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Thermodynamics of Materials

Naeem ul Haq Tariq


Thermodynamics and Phase
Diagrams
• Thermodynamics: Prediction about the
equilibrium of an alloy

• Kinetics: Rate at which equilibrium is reached

• Phase: A Portion of the system whose


properties and composition are homogenious
and which is physically distinct from other
parts of the system
Phase Transformation

New Phase or
One or more
mixture of
Phases in an
new phases
alloy

Q: Why transformation occurs?


Q: How is phase stability measured?
Ans1: Because the initial state of the alloy is unstable relative to the final state.

Ans2: By thermodynamics ( for transformations that occur at constant


temperature and pressure, the relative stability of a system is determines by its
Gibbs Free Energy )

G = H - TS

Enthalpy: Measure of heat content of the system

H = E + PV
Internal Energy: (Kinetic energy) + (Potential Energy)

• Atomic vibrations in solids/liquids From interactions, or bonds


• From traslational and rotational between the atoms with in
energies for the atoms and the system
molecules with in a liquid or gas
Heat absorbed
Reaction
or evolved

volume
Change Change in
of the internal
H = E + PV system energy
PV E

At constant volume : W = P dV = 0
dE = q – W =q , Increase or decrease in E => Heat absorbed or released
At constant pressure: dH = q , Increase in enthalpy => Heat absorbed
Decrease in enthalpy => Heat released
For condensed phases: PV <<<< E => H ~ E
Entropy: Measure of randomness of the system

Equilibrium: The state of a physical system evolves irreversibly towards a


time-independent state in which we see no further macroscopic
physical or chemical changes
• At lower temperature solids are stable
• Diamond (metastable) => Graphite (stable)
• Any transformation that results in a decrease in free
energy is possible, i.e ∆G = G2-G1<0
• Higher the energy hump => Slow
transformation

sive Properties: Independent of the size of the system, e.g T, P

nsive Properties Dependent of the size of the system,e.g V,E, H, S, G


Gibbs Free energy as a Function
of Temperature
Specific Heat: The quantity of heat(in joules)
required to raise the temperature of the
substance by one degree kelvin. At constant
pressure it is given by;
Cp = (δH / δΤ)p
H=0 for a pure element in its most stable
state at 298K
Variation of entropy with temperature can
be given as ;
Cp= (δΗ/δT)p
Variation of H with T can calculated by:

Variation of entropy with temperature is given by:

Taking entropy at zero K as zero =>

Variation of G with temperature is shown in fig.

When temperature and pressure vary


the change in Gibbs Free energy can
be given as follows; dG = -SdT + VdP
At constant P => (δG/δT )p= -S
As we can't measure entropy directly
For a phase transition of a pure
substance betwen the liquid and
vapour phases, the Clapeyron
equation reduces to the Clausius-
Clapeyron equation under the
approximations that the vapour is
ideal and the liquid phase volume
is negligible next to the vapour

volume.
Binary Solutions
• In single component systems all phases
have the same compositions

• Equilibrium involves P & T variables

• In alloys composition is also a variable


Dependence of
free energy on
To understand composition,
phase changes temperature and
in alloys pressure should
be known

n and T are important


Gibbs Free Energy of Binary
Solutions
• The Gibbs free energy of a binary solution of
A and B atoms can be calculated from the
free energies of pure A and pure B
Assumptions:
A and B have the same crystal structure in
there pure states
Can be mixed in any proportion to make solid
solution with the same crystal structure
• Imagine that 1 mol of homogeneous
solid solution is made by mixing together
XA mol of A and XB mol of B such that
XA + XB = 1
XA & XB are the mole fractions of A and B in
the alloy respectively
• In order to calculate the free energy of
the alloy, mixing can be made in two
steps:
 Bring together XA mol & XB mol of A & B
 Allow the A and B atoms to mix together
to make a homogeneous solid solution
Before Mixing After Mixing

Mixing
• After step 1 the free energy of the system is
given by; G1 = XAGA+XBGB Jmol-1

• GA & GB are the molar free energies of pure A


& B at the temperature & Pressure of the
above experiment
• G1 can be most conveniently represented on
a molar free energy diagram
• For all alloy compositions G1 lies on the
straight line between GA & GB
• After step 2 the free energy of the solid
solution G2 can be expressed as;
G2 = G1 + ∆Gmix

Since, G1 = H1- TS1 & G2 = H2- TS2


Putting, ∆Η mix = H2 - H1 & ∆Smix = S2 - S1

 ∆Gmix = ∆Η mix - T ∆Smix

∆Η mix is the heat absorbed or evolved during step 2, i.e it is the heat of
solution , and ignoring volume changes during the process, it represents
only the difference in internal energy (E) before and after mixing.
Ideal Solutions
∆Η mix = 0 =0

∆Gmix = ∆Η mix - T ∆Smix


∆Gmix = - T ∆Smix (1)

In statistical thermodynamics,

S = k ln ω
(2)
S

S th
S config
• In case of thermal entropy, ω is the number of
ways in which the thermal energy of the solid
can be divided among the atoms or
The total numbers of ways in which vibrations
can be set up in the solid
• In solutions, additional randomness exist due to
the different ways in which the atoms can be
arranged leading to the configurational entropy
• If there is no volume change or heat exchange
during mixing then the only contribution to ∆
Smix is the change in configurational entropy
• If there is no volume change or heat
change during mixing then the only
contribution to ∆Smix is the change in
configurational entropy
• Before mixing , A & B atoms are held
separately in the system and there is only
one distinguishable way in which the
atoms can be arranged
 S1= k ln 1 = 0
 ∆Smix = S2
• Assuming that A & B mix to form a
substitutional solid solution
• All configurations of A & B atoms are equally
probable
• The number of distinguishable ways of
arranging the atoms on atom sites is
 ω = (NA+ NB) ! / NA ! NB ! (3)

NA & NB are number of A & B atoms


• Since we are dealing with 1 mol of solution
i.e. Na atoms ( Avogadro’s number),
 NA = X A Na & NB = X BNa
• Using 1, 2 & Stirling approximatiom i.e,

(
Ln N ! = N ln N - N 1
)

Na k = R (
2
 ∆Smix = - R (X A ln X A + X B ln X B)

Note: Since X A & X B < 1 => ∆Smix >0


From equation (1);
∆Gmix = - T ∆Smix
 ∆Gmix = RT(X A ln X A + X B ln X B)
• The actual free energy of the solution G
will also depend on GA & GA
G1 = XAGA+XBGB
G2 = G1 + ∆Gmix
∆Gmix = RT(X A ln X A + X B ln X B)
G = G2 = XAGA+XBGB +RT(X A ln X A + X B ln X B)

• As the temperature increases, GA&GB decrease and


the free energy curves assume a greater curvature.
GB
G1

GA G2
G
A
Chemical Potential
• In alloys it is of interest to know how the free
energy of a given phase will change when atoms
are added or removed
• If a small quantity of A, dnA mol, is added to a
large amount of a phase at constant T & P , the
size of the system will be increase by dnA
• Therefore, the total free energy of the system will
also increase by a small amount dG’
• If dnA is a small enough dG’ will be proportional to
the amount of A added
 dG’ = µ A dnA ( T, P , nB constant )
• The proportionality constant is called the
partial molar free energy of A or alternatively
the chemical potential of A in the phase.
∀ µ A depends on the composition of the , and
therefore dnA must be so small that the
composition is not significantly altered
µ A = (δG’ / δnA) T,P,n(B)

G’ is the free energy of the whole system not molar

For binary system;


dG’ = µ A dnA + µ B dnB
If T & P changes are also allowed,
dG’ = -SdT + VdP + µ A dnA + µ B dnB +…..
• If 1 mol of the original phase contained X A & X B mol
of A & B, the size of the system can be increased
without altering its composition if A & B are added in
the correct proportions, i.e. such that
dnA : dnB = X A : X B
For example: If the phase contains twice as many A
as B atoms (X A = 2/3, X B = 1/3), the composition
can be maintained constant by adding two A
atoms for every B atoms,In this way the size of
the system can be increased by one mole
without changing µ A & µ Β
• To do this X A mol A and X B mol B must be added
and the free energy of the system will increase
by molar free energy G
• So,
dG’ = µ A dnA + µ B dnB gives;
G= µ A XA + µ B XB
Compairing with;
G = G2 = XAGA+XBGB +RT(X A ln X A + X B ln X B)
µ A = GA+ RT ln X A
µ A = GA+ RT ln X A
Molar
Free
Energy
GA GA
Regular Solutions
• In practice ∆Η mix = 0
• So, the simple model for for an ideal solution can
be extented to include the ∆Η mix term by using
quasi-chemical approach
Assumption:
• The heat of mixing, ∆Ηmix is only due the bond
energies between the adjacent atoms
• For this assumption to be valid, it is necessary
that the volumes of pure A & B are equal and do
not change during mixing so that the interatomic
distances and bond energies are independent of
the compositions
• A-A bonds each with an energy ε AA
• B-B bonds each with an energy ε BB
• A-B bonds each with an energy ε AB
 Consider zero energy to be the state wherethe atoms
are separated to infinity ε AA,ε BB, ε AB are negative quantities
and become more negative as the bond become more
stronger
 The internal energy of the solution E will depend on the
number of bonds of each type, PAA, PBB, PAB such that :

E = PAA ε AA + PBB ε BB + PAB ε AB


• Before mixing pure A and B contain only A-A, & B-B bonds
respectively
• By considering the relationship between PAA, PBB and PAB in
the solution it can be shown that the change in internal
energy on mixing is given by,
∆Η mix = PAB ε
Where, ε = ε AB - (ε AA+ ε BB)/2
∀ε is the difference between th A-B bond energy and the
average of the A-A and B-B bond energies
• If ε= 0, ∆Η mix = 0 and the solution is ideal
• In this case the atoms are completely
randomly arranged and entropy of mixing is
given by: ∆Smix = - R (X A ln X A + X B ln X B)
• In such solutions it can be shown that:
PAB = Na z X A X B bonds / mol ……………………..(1)
• If ε < 0, the atoms in the solution will prefer to
be surrounded by atoms of the opposite type
and this will increase PAB
• If ε > 0, PAB tend to be less than in a random
solution
• If ε is not too different from zero, (1) is still
good approximation in which case
∆Η mix = Ω X A X B , where Ω = Na z ε ……….(2)
• Real solutions that closely obey equation (2)
are known as regular solutions
• The variation of ∆Η mix with composition is
parabolic and is shown in fig. for Ω >0
• Tangents at X A = 0 and X A = 0 are related to Ω
• The free energy change on mixing a regular
solution is given as:
∆Gmix = Ω X A X B + RT(X A ln X A + X B ln X B)

∆ Hmix - T ∆ Smix
• For exothermic solutions ∆Η mix < 0 and
mixing results in a free energy decrease at
all temperatures
• For ∆Η mix > 0 , the situation is more
complecated,
At high temperature: T∆Smix > ∆Η mix
For all compositions and free energy curve
has a positive curvature at all points.
At low temperature: T∆Smix < ∆Η mix
Free energy develops a negative curvature
in the middle
>
Pringles
• Differentiating; ∆Smix = - R (X A ln X A + X B ln X B)
• As X A or X B 0 the T∆Smix curve becomes
vertical whereas the slope of ∆Hmix curve tends to
a finitevalue Ω, this means that, except at absolute
zero, ∆Gmix always decreases on addition of a
small amount of solute
• The actual free energy of the alloy depends on the
values chosen for G A & G A and is given by;

G = XAGA+XBGB +Ω X A X B + RT(X A ln X A + X B ln X B)
Using, X A X B = X A X 2B + X 2A X B
G = XAGA+XBGB + Ω X A X B + RT(X A ln X A + X B ln X B)

G= µ A XA + µ B XB

µ A = GA+ Ω (1− XA)2 + RT ln X A

µ B = GB+ Ω (1− XB)2 + RT ln X B


Activity
• For any solution chemical potential
expression can be written by defining
activity of a component ‘a’
 µ A = GA+ RT ln a A
 µ A = GA+ RT ln a A Comparing with

µ A = GA+ Ω (1− XA)2 + RT ln X A

2
 ln (a A / X A ) = Ω (1 - X A )2/ RT
 ln (a B / X B ) = Ω (1 - X B )2/ RT
Assuming A & B have the same crystal
structure, the relationship between a
and X can be represented as shown in
fig.
For an ideal solution a A = X A
If ∆Hmix< 0 , activity of the components
in the solution will be less in an ideal
solution (line 2)
If ∆Hmix> 0, vice versa
• The ratio (a A / X A ) is usually referred
to as , γ Α the activity coefficient of A,
that is
γ Α = (a A / X A )
• For the dilute solution of B in A
• Letting in above equation X B 0
γ Α = (a A / X A ) ~ 1 (Raoult’s law)
γ Β = (a B / X B) ~ constant (Henry’s law)
• The activity of a component is just
another means of describing the
state of the component in a
solution

• Activity and chemical potential are


simply a measure of the tendency
of an atom to leave a solution
Real Solutions
• When ε and Ω = 0, the assumption that a
random arrangement of atoms is the
equilibrium, or most stable arrangement is not
true
• Gmix will not give the minimum free energy
• The actual arrangement of atoms will be a
compromise that gives the lowest internal
energy consistent with sufficient entropy, or
randomness, to achieve the minimum free
energy
• In the systems with ε < 0 the internal energy of
the system is reduced by increasing the number
of A-B bonds, by ordering the atoms as shown
• In the systems with ε > 0 the internal energy of
the system is reduced by increasing the number
of A-A & B-B bonds, by clustering of the atoms
into A-rich and B-rich groups
• However, the degree of ordering or clustering
will decrease as temperature increases due to
increasing importance of entropy
• In systems where there is a size difference
between the atoms , the quasichemical model
will underestimate the change in internal
energyon mixing
• Since no account is taken of the elastic strain
fields which introduces a strain energy term to
∆Η mix
• When the size difference is large this effect can
dominate over the chemical term
• When the size difference between the atoms is very
large then interstitial solid solutions are energetically
most favourable
• New mathematical models are needed to describe
these solutions
• In the systems where there is strong chemical
bonding between the atoms there is a tendency
for the formation of intermetallic phases
• These are distinct from the solutions based on
pure components
• Since they have a different crystal structure and
may also be highly ordered
Ordered Phases
• If atoms in a substitutional solid solution are
completely randomly arranged each atom
position is equivalent and probability that any
given site in the lattice will contain an A atom will
be equal to the fraction of A atoms in the solution
XA ,similarly XB for B atoms
• In such solutions number of A-B bonds (PAB) is
given by

PAB = Na z X A X B bonds / mol


• If Ω < 0, and number of A-B bonds is greater
than this, the solution is said to contain SRO
• The degree of ordering can be quantified by
defining a SRO parameter S

S = PAB - PAB (random) / PAB (max)- PAB (random)

PAB (max) = max. no. of bonds possible


PAB (random) = no. of bonds for random solution
• In solutions with compositions that are very close to a
simple ratio of A : B atoms another type of order can
be found known as long range order

Now the atom sites are no longer equivalent but can be


labelled as A-rich and B-rich, such solution can be
considered to be a different (ordered)phase separate from
the random or nearly random solution
Q
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