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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.
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Effect of Pressure
Different trends
If two phases in equilibrium are and , then for one mole of each
phase
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.
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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
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Binary Solution
Gibbs Free energy of a binary solution can be calculated in the
following way
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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.
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G1 = H1-TS1
G2 = H2 TS2
Hmix =H2 H1
Smix = S2 S1
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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)
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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,
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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
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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
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bond energies.
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Activity
Ideal Solution
Regular Solution
A = GA + RTlnXA
B = GB + RTlnXB
A = GA + RTlnaA
B = GB + RTlnaB
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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.
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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.
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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.
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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.
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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.
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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
11 + s
s1 + s3
1 + s2 .
s1
(ii) Syntectics in which =liquid1, =solid, =liquid2. The syntectic reaction is 11 +12
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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.
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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.
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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
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(point B) at the center.
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Chemical
potential
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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.
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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.
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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".
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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.
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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.
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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.
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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
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in the (L+ ) region (called pro-eutectic ); and the ner (called eutectic ) in the eutectic microstructure.
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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.
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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.
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.
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Intermediate phases
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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
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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.
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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.
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Order-disorder transformations
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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
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At temperature T1
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 .
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Gibbs-Thompson Effect
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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
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for dilute
solutions or
solutions which
obey Henry's law
R
R
is constant
A=O
;
For dilute solution of B in A
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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.
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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
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
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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
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
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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.
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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,
example
(111) Ag50Ni50
0.220 nm
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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.
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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.
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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
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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.
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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.
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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
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
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
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.
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.
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
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
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
We obtain
and
145
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
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
151
152
constant
Marker velocity is given by
= k/2x
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.
The molar free energy of the crystal containing Xv mol of vacancies is therefore given by
155
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.
157
Combining equations
QSD = Hm + Hv
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
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
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
166
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
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
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).
173
Duplex Microstructure
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
177
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
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
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)
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
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.
186
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
189
190
191
192
This relation ship can be used to derive the energy of the low angle
grain boundary as dependent on the angle of misorientation.
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
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,
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
201
202
203
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
205
206
207
208
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
209
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,
212
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)
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
(a)
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
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.
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.
222
223
224
225
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
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
229
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.
231
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
232
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
236
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
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
243
Freezing
Rate at which
atoms can attach
itself to the embryo
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
Entropy of fusion/atom
Heat of fusion/atom
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
245
Heterogeneous nucleation
For smaller undercooling, the activation energy for
the nucleation can be reduced if the SL can be
reduced
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
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
249
250
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
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
253
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
257
If the local concentration around an interface is not the equilibrium one we can write a
velocity equation of the form
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,
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
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.
262
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.
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
266
267
268
269
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.
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.
272
273
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.
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
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
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.
286
287
Constitutional supercooling
288
TL
Te
Supercooling happens
inspite of the fact that
the temperature
gradient is positive
289
k = Xs/XL
Where Xs and XL are the mole fractions of solute in the
solid and liquid in equilibrium at any temperature
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
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.
Just after
pouring
Temperature
gradient
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
Precipitate thickening
obeys a parabolic growth
law
Supersaturation
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
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
u is the rate of
lateral migration
Rate of growth
304
f dependent on rate of
nucleation and rate of growth
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
Growth dominated
Nucleation
dominated
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
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
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:
GP Zones
The alloy is now aged by holding for a period of time at room temperature or some other
temperature below about Tx
312
The zone minimizes their strain energy by choosing a disc shape perpendicular to the
Elastically soft <100> direction in the fcc matrix
313
Al-4.4 % Ag
Al-1.7 % Cu
315
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
321
323
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 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
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
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
334
335
337
338
Diffusionless transformation
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
In the vast majority of cases, the extent of reaction is found to be virtually independent
of time:
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
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
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.
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
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
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