K. The
two common tangents define the two-phase
regions. As the temperature is decreased below
1100 K, the gl curve moves relative to gs, and the
two points of tangency, P1 and P2, approach
each other until, at T= 1052 K, P1 and P2
become coincident at the composition E. That is,
at T=1052 K there is just one common tangent
line contacting the two portions of the gs curve at
compositions A and B and contacting the curve
at E. This temperature is known as the eutectic
temperature, TE, and the composition E is the
eutectic composition. For temperatures below
TE, gl lies completely above the common tangent
to the two portions of the gs curve and so, for T<
TE a solid-solid immiscibility is observed.

69

70

When each solid phase has different crystal structure

71

Suppose a Ag-Cu alloy of composition XCu = 0.28 (composition P1) is cooled from the liquid state very
slowly under equilibrium conditions. At 1100 K the first solid appears with composition QI. As T
decreases further, solidification continues with the liquid composition following the liquidus curve from
P, to E and the composition of the solid phase following the solidus curve from Q1 to A. The relative
proportions of the two phases at any T are given by the lever rule. At a temperature T= (TE + ) just
above TE, two phases are observed: a solid of composition A and a liquid of composition E. At a
temperature T=(TE-) just below TE two solids with compositions A and B are observed. Therefore, at TE
during cooling, the following binary eutectic reaction occurs
Under equilibrium conditions the temperature will remain constant at T= TE until all the liquid has
solidified, and during the reaction the compositions of the three phases will remain fixed at A, B and E.
For this reason the eutectic reaction is called an invariant reaction.

72

Microstructural development during the slow cooling of a

eutectic composition

73

Microstructural development during the slow cooling of a hypereutectic

composition

Upon reaching the liquidus curve, phase appears in growing amounts as we further cool towards the
eutectic temperature.
Just before reaching the eutectic temperature, 33% of the microstructure is liquid. This amount of liquid
undergoes the eutectic reaction and it is transformed to the ne grained eutectic microstructure (17% 3 and
83% 3). At this point the phase is present in two distinct forms: The large grains produced during cooling
74
in the (L+ ) region (called pro-eutectic ); and the ner (called eutectic ) in the eutectic microstructure.

Microstructural development during the slow cooling of a

hypoeutectic composition

75

76

The fundamental requirement for a miscibility gap is a tendency

for atoms of the same kind to segregate in the solid state. The
same is also true for an eutectic system. A true miscibility gap
can only occur if the component metals crystallize in the same
lattice form, since the components must be capable of
dissolving each other at high temperatures.
In an eutectic system, the component do not have to crystallize
in the same structure. If the two atomic forms are quite different
chemically, however, then intermediate crystal structures are
liable to form in the alloy system. Eutectics can still be
observed in such systems, but they will not form between
terminal phases.
77

Gibbs energy curves at a temperature below the

eutectic are shown schematically in the upper
panel. Let us derive an expression for gfcc under
the assumption that the Pb-rich fcc solid
solution is a Henrian solution. The activity of
the solvent is ideal (asolvent=Xsolvent) , while for
the solute, asolute= soluteXsolute, the Henrian
activity coefficient, independent of composition.

Need concept of activity

78

79

80

At TE=247.8 C, Cd in the Pb-rich fcc solution at XPb

= 0.940 exists in equilibrium with virtually pure solid
hcp Cd. Thus, in the fcc solution, aCd=l with respect
to pure solid hcp Cd as standard state.
Hence,
Cd = aCd/XCd = 1/0.06 = 16.67 for eutectic
temperature
gfcc can be expressed as,

The activity also depends on the choice of standard state, as it describes the difference between an
actual chemical potential and a standard chemical potential. In principle, the choice of standard state is
arbitrary, although there are certain conventional standard states which are 81
usually used in different
situations.

The solubility of Pb in solid Cd is

very small. The actual solubility at
TE is about 0.14 mol%. In
thermodynamic terms this means
that ghcp curve increases very
rapidly as Pb is added to solid Cd or
that the Henrian activity coefficient
Pb is very large. The fact that the
solubility of Cd in solid Pb is much
greater than that of Pb in solid Cd
can be understood in terms of the
Hume-Rothery rule that solubilities
are greater when the solute atoms
are smaller than the solvent atoms,
since the lattice strain energy will be
less and hence g will rise less
rapidly upon addition of solute.

82

Monotectic
Monotectic represent a three phase transformation in which a liquid
phase transforms into a solid phase and a liquid phase of different
composition. Monotectic transformations are associated with a
miscibility gap in the liquid state.
where liquidA and liquidB are liquids
with compositions at points A and B.
The temperature remains constant at
the monotectic temperature and the
compositions of all phases remain
fixed until liquid, is completely
consumed. Cooling then continues
with precipitation of copper with the
liquid composition following the
liquidus line from B83
to the eutectic E.

Peritectic transformations
Peritectic represents a three phase
transformation which involves reaction
between a liquid phase and a solid to
form a different solid phase.

A peritectic reaction between a

liquid and solid, occurs on the
surface of the particles of solid2,
which can rapidly become coated
with solid1, by preventing contact
between liquid and solid2 this
coating may greatly retard further
reaction to such an extent that
equilibrium conditions can only
be achieved by extremely slow
84
cooling.

gE(l) < gE(s)

gE(l) > gE(s)

When the boundaries of the two phase region intersect, they meet at a maximum or a minimum, and both
curves are tangent to each other and to the isothermal line at the point of intersection: congruent point.

85

Intermediate phases

86

Intermediate phases
For some systems, discrete intermediate compounds rather than solid
solutions may be found on the phase diagram. These are called
intermetallic compounds. An intermetallic compound can be defined as
a compound made up of two or more elements, producing a new phase
with its own composition, crystal structure, and properties.
There are two types of intermetallic compounds which are often
encountered:
1. Electron compounds: These compounds are of definite chemical crystal
structure and arise if the two alloying metals are of different crystal
structure, valency, and if one of these metals is electropositive with the
other being electronegative.
2. Interstitial compounds: These compounds form between metals, or
metals and nonmetallic elements, with atoms very similar to those that
form interstitial solid solution. Iron carbide (Fe3C) or cementite is an
87
example of an interstitial metallic compound.

Intermediate Phases
The presence of an intermetallic splits the phase diagram so that each part can be treated
separately as individual diagrams.
Stoichiometric intermetallic compounds have a fixed composition. For example, steels are
strengthened by a stoichiometric compound Fe3C, that has a fixed ratio of three iron atoms
to one carbon atom. Stoichiometric intermetallic compounds are represented in phase
diagrams by a vertical line.
Non stoichiometric intermetallic compounds have a range of compositions and are the
intermediate solid solutions.

88

Non-stoichiometric compound phases

are conveniently described as a dilute
solution
of
defects
in the
stoichiometric
compound. For
example, consider a compound A1-yBy.
The lattice sites normally occupied by
A atoms we shall call "A sites", and
those normally occupied by B atoms
are "B sites". The dissolution of excess
B in the compound can occur by the
formation of defects.
Example of such defects are (i) B
atoms occupying A sites; (ii) vacant A
sites;
(iii)
B
atoms occupying
interstitial sites; etc.
89

In the Na-Bi phase diagram g(Na3/4Bi1/4) rises

extremely rapidly on either side of its minimum
which occurs at XNa = 3/4, XBi = 1/4.
The points of tangency Q1 and Q2 of the common
tangents P1Q1 and P2Q2 are nearly (but not exactly)
coincident. Hence, the composition range over which
single-phase Na3Bi exists is very narrow (but never
zero).
The two regions labelled (Na3Bi+liquid) are the two
sides of a two-phase region which passes through a
maximum . Because the Na3Bi single-phase region is
so narrow we refer to Na3Bi as an intermetallic
compound.
In the case of Na3Bi, any slight deviation from the
stoichiometric composition causes a very large
increase in Gibbs energy. Owing to the large
difference in electronegativities of Na and Bi, Na3Bi
could be considered to be a semi-ionic compound.
Deviations from stoichiometry would require the
substitution of Na on Bi sites or vice versa which
would be energetically very unfavourable.

90

If stoichiometric Na3Bi is heated, it will melt

isothermally at 775 C to form a liquid of the same
composition. That is, the melting behavior of Na3Bi
is similar to that of a pure element. Such intermetallic
compounds
are
called
congruently melting
compounds.

91

The electrochemical differences among the components

Formation of stable intermediate compounds will restrict primary solid solubility. The
likelihood of the formation of such compounds in an alloy system is related to the chemical
affinity of the participating elements and will be increased the more electronegative one of
the elements and the more electropositive the other.

The width of the shaded area represents the extent of primary solid solubility; it
becomes more restricted the greater the stability of the intermediate phase.
electrochemical effect; related to the difference in the electronegativities of the two
components.
92

In these simple cases where the

octet
rule
is obeyed,
the valence of an atom equals
the number of electrons gained,
lost or shared to form the stable
octet.

93

Order-disorder transformations

Activities of the components exhibit negative deviation. Activities are smaller

than the corresponding mole fractions. Negative deviation of the activities is the
evidence that the components of the binary system posses a definite attraction
for each other or at least preference for opposite atom forms as neighbors.
Au and Cu atoms alternate in the lattice positions in such a way as to form the
maximum number of Au-Cu atomic bonds and the minimum number of Au-Au
94
and Cu-Cu bonds.

At higher temperatures, thermally induced

atomic movements are too rapid to permit
the grouping together of a large number
of atoms in a stable ordered structure
Two opposing factors, attraction of unlike
forms for each other and the disrupting
influence of thermal motion lead to short
range order. Au atoms have statistically
greater number of Cu atoms as their
neighbors than would be expected if the
two atom forms would be arranged in a
completely random fashion.
At lower temperatures and at the required
compositions component atoms arrange
themselves in stable configuration that
extend through the large regions of the
crystal. Such state of long range ordered
structure is called a superlattice.

95

The entropy of mixing of structures

with long-range order is extremely
small and with increasing temperature
the degree of order decreases until
above some critical temperature there
is no long-range order at all. This
temperature is a maximum when the
composition is the ideal required for
the superlattice.
long-range order can still be obtained
when the composition deviates from
the ideal if some of the atom sites are
left vacant or if some atoms sit on
wrong sites. In such cases it can be
easier to disrupt the order with
increasing temperature and the critical
temperature is lower
96

The five common ordered lattices, examples of which are: (a) L20:CuZn, FeCo. NiA1,
FeAl, AgMg. (b) L12:Cu3Au. Au3Cu. Ni3Mn. Ni3Fe, Ni3Al. Pt3Fe; (c) Ll0:CuAu. CoPt.
FePt: (d) DO3: Fe3Al. Fe3Si. Fe3Be, Cu3Al; (e) DO19:Mg3Cd, Cd3Mg. Ti3Al, Ni3Sn
97

The ordered region of crystal is

known as domain.
At the junction of between two
domains, the sequence of the A and
B atoms is reversed and it is called
the domain antiphase domains and
the
boundary
as antiphase
boundaries.
The chemically disordered-to-ordered state requires the rearrangement of atoms
to specified lattice sites. The degree to which individual atoms occupy the correct
lattice site is given by an order parameter, S. The order parameter is extensively
applied to quantify the degree of ordering In a binary alloy of A-B, the order
parameter is defined as
S = rA + rB -1 = (rA xB)/yB = (rB-xA)/yA
where xA and xB are the atom fractions of A and B, respectively, rA and rB are the
fraction of A and B sites occupied by the correct atom in the L10 phase, and yA and yB
are the fraction of A and B sites, which is 0.5 for L10. For perfect order, e.g. all A and
98
all B atoms on the correct L10 sites, S=1 while complete disorder
is S=0.

Effect of Temperature on Solid Solubility

At temperature T1

H, is the difference in enthalpy between the -form of

B and the form. is the change in energy when 1 mol
of B with the structure dissolves in A to make a dilute
solution.
The solubility of B in increases exponentially with
99by Q.
temperature at a rate determined

The free energy curves so far have been based on the molar free
energies of infinitely large amounts of material of a perfect single
crystal. In real situation crystal defects such as dislocations do exist
and raise the free energy of the phase. Therefore the minimum free
energy of an alloy (the equilibrium state) is not reached until virtually
all the interfaces and dislocations have been annealed out.
Interphase interfaces can become extremely important in the early
stages of phase transformations where one phase, , can be present as
very fine particles in the other phase .

100

Influence of Interface on equilibrium

101

G : molar free energy difference

between the two particles
If dn moles of atoms are transferred
from large to the small precipitate
then the change in free energy of the
system is:
dG = G dn
Increase in the free energy is primarily
due to the increase in the interfacial
area
of
the
spherical particle.
Assuming is constant:

102

The concentration of solute B in in

equilibrium with across a curved
interface
is
greater
than the
equilibrium concentration for a planar
interface

Assuming that the phase is

regular solution and phase
is almost pure B

103

Gibbs-Thompson Effect

An important practical consequence of the Gibbs-Thompson effect

is that the solubility of In is sensitive to the size of the
particle
104

Interfaces and Equilibrium

When interfaces are curved there are additional energy terms which can not be neglected
Consider an assembly in which particles of surface area O and surface free energy per unit
area are in equilibrium with the matrix.
The energy of the interfaces displaces the equilibrium condition
so that both the solubility limit x and the equilibrium composition x of the phase vary
with the size of the particles. We now denote these quantities as x(r) and x (r) and the
equilibrium compositions for infinite planar interfaces by x() and x() .

105

In a change in which dn moles of atoms are transferred to the phase, there is now an
additional energy term dO due to the increase in surface area of the particles
This may be represented as a displacement of g to g (r) =
The new equilibrium compositions are given by
the points of contact of the tangent common to
the curves of g and g(r) against x
The new equilibrium conditions are

From the geometry of the figure

106

In terms of activity coefficient

for dilute
solutions or
solutions which
obey Henry's law

R
R

is constant

For spherical particles

A=O

;
For dilute solution of B in A
107

If the particles are cylinders (needles) rather than spheres

In the general case of equilibrium at a curved interface

The curvature of a surface may in fact be regarded as

introducing a pressure differential

free energy change per atom is now pv.

This concept leads to the same expression for

the change in solubility with particle size since
the free energy of phase change
108

Interfacial-free energy between two solid phases- Turnbull model

D. Turnbull, in: Impurities and Imperfections,
Amer. Soc. Met., Ohio 1955 (p. 121).

Interfacial-free energy between two solid phases can be split into physical and
chemical contributions written as

For two solids of quite different lattice structure, the geometrical term stands for the energy of a
large angle grain boundary. It is estimated that the grain boundary enthalpy is about 30% of the
surface energy at 0 K and the entropy contribution is neglected.

109

 is the surface energy of metal

Where C0 is constant being 4.5X 108 .

Interfacial-free energy can be calculated as

Sf is the surface area occupied by one mole interfacial atoms

110

Are the fractions of interfacial A atoms versus total

number of A and B atoms versus total number of B,
respectively. These terms multiplied by XA and XB ,
respectively, give number of (A+B) atoms in the
multilayer interfaces.

111

A.R. Miedema , Z Metall, 69 (5) (1978), pp. 287292

GBulk = XAGA + XBGB + Gmix

H mix H c H e H s
The chemical contribution (Hc ) to the enthalpy :

H c H mix (L)
c
c
H mix ( L) x A x B [ x AhBinA
x Bi hAinB
]
c
c
and hAinB are the chemical interaction parameters which is interfacial enthalpy
hBinA

for A surrounded by B and B surrounded by A

Here VA is the atomic volume, and consequently V2/3 is proportional to the surface area of the atomic cell.
F(A, B) depends only on properties of the pure metals, namely the electronegativities A and B, and the
electron densities nA and nB. Specifically,
where P and Q are constants. F(A, B) is thus proportional to the interaction energy per
112
unit area of contact between A and B.

The elastic contribution to the enthalpy of mixing arises due to the distortion of
the crystal lattice due to a difference in the sizes of the atoms of the two
components
e
e
H e x A xB [ x AhBinA
xB hAinB
]

Where, h e

the elastic interaction parameter which is the elastic contribution of heat of

solution of A in B. This can be estimated from:
'
*
* 2
2
S
(
V

V
)
e
hBinA
*A B ' A *
3VA 4 S Ak BVB

Where SAg & SBi are the shear modulii of the elements A and B, kA & kB are
the compressibilities and V*A & V*B are the effective molar volumes corrected
for the charge transfer effects.
The molar volumes of the pure elements VA & VB have to be corrected, since in
solution the molar volume of the matrix and solute will change due to chemical
interaction. The correction term for the molar volumes dV is given by

PVA2 / 3 ( A B ) 1
1
dVA
n

n
wsA
wsB
1 / 3
1 / 3
nwsA
nwsB
113

PVA2 / 3 ( A B ) 1
1
dVA
n

n
wsA
wsB
1 / 3
1 / 3
nwsA
nwsB
where is the electro negativity nws is the electron density at the Wigner Seitz cell
boundary and V is the molar volume. P is the empirically determined constant whose value
is 1.5
dV calculated as above is then added on to the respective molar volumes
*
m
VAg
VAg
dV Ag

These calculated volumes are then substituted in equation to calculate the elastic
energy contribution to the enthalpy.
The cell may be chosen by first picking a lattice point. Then, lines are
drawn to all nearby (closest) lattice points. At the midpoint of each line,
another line is drawn normal to each of the first set of lines. In the case
of a three-dimensional lattice, a perpendicular plane is drawn at the
midpoint of the lines between the lattice points. By using this method,
the smallest area (or volume) is enclosed in this way and is called the
WignerSeitz primitive cell. All area (or space) within the lattice will
be filled by this type of primitive cell and will leave no gaps.

114

The structural contribution arises from the fact that depending on the number of
outer electrons there exists a preference (for transition) to crystallize in a particular
structure. Therefore, dissolving one metal in other changes the number of outer
electrons and this stabilizes a particular structure. Accounts for the difference between
the valences and the crystal structure of the solute and solvent
The form of this structural enthalpy is given by
FCC
H s Ealloy
( Z alloy ) [(1 xB ) E A ( Z A ) xB EB ( Z B )]

Ealloy, EA, EB lattice stability parameter of the alloy, A and B evaluated at the respective
values of their Z. The Zalloy, ZA and ZB are the number of valance electrons per atom for A
and B.
The average number of valence electrons in the alloy and the E (Z) the lattice stabilities is
found as functions of the number Z of valence electrons for each crystal structure (BCC, HCP
or FCC).

The average number of valance electron for the alloy is given by,

Zalloy x Ag ZAg x Bi ZBi

The lattice stability parameters are related to Gibbs energies, which describe the relative
115
stability of phases.

example

(111) Ag50Ni50
0.220 nm

116

117

118

119

Diffusion
The study of phase transformations concerns those mechanisms by which a system attempts to
reach the state of equilibrium arrangement of atoms and how long it takes to attain the
equilibrium. One of the most fundamental processes that controls the rate at which many
transformations occur is the diffusion of atoms.
The fundamental reason why diffusion occurs is to produce a decrease in the Gibbs free
energy
Two blocks of composition B-rich and A-rich
are held together at a temperature high enough
for long range diffusion to occur.
The total free energy of the assembly is given
by G3. G1; free energy of A-rich part and G2;
free energy of B rich part. Physical mixture
condition.
If diffusion occurs then so that a homogenous
alloy is formed then the free energy of the
system is given by G4 (figure (b)). Here atoms
are diffusing down the concentration gradient.
120

In an alloy system that contains a miscibility

gap the free energy curve can have a
negative curvature at the lower temperatures.
If the free energy of curve and composition
for A-B alloy shown in figure (a) were as
drawn in figure (d), the A and B atoms
would diffuse towards the region of high
concentration. That is UP the concentration
gradient, as shown in figure (c)
The movement of the atoms up the
concentration gradient is a natural process
as it still decreases the free energy of the
system

121

121

A and B atoms are diffusing form

regions where the chemical potential is
high to regions where it is low that is
down the chemical potential gradient
in both the cases (figure (b) and figure
(c).
Diffusion ceases when the chemical
potential of all atoms are everywhere
the same and the system is in
equilibrium.
Driving force for the diffusion is
decrease in chemical potential.

122

In crystalline solids, the atoms occupy well defined equilibrium positions (regardless of thermal
vibrations); they move by jumping successively from an equilibrium site to another. There are
two common mechanisms by which atoms can diffuse through a solid; substitutional atoms
usually diffuse by a vacancy mechanism whereas the smaller interstitial atoms migrate by
forcing their way between the larger atoms. i.e, interstitially.

Mechanisms of diffusion in crystals: (1) direct exchange, (2) cyclic

exchange, (3) vacancy, (4) interstitial, (5) interstitialcy, (6) crowdion.
123

MECHANISM OF ATOMIC MIGRATION

Consider the chemical diffusion of an atomic species, B. The B atoms may share a set of
sites with the other components, forming a substitutional solid solution, or they may partially
occupy a separate set of sites, so that B is an interstitial solute.
In all interstitial solutions, the fraction of possible
solute sites which are actually occupied by atoms
is quite small, and most of these sites are vacant. An
interstitial atom can then migrate by jumping from
one such site to a neighbouring vacant site

Substitutional solid solutions; atomic mechanism

Involves the direct interchange of two atoms on
neighbouring sites. If this interchange is imagined to
occur by the rotation of the two atoms about their
common centre of separation, it is obvious that
considerable distortion of the surrounding structure will
be required. For this reason, the probability of such a
direct interchange is believed to be very low in metallic
crystals.
124

In the ring mechanism (Zener ring mechanism), it is

assumed that the thermal vibrations are sufficient to cause
a number of atoms, which form a natural ring in a crystal,
to jump simultaneously and in a synchronized manner such
that each atom in the ring advances one position around the
ring.
A small number of atoms n move together in a ring, thus
enabling the distortion to be spread over a larger volume,
and reducing the energy
Zener has suggested that a ring of four atoms might be
preferred diffusion mechanism in a body centered cubic
metal because of their more open structure as compared to
closed pack metals.
The second basic mechanism is the movement of atoms
through the interstices of the lattice, as for interstitial solid
solutions. An individual atom migrates by leaving a
normal site and successively occupying a series of
interstitial sites, until it meets a vacancy and returns to the
normal sites. Such migration will be energetically
unfavourable unless the structure is very "open".

125

The figure shows the mechanism for atomic migration

which depends on the presence of vacancies in the
structure. An atom next to a vacant site may jump into
that site, thus in effect changing places with the
vacancy. The relative motion of A and B atoms results
from the migration of vacancies through the lattice, and
diffusion by vacancies is in some of its effects
intermediate between the interstitial and place exchange
mechanisms.
If only B atoms could change places with a vacancy, the
motion of B would take place with reference to an
unchanging lattice frame of A atoms. On the other hand,
if the probabilities of A and B atoms jumping into a
neighbouring vacant site were equal, the average
displacement of the two kinds of atom would be equal
and opposite, as in place exchange.

126

In metals and alloys, near the melting point, the vacancy

concentration is about 10-4 to 10-3 site fraction. These
vacancies allow the atoms to move rather easily, and this
mechanism is operating in most cases, with jumps to
nearest neighbour sites.
Besides monovacancies there are vacancy aggregates:
divancancies, trivacancies, etc., which can contribute to
the diffusion . The ratio divacancies/ monovacancies
generally increases with temperature, so that the
divacancy contribution to the diffusion also increases.
Molecular dynamics calculations have shown that
at high temperatures, when the atom jump frequency
becomes large, a dynamical correlation between
successive jumps can occur so that a vacancy can move
more than one jump distance creating divacancies
Mechanisms involving extended defects
Linear defects (dislocations) and planar defects (surfaces, interfaces, grain boundaries,
etc.) are disordered regions in which the atomic migration is easier than in the bulk.
These preferential paths of diffusion are called short-circuits.
127

Normally a substitutional atom in a crystal oscillates about

a given site and is surrounded by neighboring atoms on
similar sites. The mean vibrational energy possessed by
each atom is given by 3 kBT, and therefore increases in
proportion to the absolute temperature. The vibrational
energy is increased by increasing the amplitude of the
oscillations. Normally the movement of a substitutional
atom is limited by its neighbours and the atom cannot
move to another site. However, if an adjacent site is vacant
it can happen that a particularly violent oscillation results
in the atom jumping over on to the vacancy

Note that in order for the jump to occur the shaded

atoms in Fig. must move apart to create enough space
for the migrating atom to pass between. Therefore the
probability that any atom will be able to jump into a
vacant site depends on the probability that it can
acquire sufficient vibrational energy. The rate at
which any given atom is able to migrate through the
solid will clearly be determined by the frequency with
which it encounters a vacancy, atomic environment and this in turn depends
on the concentration of vacancies in the solid.

128

The activation energy depends on the process concerned, and since the rate of the process is
inversely proportional to the exponential of the corresponding free energy of activation, the
mechanism with the lowest activation energy will probably be much more important than
any other mechanism.

The 'dominant' mechanism however need not be that of lowest activation energy if different
geometries exist to compensate for the different probabilities of individual atom movements.
For example, the activation energy for grain boundary migration is normally much lower
than that for migration through the lattice. Nevertheless, the lattice makes the greater
contribution to the overall diffusion rate at high temperatures because so few of the atoms
are in grain boundary regions. As the temperature is lowered, the effect of the lower
activation energy for boundary motion becomes progressively more important, and at
sufficiently low temperatures virtually the whole of the diffusion may be along the
boundaries

129

129

Diffusion in Ideal solutions

Consider a solid solution composed of two atoms A and B, where A component is the solute
and B component as the solvent.
Let us assume that the jump of atoms to a vacancy is entirely random; that is probability of
jumping is the same for all of the atoms surrounding a given vacancy. The jump does not
depend upon the concentration.
In the figure, the composition of the solute
varies continuously length of the bar, but
it is uniform over a cross section. It is
further assumed that the concentration is
greatest at the right end of the bar and
least at the left end, and that a
macroscopic concentration gradient dnA/dx
applies on an atomic scale.
The difference in composition between
two adjacent transverse atomic plane is
Where a is the interatomic or lattice spacing
130

Let the mean time of stay of an atom in a lattice site

be . The average frequency with which atoms
jump is therefore 1/.
Any atom can jump in six different directions:
right or left, up or down and into and out of the
plane of the paper. Of the six possible jumps
which an atom A can make to exchange its
position between the two transverse atomic
planes, only one will carry it over to the other
indicated plane Y. So the average frequency with
which an A atom jumps from X to Y is 1/6.
The number of these atoms that will jump per
second from plane X to plane Y equals the total
number of atoms in plane X times the average
frequency with which an atom jumps from plane
X to plane Y.
The number of solute atoms in plane X equals
the number of solute atoms per unit volume
(concentration nA) times the volume of the atoms
in plane X (Aa)

131

The concentration of A atoms in plane Y

is

Where nA is the concentration at the plane

X, and a is the lattice constant. The rate at
which A atoms move from plane Y to X is
thus

The net flux (J) thus can be expressed as

Flux of atoms A is negative when the concentration

gradient is positive; the diffusion flux is down the
concentration gradient
132

Making the substitution

Equation for the net flux is

Ficks first law of
diffusion.

J is the flux, or quantity per second, of

diffusing
matter
passing normally
through an area A under the action of a
concentration gradient dnA/dx. The
factor D is known as the diffusivity or
the diffusion coefficient

A diffusion process of the type, which tends to produce a homogeneous assembly, is easily
visualized. If the probability of an atomic migration were independent of direction, i.e. of the
neighbours of the atom which moves, then diffusion would be merely the statistical result of
a large number of chance migrations. This is often referred to as a "random walk" problem
The net statistical flow of any component would obviously be from regions of high
concentration of that component to regions of low concentration.
In practice, the probability of atomic migration usually depends both on the type of atom and
the direction of motion, and simple statistical flow does not occur. However, it is often
convenient to divide the net atomic movements into a random flow and a superimposed
drift velocity. The driving force for the random flow is the change in the configurational
entropy of the assembly, whilst the drift velocity may be attributed to internal or external
stresses, potential gradients, or electrical fields, etc.
133

As originally conceived, the diffusivity D in Fick s Law was assumed to be constant for
measurements made at a fixed temperature. However only in case of a solution composed of
two gasses has it been experimentally verified that the diffusivity approaches a constant value
at a fixed temperature.
In contrast to the gaseous solutions, the diffusivity in both liquid and solid solutions is
seldom constant.

134

Kirkendall Effect
This experiment shows that in a binary solid solution each of the two atomic forms can move
with different velocities.
A Kirkendall Diffusion Couple

Fine wires (some refractory

metal that will not dissolve in
the alloy system to be studies).
These wires serve as the marker
with which to study the
diffusion process.

In order to have diffusion that is large enough to be experimentally measured the it is

necessary that the diffusion couple be heated to a temperature close to the melting point of
the metals comprising the bar, and maintain there for relatively long time, usually in the
order of days.
Upon cooling to the room temperature, the thin layer parallel to the weld surface is
removed from the bar. Each layer is then analyzed chemically and the results plotted to
give a curve showing the composition of the bar as a function of distance along the bar.
135

Kirkendall Effect
This experiment shows that in a binary solid solution each of the two atomic forms can move
with different velocities.
A Kirkendall Diffusion Couple

Fine wires (some refractory

metal that will not dissolve in
the alloy system to be studies).
These wires serve as the marker
with which to study the
diffusion process.

In order to have diffusion that is large enough to be experimentally measured then it is

necessary that the diffusion couple be heated to a temperature close to the melting point of
the metals comprising the bar, and maintain there for relatively long time, usually in the
order of days.
Upon cooling to the room temperature, the thin layer parallel to the weld surface is
removed from the bar. Each layer is then analyzed chemically and the results plotted to
give a curve showing the composition of the bar as a function of distance along the bar.
136

In copper-zinc alloys, the mass motion was detected by inserting inert markers
(molybdenum wires) at the original interfaces of a copper-brass-copper diffusion couple.
At the end of the experiment, the separation of the wires was found to have decreased, and
the magnitude of the change was too great for it to be attributed simply to the different
atomic volumes of the diffusing species. If the wires, which take no part in the diffusion
process, are assumed to be fixed to the lattice, the effect can only be explained by
assuming that the number of zinc atoms which diffuse out of the brass is greater than the
number of copper atoms which diffuse into it.

The zinc atoms could diffuse interstitially from the brass, leaving vacancies, and take up
normal sites in the copper. Alternatively, the zinc atoms may diffuse via vacancies, the net
current of atoms being balanced by an opposite current of vacancies into the brass. The
vacancies could coagulate together, forming macroscopic holes, or could diffuse to
dislocations, with a resultant shrinking of the structure. The extra atoms in the copper would
similarly cause an expansion of the surrounding region.
137

There has been a flow

of B atoms from the
left size of the bar
towards the right side,
and
a corresponding
flow of A atoms in the
other direction

Original position of the weld interface

The upper figure represents the diffusion

couple before the isothermal treatment and
the lower, the same bar after the diffusion
has occurred. The wire has moved to the
right through a distance x, the distance has
been found to vary as the square root of the
time during which the specimen was
maintained at the diffusion temperature.
Movement of wire to the right denotes that
the A atoms diffuse faster than the B atoms.
A net flow of mass through the wires from
right to left.
138

The probability of atomic migration usually depends both on the type of atom and the
direction of motion it is often convenient to divide the net atomic movements into a random
flow and a superimposed drift velocity. The driving force for the random flow is the change
in the configurational entropy of the assembly, whilst the drift velocity may be attributed to
internal or external stresses, thermal gradients, or electrical fields, etc.

In a copper-nickel diffusion couple the

copper diffuses faster into the nickel
than the nickel does in copper

Mass gain
expansion

Mass loss
shrinkage

Experimental
measurements have
shown that the element with lower
melting point diffuses faster. Copper
melts at lower temperature than Ni

The dimensional changes are essentially one dimensional (along the axis of the bar laying
perpendicular to the weld surface. A state of stress is set up in the diffusion zone. This stress
field brings about plastic flow, with resulting structural changes normally associated with
plastic deformation and high temperatures; formation of substructures, recrystallization and
grain growth
139

It has frequently been observed that voids or pores form in that region of the diffusion zone
from which there is a flow of mass. Every time an atom makes a jump a vacancy moves in the
opposite direction , an unequal flow of two types of atoms must result in an equivalent flow of
vacancies in the reverse direction to the net flow of atoms.
In Cu-Ni diffusion couple, the movement of atoms reduces the equilibrium number of
vacancies on the nickel-rich side and of the diffusion range while increasing it on the copper
side. Vacancies must be created on the side of a couple that gains mass and absorbed on the
size that looses mass.
Grain boundaries, exterior surfaces and dislocations are probable positions for both the
creation and elimination of vacancies. Dislocation climb and void formation account for most
of the absorbed vacancies, positive climb being associated with the removal of vacancies and
negative climb with the creation of vacancies.
Formation of voids, as a result of the
vacancy current that accompanies the
unequal flow in a diffusion couple, is
influenced by several factors. It is generally
believed that the voids are heterogeneously
nucleated that is they form on impurity
particles. The tensile stress that exists in the
region of the specimen where the voids form
is also recognized as a contributing factor in
the development of voids.

140

Darkens Equation
Kikendall effect shows that in a diffusion couple, two types of atoms move at different rates,
and the flux of atom through the marker is not the same for both the atoms. Therefore it is
logical to think in terms of two diffusivities DA and DB corresponding to the movement of A
and B atoms respectively.

Where,
JA and JB = fluxes (number of atoms per second passing through a given
cross section of area A)
DA and DB = Diffusivities of A and B atoms
nA and nB = number of A and B atoms per unit volume respectively
The diffusivities DA and DB are known as the intrinsic diffusivities and are functions of
compositions and therefore of position along a diffusion couple.
Darkens equation makes it possible to determine the intrinsic diffusivities experimentally.
Assumptions in the derivation of Darkens equation are
(a) Volume change during the diffusion occurs in a direction perpendicular to the weld
interface. The cross section area does not change
141
(b) Total number of atoms per-unit volume is constant nA+nB=constant.

v = velocity of the kirkendall marker

The marker velocity is equal in magnitude, but opposite in direction to the volume of matter
flowing past the marker per second divided by the cross-section area A of the bar at the
marker

The volume of matter that flows through the markers per second is equal to the net flux of
atoms passing the wires times the volume per atom

142

NA and NB are atom fractions of A and B

In principle it is possible to insert an

imaginary set of markers on any
cross-section along a diffusion couple.
The derived equation may therefore be
used to compute the velocity with
which any lattice plane, normal to the
diffusion flux , moves. Since DA and
DB are the functions of composition, v
is a function of composition of the
specimen at any cross-section where v
is measure

The above equation relates the two intrinsic diffusivities to the marker velocity and the
concentration gradient, the two quantities that can be experimentally determined. However
we still have two unknowns DA and DB so we need one more
143 equation

In the case shown in figure. The

cross section (mm) at a distance x
from the left end of the bar
represents a cross section fixed in
the space; that is fixed with respect
to the end of the bar which is
assumed out side the diffusion zone.
A second cross-section of the bar
(nn) is at a distance x+dx from the
end of the bar. The two cross section
defines a volume element A(dx)
Consider the rate at which the number of A atoms changes inside the volume bounded by
mm and nn. This quantity is equal to the difference in the number of A atoms moving into
and out of the volume per second or to the difference in flux of A atoms across the surface at
x and x+dx. Because a cross section fixed, the lattice moves relative to the cross-section fixed
in space, the flux of A atoms through one of these space fixed boundaries is due to two
effects. First, because the metal is moving with a velocity v, a number (nAvA) of A atoms
is carried each second through the cross section at x, where nA is the number of A
atoms per unit volume, and vA is the volume of metal flowing past the cross section at x
in a second. This flux must be added to the usual diffusion flux, so the total number of
atoms per second crossing the boundary at x is:
144

The flux of A atoms through the cross section at x+dx is

The rate at which number of atoms inside the volume Adx changes is therefore

The rate at which the number of A atoms per unit volume changes is

This equation can also be written as

Substituting the equation

We obtain

and

145

Ficks second law

This equation is generally written as

If the diffusivity D is assumed to vary slightly with composition, then Ficks second law
can be written as

In case of diffusion couple consisting originally of two alloys of the element A and B, one
having the composition NA1 and other having the composition NA2
NA is the composition or atom
fraction at a distance x from the
weld interface,
t is the time in
146
seconds

The symbol
argument

represents the error function, or probability integral with the

This function is defined by the equation

147

148

149

Matanos Method
In this method the diffusivity is assumed to be a function of concentration, which requires the
solution of Ficks second law in the form

The first step in this procedure, after

the diffusion anneal and the chemical
analysis of the specimen, is to plot the
curve of concentration Vs distance
along the bar measures from a suitable
point of the reference, say from one
end of the couple. The number of
atoms per unit volume is assumed to
be constant.
The second step is to determine the
cross-section of the bar there have
been equal total fluxes of the two
atomic forms (A and B). This crosssection is called Matano interface
and lies at the position where area M
and N are equal.

Once the Matano interface has been located it

serves as the origin of the x coordinate. With
coordinate system defined the Boltzmann
solution to the Ficks equation is

Where, t is the time of diffusion, NA is

concentration in atomic units at a distance x
from the Matano interface, and NA1 is the
concentration at one side of the diffusion
couple at a
point not affected by the
150
diffusion process

We want to determine the diffusivity at

point C. Concentration at point C = 0.375

151

152

Determination of intrinsic diffusivities

Experimentally it has been determined
that the marker moves in such a manner
that the ratio of their displacement
squared to the time of diffusion is a
constant

constant
Marker velocity is given by
= k/2x

In the figure the position of the

marker is assumed at a distance,
x = 0.01 cm from the Matano
interface.
153

The diffusion time t taken for the data is 50 hours or 18000 sec. these numbers correspond
to the marker velocity:

154

Self diffusion
Equilibrium vacancy concentration
The removal of atoms from their sites not only increases the internal energy of the metal,
due to the broken bonds around the vacancy, but also increases the randomness or
configurational entropy of the system. The free energy of the alloy will depend on the
concentration of vacancies and the equilibrium concentration Xe will be that which gives the
minimum free energy.

Xv is the mole fraction of vacancies; Hv is the increase in enthalpy per mole of

vacancies added
There are two contributions to the entropy change S on adding vacancies; thermal entropy
of S, per mole of vacancies added (due to changes in the vibrational frequencies of the
atoms around a vacancy) and configurational entropy. Total entropy is given as

The molar free energy of the crystal containing Xv mol of vacancies is therefore given by

155

Given time the number of vacancies will adjust

so as to reduce G to a minimum. The
equilibrium concentration of vacancies Xe is
therefore given by (under approximation Xv<<1)

In practice Hv is of the order of 1eV per

atom and Xev reaches a value of about 10-4
to 10-3 at the melting point

156

Self diffusion
The rate of self-diffusion can be measured experimentally by introducing a few radioactive A
atoms (A*) in to pure A and measuring the rate at which penetration occurs at various
temperatures. Since A* and A atoms are chemically identical their jump frequencies are also
almost identical.

is the jump frequency of both A and A*

is the lattice parameter
An atom next to a vacancy can make a jump provided it has enough thermal energy to
overcome the activation energy of migration Gm . Probability that any jump attempt will
be successful is given by exp (-Gm/RT). However, most of the time an adjacent site will
not be vacant and the jump will not be possible. The probability that an adjacent site is
vacant is given by zXv, where z is the number of nearest neighbours and Xv is the mole
fraction of vacancies in the metal.
If the atoms are vibrating with a temperature dependent probability v Number of successful
jumps any atoms would make in per second is

157

For vacancies in thermodynamic equilibrium

Combining equations

QSD = Hm + Hv

Experimentally the usual method for determining the

self-diffusion coefficient is to deposit a known
quantity (M) of a radioactive isotope A* onto the
ends of two bars of A which arc then joined as after
annealing for a known time at a fixed temperature.
A* will have diffused into A and the concentration
profile can be determined by machining away thin
layers of the bar and measuring the radioactivity as a
function of position,

158

Vacancy Diffusion
The jumping of atoms into vacant sites can equally
well be considered as the jumping of vacancies onto
atom sites. If excess vacancies are introduced into the
lattice they will diffuse at a rate which depends on the
jump frequency. However, a vacancy is always
surrounded by sites to which it can jump and it is thus
analogous to an interstitial atom. Therefore a vacancy
can be considered to have its own diffusion
coefficient given by

Sm and Hm applies to the migration of vacancies

159

Atomic Mobility
Some atom can lower their free energies if they migrate to defects and at equilibrium their
concentrations will be higher in the vicinity of the defect than in the matrix. Diffusion in the
vicinity of these defects is therefore affected by both the concentration gradient and the
gradient of the interaction energy.
To describe a flux of atoms is to consider a net drift velocity ( vB ) superimposed on the
random jumping motion of each diffusing atom. The drift velocity is related to the
diffusive flux via the equation
CB = number of atoms per unit volume
Since atoms always migrate so as to remove differences in chemical potential it is
reasonable to suppose that the drift velocity is proportional to the local chemica1 potential
gradient
MB is a constant of proportionality known as
the atomic mobility,
Is the chemical force causing the drift
+

160

For ideal or dilute solutions (XB

0) B is a constant and the term in brackets is unity

DB = MBRT
161

For Non-Ideal concentrated solution

When the diffusion occurs in the presence of a strain energy gradient,

for example, the expression for the chemical potential can be modified
to include the effect of elastic strain energy term E which depends on
the position relative to a dislocation
162

Diffusion along grain boundary and free surfaces

Atomic movements in solids occurs on the surfaces and through the grain boundaries
Experimental measurements have shown that the surface and grain boundary forms of
diffusion obey activation, or Arhennius type laws.
Ds and Db are surface and grain boundary
diffusivities respectively.
Ds0 and Db0 are constants,
Qs and Qb are the activation energies for surface
and grain boundary diffusion.
Experimentally it has been observed that
Dl is the diffusivity in the lattice
This is because of the more open structure present in the grain boundaries and the surfaces
In an average metallurgical specimen the grain boundary area is greater than the surface so
with respect to the geometry concerns grain boundary diffusion dominates
When diffusivity of a metal is measured with a polycrystalline samples, the results are
usually representative of the combined effect of volume and grain boundary diffusion.
Under such condition the apparent diffusivity may not correspond to either the volume or
the grain boundary diffusion coefficient.
163

Diffusion in a polycrystalline sample can be described as a simple summation of diffusion

through the grain boundary and diffusion through the crystal.

Diffusion though the grain boundary progresses more rapidly than through the crystal but
its effect if counteracted because as the concentration of the solute atoms builds up in the
boundaries , a steady loss of atoms occurs from the boundaries into the metal on the either
side of the boundary.
The figure shows a diffusion couple made up of pure A and pure B. arrows in the figure
represents the nature of movement of A atoms into the B matrix. Group of parallel arrows
perpendicular to the weld interface represents the volume component of the diffusion.
Arrows parallel to the grain boundaries represents the movement of atoms along the
boundaries and the arrows perpendicular to the boundaries represents the diffusion from the
boundary into the crystal
164

Points in the lattice close to the grain boundaries receive solute via the high-conductivity the
path much more rapidly than if the boundaries were absent.
For a give ratio of the grain boundary diffusivity and the lattice diffusivity , the relative
number of A atoms that reach the layer dx by travelling along the grain boundary and by the
lattice diffusion is a function of the grain size.
The smaller the grain size, the greater the total grain-boundary area available for boundary
diffusion and, therefore the greater the importance of boundary in the diffusion process.
165

Take the case of steady state diffusion through a sheet materials in which the grain boundaries
are perpendicular to the sheet.
Assuming that the concentration gradient in the lattice
and along the boundary are identical, the fluxes of
solute through the lattice (J1) and along the boundary
(Jb) will be given by

If the grain boundary has an effective thickness

and the grain size is d the total flux will be given by

The apparent diffusion coefficient is given by

166

The figure shows two sets of diffusion data

plotted for silver specimen.
For the grain boundary self diffusion the
equation of the line is

For volume/lattice diffusion

In this example the activation energy for the grain boundary diffusion is only about half that
for volume diffusion. This is significant for two reasons
(a) It emphasizes the fact that diffusion is easier along grain boundaries
(b) the grain boundary and the volume diffusion have different temperature dependence
As the temperature is raised, the rate of diffusion along the lattice rises more rapidly than the
rate of diffusion along the grain boundary. Conversely, as the temperature is lowered, the
rate of diffusion along the boundaries decreases less rapidly. At high temperature diffusion
through the lattice tend to over power the grain boundary component, and vice versa.
167

The above fact is illustrated in the figure

The solid line curve corresponds to the self
diffusion measurements made on fine grain
polycrystalline silver specimen. The solid curve
consists of two segments, one part with equation

For temperatures below 700C, and other coinciding with the single crystal volume diffusion
data. It can be concluded form the data that above 700C the volume diffusion component is
over powering and below 700C the grain boundary component is a factor in determining the
measured diffusivity.
For accurate measurements of lattice diffusivity using poly crystalline specimen, high
temperature and large grain specimen should be used.
168

Electrotransport
Temperature gradient and electrical potential gradient can also produce diffusion phenomena.
Electrotransport: study of atomic diffusion under an electric field; thermomigration: study of
diffusion phenomena occurring due to temperature gradient.

169

The effective force that an electric field applies to the carbon ion may be represented by the
product of Avogardo number (N), the electric field intensity E, and the effective charge on
the carbon ion Z*e. The product Z*eE represents the effective force on one ion. So,

Where B is the mobility under the electric field, nA is the number of carbon atoms per unit
volume.
It has been seen that the small size of the electrical bias has no effect on the mean jump
frequency at a given temperature. In effect, the electrotransport mobility B should be
proportional to the diffusivity D and therefore to the mobility under a concentration gradient.
When the steady state is attained a composition
gradient is also developed across the specimen. This
gradient will produce a flux of carbon atoms in the
direction opposite to that due to the potential gradient
equal to

170

At the steady state

If a steady state condition does not exists, the net flux is

not zero, and

171

Microstructure
Basic elements of microstructure are grains, lattice defects and second-phase
components. A complete description of the topology and crystallography of the
microstructure requires the following information:
(a) Characterization of the shape, type, size and spacial distribution of all the
components of the microstructure;
(b) Characterization of the orientation distribution of these elements in space and
between the features (microstructural anisotropy).

In the straightforward situation of randomly distributed defects and/or second phase

particles, the microstructure may be characterized to a first approximation by an
average density, . of defects and/or second-phase particles. Depending on the type
of microstructural element involved, describes the number of 0-dimensional
defects (e.g., vacancies) per volume, the total length of one-dimensional defects
(e.g., dislocations), the total area of two-dimensional defects (e.g., grain
boundaries) per volume, or the total volume fraction of three-dimensional objects
(e.g., pores, precipitates).
172

In multiphase alloys, different types of microstructures result depending on the volume

fraction, shape and the distribution of the phases.
For the sake of simplicity let us limit the discussion first to two-phase systems (called
and phases) with equiaxed grains or particles. In alloys of this type a variety of
microstructures can be formed.

ideal dispersion of particles in a matrix

173

Duplex Microstructure

particles cover all

grain boundaries
completely. In other
words, the
boundaries disappear
and we are left with
interfaces and
boundaries the
relative density of
which depends on the
crystal size
174

In the cases considered so far, the two phases were assumed to have no shape anisotropy.
In reality, this is often not so. In order to exemplify the role of anisotropy, a few
microstructures with different degrees of anisotropy are displayed in the figure. Depending
on the aspect ratios of the second-phase crystals, a fibrous or lamellar structure may result.

175

Microstructural transformations
(a) Transformation of microstructural elements: Well known examples for this type of
transformation of microstructural elements are as follows. the transformation of smallangle boundaries into high-angle grain boundaries by incorporation of additional
dislocations, incorporation of dislocations into high-angle grain boundaries which
transforms them, for example, from a special (low-energy) boundary into a random
(high-energy) one, change from coherent to incoherent interphase boundaries during
the growth of precipitates are examples of this kind.
b) Transformation of a crystalline material with a high defect density to a new phase:
Such a transformation may occur if the spacing between microstructural elements (e.g.,
dislocations, grain boundaries) in a crystal approaches atomic dimensions. If this is so, it
may transform into an amorphous phase
(c)Transformations between different types of microstructures: Transformations of
this type are defined by the appearance of new microstructural elements. Two-phase
microstructures shall serve as examples for such transformations. A transformation of one
type of microstructure to another is associated with the appearance or disappearance of a
particular type of boundary which represents a characteristic topological feature.
Transformations can take place as a function of volume fraction of the phases, and of
their shape and orientation
176

Types of interfaces in metallic systems

Three type of interfaces are important in metallic systems

(a) Free surfaces of a crystal (solid/vapour interface)
(b) Grain boundary (/ interface)
(c) Interfaces between phases (/ interface)
All crystals posses the first type
The second type separates crystals with essentially the same composition but
different orientations in space.
The third separates two different phases that may have different crystal structures
and/or different compositions (includes solid/liquid interface)

177

Interfacial free energy

Free energy of a system containing an interface of area A and free energy per unit
area A is

where Go is the free energy of the system assuming that all material in the system has the
properties of the bulk.
the excess free energy from the fact that some material lies in or close to the interface. It
is also the work that must be done at constant T and P to create unit area of interface.
Consider a wire frame suspending a liquid film with a movable bar
If a force F per unit length moves the frame
so that the total area increases by dA , then
the work done by the force is FdA. This
work increases the free energy of the system
by dG

178

A surface with free energy Jm-2 exerts a surface tension of Nm-2

Since a liquid is unable to support shear stresses. the atoms within the liquid can
rearrange during the stretching process and thereby maintain a constant surface
structure.
Solids. however, are much more viscous and the transfer of atoms from the bulk to
the surface, which is necessary to maintain an unchanged surface structure and
energy, will take much longer. If this time is long in comparison to the time of the
experiment then d/dA in not zero and surface free energy and surface tension will
not be identical. Nevertheless, at temperatures near the melting point the atomic
mobility is usually high enough for d/dA be nearly equal to zero
The distinction between the surface free energy and the surface stress is that the
former measures the work required to create new boundary, while the latter is a
measure of the work required to increase the boundary area by deformation,
without changing the number of atoms in the boundary
179

Surface Vapour Interface

Assume that the structures of solids may be discussed in terms of hard sphere models
Atomic configuration on three closed pack planes of a fcc crystal are

Atoms in the layers nearest to the surface are without some of their neighbors as
compared to the atoms in the bulk of the crystal. Atoms on the (111) surface are
missing three of their 12 nearest neighbours.
If the bond strength of the materials is then each bond may be considered to lower
the internal energy of each atom by /2.
Every surface atom with three broken bonds has an excess internal energy of (3)/2
as compared to the atoms in the bulk .
180

For pure metal, may be estimated from the latent heat of sublimation Ls (sum of
latent heat of fusion and vaporization)

The energy of a {111} surface Ev (J/surface atoms) is therefore approximately

From the definition of the Gibbs free energy the surface free energy can be given by

Surface atoms will have higher configurational (due to the presence of vacancies on
the surface) and thermal entropy (more freedom of movement) as compared to the
atoms in the bulk. The surface thus will have a positive excess entropy which will
compensate for the high internal energy.
The measured values for pure metals indicate that near the melting temperature the
surface free energy averaged over many surface planes is given by
181

It can be seen from the above simple model that different crystal surfaces should have
different values for E, depending on the number of broken bonds. For the surfaces shown in
Fig the number of broken bonds at the surface will increase through the series {111} {200}
{220}. Therefore ignoring possible differences in the entropy terms, should also increase
along the same series.

182

Variation of surface energy with plane orientation

A crystal plane at an angle to the closed pack plane:

No. of broken bonds out of the closed pack plane:
(Cos /a)(1/a)
No. of broken bonds from the atoms on the step
(Sin/a)(1/a)

A crystal plane at an angle to the close-packed plane

will contain broken bonds in excess of the close-packed
plane due to the atoms at the steps. Attributing /2
energy to each broken bond

Note that the close-packed

orientation ( = 0) lies at a
cusped minimum in the
energy
plot. Similar
arguments can be applied to
any crystal structure for
rotations about any axis
from any reasonably closepacked plane. All low-index
planes should therefore
be located at low-energy
cusps.
183

A convenient method for plotting the variation of with surface orientation in three
dimensions is to construct a surface about an origin such that the free energy of any plane is
equal to the distance between the surface and the origin when measured along the normal to
the plane in question.
For an isolated crystal bounded by
several planes Al, A2, etc. with
energies 1, 2, etc. the total surface
energy will be given by the sum
A1 1 + A2 2+ .. The equilibrium
shape has the property that Aii is a
minimum and the shape that satisfies
this condition is given by the
following,
so-called Wulff
construction
Equilibrium shape is a polyhedron with the
Largest facets having the lowest interfacial surface
energy

184

185

Grain Boundaries
In a single-phase assembly, neighboring crystals differ only in the orientations of their
respective lattices: it is then usual to refer to the individual crystals as the grains of the
structure and the regions over which the lattice orientation changes are the grain boundaries.
The atoms in a grain boundary region
are acted upon by forces tending to
move
them
into positions
corresponding to the two competing
orientations. In general, this implies a
considerable
distortion
of the
periodic structure, and part or all of
the grain boundary must be highly
distorted crystal. As we have seen, the
atoms in a free surface are distorted
little
from
equilibrium positions;
nevertheless, the energy of a grain
boundary is less than that of a free
surface, since there are fewer
unsatisfied atomic bonds in the
former.

A one-phase assembly is in true thermodynamical

equilibrium only when it forms a single crystal. In practice
the energies of the free surface and the grain boundaries of a
polycrystalline specimen are very small, and there is a
negligible rate of approach to this equilibrium except at
temperatures near the melting point.

186

Small angle grain boundary

If two grains differ only slightly in their relative orientation, it is possible to draw a
dislocation model of the boundary
The figure shows an example of an elementary
boundary in a simple cubic structure in which the
crystal on the right is rotated with respect to the crystal
on the left about the [100] direction.
The lattice on both sides of the boundary is inclined
downwards towards the boundary, with a result that
certain nearly vertical lattice planes on both the
crystals terminate at the boundary as positive edge
dislocations.

The greater the angular rotation of one crystal

relative to the other the greater the inclination of
the planes that terminate as dislocations at the
boundary and closer is the spacing of the
dislocations in the vertical boundary.

Where b is the Burgers vector of a dislocation in the boundary, and d

is the spacing between the dislocations

187

If the angle of rotation of the crystal structure across the boundary is small, then sin /2
may be replaced by /2, and the equation relating the angle of tilt across a boundary
composed of simple edge dislocations becomes

When the angle of the rotation increases the dislocations comes closer and in doing so
looses their identity; large angle grain boundaries
Experimental evidence of small angle
boundaries have been obtained through
the use of suitable etching reagents that
locally attack the surface. After etching
small angle boundaries consisting of
rows of edge dislocation appear as
arrays of well defined etch pits.
The separation between the etch pits
determine the angular rotation of the
lattice on one side of the boundary
relative to that on the other.
188

A tilt boundary may be formed in

an originally single but imperfect
crystal if a number of edge
dislocations of the same sign
move by glide and/or climb
processes until they are aligned
parallel to each other and normal
to the slip planes. As each
dislocation moves, the lattice and
shape deformations change, and
when the dislocations are aligned,
the lattice dislocations have added
together so as to produce a small
rotation.
Once formed, the tilt boundary is
stable against dissociation by loss
of individual dislocations
into the crystals on each side. This
is because the force between
parallel dislocations on parallel,
glide planes pulls them into
alignment

189

Energy of Grain Boundary

Elastic strain energy is stored in a material when it is elastically stressed. If a tensile stress is
applied on an elastic rod, and if max is the elastic strain produced by the stress max , then,
Elastic strain energy per unit volume = max max
As atoms around the dislocation are elastically displaced from their equilibrium position
thus, there is an increase in the energy of the crystal due to the stored elastic strain
energy. But around the dislocation strain energy has two components.
1. The region in the intermediate vicinity of the dislocation line, called the core of the
dislocation, has considerable disturbance of the atoms, and where Hooks Law cannot be
assumed to hold good and whose exact determination is difficult. This energy is called
energy of the core, Ecore
2. The region outside this core, where the atomic displacement is small, and the Hook s
law can be assumed to hold and gives rise to the elastic strain energy.
Total strain energy of the dislocation is made up of
Etotal = Ecore + Eelastic

190

Suppose in a cylindrical crystal a screw

dislocation, AB is created with a burger vector b.
This is similar to a strip of 2r being sheared to a
displacement of b at one end. Assuming Hooks
law is being followed the shear strain, at a
distance r from the screw dislocation is

If G is the shear modulus of this material, the

required shear stress is

Let us consider an annulus of length L with

inner and outer radii, of r and r + dr. Volume
of the annulus is
Strain energy per unit volume

191

The total elastic strain energy is obtained by

integrating the strain energy between the core radius,
ro to R (external dimensions of the crystals)

192

If is the Poisson's ratio then elastic strain energy of an edge

dislocation per unit length is:
Eelastic (Edge)

This relation ship can be used to derive the energy of the low angle
grain boundary as dependent on the angle of misorientation.

Where Ec is the energy per unit length of the

dislocation core. If we assume that r0 = 2b, the
total energy of the dislocation per unit length is,

193

If d is the distance between two dislocations, then energy of unit area of the boundary is
approximated as

194

The energy of the grain boundary is the total energy of the dislocations
within unit area of the boundary.
At very small values of the
dislocation spacing is very
large and the grain boundary
energy is proportional to the
density of the dislocations. As
increases the strain fields of
the dislocations start to interact
and progressively cancels out
so the grain boundary energy
increases at a decreasing rate.
When increases beyond 10150 the dislocation cores starts
to overlap, at this stage the
grain
boundary energy
becomes independent of the
orientation

195

When > 10-150 the boundary is known as a random highangle grain boundary. High angle boundaries contain large
areas of poor fit and have a relatively open structure. The
bonds between the atoms are broken or highly distorted and
consequently the boundary is associated with a relatively high
energy.
Measured high angle grain boundary energies (b) are often found to be
given by

Where sv is the surface energy

As for surface energies b is temperature dependent
decreasing somewhat with
increasing temperature. 196

Degrees of freedom of a grain boundary

The boundary is symmetrically positioned between the
two crystals that are tilted with respect to each other
about an horizontal axis that runs out of the plane of the
paper-symmetrical tilt boundary

Symmetrical tilt boundary with a vertical tilt axis

The crystals are rotated about an axis normal to the

boundary; twist boundary.
197

The boundary itself has

two degrees of freedom, as
indicated in the figures.

198

The energies of the large-angle grain boundaries are usually estimated by thermal-etching.
When a polycrystalline material is heated to high temperatures, thermal grooves form at the
free surface, where ever a grain boundary intersects the surface perpendicularly.
Figure consists of one grain boundary and
free surfaces to the right and to the left of the
point X. If s is the free surface tension and
b is the surface energy of the boundary, then
the two surface tensions of the free surfaces
balance each other , but the vertically down
component due to the grain boundary remains
unbalanced.
In order to balance this grain boundary energy
a groove must form. With a dihedral angle,
between the two surfaces energies of the free
surface to satisfy the equation,

b can be estimated if s and are known

199

Surface defects, which separate two orientations that are mirror image of one another are twin
boundaries.
Twin boundaries occur in pairs, such that the change in orientation (of atoms) introduced by
the boundary is restored by the other boundary.
200

Special High-Angle Grain Boundaries

The simplest special high-angle grain boundary
is the boundary between two twins. If the twin
boundary is parallel to the twinning plane the
atoms in the boundary fit perfectly into both
grains. The result is a coherent twin boundary.
In fcc metals this is a (111) close-packed plane.
Because the atoms in the boundary are
essentially in undistorted positions the energy
of a coherent twin boundary is extremely low
in comparison to the energy of a random highangle boundary.
If the twin boundary does not lie exactly
parallel to the twinning plane, the atoms do not
fit perfectly into each grain and the boundary
energy is much higher. This is known as an
incoherent twin boundary. The energy of a
twin boundary is therefore very sensitive to the
orientation of the boundary plane

201

202

Equilibrium in polycrystalline materials

The conditions for equilibrium at a grain-boundary Junction can be obtained either by
considering the total grain boundary energy associated with a particular configuration or,
more simply, by considering the forces that each boundary exerts on the junction.
Let us first consider a grain-boundary segment of
unit width and length OP as shown in Figure (a).
If the boundary is mobile then forces Fx and Fy must
act at O and P to maintain the boundary in
equilibrium. (Fx = )
If P is moved a small distance y while O remains
stationary, the work done will be Fy y. this must
match the increase in the boundary energy caused
by the change in orientation , ie,
This means that if the grainboundary energy is dependent on the
orientation of the boundary a force d
/d must be applied to the ends of
the boundary to prevent it from
rotating
into
a
lower energy
orientation. d /d is therefore
known as a torque term.

203

If the boundary energy is independent of orientation the

torque term is zero. Under these conditions the
requirement for metastable equilibrium at a junction
between three grains, Figure, is that the. boundary
tensions 1, 2 and 3 must balance.

The equation applies to any three boundaries so that grain 1 for example could be a
different phase to grain 2 and 3. Alternatively grain 1 could be a vapor phase in which case
13 and 12 would be the surface energies of the solid. This relation ship can be used to
determine the relative boundary energies as seen before.
If energies are equal in each of the three
boundaries that meet at a common line,
and if boundaries have attained an
equilibrium configuration,
the three
dihedral angles must be equal

204

In alloys consisting of two phases

two types of boundaries are possible;
boundaries separating crystals of the
same
phase,
and boundaries
separating crystals of the two phases.
If surface tension of the boundaries
is in a static equilibrium then

Rearranging the equations

As the dihedral angle approaches

zero, the second phase moves to
form a thin film between the
crystals of the first phase.
Ex, Bi-Cu system shows this

205

Gas enclosed by the soap

film is always at a greater
pressure than that on the
outside of the bubble because
of the surface tension of in
the soap film. The pressure
difference between the inside
and outside of the soap
bubble can be expressed by
the equation
Where is the surface tension of one surface of the film, R is the
radius of the soap bubble and D is its diameter.
The excess pressure causes gaseous diffusion from inside to the outside of the bubble,
resulting in a decrease in the size of the bubbles and a movement of its walls inwards towards
their center of curvature
In order to maintain an equilibrium angle of 1200 required when
three surfaces of equal surface tension meet at a common junction,
the cell walls of the three sided cell have to have a pronounced
curvature. Since the curvature is concave towards the center of
the cell, the wall can be expected to migrate, thus deceasing the
volume of the cell and causing to disappear completely.

206

Cells with less than six sides have walls that

are primarily concave towards their center,
while those with more than six sides have
walls convex towards their centers, this effect
being more pronounced the larger the number
of sides above six. All cells with less than six
sides are basically unstable and tend to shrink
in size, while those with more than six sides
tens to grow in size.
The overall effect of such boundary migration is to reduce the number of grains, thereby
increasing the mean grain size and reducing the total grain boundary energy. This
phenomenon is known as grain growth or grain coarsening. This phenomenon occurs in a
metal at a temperature of about 0.5Tm when the boundaries have significant mobility.

207

208

Pressure difference across a grain boundary creates a difference in free energy

(G) or chemical potential () which drives the atoms across the boundary.

Vm is the molar volume

If unit area of the boundary advances a distance

x, then the number of moles of material that
enters the grain with lower energy is
x (1/Vm ) The free energy release is given by

This is equal to the work done by the pulling force Fx. the pulling force per unit area of the
boundary is given by
Pulling force on the boundary is free energy difference per unit
volume of material

The difference in the free energy

provided the required driving force
for the boundary migration. The
reason for the difference in the free
energy can be due to the curvature
of the grain boundary or may be
due to the strain energy due to the
presence
of
the defects
(recrystallization).

209

Driving force for boundary migration

Let
Ga = activation energy for the atomic migration from one grain to the another
1 = frequency of vibration of atoms
n1 = atoms per unit area in a favorable position to make a jump.
A2 = probability that an atom jumping from grain 1 to grain 2 be accommodated in grain 2.
Effective flux of atoms from grain 1 to grain 2 is given by

Flux of atoms from grain 2 to grain 1 is given by

G is the difference in the free

energy per mole of atoms
between the grain 1 and grain 2

For a zero driving force (G = 0 )

Assuming that the above equality also holds for small non-zero driving force, the net flux
from grain 1 to grain two is given by
210

If the boundary is moving with a velocity v then the flux of atoms is given by v/(Vm/Na)

v = M (G/Vm)
Where,

Velocity under unit driving

force

Velocity of the movement of the atoms (grain boundary) is depends on

The driving force for migration (difference in the free energy induced due to
the curvature effect).
Temperature.
Alloying, concentration of solute atoms at the grain boundaries.
211

Grain boundary mobility and alloying

In grain boundary segregation theory, grain boundary solute concentrations (Xb) are
expressed as fractions of a monolayer. One monolayer (Xb = 1) means that the solute atoms
in the boundary could be arranged to form a single close-packed layer of atoms.
Xo = mole fraction of solute in the matrix
Xb = boundary solute concentration
Gb = free energy released per mole when a solute
atom is moved from the matrix to the boundary
Gb is usually positive due to Entropy effect, atomic size differences (elastic stress field)
Grain boundary segregation decreases as
temperature
increases,
i.e.
the solute
'evaporates' into the matrix.
When the boundary moves the solute atoms
migrate along with the boundary and exert a
drag that reduces the boundary velocity. The
magnitude of the drag will depend on the
concentration in the boundary. The higher
mobility of special boundaries can, therefore,
possibly be attributed to a low solute drag on
account of the relatively more close-packed
structure of the special boundaries.

212

Grain growth law

During the grain growth, the average grain size uniformly increases and thus, the grain
boundary area per unit volume decreases. The corresponding decrease in the grain boundary
energy per unit volume becomes the driving force for the grain growth.
For a spherical grain of radius, R,
the grain boundary energy per unit volume

Where D is the grain diameter

The instantaneous rate of growth dD/dt can be taken to be proportional to the grain boundary
energy per unit volume of the metal, which in turn can be taken to be inversely proportional
to D

Where, t is the time and K is a constant of proportionality

213

If Do is the average grain size at the start (when t=0), then, after the after the evaluation of the
integration constant C

Defining K
If we assume that the mean radius of curvature of all the grain boundaries is
proportional to the mean grain diameter D the mean driving force for grain
growth will be proportional to 2/D. Therefore,
Where M = mobility
v is the boundary velocity
D = D = grain diameter
Note that this equation implies that the rate of grain growth is inversely
proportional to D and increases rapidly with increasing temperature due to
increased boundary mobility, M. Integration of Equation taking D = Do
when t = 0 gives

214

If Do is the average grain size at the start (when t=0), then, after the after the evaluation of the
integration constant C

If the initial diameter of the grain is very small as compared to the final diameter, the putting
D0 = 0
D = Bt1/2
This is a parabolic growth law. It is observed experimentally only in a few ideal cases. In
pure metals and single phase alloys, an analogous and empirical equation governing the grain
growth is
D1/n D(o)1/n = Kt
For small initial grain size (D0 = 0)

The value of n and C are independent of time but

vary with composition and temperature. The
value of C increases with increasing the
temperature.
215

Effect of impurities in the form of inclusions

Impurity atoms in the form of second-phase inclusions or particles can inhibit grain growth in
metals.
A spherical inclusion is taken to be present at
the grain boundary and this is also the
minimum energy state for the inclusion and the
grain boundary. If the boundary moves away
from the inclusion, the missing segment of the
boundary (due to the inclusion) has to be
created, which required extra energy.
Suppose the boundary is moved to the right
boundary remains normal to the surface of the
inclusion due to which the boundary takes a
curved shape.
The vector marked denotes the direction and magnitude of the surface tension stress at the
line of contact
The total length of the line of contact between the inclusion and the boundary is
2rcos,
Where is the angle between the equilibrium position of the boundary and the and the
surface where it meets the boundary in the new position, r is the radius of the spherical
216
particle

The product of horizontal component of the

vector sin and the length of the line of
the contact between particle and the
boundary gives the pull of the boundary on
the particle, this force is also the drag force
of the particle on the boundary
Force
This force has maximum value when the =450
Force

Note =

The drag of a single particle varies directly as the radius of the particle
Force by inclusions per unit area of the boundary is
In many cases the second phase
particle tend to dissolve at higher
temperatures. In some other cases
the second phase particle tend to
coalesce at high temperatures and
form fewer large particles. Both
these
effects
removes the
retarding effect of the inclusions
217growth in metals.
on grain

Interphase Interfaces in Solids

A coherent boundary has all the atom sites in
it common to both the crystals joined by it.
There is thus continuity of crystal structure
from one grain to the other (there is one-toone correspondence of atoms at the
boundary). As the grains in the boundary fit
together well, coherent boundaries have low
energies.
The important requirement for the formation
of coherent boundary is that the atoms in the
adjacent crystal must at the common
boundary have closely similar crystal
structure and or the interfacial plane as same
atomic arrangement in both the phases.

(a)

The best-known examples of nearly exact

matching are those involving f.c.c. and h.c.p.
structures with virtually identical interatomic
distances in the octahedral and basal planes
respectively.
218

Within the bulk of each phase every atom has an optimum arrangement of nearest
neighbours that reduces energy. At the interface, however, there is usually a change in
composition so that each atom is partly bonded to wrong neighbours across the interface.
This increases the energy of the interfacial atoms leads to a chemical contribution to the
interfacial energy (ch). For a coherent interface this is the only contribution, i.e.

When the distance between the atoms in the interface is not identical it is still possible to
maintain coherency by straining one or both of the two lattices as illustrated in Fig. The
resultant lattice distortions are known as coherency strains.
219

If dislocations get introduced in the coherent

boundary the resultant boundary is called the
semi-coherent boundary. The presence of
dislocation reduced the total energy of the
system due to the strains associated with a
coherent interface.
If d , and d are the unstressed interplanar
spacings of matching planes in the and
phases respectively, the disregistry. or misfit
between the two lattices () is defined by

It can be shown that in one dimension the lattice misfit can be completely accommodated
without any long-range strain fields by a set of edge dislocations with a spacing D given by
figure.

Where, b = (d + d)/2 is the Burgers vector of the dislocations

220

For example for the above dislocation (a type of misfit), if a = 1.0 , a = 1.2 , then =
20% (i.e. every 5 continuous planes in the phase will take a dislocation to accommodate
the misfit of the two lattice).
If a = 1.0 , a = 1.01 , i.e., no significant difference between the two phase lattice, then
= 1% (i.e. the dislocation density decreases to every 100 planes in the phase, approaching
to the case of coherent interface
If the two phases differ dramatically in lattice, say a = 1.0 , a = 1.5 , then = 50% (i.e.,
now every 2 continuous planes in the phase will take a dislocation, very worse for the two
phases to match or fit, thus falling to the category of incoherent interface.)
The interfaces with intermediate < 25%, usually called semicoherent221
interface.

The interfacial energy of a semicoherent interface can be approximately considered as the

sum of two parts: (a) a chemical contribution, ch, as for a fully coherent interface, and (b)
a structural term st, which is the extra energy due to the structural distortions caused by
the misfit dislocations.
As the misfit increases, the dislocation spacing diminishes. For small values of , the
structural contribution to the interfacial energy is roughly proportional to the density of
the dislocations in the interface: st . owever, st increases less rapidly as
becomes larger and it levels out when 0.25. The reason for such behavior is that as the
misfit dislocation spacing decreases, the associated strain field increasingly overlap and
annual each other.
When the interface plane has a very different
atomic configuration in the two adjacent phases,
there is no possibility of good matching across the
interface. The pattern of atoms may either be very
different in the two phases or, if it is similar, the
interatomic distances may differ by more than
25%. In both cases the interface is defined as
incoherent.
The incoherent phase interface is the analogue of
the high-angle grain boundary. High energy and
non-sensitive to the orientation of the interfacial
plane.

222

Coherent precipitate (shape)

If the precipitate has similar crystal structure and similar lattice
parameter to the parent phase then the two phases can form lowenergy coherent interfaces on all sides.
The plot of the / interface energy would be largely spherical
and ignoring coherency strains the equilibrium shape should be a
sphere sphere

223

Partially coherent precipitate (shape)

Partially coherent precipitates have interfaces with the matrix which are either semi-coherent
and/or incoherent. Such situation arises when the precipitate and matrix have different crystal
structures.
It is usually difficult to find a lattice plane that is common to both phases. Nevertheless, for
certain phase combinations there may be one plane that is more or less identical in each crystal,
and by choosing the correct orientation relationship it is then possible for a low-energy
coherent or semicoherent interface to be formed. There are, however, usually no other planes
of good matching and the precipitate must consequently also be bounded by high-energy
incoherent interfaces.
The Wulff theorem would then predict the equilibrium shape to be a disc with a
thickness/diameter ratio of c/ i where c and i, are the energies of the (semi-) coherent
and incoherent interfaces.

224

Incoherent precipitates (shape)

When the two phases have completely different crystal structures, or when the two
lattices are in a random orientation, it is unlikely that any coherent or semicoherent
interfaces form and the precipitate is said to be incoherent. Since the interfacial
energy should be high for all interfacial planes, the -plot and the equilibrium
inclusion shape will be roughly spherical.
It is possible that certain crystallographic planes of the inclusion lie at cusps in the -plot so
that polyhedral shapes are also possible.

225

Precipitation on the grain boundaries (shape)

Three possibilities; the precipitate can have (i) incoherent interfaces

with both grains, (ii) a coherent or semicoherent interface with one
grain and an incoherent interface with the other, or (iii) it can have a
coherent or semicoherent interface with both grains.
The first two cases are commonly encountered but the third
possibility is unlikely since the very restrictive crystallographic
conditions imposed by coherency with one grain are unlikely to yield
a favorable orientation relationship towards the other grain.
226

Misfit Strain Effect

When misfit is present the formation of coherent interfaces raises

the free energy of the system on account of the elastic strain.
Condition for equilibrium

Elastic strain energy

Aii + Gs = minimum
In order to produce a fully coherent precipitate the matrix and
inclusion must be strained by equal and opposite forces as shown
In the figure.
If the elastic moduli of the matrix and inclusion are equal and
Poissons ratio is 1/3, then the unconstrained misfit () and
constrained misfit () are related as

Where the unconstrained misfit () is given by

Constrained misfit () is given by

Where, a is the new lattice
parameter for the precipitate.

227

In general the total elastic energy depends on the shape and elastic properties
of both matrix and inclusion
Elastic strain energy is given by

Where is the shear modulus of the matrix and V is the volume of the precipitate. Therefore
coherency strains produce an elastic strain energy which is proportional to the volume of the
precipitate and increases as the square of the lattice misfit 2
228

Precipitates with coherent interfaces; low interfacial energy, high coherency strain energy,
Precipitate with non-coherent interfaces; higher interfacial energy, no coherency strain
energy
For fully coherent spherical precipitate

Coherency strain energy

Chemical interfacial energy

For incoherent or semicoherent interfaces

For small r (radius of the precipitate), the coherent

state gives the lowest total energy. while for
larger r, semicoherent or incoherent (depending
on the magnitude of ) state provides lower total
energy
The critical radius for the transition is given by
the condition

229

In a multiphase material when the second

phase forms in an alloy crystal then to get a
coherent interface between the phases, the
crystal structure of both phases have to be
matched. If the size of the precipitate is very
small, it may adopt a crystal structure that
allows it to be coherent with the matrix
crystal , even if for the matching the atomic
bonds of the two crystals structure at the
boundary
produces
considerable elastic
distortion in it and its immediate surrounding.
The lattice constant of one phase increases
and other decreases. GP Zones (Guinier and
Preston)
When such coherent particles grow larger by
obtaining atoms from matrix and crystal
structure changes, it may break away from its
coherent attachment to the matrix in order to
reduce the increasing elastic coherency strains,
and adopt a more stable structure by
introducing dislocations in its interface to
make the interface semi-coherent, which on
further change of the precipitate forms an
incoherent interface.

230

Nucleation
Consider a given volume of liquid at a temperature T below the Tm with a free energy G1. if
some of the atoms of liquid cluster together to form a small sphere of solid then the change in
the free energy of the system to G2 will be given by.

Where Vs is the volume of the solid sphere, VL

the volume of liquid, AsL, is the solid/liquid
interfacial area, Gvs and Gvl are the free energies
per unit volume of solid and liquid respectively.
and sL the solid/liquid interfacial free energy.
Free energy of the system without the solid
is given by
The formation of solid thus results is a free energy
change given by

231

For undercooling T, Gv is given by

Where Lv is the latent heat of

fusion per unit volume.

Below Tm , Gv , is positive so that the free energy change associated with the formation of a
small volume of solid has a negative contribution due to the lower free energy of a bulk solid,
but there is also a positive contribution due to the creation of a solid/liquid interface. If sL is
isotropic then a sphere of radius r forms

Unstable solid particles with r < r* are known

as clusters or embryos while stable particles
with r > r* are referred to as nuclei. r* is known
as the critical nucleus size. dG = 0 when r =
r* the critical nucleus is effectively in
(unstable) equilibrium with the surrounding
Liquid.
The critical radius is given by

232

Substituting the expression for Gv gives

The critical radius becomes smaller

with greater undercooling
The free energy barrier also gets
smaller with greater undercooling
233

Kinetics of Homogeneous Nucleation

The essential driving force for a phase transformation is the difference in the free energies
of the initial and final configurations of the assembly, but when small particles of the new
phase are formed, the free energy rises at first. The increase is due to the considerable
proportion of atoms in these particles which are situated in transition regions between the
phases, where they do not have the environment characteristic of the new phase or the bulk.
The situation is conventionally described by assigning volume free energies to the new bulk
phases, and a surface free energy to the interface region (of the interface between the parent
and the new formed phase) for sufficiently small particles of the new phase, the surface term
is dominant.
For vapour-liquid transformation where there are no strain energies to be considered.
Expression for the variation of the free energy change (Fr) with increase in the radius (r) of
the new phase is given by

Where,

Is the chemical free energy change per atom associated with the transfer
of atoms from the vapour phase to the liquid phase
vl is the volume of an atom in the liquid phase
is the specific surface free energy
r is the radius of the droplet.

234

In terms of number of atoms in the particles (n) the expression for the variation of free
energy change can be written as
Where, is the shape factor given by

vapour is
supersaturated

235

At point c the vapour phase is the stable phase and

is positive. Therefore there is no
tendency for the liquid droplet to continue to grow and to form a stable liquid droplet.

236

At point c the vapour phase is the stable phase and

is
positive. Therefore there is no tendency for the liquid
embryo to continue to grow and to form a stable liquid
droplet.
Heterophase fluctuations however does occur at point c.
Heterophase fluctuations occurring at point c bring a
sufficient number of atoms close enough together so that, in
a small volume, the atoms may tend to arrange themselves in
a structure more characteristic of the liquid phase.
At the point c, the probability of observing an embryo of a given size containing n atoms may
be shown proportional to

Number of particles containing n atoms (Nn) is given by

Where, N is the total number of atoms in the system

T is the temperature
k is the Boltzmann constant
237

At point b, the change in the chemical free energy

per atom, on going from the vapour to liquid phase
is approximately zero. Therefore,

In a stable assembly, embryos varying through a

wide range of sizes can exist. However, this
situation is dynamic. Individual embryos are
constantly growing and shrinking in size as they
either add or loose atoms.
Condition at point a
Here the situation is metastable. The vapour wants to transform to liquid but liquid has to be
nucleated.
In this situation the larger embryos have to grow to form a nucleus, this implies that there is
a constant net rate of particle growth. In the stable state, since the number of embryos of any
particular size is fixed, as many embryos leave a particular class as enter it. In the metastable
state more embryos of a given size class will increase their size by gaining an atom than will
decrease their size by loosing an atom in a given interval of time. The net result is the steady
progression of embryos that increase their size to eventually become nuclei.
238

A nucleus can be considered to be

formed when an embryo of a critical
size captures an additional atom
239

The rate of nucleation would be proportional to the number of critical size embryos, Znc and
the rate of the condensation of vapour atoms on this embryo.
Number of critical size embryos, Znc =
Rate of the condensation of vapour atoms is proportional to (a) the surface area of the
critical sized embryos and (b) the probability per unit area per unit time of a vapor atom
condensing on the surface

Where, I is the number of stable nuclei created per second

N is the total number of atoms in the assembly
Oc is the area of the critical embryos
q0 is the probability per unit time per unit area of capturing a vapour atom
Fc is the free energy change associated with forming an embryo of critical size

240

241

Becker-Doring Theory
The discussion in the preceding slides assume that once a nucleus of a critical size obtains an
additional atom , it always grows into a stable nucleus. This assumption is not strictly true.
The addition of an atom to a critical nucleus will certainly tend to make it more stable.
However, this increase in stability has to be small. This is because, at nc the free energy
reached the maximum and at the same time the dFn/dt passes through zero. Therefore
an embryo that has grown slightly beyond the critical size always has a nearly equal chance
of shrinking back and becoming smaller.
Becker-Doring theory postulates that the
nucleation rate I must equal the difference in
the two rates at which embryos of a given size
containing n atoms grow into embryo
containing n+1 atoms and the inverse rate
corresponding to the reversion of embryos
containing n+1 atoms into those containing n
atoms.
Where, I is the number is nuclei formed per sec per
cm3.
is the rate of conversion of embroys
of size n to n+1, and
is the corresponding
opposite rate.

242

In case of liquid nucleating into vapor the equation may be written as

Where, Zn is the number of embryos containing n atoms,

q0 is the probability per cm2 per sec of an atom jumping from the
vapor to the liquid.
On is the surface area of a droplet containing n atoms
Symbol with a n+1 subscript relate to an embryo containing n+1 atoms that is assumed to
lose an atom
The flux of atom from the embryo to the surrounding should depend on the free energy of the
droplet and thus on its size. The free energy of an atom in the embryo becomes more positive
with increase in size of the particles. This means that the rate of evaporation of atoms from
unit area of the surface of an embryo should increase as it becomes larger. Vice versa at the
critical size..
Becker-Doring Theory provides the following expression for
the nucleation current

243

Freezing
Rate at which
atoms can attach
itself to the embryo

Nucleation rate for freezing can be given by

Number of
critical nuclei

Where, Fc is the free energy change associated with the formation of a critical embryo.
N is the total number of atoms in the assembly.
v is the atomic vibration frequency.
fa is the free energy barrier associated with the jump from the liquid state to the
solid nuclei.
In analogy with the equation for the free energy associated with the formation of a liquid
embryo in a vapour, the expression for Fn is given by

Where, n is the number of atoms in an embryo.

is the free energy difference between an atom in the
liquid and the solid phase.
is the shape factor
is the surface free energy of the liquid-solid boundary
At the freezing point
244

Entropy of fusion/atom

Heat of fusion/atom

T denotes the temperature change measured with respect to the freezing

point and therefore represents the degree of supercooling
Free energy associated with
the formation of nucleus may
now be written as

Nucleation rate
controlled by
jump rate of
atoms

Nucleation rate
controlled by
energy barrier
associated with
formation of an
embryo

At
the melting
temperature the
nucleation rate is
almost zero.
Pure metal; a very
high
degree of
supercooling can
be achieved

The rate of nucleation for freezing

can thus be given by

245

Solid state reactions

In the solid state reaction, the reaction is largely controlled by the diffusion process.
Precipitation of a new phase in a matrix. This situation would occur when solute, present in a
relatively small concentration has to diffuse through the matrix for the embryo grow.
In such situation the nucleation current is given by
Where, A is constant
Qd is the activation energy for the diffusion of the solute
Fnc is the free energy required to form a critical embryo
In condense systems involving solid state reactions strain energy is usually an important
factor. Strain energy opposes the formation of a nucleus. As the strain energy is proportional
to the volume (number of atoms) of an embryo. The total free energy associated with an
embryo becomes

Where fs is the strain free energy per atom

Coherent interfaces have the greatest strain energy.
When the strain energy decreases the surface energy increases - A compromise has to be
246
reached.

Heterogeneous nucleation
For smaller undercooling, the activation energy for
the nucleation can be reduced if the SL can be
reduced

Consider a solid embryo formed on the

mold wall as a spherical cap.
Let us assume that at the position where
the surfaces of the cap make contact with
the mold wall, there exists a state of
equilibrium between the surface forces.
Equation relating the surfaces forces is

lm; surface tension between liquid and mold wall

sm; surface tension between solid and mold wall
ls; surface tension between liquid and solid

247

Equation that would express the free energy of the embryo is given by

Where, Fhet is the free energy associated with the heterogeneously nucleated embryo,
Vc is the volume of the cap shaped embryo
Als is the area of the cap that faces the liquid
Asm is the area of the interface between the embryo and the mould wall
fv is the free energy per unit volume associated with the freezing process
Considering the spherical cap geometry

Substituting the relationships

Where, Vsph and Asph represents the volume and the area of sphere
248 respectively

The free energy to form a nucleus heterogeneously at the mold wall varied directly as the
homogeneous free energy modified by a factor that is a function only of the angle of contact
between the mold wall and the embryo
The angle of contact is determined by the relative surface energies of the three surfaces
(liquid-mold; liquid-solid; and mold-solid). The free energy of the heterogeneous nucleation
is dependent on the three surface energies.
For critical radius rc

There is a large decrease in the free energy for

the formation of a nucleus heterogeneously as
compared to the homogeneous nucleation

249

250

Rate of heterogeneous nucleation

In the case of heterogeneous nucleation the rate of nucleation is given by
Nm is the number of atoms in the liquid phase facing the mold wall (only the atoms in contact
with the mold can form an embryo at the surface)
Nm is very small; rate compensated by the low value of Fhet
The generalized equation for the heterogeneous nucleation rate is given by

Where is a frequency and fa is the free energy associated with the jump of an atom across
the interface between the liquid and solid embryo

251

Growth kinetics
For the growth of beta phase in alpha
phase
In crossing the beta-to-alpha phase
boundary, the atom has to pass over an
energy barrier equal to fa and when it
joins the beta phase it has lower energy
that it has in the alpha phase. The decrease
in the free energy is denoted in the
diagram by f
The net rate of atom transfer from the matrix to the particle is equal to the difference in the
rate of atom movement to and away from the particle

S is the number of atoms facing the surface, is an atomic vibration frequency, and I is the
net number of atoms per second leaving the matrix to join the particle
For an atom movement through a distance the velocity
of the boundary will be given by

252

Combining the equations:

and
The velocity may now be expressed as

For a sufficiently small supercooling we can assume

The growth velocity can be then expressed as

For small undercooling; The growth velocity is proportional to the degree of supercooling;
varies approximately as T (degree of supercooling)-limiting condition
For sufficiently large supercooling
=1

For large supercooling the jump

frequency becomes the limiting
condition

253

Diffusion controlled growth

When the precipitate forming in a matrix has different composition from the matrix
Zeners Theory;
In figure A the cross-hatched region represents the
precipitate after it has grown to a thickness equal to
x.
Figure B is a schematic plot of the concentration of
the solute B as a function of distance in which
concentration is expressed in atoms per cm3.
If the time for an atom to cross the boundary
between the matrix and the precipitate is small
compared to the time for the solute to diffuse
upto the precipitate then the concentration B in
that part of the matrix immediately facing the
beta phase may be assumed to be equal to the
equilibrium concentration. This concentration of
B in the alpha phase that would be in equilibrium
with the beta phase is denoted by n

Because of concentration
gradient
there is a flux of B atoms
towards the interface

Local equilibrium at
the interface

254

Lets assume that in a small time dt the boundary of the precipitate moves forward into the
matrix through a distance dx. Because of this motion
number of atoms of
B have to diffuse upto the interface and cross it. Where, A is the area of the interface.
By Ficks law this flux can be given by

Where, J is the flux or number of atoms (B) crossing the area per second.
D is the composition independent diffusion coefficient
And,
is the concentration gradient of the B component in the matrix at the interface
Equating the two equations

Interface velocity

255

Slope of the inclined straight line is determined by

the fact that the two cross-hatched regions shown
in the diagram should have an equal area.
Equating these areas give

Slope of the straight line concentration gradient is

(substituting into the velocity

equation)
Integration of this differential equation leads to the following relation for the position of the
boundary with time
For one dimensional growth the interface
position varies as (Dt)1/2 and its velocity as
(D/t)1/2
256

According to the Zener theory, the

growth velocity varies inversely
as (time)1/2 .
The rate of boundary migration
decreases with time.
The decrease in the growth
velocity is due to the fact that as
the
particle
grows, its
concentration gradient next to the
particle decreases.

Initial stages of the diffusion controlled growth

With the continued growth the

region of the matrix from where
atoms are being drawn by the
growing
precipitates
starts to
overlap.
This leads to a decrease in the
concentration gradient and thus a
decrease in the driving force.

later stages of the diffusion controlled growth

257

Interface Controlled Growth

Here the growth rate is controlled by the

mechanism that allows the solute atoms to
cross over from the matrix to the
precipitate.
Suppose that the time required for an atom
to jump across an interface is very long
compared to the time required for it to
diffuse to the interface.
In this case, the solute concentration in the
matrix will remain effectively constant
throughout the matrix.
When the interface has lower mobility,
there will be a departure form the local
equilibrium at the interface.
258

If the local concentration around an interface is not the equilibrium one we can write a
velocity equation of the form

Where, is the factor proportional to the jump distance of an atom

is an atomic vibration frequency.

is the free energy difference between a B atom in the alpha and beta phases.
fa is the energy barrier at the interface that a B atom has to pass over in order to
join the precipitate.
From the definition of partial molar free energy

Where,

is the partial molar free energy of B in the alpha phase

is the partial molar free energy of B in the beta phase.
The subscript t signifies that the quantities change with time.
Substituting into velocity equation

259

Where,
is the partial molar free energy of B in the alpha
phase when latter is in equilibrium with the beta phase
If alpha phase is assumed as an ideal solution

Substituting into velocity equation

As the concentration of B in the alpha phase approaches the equilibrium concentration the
above expression can be written as
reaction also varies with time. The time dependence appears
Growth rate in interface controlled
in the term
, which decreases as the solute leaves the matrix

260

Solidification
When a pure crystalline metal melts, practically all its properties change sharply by finite
amount.
Change of rigidity associated with solid to fluidity associated with liquid.
Change in viscosity due to several orders of magnitude faster atomic diffusion in liquids than
in solid.
Increase in volume. Generally 2-6 percent. This small change in volume means that atoms in
liquid, have almost same distance of separation as atoms in solid; the coordination number is
almost identical. But the characteristic of all liquid melts is that all of them have almost same
co-ordination number irrespective of the fact weather the solid metal has close-packed
structure or open structure. (closed pack metals expand and metals of loose packing contract
Ga, Bi)
The latent heat of melting is only about 3-4 percent of the corresponding latent heat of
vaporization (in which the atoms are pulled apart completely). This thus leads to the
conclusion that bonding of atoms in solid and liquid phase are probably similar.
Liquid however, lack extended lattice structure and long range ordered arrangement (because
of the fact that liquid are isotropic) of atoms which are the characteristic of crystalline solids.
Atoms in the liquid are arranges in an ordered manner over short distances but lack long range
261
order.

The short range order in liquid is due to the presence of

increased structural defects like vacancies, interstitial,
dislocations etc. These defects are also responsible for the much
higher atomic diffusion in the liquids. In solids-bonding; liquiddefects)
The faster motion of atoms also results in the typical everchanging structure of liquids. Order of atoms, existing at one
position in space changes continuously with time. Open
structure that allows greater intense thermal motion of atoms
makes the short range order dynamically unstable.
As the temperature of liquid approaches the freezing point, the
degree of short range order increases. The size of clusters of
atoms in which atoms are packed in the same order as in the
solid crystal increases. The larger size clusters may become
nuclei when they attain a definite size.
The X-ray diffraction studies have confirmed the presence of
gaps or holes in liquid. The atoms can move into the holes and
the vacant sites in turn may be occupied by another atoms and so
on. Thus the holes in the liquid structure provides a flow
mechanism in which only a few atoms need to move
simultaneously, and thus provide low energy paths by which
atoms can be displaced. The presence of holes accounts for the
fluidity of the liquids, their low viscosity, grater thermal
expansion, change in density etc.

262

Supercooling for solidification of some elements

It is possible to supercool copper-nickel alloys approximately 3000C at all compositions.

The very large magnitude of the supercooling shown in above are only observed under
controlled experimental conditions designed to prevent the occurrence of heterogeneous
nucleation.
In practical situations the nucleation during freezing is almost always heterogeneous. The
formation of the nuclei is aided by the presence in the liquid melt of accidental impurity
particles, or by the mold surfaces.
263

Although liquid metals are easily supercooled, but, metals donot normally superheat (heated
above the melting point without melting).
If a small quantity of liquid metal forms over the solid
surface, it tries to cover the solid surface to a maximum
possible extent as the liquid metal always wets their own
solid.
Here, the solid-vapour interface is replaced by two
interfaces, solid-liquid interface and liquid-vapour
interface. The process of wetting requires that the surfaces
energies to have the relationships.

Where, gs is the gas-solid interface energy; sl is the solid-liquid interface energy; gl is

the gas-liquid energy interface
Formation of the liquid nucleus decreases the surface free energy of the assembly
There is no surface barrier on melting (reverse of solidification) and thus no superheating is
required, and does not occur. Both terms volume free energy term and the surface free energy
term favor the process of melting
264

Growth of crystal occurs by the thermally activated

jump of atoms from the liquid to the solid phase.
Consider a moving solid-liquid interface. Its
movement can be considered to the resultant
movement of two atomic processes occurring at the
interface;
Solid atom moving to the liquid phase (melting)
and
Liquid atom moving to the solid phase (freezing)
If Gm and Gf are activation energies for an atom
jumping from the solid to liquid phase and from
liquid to solid phase respectively, the former is lager
by the latent heat of fusion as compared to the later,
then

Where, Kf and Km are constants

Depending on weather rate of melting is larger or smaller than the rate of freezing the
interface moves inside the solid or liquid 265

The figure shows both curves for freezing rate and the melting
rate of Cu as a function of temperature. Observations (a) On
either side of the true melting point the curves deviate sharply;
the difference in the individual rates determine the actual rate
with which the interface moves . Which signifies that the
actual growth rate or the melting rate increases as the
temperature deviated from the equilibrium freezing point.

Gap:
entropy and
enthalpy
effect

Constants (Kf and Km) in the rate equation are the

accommodating factor. It is the probability that an atom in a
given phase can find a position to be accommodated on the
otherside of the interface. As the structure of all liquid metals
are similar this accommodation factor for atoms to diffuse
form the solid to the liquid phase is constant being
independent of the chemical nature of the atoms of the liquid.
The accommodation factor for the diffusion of atoms from
liquid to solid depends on the nature of solid and the indices of
the crystallographic planes of the solid nucleus facing the
liquid. The less closely packed the planes, the easier it is for
the liquid atoms to attach themselves to the crystal (bonding is
better).
For a given amount of super cooling there is a difference in the
growth velocity of the different crystallographic planes; the
least closed pack plane grows with grater velocity.

266

The result is that low density plane of fast

growth soon tend to grow themselves out
of existence and the closed packed planes
of low growth rate remains behind. This is
the reason why the final shape assumes
faces that are closed packed.
The growth of the solid demands the
interface to be under-cooled, and the
growth rate is thus a function of the
amount of supercooling of the liquid
ahead of the interface. The growth rate
is also dependent on the nature of
temperature gradient in front of the
interface. There can be two types of the
temperature gradient;
(a) Temperature in the liquid rises ahead of
the interface, that is the positive
temperature gradient.
(b) Temperature falls ahead of the interface,
that is the negative temperature
gradient (temperature inversion).

267

Stable Interface Growth

When the liquid ahead of the solid liquid interface has positive temperature gradient. That
means heat is being lost by its flow from right to left. Latent heat of fusion is being removed
from conduction through the solid. The temperature gradient is linear. Under such condition
smooth interface is stable , which moves into liquid almost as a unit.
The interface may have a steps, some of which have
dense-packed plane and some of them have loosepacked planes. The most advanced portions of the
solid interface correspond to the loose-packed planes
that is high accommodating factor surfaces, while
most retarded correspond to slow growing, that is
low accommodating factor surfaces. As there is
rising temperature ahead of the interface, those
portions which are most advanced are in contact with
hotter liquid than those portions to the rear. But the
rate of growth is also a function of the degree of
undercooling. Thus a fast growing plane is in
contact with hotter liquid, while slow growing plane
is in contact with cooler liquid. When both these
factors balance, an interface is obtained that grows
with a constant speed as it takes a similar shape after
some time.

268

Temperature Inversion and dendritic growth

Dendritic growth occurs when the liquid-solid
interface moves into a liquid whose temperature
falls in advance of the interface. The smooth
interface is then unstable because any part of the
interface that grows ahead of the remainder is in
region of liquid metal at lower temperature, and
therefore more rapid growth. The result is a spike
that grows into the liquid.
The spike remains isolated as the released latent heat
raises the temperature of the immediately
surrounding liquid and thus, retard the formation of
other similar projections on the general interface in
the immediate vicinity of a given spike. Thus a
number of spikes of almost equal spacing are
formed which grow parallel to each other.
These spikes grow in certain crystallographic
direction called dendritic growth direction, which
depends on the crystal structure of the metal.

269

The branches or spikes shown in figure A are first order or

primary in nature. And are called primary arms of the dendrite.
Consider figure B, Once the spikes have formed the growth at
the general interface will be slow because here the
supercooling is small and the latent heat of fusion associated
with the formation of a spike tend to further decrease its
magnitude. At section bb the average temperature of the
liquid is lower than the temperature of the general interface.

At the section bb, at points in the liquid close to the spikes the
temperature will be higher than the midway between the
spikes (Ta>Tb) because of the latent heat released at the spikes.
There is a temperature inversion in direction perpendicular to
the primary arm. This temperature gradient is responsible for
the formation of the secondary braches which form more or
less at regular interval along the primary branch.
The growth direction of the
crystallographically equivalent.

secondary

branches are

270

Pure metal can be supercooled only by the process of thermal supercooling. But to get complete dendritic
freezing in pure metals, a very large supercooling of about 1000C is needed to counteract the effect of
latent heat of fusion released as the dendrites grow, and still maintain a supercool liquid ahead. But it is
difficult to obtain such large thermal supercooling in relatively pure metal in practice as heterogeneous
nucleation takes place in them. Usually only 10 percent of pure metal may solidify dendritically, but by
then the heat of fusion overcomes the thermal supercooling, and the negative temperature gradient
becomes positive temperature gradient. Further solidification occurs by smooth interface growth.

The dentritic fraction in pure metal is given by

Where, C is the specific heat of the liquid

T is the supercooling
Hf is the enthalpy of fusion

271

Interface structure
There are two approaches involved in the description of
the transition from a liquid to a crystal across an
interface;
(a) Atoms are considered to belong to either the crystal or
the liquid and the interface is considered to be sharp.
The geometry of the surface that separates the two
types of atoms may be smooth or meandering on an
atomic scale. The former is called a facetted interface
while the later is called a rough interface. This kind of
interface contains few ledges and jogs
(b) gradual transition in atomic position from the
randomness associated with a liquid to the perfect
registry of the crystal. This later is called a diffuse
interface. This type of interface contains numerous
closely spaced ledges and jogs. This type of interface
has very high accommodation factor.

Rough interfaces migrate by a continuous

growth process while flat interfaces
migrate by a lateral growth process
involving ledges.

272

Solid liquid Interfaces

Type of interface will be the one that
minimizes the interfacial energy.
According to theory by Jackson:
Lf/Tm > 4R : flat interface
Lf/Tm < 4R: diffuse interface
Most metals have diffused interface
Some intermetallic compounds Si, Ge,
Sb as well as most nonmetals have flat
closed packed interfaces

273

To obtain the velocity-supercooling function for continuous growth of single-component

melts, the growth velocity is typically expressed as a product of a factor involving the
thermodynamic driving force for solidification and a kinetic factor involving the
interface mobility:

Where Ti is the interface temperature and G is the Gibbs free energy change per mole
of material solidified (defined to be negative for solidification). The bracketed term
represents a difference between the forward flux ( here, liquid to solid) and the
backward flux (solid to liquid). The kinetic prefactor, Ve(T).
Near equilibrium, the exponential can be expanded, resulting in a linear relation between
velocity and supercooling

Where, is the linear interface kinetic coefficient and is connected to the boundary mobility
274

Lateral Growth
If a single atom leaves the liquid and
attaches itself to the flat solid surface, the
number of broken bonds associated with the
interface, i.e. the interfacial energy, will be
increased. There is therefore little probability
of the atom remaining attached to the solid
and it is likely to jump back into the liquid.
In other words, atomically smooth interfaces
have inherently low accommodation factors.
If the interface contains ledges, liquid atoms
will be able to join the ledges with a much
lower resulting increase in interfacial energy.
If the ledge contains a jog, J, atoms from the
liquid can join the solid without any increase
in the number of broken bonds and the
interfacial
energy
remains unchanged.
Consequently the probability of an atom
remaining attached to the solid at these
positions is much greater than for an atom
joining a facet.
275

Smooth solid/liquid interfaces can therefore be expected to advance by the lateral growth of ledges. Since
the ledges and jogs are a non-equilibrium feature of the interface, growth will be very dependent on how
the ledges and jogs can be supplied. It is thought that there are different ways in which this can be
achieved. These are (i) by repeated surface nucleation, (ii) by spiral growth.

Surface Nucleation
If the interface is atomically smooth and free of any defects, the growth rate is limited by the
nucleation of surface clusters. These clusters must form on the interface in order to create the
necessary surface steps for lateral growth. The lateral spreading rate is assumed to occur quite rapidly
at a speed determined by the continuous growth law
If a sufficiently large number of atoms can come
together to form a disc-shaped layer as shown in
Figure it is possible for the arrangement to become
self-stabilized and continue to grow. The problem of
disc creation is the two-dimensional analogue of
cluster formation during homogeneous nucleation. In
this case the edges of the disc contribute a positive
energy which must be counterbalanced by the
volume free energy released in the process.
There will therefore be a critical radius (r.*) associated with the two-dimensional nucleus which will
decrease with increasing interface undercooling. Once nucleated the disc will spread rapidly over the
surface and the rate of growth normal to the interface will be governed by the surface nucleation
rate.

276
This mechanism is very ineffective at small undercoolings where r* is very large.

The growth law (for the formation of

cylindrical surface clusters) has the form:

Where, V is the growth velocity

e is the ledge energy per unit area
h is the step height
The growth rate is effectively zero at small supercooling
and increases sharply at some critical supercooling. the
constant of proportionality scales with the diffusion
coefficient.

Spiral Growth
If one or more screw dislocations emerge at the SL interface it is not necessary to nucleate new
layers to provide the sites for lateral attachment.
The step generated by each dislocation moves one
plane each time it sweeps around the dislocation
Growth velocity in this case is given by
277

278

280

281

Eutectic solidification
Figure shows how two phases can grow
cooperatively
behind
an
essentially planar
solidification front. As the A-rich phase solidifies
excess B diffuses a short distance laterally where it is
incorporated in the B-rich phase. Similarly the A
atoms rejected ahead of the diffuse to the tips of the
adjacent a lamellae. The rate at which the eutectic
grows will depend on how fast this diffusion can
occur and this in turn will depend on the
interlamellar spacing. Thus small interlamellar
spacings should lead to rapid growth.
For an interlamellar spacing, , there is a total of (2/) m2 of / interface per m3 of
eutectic. Thus the free energy change associated with the solidification of 1 mol of liquid is
given by
where V, is the molar volume of the eutectic and G(infinity) is the free energy decrease for
very large values of .
Since solidification will not take place if G( ) is positive, G(infinity) must be large
enough to compensate for the interfacial energy term, i.e. the eutectic-liquid interface must
282
be undercooled below the equilibrium eutectic temperature T

If the total undercooling is To then

G(infinity) is given approximately by

where H is an enthalpy term. The minimum

possible spacing (*) is obtained by using the
relation G(*) = 0, where,

When the eutectic has this spacing the free energy of the liquid and eutectic is the same, i.e.
all three phases are in equilibrium. This is because the / interface raises the free energies
of the and from
and
to G(*) and G (*). The cause of the increase is
the curvature of the /L and /L interfaces arising from the need to balance the interfacial
tensions at the //L triple point

283

If solidification is to occur at a finite rate there must

be a flux of atoms between the tips of the and
lamellae and this requires a finite composition
difference.
The concentration of B must be higher ahead of the
phase than ahead of the phase so that B rejected
from the can diffuse to the tips of the growing .
If,
= * growth will be infinitely slow because the
liquid in contact with both phases has the same
composition, XE. However if the chosen spacing is
greater than * less free energy is locked in the
interfaces and G and G are correspondingly
reduced. Under these circumstances the liquid in
local equilibrium with the has a composition
which is richer in B than the composition
in equilibrium with the phase
.
There is a net flux of B atoms towards the phase

284

If the /L and /L interfaces are highly mobile it is reasonable to assume that growth is
diffusion controlled in which case the eutectic growth rate (v) should be proportional to the
flux of solute through the liquid. This in turn will vary as D dC/dl where D is the liquid
diffusivity and dC/dl is the concentration gradient driving the diffusion. L is measured along
the direction of diffusion
dC/dl is proportional to the maximum composition difference X =
and
inversely proportional to the effective diffusion distance, which, in turn, will be linearly
related to the interlamellar spacing ().

285

Pure metal can be supercooled only by the process of thermal supercooling. But to get complete dendritic
freezing in pure metals, a very large supercooling of about 1000C is needed to counteract the effect of
latent heat of fusion released as the dendrites grow, and still maintain a supercool liquid ahead. But it is
difficult to obtain such large thermal supercooling in relatively pure metal in practice as heterogeneous
nucleation takes place in them. Usually only 10 percent of pure metal may solidify dendritically, but by
then the heat of fusion overcomes the thermal supercooling, and the negative temperature gradient
becomes positive temperature gradient. Further solidification occurs by smooth interface growth.

The dentritic fraction in pure metal is given by

Where, C is the specific heat of the liquid

T is the supercooling
Hf is the enthalpy of fusion

286

When each solid phase has different crystal structure

287

Constitutional supercooling

Some alloys show supercooling of a

different
kind
called constitutional
supercooling. In this case the solid freezes
with a composition different from the
liquid from which it forms.

288

In most practical situations, liquid metal is poured

into a mold cavity and freezes as a consequence of
heat loss through the mold shell. As a result the
temperature is always lowest at the mold wall
and rises towards the center of the mold.
Solidification accordingly starts at the walls and
proceeds inwards. In this situation the temperature
rises in advance of the liquid-solid interface.
Consider a steady-state solidification at a planar
interface as shown in figure. As a result of the
varying solute concentration ahead of the
solidification front there is a corresponding
variation of the
equilibrium solidification
temperature,
i.e.
the
liquidus temperature
However, apart from the temperature of the
interface which is fixed by the local equilibrium
requirements, the actual temperature of the liquid
can follow any line (TL). At the interface Te = TL
= T3 . If the temperature gradient is less than the
critical value shown in Fig. the liquid in front of
the solidification front exists below its equilibrium
freezing temperature, i.e. it is supercooled. Since
the supercooling arises from compositional, or
constitutional effects it is known as constitutional
supercooling.

TL
Te

Supercooling happens
inspite of the fact that
the temperature
gradient is positive

289

During the steady state growth the concentration

profile in the liquid be such that the rate at which the
solute diffuses down the concentration gradient away
from the interface is balanced by the rate at which
solute is rejected from the solidifying interface.

k = Xs/XL
Where Xs and XL are the mole fractions of solute in the
solid and liquid in equilibrium at any temperature

XL decreases exponentially from X0/k at x=0, the

interface, to X0 at large distances from the interface.
290

If the supercooled layer is large: a dendrite structure develops.

If the supercooled layer is thin then a cellular structure develops
Instabilities at the interface can result in the formation of a surface
composed of more or less oval projections. In order for the
interface to maintain its shape the freezing must occur uniformly
over the entire surface. However, the solid laying on the surface at
the center of the projection (T1), lies at temperature higher than
the cusp (T2). Couples with the temperature difference there is a
difference in the composition of the liquid that freezes at the two
positions.
The liquid that solidifies at the cusp has a higher concentration of
solute than the one which solidifies at the center of the projection.
The result of this freezing process is the formation of cellular
structure in which the cell walls are defined as the region of higher
solute concentration.
The center of each cell is the growing point. The rejection of
solute at such points sets up lateral concentration gradient that
causes the diffusion of solute towards the cell wall. This lowers
the liquidus temperature of the liquid ahead of the cell-walls,
and thus, stabilizes the shape of the surface. The cell wall
contains higher concentration of solute than the cell centers. This
is called microsegregation. As T1>T2 but solute content at T1 is
less than at T2 the freezing occurs uniformly over the entire
surface maintaining its shape.

291

Freezing of ingots
Chill zone: This is a thin layer of frozen metal,
following the contour of the inside of the mold wall,
consisting of very small equiaxed grains, which have
random orientation.

Stable nuclei
form on the
mould wall and
in the layer of
the
supercooled
liquid near the
wall

When the liquid metal is poured into the cold mould, the
liquid near the mould wall is quickly supercooled below
the equilibrium freezing temperature. Stable nuclei form
both in the mould wall and in the supercooled liquid
layer. The rate of nucleation is high, thus average size of
the grain is small. As grains form independently, their
orientation is random.
As large amounts of latent heat of fusion is liberated,
and super heat of liquid metal is also to be dissipated,
rate of growth becomes less. The growth is also limited
by the impinging similar neighboring grains nucleated
at the same time, making their size to be small and
uniform.

Chill zone
forms

If the removal of heat from the surface is very rapid and

the amount of the liquid is small, the chill zone may
form in the whole of the liquid

292

Columnar zone
Very soon after pouring the temperature gradient at the mould
walls decreases and the crystals in the chill zone grow
dendritically in certain crystallographic directions, e.g. (100)
in the case of cubic metals. Those crystals with a (100)
direction close to the direction of heat flow, i.e. perpendicular
to the mould walls, grow fastest and are able to outgrow less
favorably oriented neighbors. This leads to the formation of
the columnar grains with (100) almost parallel to the column
axis.
When the grains in the chill-zone form, the latent heat of
fusion released raises its temperature to change the
temperature distribution from that given in figure A to figure
B. thus there is a temperature inversion just ahead of the
interface. This promotes dendritic growth. The chill zone
grains at the interface shoots out spikes in the super cooled
liquid. Columnar grains begin to form.

In alloys in addition to thermal supercooling, there is

possibility of obtaining constitutional supercooling. If it
occurs, the interface always has a supercooled liquid layer
ahead of it. Columnar crystals grow completely by dendritic
freezing, and thus have a preferred orientation

Just after
pouring

Just after nucleation

in the chill293
zone

Temperature
gradient

Central Equi-axed zone

Central equiaxed zone is not found in pure metal

ingots, it is a phenomenon that is commonly
observed in the freezing of alloys.
Two main reasons have been advanced for the
formation of these equiaxed grains;
(a) The
constitutionally
supercooling layers
overlap in the center of the ingot as the
opposite solid-liquid interfaces approach each
other with their respective supercooled layers.
A large amount of constitutional supercooling
results in there. This causes the independent
nucleation and growth of nuclei.
(b) The initial dendrites formed on the grains of
the chill zone are torn off due to initial
convection currents. These fragments of solid
are swept into the center of the ingot by these
currents, which are nucleating source for the
formation of equiaxed central zone.

The development of the constitutional

supercooled region at the center of an alloy
ingot that produces the central equiaxed
294
zone of the ingot

295

Widmanstatten Morphology

296

Precipitation Growth
Planar interfaces in crystalline solids will usually not be
incoherent. However, one situation where approximately
planar incoherent interfaces may be found is after grain
boundary nucleation. If many incoherent nuclei form on a
grain boundary they might subsequently grow together to
form a slab of precipitate as shown in figure
Since the concentration of solute in the precipitate (C )
is higher than in the bulk (Co) the matrix adjacent to the
precipitate will be depleted of solute. In this case the
growth rate (v) will depend on the concentration
gradient at the interface dC/dx.
For unit area of interface to advance a distance dx a
volume of material 1 . dx must be converted from
containing Ce to containing C moles of B per unit
volume. i.e. (C - Ce)dx moles of B must be supplied by
diffusion through the . The flux of B through unit area
in time dt is given by D(dC/dx)dt. where D is the
interdifusion coefficient (or interstitial diffusion
coefficient). Equating these two quantities gives
297

As the precipitate grows solute must be depleted from the matrix so that dC/dx in the above
equation decreases with time-velocity of the interface decreases with time
If the concentration profile is simplified to that
dC/dx is given by C0/L where Co = Co - Ce . The
width of the diffusion zone L can be obtained by
noting that the conservation of solute requires the
two shaded areas in Figure to be equal

The growth rate is then given by

Ce is the concentration of B
in the phase in equilibrium
with the phase
If the concentration is replace by mole fraction (X=CVm) and (C C0) ~ (C Ce) then
and
298
where X0 = X0 - Xe (the supersaturation in prior to precipitation).

Precipitate thickening
obeys a parabolic growth
law

for a given time the growth

rate is proportional to the
supersaturation.
Undercooling

Supersaturation

Growth rate are low at small

undercooling due to small
supersaturation

Growth rate is low at large

undercooling due to slow diffusion

299

With continued growth of precipitate the concentration gradient with decrease and the growth
would stop when the matrix concentration is Xe everywhere
Overlapping
diffusion fields

Growth of grain boundary precipitates

Volume diffusion of
solute to the grain
boundary

Diffusion of solute along the

grain boundary

Diffusion along the / interfaces

allowing accelerated thickening

The growth of isolated

grain boundary precipitates
occur at a rate that is far
greater than the volume
diffusion
This mechanism is of greatest significance when substitutional diffusion is involved. In the case of interstitial
300
solutions diffusion short circuits are comparatively unimportant due to the high volume diffusion rates.

Diffusion-Controlled Lengthening of Plates or Needles

precipitate is a plate of constant thickness
having a cylindrically curved incoherent edge
of radius r.
Due to the Gibbs-Thomson effect, the
equilibrium concentration in the matrix
adjacent to the edge will be increased to Cr
The concentration gradient available to drive
diffusion to the advancing edge is reduced to
C/L where C = C0 - Cr and L is a
characteristic diffusion distance.
The precipitate lengthening rate in such cases is given by

L is given by kr where k is a
numerical constant.
The composition difference available to drive
diffusion will depend on the tip radius (r)

301

Where X = X0 - Xr, X0 = Xo - Xe,

and r* is the critical radius; the value
of r required to reduce X to zero.
Again,
assuming
constant molar
volume;

For a given plate thickness the lengthening

rate should be constant, i.e. x is proportional to t (linear
growth).
Thickening of plate like precipitates

u is the rate of
lateral migration

The rate of lateral migration

Rate of growth

Consider a plate like precipitate that is thickening by

the lateral movement of linear ledges of constant
spacing and height h

The necessary composition changes required for

precipitate growth must be achieved by longrange diffusion to and from the ledges.
The rate at which plates thicken will be
inversely proportional to the inter-ledge
spacing .
302

Thickening of a plate in an Al-15 wt% Ag alloy at 4000C

303

Time Temperature Transformation (TTT) diagrams

TTT diagrams depicts the progress of an isothermal phase transformation. TTT diagrams
represent the fraction transformed (f) as a function of time and temperature.
For transformations of the type to , f is the
volume fraction of at any time. For precipitation
reactions
+ , f can be defined as the
volume of at time t divided by the final volume
of . In both cases f varies from 0 to 1 from the
beginning to the end of the transformation.
Factors that determine f ( t , T) are
The nucleation rate.
The growth rate.
The density and distribution of nucleation
sites.
Overlap of diffusion fields.
The impingement of adjacent transformed
volumes.

304

f dependent on rate of
nucleation and rate of growth

Nuclei form throughout the transformation

f depends on number of
nucleation sites and growth
rate
Nuclei form right at the beginning of the transformation

f depends on the
impingement of adjacent
growing (with constant
velocity) cells
305

Rate
of
transformation is
practically nil at T1; as two phases
are in thermodynamic equilibrium
with each other. The free energies
are equal.
As the temperature falls, the rate
increases first and reaches a
maximum because the free energy
change
increases
as the
undercooling increases. This also
increases the rate of nucleation
because the critical nucleus size
decreases.
The
rate of
transformation is maximum at the
nose of the curve.
The rate decreases further as the
undercooling
increases, because
diffusion becomes sluggish as the
temperature becomes too low. The
rate of diffusion is exponential
function of temperature

Regions in a TTT diagram

Equilibrium transformation temperature
Transformation starts
Transformation ends

Growth dominated
Nucleation
dominated

Existence of a nose: competing mechanism.

High T favorable to diffusion > growth
Dominated.
Low T favors nucleation as the driving force
(difference in free energy G) is large.
306

Consider a cellular transformation ( to ) in which cells are continuously nucleated

throughout the transformation at a constant rate N. If the cells grow as spheres at a constant
rate v, the volume of a cell nucleated at time zero will be given by

A cell which does not nucleate until time

will have a volume

In a homogeneous reaction, the probability of

any small region transforming in a given time
interval will be the same in all parts of the
untransformed volume. The volume transforming
in a short time interval will thus be proportional
to the volume remaining untransformed at the
beginning of this interval; first-order rate
process.

The number of nuclei that formed in a time increment of d will be Nd per unit volume of
untransformed . Thus if the particles do not impinge on one another, for a unit total volume

This equation will only be valid for f << 1. As time passes the cells will eventually
impinge on one another and the rate of transformation will decrease
307 again.

The equation valid for randomly distributed nuclei for both long and short times is
Johnson-Mehl-Avrami equation
For short times;1 - exp ( - z ) = z when z << 1.
For long times since as t tends to infinity, f tends to 1.
In general, depending on the assumptions made regarding the nucleation and growth
processes. a variety of similar equations can be obtained with the form

Where n is a numerical exponent whose value can vary from 1 to 4. k, depends on the
nucleation and growth rates and is therefore very sensitive to temperature.

308

For nucleation and growth reactions, consider first the size of an individual transformed
region. The region is formed at a time t = ( may be called the induction period).
If the transformation product has the same
composition as the original phase, it is found
experimentally that in nearly all reactions any
dimension of the transformed region is a linear
function of time.
The reduction of growth rate when t becomes
large is due to the mutual impingement of
regions transforming from separate nuclei,
which must ultimately interfere with each
other's growth.
The intercept on the time axis, which gives the induction period for nucleation of the region,
naturally cannot be observed experimentally, and is inferred by extrapolating back the linear
portion of the curve. In most transformations, this procedure probably represents the actual
way in which the regions form, but in some cases alternative extrapolations, such as that
shown to zero time, may be more correct. Such a curve implies that stable nuclei of the new
phase are already present in the assembly at the beginning of the transformation, but that the
initial growth rate is an increasing function of the time.
309

Continuous cooling transformation (CCT) diagrams

Practical heat treatments, however, are usually concerned with

transformations that during continuous cooling, and under these
conditions TTT diagrams cannot be used to give the times and
temperatures of the various transformations. A continuous cooling
transformation (CCT) diagram must be used instead.
The CCT diagram is the TTT diagram shifted to lower
temperatures and longer times.

In a specimen held at a constant temperature the transformation starts when the product (Nt) reaches a
certain value, , say (N is the nucleation rate and t is the time at a particular temperature). In a
continuously cooled sample, time near the start of cooling is not very effective since N is low at low
supercoolings. Therefore when the cooling curve reaches the TTT start curve the total value of Nt will be
less than and further time (and therefore cooling) will be required before the start of the CCT diagram
is reached. Similarly the end of the reaction will be displaced to lower temperatures and longer times.
Note that whereas the TTT diagram is interpreted by reading from left to right at a constant temperature
the CCT diagram is read along the cooling curves from the top left to bottom right.

310

Activation Energy for Transformation Onset

It has been reported that for a first order transformation, an Arrhenius plot can be created
for the transformation onset incubation period as a function of the annealing
temperature T according to the following equation:

where t0 is a pre-exponential factor, En is the

activation energy for the nucleation of a new
phase, and R is the gas constant.
A linear fitting of the ln () versus (1/T) plot
provides the slope En/R and the intercept
ln (t0) values.
311

GP Zones

Alloy heated to ~5400C;

all Cu will be in solid
solution fcc phase

Alloy composition taken

Tx

Alloy quenched in water; the alloy is

now a solid solution supersaturated with
Cu and there is a driving force for
precipitation of the equilibrium CuAl2
phase

The alloy is now aged by holding for a period of time at room temperature or some other
temperature below about Tx
312

The first precipitate to nucleate is not but coherent Cu-rich GP zones.

GP zones are fully coherent with the matrix and therefore have a very low interfacial energy,
whereas the phase has a complex tetragonal crystal structure which can only form with
high-energy incoherent interfaces.

The zone minimizes their strain energy by choosing a disc shape perpendicular to the
Elastically soft <100> direction in the fcc matrix
313

2 atomic layers thick, ~10 nm in

diameter and ~ 10 nm in spacing
314

Microstructure depending upon the extent of misfit

Al-4.4 % Ag

Al-1.7 % Cu

315

The first precipitate to nucleate is not but

coherent Cu-rich GP zones.
GP zones are fully coherent with the matrix and
therefore have a very low interfacial energy,
whereas the phase has a complex tetragonal
crystal structure which can only form with highenergy incoherent interfaces.
Therefore, despite the fact that the driving force
for precipitation of GP zones (Gv - Gs) is less
than for the equilibrium phase, the barrier to
nucleation ( G*) is still less, and the zones
nucleate most rapidly.
The formation of GP zones is usually followed by
the precipitation of so called transition phases. In
the case of A1-Cu alloys the equilibrium phase is
preceded by " and '. The total precipitation
process can be written

Where 0 is the original supersaturated solid solution, 1,

is the composition of the matrix in equilibrium with GP
zones. 2, the composition in equilibrium with " etc.

316

Transition phases form because, like GP zones, they have a lower activation energy barrier for
nucleation than the equilibrium phase. The free energy of the alloy therefore decreases more
rapidly via the transition phases than by direct transformation to the equilibrium phase.
The lower activation energy barriers are achieved because the crystal structures
of the transition phases are intermediate between those of the matrix and the equilibrium
phase. In this way the transition phases can achieve a high degree of coherence and thus a
low interfacial energy contribution to G*. The equilibrium phase on the other hand usually
317G*
has a complex crystal structure results in high-energy interfaces and high

318

319

320

Spinodal Decomposition
In case of spinodal decomposition there is no barrier to nucleation
The free-energy charge is negative for an arbitrarily
small fluctuation in composition such that one part of
the system gets more concentrated at the expense of
another. The system is inherently unstable and phase
separation will proceed

The system is ``stable'' with

respect to small fluctuations. In
other words, it is metastable
with respect to infinitesimal
composition fluctuations.

Spinodal decomposition occurs when

321

Alloys between the spinodal points

are unstable and can decompose into
two coherent phases 1 and 2
without overcoming the activation
energy barrier. Alloys between the
coherent miscibility gaps and the
spinodal are metastable and can
decompose only after nucleation of
the other phases.
In side the chemical spinodal, a
continued decrease in the free
energy can happen if A rich and B
rich precipitates can form from the
up-hill diffusion process.
MA = mobility
If A/ CA > 0 then the di usion coe
cient is positive and the chemical potential
gradient is along the same direction as the
concentration
gradient.
However, if
A/CA < 0 then the diffusion coefficient
is negative di usion will occur against a
322
concentration gradient.

Up-hill diffusion process

A(1) > A(2) ,

Therefore A
atoms move
from 1 to 2
B(2) > B(1) ,
Therefore B
atoms move
from 2 to 1

323

The rate of transformation can

be increased by making
(wave
length of
compositional fluctuation)
as
small
as possible.
However
there
is a
minimum value of below
which spinodal
decomposition cannot
occur.
This value of depends upon
two important factors
(a)Interfacial energy effect
(b)Coherency strain energy
effect.
324

Wavelength of composition fluctuation

For decomposition of homogenous alloy of composition X0 into two parts of composition
X0-X and X0+X. The chemical free energy change is given by:

During the early stages of spinodal decomposition. The interface between A-rich and B-rich
regions is not sharp but very diffuse, there is still an effective interfacial energy contribution.
The magnitude of the interfacial energy depends on the composition gradient across the
interface ('gradient energy).
In solid solutions which tend to cluster the energy of like atom-pairs is less than that of unlike
pairs. Thus the origin of the gradient energy is the increased number of unlike nearest
neighbors in a solution containing composition gradients compared to a homogeneous solution.
For a sinusoidal composition modulation of wavelength and amplitude X the maximum
composition gradient is proportional to (X/) and the gradient energy term G , is given
by
Where K is a proportionality constant
dependent on the difference in the bond
energies of like and unlike atom pairs.
325

As the sizes of the atoms making up the solid solution are different, the generation of
composition differences will introduce a coherency strain energy term, Gs. If the misfit
between the A-rich and B-rich regions is , Gs = E2 where E is Young's modulus.
For a total composition difference X, will be given by (da/dX) X/a, where a is the
lattice parameter. An exact treatment of the elastic strain energy shows that

is the fractional change in lattice parameter per unit composition change. E' = E/(1 - v),
where v is Poisson's ratio, and Vm, is the molar volume.
Total free energy change accompanying the formation of a composition fluctuation

The condition for a homogeneous solid solution

to be unstable and decompose spinodally is
326

Thus the limits of temperature and composition

within which spinodal decomposition is
possible are given by the conditions

The line in the phase diagram defined by this

condition is known as the coherent spinodal
and it lies entirely within the chemical spinodal
Schematic phase diagram for a clustering system. Region 1:
homogeneous and stable. Region 2: homogeneous a
metastable, only incoherent phases can nucleate. Region 3:
homogeneous a metastable. coherent phases can nucleate.
Region 4:homogeneous a unstable , no nucleation barrier,
spinodal decomposition occurs.

The wavelength of the composition modulations that can develop inside the coherent spinodal
must satisfy the condition
minimum possible wavelength decreases with increasing undercooling
below the coherent spinodal.
327

Eutectoid transformations
Austenite

Ferrite

Cementite

At small undercoolings below A1 the number of

pearlite nodules that nucleate is relatively small, and
the nodules can grow as hemispheres or spheres
without interfering with each other. At larger
undercoolings the nucleation rate is much higher and
site saturation occurs, that is all boundaries become
quickly covered with nodules which grow together
forming layers of pearlite outlining the prior austenite
grain boundaries

Austenite surrounding the cementite nucleus gets depleted in C; driving force for the formation of
ferrite increases
Nucleation and growth of pearlite. (a) On a grain boundary (i) Cementite nucleates on grain boundary
with coherent interface and orientation relationship with 1, and incoherent interface with 2 ( ii )
nucleates adjacent to cementite also with a orientation relationship with 1(This also produces an
orientation relationship between the cementite and ferrite.), (iii)The nucleation process repeats sideways.
while incoherent interfaces grow into 2 (iv) New plates can also form by a branching mechanism.

329

Presence of proeutectic cementite

If the alloy composition does not perfectly correspond to the eutectoid composition the grain
boundaries may already be covered with a proeutectoid ferrite or cementite phase. If, for example.
the grain boundary already contains a laver of cementite. the first ferrite nucleus will form with
an orientation relationship to this cementite on the mobile incoherent side of the
Allotriomorphs. Again due to the higher mobility of the incoherent interfaces the pearlite will
grow into the austenite with which there is no orientation relationship.
Whatever the pearlite nucleation mechanism. new cementite lamellae
are able to form by the branching of a single lamella into two new
lamellae. The resultant pearlite colony is effectively two
Interpenetrating single crystals.

331

Bainitic Transformation
Bainite forms when austenite is cooled to large supersaturation
below the nose of the pearlite transformation curve

Bainite is a mixture of ferrite and carbide.

332

Microstructure of Bainite depends on the temperature at which it

forms
Upper Bainite: forms at higher temperature 350C to 550C

Undercooling is large so nucleation

happens at several sites and ferrite
plates are fine.
Lath thickens. Carbon content of
austenite
increases. Cementite
nucleates and333
grows

Lower Bainite : Transformation at low temperatures. Transformation temperature depends on the

carbon content.
Carbide precipitates in ferrite with an orientation relationship. The carbide is either cementite or
metastable transition carbides such as -carbide (hexagonal, 8.4 %C).
The carbides are aligned at approximately same angle to the ferrite plate.

334

335

Massive Transformations-diffusion-less civilian transformation

If the parent phase by cooling is brought into the one phase field of the new phase, no longrange diffusion will be required and the transformation could turn composition invariant. The
thermodynamic conditions for a composition invariant transformation may even be fulfilled
already when the parent phase is cooled below T0, the temperature of equal Gibbs energy for
the two phases.
The condition that must be satisfied for a massive transformation is that
(a) The free energy of the new phase must be lower than the parent phase
(b) Both phases having the same composition.
Massive a grains nucleate at grain boundaries and grow rapidly into the Surrounding . Note
also that because of the rapid growth the / boundaries have a characteristic irregular
appearance. Since both the and phases have the same composition, massive can grow as
fast as the A and B atoms can cross the / interface, without the need for long-range
diffusion.
The massive transformation is sometimes described as diffusional. However, it should be
emphasized that then one does not refer to the intermixture of different species, which would
result in local changes in composition. Instead, one refers to a mechanism of migration of the
interface, sometimes described as atomic jump across the interface

337

338

Diffusionless transformation

Martensitic transformation is a term used in physical metallurgy to

describe any diffusionless transformation. Any transformation in which
from start to completion of the transformation individual atomic
movements are less than one interatomic spacing.
The phase change that occurs in the martensitic transformation is
brought about by the movement of interface separating parent phase
from the product phase. As the interface moves, atoms in the lattice
structure of the parent phase are realinged into the lattice of the
martensite phase.
As the atomic interchange does not play a significant role in the
mechanism of transformation, the martensite phase has the same
chemical composition as the parent phase. The absence of atomic
interchange is confirmed by the growth of martensite at very low
temperatures.
339

340

341

The atomic realignments associated with martensitic reaction produces a shape deformation . The
new lattice that is formed has symmetry different from the parent phase.
The habit plane or the plane on which the martensite forms is an undistorted plane. The
macroscopic shape deformation in the formation of the martensite plane is believed to be a shear
parallel to the habit plane plus a uniaxial tensile or compressive strain perpendicular to the habit
plane. A strain of this nature , known as an invariant plane strain, is the most general that can
occur still maintaining the invariance of the habit plane.
A fine-scale inhomogeneity in the martensite, such as slip, twinning or faulting, is usually
observed at the electron microscope scale. This secondary deformation, an intrinsic part of the
transformation process, produces the invariant-plane condition at the macroscopic scale and
provides a semi-coherent glissile interface between the martensite and the parent phase.
The martensitic phase is
often in shape of a lens and
spans initially an entire
grain
diameter. The
density of plates does not
appear to be a function of
the grain size of the
austenite. For example it is
observed to form randomly
throughout a sample with a
plate
density which
appears to be independent
of grain size.

342

Diusionless Character

Martensite can form at very low temperatures, where di

usion, even of interstitial atoms, is not conceivable over
the time period of the experiment.
Martensite plates can grow at speeds which approach that
of sound in the metal.
The chemical composition of martensite can be measured
and shown to be identical to that of the parent austenite.
The
totality
of
these
observations demonstrate
convincingly that martensitic transformations are di
usionless.
Athermal Nature of Transformation

In the vast majority of cases, the extent of reaction is found to be virtually independent
of time:

V is the fraction of martensite and T is a temperature below MS This is

the Koistinen and Marburger equation; notice that time does not feature
in this relation, so that the fraction of martensite depends only on the
undercooling below the martensitestart temperature. 343

Thermodynamics of Martensitic Transformations

Martensite is not represented on phase diagrams because the latter deal with equilibrium. Martensite deviates
from equilibrium in two important ways:
Martensite grows without di usion, so it inherits the chemical composition of the parent austenite. In an
equilibrium transformation the chemical elements partition into the parent and product phases in a manner
which leads to a minimization of free energy.
The shape deformation associated with martensitic transformation causes strains; the resulting strain energy
has to be accounted for before the transformation can happen.

The distance ac represents the free energy decrease

when austenite of composition x decomposes into an
equilibrium mixture of ferrite and austenite of
compositions x and x respectively. The distance
ab is the smaller decrease in free energy when
martensite forms without any composition change,
taking into account the strain associated with the
transformation.

344

The first plates form at the ;MS (martensite start) temperature. This
temperature is associated with a certain driving force for the
diffusionless transformation of into .
The Mf temperature (martensite finish) corresponds to that temperature
below which further cooling does not increase the amount of martensite.
In practice the Mf may not correspond to 100% martensite, and some
retained austenite can be left even below Mf. The retention of austenite
in such cases may be due to the high elastic stresses between the last
martensite plates to form, which tend to suppress further growth or
thickening of existing plates.
Athermal Transformation: Ms and Mf temperatures start from the yaxis of the TTT curve, indicating the absence of incubation period for
this transformation. This transformation in still occurs normally
athermally.
The driving force for the nucleation of martensite at the Ms
temperature is given by:

345

In the Martensitic transformation the shape deformation

resembles a simple shear, but in general is better described
as an invariant-plane strain in which one plane is left
undistorted and unrotated; this invariant plane is also known
as the habit plane.
An invariant-plane strain is a homogeneous distortion such
that the displacement of any point is in a common direction.
The magnitude of the displacement is proportional to the
distance from a fixed plane of reference, which is the
invariant-plane (itself unaffected by the strain). In most
martensitic
transformations
a
volume change
accompanies the structural change which produces a
normal component to the invariant-plane strain.
A shear parallel to
the habit plane or an
extension or
contraction
perpendicular to it
cannot change the
positions or
magnitude of vectors
lying in the plane

An
invariant-plane
strain
characteristic of
martensitic transformation. The initially straight line
DE is displaced to the position DF when the
martensite plate with habit plane ABC is formed. The
plane ABC is invariant (unmtated and undistorted) as
a result of the formation of martensite. (b) An
illustration of the difference between a simple. shear
and a general invariant-plane strain. s is the shear
component of the strain and the dilatational
component of strain. The dilatational strain defines
the volume change of transformation.

346

The passage of a slip dislocation through a crystal causes the

formation of a step where the glide plane intersects the free surface
(Figure). The passage of many such dislocations on parallel slip
planes causes macroscopic shear (Figure). Slip causes a change in
shape but not a change in the crystal structure, because the Burgers
vectors of the dislocations are also lattice vectors. 347

Structure of the Martensite ()-Matrix () Interface

Any process which contributes to the formation of martensite cannot rely on assistance from
thermal activation. There must therefore exist a high level of continuity across the interface, which
must be semicoherent.
A semicoherent interface must be such that the interfacial dislocations can glide as the interface
moves (climb is not permitted). It follows that the Burgers vectors of the interface dislocations must
not lie in the interface plane.
There is an additional condition for a semicoherent interface to be glissile. The line vectors of the
interfacial dislocations must lie along an invariantline, i.e. a line which joins the parent and product
crystals without any rotation or distortion. If there is any distortion along the dislocation line, then
other dislocations are needed to accommodate that mist. It will then be necessary to have more
than one set of non parallel dislocations in the interface. These non parallel dislocations can
intersect to form jogs which render the interface sessile.
It follows that for martensitic transformation to be possible, the deformation which changes the
parent into the product must leave one or more lines invariant (unrotated, undistorted). A
deformation which leaves one line invariant is called an invariantline strain.
In view of the very high speeds of growth, it has been conjectured that the Interface between
austenite and martensite must be a glissile semi-coherent boundary consisting of a set of parallel
dislocations with Burgers vector common to both phases, i.e. transformation dislocations. The
motion of the dislocations brings about the required invariant shear transformation.

348

Bain Model
This model demonstrates how the bcc lattice can be obtained from the fcc structure with the
minimum of atomic movement, and the minimum of strain in the parent lattice. According to
the Bain distortion, a tetragonal unit could be outlined within the two unit cell of the austenite.
The tetragonal unit cell can then undergo distortion in X-Y and Z direction to produce a BCT
unit cell with out the movement of any atoms.

Results in lower principle distortion

Results in much higher

349 principle distortion

From the lattice Correspondence shown in figure one

would expect for example,
[001]M parallel to [001]P
[010]M parallel to [110]p
(121)M parallel to (101)P
(011)M parallel to (111)P
However, such exact parallelisms are not observed.
For the Fe-Pt alloy, the following orientation
relationship was observed:

The correspondence cell is not only distorted according to the Bain strain, but also is rotated. This is termed a
rigid body rotation. The combined distortion-rotation is known as the lattice deformation.

The Bain strain correctly transforms the crystal structure of the austenite into that of
martensite, and when combined with an appropriate rigid body rotation leads to the
correct orientation relationship. In fact, the combined lattice deformation (Bain +
rotation) is an invariant-line strain which leaves a single line unrotated and
undistorted. This line lies in the interface between the austenite and martensite, and
permits the interfacial structure to be semi-coherent and glissile. Hence, two crystals
can only transform into one another by a martensitic mechanism if they can be
350
related by a lattice deformation which is at the very least an invariant-line
strain.

The austenite is represented as a sphere which, as a result of the Bain strain B, is deformed
into an ellipsoid of revolution which represents the martensite. There are no lines which are left
undistorted or unrotated by B. There are no lines in the (0 0 1) f cc plane which are undistorted.
The lines wx and yz are undistorted but are rotated to the new positions w x and y z such
rotated lines are not invariant. However, the combined eect of the Bain strain B and the rigid
body rotation R is indeed an invariant line strain (ILS) because it brings yz and y z into
coincidence. This is the reason why the observed orientation relationship di ers from that
implied by the Bain strain. The rotation required to convert B into an ILS precisely corrects the
Bain orientation into that which is observed experimentally.

As can be seen from Figure, there is no rotation which can make B into an
invariantplane strain since this would require two nonparallel invariantlines. Thus,
for the fcc bcc transformation, austenite cannot be transformed into martensite by
a homogeneous strain which is an IPS. And yet, the observed shape deformation
351
leaves the habit plane undistorted and unrotated, i.e. it is an invariantplane
strain.

The Bain strain converts the structure of the parent phase into that of the product phase. When
combined with an appropriate rigid body rotation, the net homogeneous lattice deformation RB is
an invariant line strain (step a to c in Figure). However, the observed shape deformation is an
invariant plane strain P1 (step a to b in Figure), but this gives the wrong crystal structure. If a
second homogeneous shear P2 is combined with P1 (step b to c), then the correct structure is
obtained but the wrong shape
These discrepancies are all resolved if the shape changing e ect of P2 is cancelled macroscopically by an
latticeinvariant deformation, which may be slip or twinning.
The theory explains all the observed features of
the martensite crystallography. The orientation
relationship is predicted by deducing the
rotation needed to change the Bain strain into
an invariant line strain. The habit plane does
not have rational indices because the amount
of lattice invariant deformation needed to
recover the correct macroscopic shape is not
usually rational. The theory predicts a
substructure in plates of martensite (either
twins or slip steps) as is observed
experimentally. The transformation goes to all
the trouble of ensuring that the shape
deformation
is
macroscopically an
invariantplane strain because this reduces the
strain energy when compared with the case
where the shape deformation might be an
invariantline strain

P1

P2

352

Twins in martensite
By using the sphere + ellipsoid transformation we can test whether the Bain deformation also
represents a pure deformation in which there is an undeformed (invariant) plane

353

Formation of coherent nuclei of martensite

The total increase in Gibbs free energy associated with the formation of a fully coherent
inclusion of martensite in a matrix of austenite can be expressed as:

Where, is the interfacial free energy

Gs is the strain energy
Gv is the volume free energy release
V is the volume of the nucleus
A is the surface area.

For a thin ellipsoid nucleus, with radius a, semithickness c and volume V. If the nucleation occurs
by simple shear, s, parallel to the plain of the disc
and complete coherency is maintained at the
interface, then

354

Where, is the coherent interfacial energy of the coherent nucleus

is the Poissons ratio
is the shear modulus of the austenite.
For = 1/3, equation can be written as

The negative term G, is the free energy difference at the Ms temperature between the austenite and
martensite phases. The middle term referring to the strain energy, is due to the shear component of strain
only and neglects the small additional strain due to the dilatation which is assumed to occur normal to the
disc.
The minimum free energy barrier to nucleation is now found by differentiating equation with respect to a
and c, and by subsequent substitution we obtain:

355

This expression is thus the nucleation barrier to be overcome by thermal fluctuations of atoms if classical,
homogeneous nucleation is assumed. It is seen that the energy barrier is extremely sensitive to the values
chosen for , G, and s. The critical nucleus size (c* and a*) is also highly dependent upon these
parameters. It can be shown that:

and

If homogenous nucleation only is taken into account then the value of G* is too large for the
thermal fluctuation alone to provide. This indicates that the martensitic nucleation is a
heterogeneous process.

356