1st Law: Conservation of Energy

Energy is conserved. Hence we can make an energy balance for

a system: Sum of the inflows – sum of the outflows is equal to
the energy change of the system

 energy
boundary
flow  ( Esystem )

NOTE: sign of flow is positive when into the system

UNITS: Joules, calories, electron volts …

 Types of Work
Electrical

W = – dq

Magnetic
W  o V HdM
Surface

W = – dA
Summary so far
 Variables and Parameters
System is only described by its macroscopic variables

Variables: Temperature + one variable for every work term that

exchanges energy with the system + one variable for every
independent component that can leave or enter the system.

Parameters: Quantities that are necessary to describe the system

but which do not change as the system undergoes changes.
e.g. for a closed system: ni are parameters
for a system at constant volume: V is parameter

Equations of State (Constitutive Relations): equation between the

variables of the system. One for each work term or matter flow
 Example of Equations of State

pV = nRT: for ideal gas

= E efor uniaxial elastic deformation
M =  H: paramagnetic material
 Properties and State Functions

U = U(variables) e.g. U(T,p) for simple system

Heat capacity 1 Q

cp 
n dT p
1 Q 
cV 
n dT V
Volumetric 1 dV 
V   
thermal expansion V dT p

Compressibility 1 dV 
V    
V dp T
 Some Properties Specific to ideal gasses

ONLY for IDEAL GASSES

1) PV = nRT
2) cp - cv = R

3) U   0
V T

Proof that for ideal gas, internal energy only depends on

temperature dU  nc vdT
 The Enthalpy (H)

H = U + PV
Gives the heat flow for any change of a simple
system that occurs under constant pressure

Example: chemical reaction

 Example: Raising temperature under constant
pressure
dH p  Qp  n c p dT
 H 
cp 
 dT p
 Enthalpy of Materials
is always relative

Elements: set to zero in their stable state at 298K and 1 atm pressure

Compounds: tabulated. Are obtained experimentally by measuring

the heat of formation of the compounds from the elements under
constant pressure.
 The Enthalpy (H)

H = U + PV
Gives the heat flow for any change of a simple
system that occurs under constant pressure

Example: chemical reaction

 Example: Raising temperature under constant
pressure
dH p  Qp  n c p dT
 H 
cp 
 dT p
 Enthalpy of Materials
is always relative

Elements: set to zero in their stable state at 298K and 1 atm pressure

Compounds: tabulated. Are obtained experimentally by measuring

the heat of formation of the compounds from the elements under
constant pressure.
 Entropy and the Second Law
There exists a Property of systems, called the Entropy (S), for
which holds:
Q
dS 
T
How does this solve our problem ?
 The Second Law leads to Evolution Laws

Isolated system
 Evolution Law for constant Temperature and
Pressure

TdS  dU  pdV
 d(TS)  dU  d(pV )

d(U  pV  TS)  0

dG ≤ 0

G (Gibbs free energy is the relevant potential to determine stability

of a material under constant pressure and temperature
 Interpretation
For purely mechanical systems: Evolution towards minimal
energy.
Why is this not the case for materials ?
Materials at constant pressure and temperature can
exchange energy with the environment.
G is the most important quantity in Materials Science

determines structure, phase

transformation between them,
morphology, mixing, etc.
 Phase Diagrams: One component
Describes stable phase (the one with lowest Gibbs free
energy) as function of temperature and pressure.
Water
Carbon
 Temperature Dependence of the Entropy

Q
dS 
T
Qp Cp dT p
dS p  
T T
S   C p
T p T
 Temperature Dependence of the Entropy

Q
dS 
T
Qp Cp dT p
dS p  
T T
S   C p
T p T
 What is a solution ?

SYSTEM with multiple chemical components that is mixed

homogeneously at the atomic scale

•Liquid solutions
•Vapor solutions
•Solid Solutions
 Composition Variables

ni
MOLE FRACTION: Xi 
ntot
ATOMIC PERCENT: (at%)i  100% Xi

ni Wi
CONCENTRATION: Ci  or
V V
Wi
WEIGHT FRACTION: wi 
Wtot
 Variables to describe Solutions

G=G(T,p,n1,n2, …, nN)
G  G  G 
dG    dT    dp    dni Partial Molar Quantity
T p,n p T , n ni p,T
i i
V 
Vi   
 ni T , p,n
Partial Molar Quantity j

 H 
G  Hi   
chemical i    ni T , p,n
potential ni p,T j

S 
S i   
dG  S dT  V dp  i dni n i T ,p, n j
Partial molar quantities give the contribution of a component to a property of the solution

G    i ni
i

V   Vi ni
i
 Properties of Mixing

Change in reaction:
XA A + XB B -> (XA, XB )

 H mix  H mix  X A H A  X B H B
 H mix  H A  X B H B  H A 
 Cu-Pd
Ni-Pt
Intercept rule with quantity of mixing
 General Equilibrium Condition in Solutions

Chemical potential for a component has to be the same in all phases

i  i  i  ...
   For all components i

OPEN SYSTEM

Components have to have the

same chemical potential in system
as in environment
e.g. vapor pressure
Example: Solubility of Solid in Liquid
 Summary so far

1) Composition variables
2) Partial Molar Quantities
3) Quantities for mixing reaction
4) Relation between 2) and 3): Intercept rule
5) Equilibrium between Solution Phases
 Standard State: Formalism for Chemical Potentials in Solutions

i    RT ln( ai )
0
i

chemical potential of i in solution effect of concentration

chemical potential of i in a standard state

Choice of standard state is arbitrary, but often it is taken as pure

state in same phase.
Choice affects value of ai
 Models for Solution: Ideal Solution

An ideal solution is one in which all components behave Raoultian

ai  xi for all i

G mi x  G mi xture  G components
x A  A  x B B x A GA  x B GB

G mi x  x A  A0  RT lnaA   xB  0B  RT lnaB   x A G A  x B G B

G mi x  RTx A lnx A  xB lnx B 

 Summary Ideal Solutions

G mi x  RT  xi ln xi
i

 H mi x  0
 S mi x  R  xi lnxi
i

V mi x  0
 Solutions: Homogeneous at the atomic level

Ordered solutions
Random solutions
 Summary so far

1) Composition variables
2) Partial Molar Quantities
3) Quantities for mixing reaction
4) Relation between 2) and 3): Intercept rule
5) Equilibrium between components in Solution Phases

For practical applications it is important to know relation between

chemical potentials and composition
 Obtaining activity information: Experimental
e.g. vapor pressure measurement
 pi 
 i  RT ln  * 
*
pi 
vapor pressure pi vapor pressure pi

Mixture with
Pure substance i
component i in it
 i  RT ln ai 

pi
*  ai
pi
 Obtaining activity information: Simple Models

Raoultian behavior

ai  xi

Henry’s behavior
ai  k xi
Usually Raoultian holds for solvent, Henry’s for solute at small enough concentrations.
Intercept rule
 General Equilibrium Condition in Solutions

Chemical potential for a component has to be the same in all phases

i  i  i  ...
   For all components i

OPEN SYSTEM

Components have to have the

same chemical potential in system
as in environment
e.g. vapor pressure
Raoultian case and Real case
 Review
• At constant T and P, a closed system strives to minimize its Gibbs free energy:
G = H - TS

• Mixing quantities are defined as the difference between the quantity of the
mixture and that of the constituents. All graphical constructions derived for
the quantity of a mixture can be used for a mixing quantity with appropriate
adjustment of standard (reference) states.
XB XB
0 1 0 1

GA
GB

A - G A

B - G B

G m ix
G
 Review (continued)

Some simple models for solutions can be me made: Ideal

solution, regular solution.
Many real solution are much more complex than these !

Regular Solution
G mi x   Hmi x – TS mi x
  xB (1  x B )  RTx A ln x A  x B ln x B 
 The Chord Rule
What is the free energy of an inhomogeneous systems
( a system that contains multiple distinct phases) ?

CHORD RULE: The molar free energy of a two-phase system

as function of composition of the total system, is given by the
chord connecting the molar free energy points of the two
constituent phases
 The Chord Rule graphically

With pure components Components are solutions

A B XB XB

overall composition is XB* overall composition is XB*

G G

0 1 0 1
XB* XB*
XB XB
 Regular Solution Model
G mi x   xB (1 xB )  RT(1  xB )ln(1 xB )  xB ln xB 

< 0 0 XB 1
 Regular Solution Model
G mi x   xB (1 xB )  RT(1  xB )ln(1 xB )  xB ln xB 

 > 0
0 XB 1
 Effect of concave portions of G

0 XB* 1
 Single-Phase and Two-phase regions

0 XB XB* XB 1

Single- Single-
Two-phase
phase phase
 Two-phase coexistence

When Gmix has concave parts (i.e. when the second

derivative is negative) the coexistence of two solid solutions
with different compositions will have lower energy.

The composition of the coexisting phases is given by the

Common Tangent construction

The chemical potential for a species is identical in both

phases when they coexist.
Common tangent does not need to be horizontal

0 XB* 1
 Temperature Dependence of Two-phase region
Hmix Hmix Hmix

XB XB XB
0 1 0 1 0 1

Low temperature Intermediate temperature High temperature

Phase Diagram of Regular Solution Model with 
>0

0 XB 1
Example: Cr-W
Miscibility gap does not have to be symmetric
Lens-Type Diagram
 Free energy curves for liquid and solid
T > TBM > TAM TBM > T > TAM
G G

0 1 0 1
XB XB
G

TBM > TAM > T

0 1
XB
 How much of each phase ? - The Lever Rule

Since the composition of each phase is fixed by the common

tangent, the fraction of each phase can be determined from
requiring that the system has the given overall composition
X *B  f X B  f X B
-> solve for f and f
1  f  f

The result is known as the Lever Rule

X B  X *B XB*  X B
f   f  
X B  X B X B  X B
 Lever Rule

f

x x
x

f

x x
x
 In a two-phase region chemical potential is
constant
0 XB 1

0 XB 1

 Comparison between Eutectic and Peritectic

Eutectic Peritectic
L
   L

Cooling: L ->  Heating:  -> L + 

 Nucleation

(1) The structure of the liquid

Many small closed packed solid clusters are present in the liquid. These clusters
would form and disperse very quickly. The number of spherical clusters of
radius r is given by
 Gr 
nr  n0 exp
kT 

nr : average number of spherical clusters with radius r.

n0: total number of atoms in the system.
Gr: excess free energy associated with the cluster.
(2) The driving force for nucleation

The free energies of the liquid and solid at a temperature T are given by

GL = HL- TSL and GS = HS- TSS

GL and GS are the free energies of the liquid and solid respectively.
HL and HS are the enthalpy of the liquid and solid respectively.
SL and SS are the entropy of the liquid and solid respectively.

At temperature T, we have
GV = GL- GS = HL-HS-T(SL-SS) =H-TS,
GV: volume free energy.
where H and S are approximately
independent of temperature.
 For a spherical solid of radius r,
4
G   r 3GV  4r 2 SL
3
For a given T, the solid reach a critical radio r*, when
d ( G )
0
dr
16 SL

3
We get G  and
3( GV ) 2
2 SL
r* 
GV
T
If GV  Lm then,
Tm

G  
3
16 SL Tm 1 2 SL Tm 1
2
T 2 and r * 
3( L m ) Lm T

When r < r, the solid is not stable, and

when r > r, the solid is stable.
The effect of temperature on the size of critical nucleation and the actual shape of a nucleus.
(4) Heterogeneous nucleation

If a solid cap is formed on a mould, the interfacial tensions balance in the plane of the mould
wall,   SM or
 ML   SM   SL cos
cos  ML
 SL
SL, SM and ML: the surface tensions of the solid/liquid, solid/mould and mould/liquid interfaces
respectively.
The excess free energy for formation of a
solid spherical cap on a mould is

Ghet = -VSGV + ASLSL + ASMSM - ASMML

Where VS: the volume of the spherical cap.

ASL and ASM: the areas of the solid/liquid and
solid/mould interfaces.

It can be easily shown that,

4
Ghet  ( r 3GV  4r 2 SL )  f ( )
3
where
(2  3 cos  cos3  )
f ( ) 
4
(c) Nucleation rate and nucleation time as a function of temperature

The overall nucleation rate, I, is influenced both by the rate

of cluster formation and by the rate of atom transport to the
nucleus, which are both influenced in term by temperature.
TTT diagram gives time required for nucleation, which is
inversely proportional to the nucleation rate.
860
840
820
800
780
760
740
720
700
680
660
640
620
600
100 1000 10000

Actual examples of TTT

diagram
 Nucleation in Solid

Interface structure
Coherency loss

3 st
rcrit 
4 2
 Homogeneous Nucleation

(a) Homogeneous nucleation

The free energy change associated with the nucleation process will have the following three
contributions.
1 . At temperatures where the  phase is stable, the creation of a volume V of  will cause a
volume free energy reduction of VGv.
2. Assuming for the moment that the / interfacial energy is isotropic the creation of an
area A of interface will give a free energy increase of A.
3. In general the transformed volume will not fit perfectly into the space originally
occupied by the matrix and this gives rise to a misfit strain energy Gv, per unit volume of
. (It was shown in Chapter 3 that, for both coherent and incoherent inclusions, Gv, is
proportional to the volume of the inclusion.) Summing all of these gives the total free
energy change as

G  VGV  A  VGS
If we assume the nucleus is spherical with a radius r, we
have 4
G   r 3 ( GV  G S )  4r 2 
3
Similarly we have

2
r* 
( GV  G S )

 163
G 
3( GV  G S )2
 Nucleation at Grain Boundary

The excess free energy associated with the embryo at a grain

boundary will be given by
G = -VGv + A - A
Where V is the volume of the embryo, A is the area of / interface of energy  created, and
A the area of / grain boundary of energy  destroyed during the process.


cos    
2  
 Fick I

It would be reasonable to take the flux across a given

plane o be proportional to the concentration gradient
across the plane:

 c 
J   D 
 x 

J: the flux, [quantity/m2s]

D: diffusion coefficient, [m2/s]
 c 
 x 
  Concentration gradient, [quantity /m-4]

Here, quantity can be atoms, moles, kg etc.

Fick II:

C  2C
D
t x 2
Solution to Fick II
1. Thin Film (Point Source) Solution

assume boundaries at infinity c(x,0)  M (x)

c(,t)  c(,t )  0

M  x 
2

c(x,t)  exp 
4 Dt  4Dt 
 M  x 
2

c(x,t)  exp 
4 Dt  4Dt 
 Measurement of diffusion coeffiecient

M  x 
2

c(x,t)  exp 
4 Dt  4Dt 
x

x2
lnc  cons tan t 
4Dt

If c versus x is known experimentally, a plot of ln(c) versus x2

can then be used to determine D.
 Error functions

2
exp(x 2 )

x
2
 exp(u ) du  erf (x)
2

0

erf ( 0 )  0
erf (  )  1
erfc( x )  1  erf ( x )
erf (  z )  erf ( z )
 c( x , t ) 
c'  
 exp   x   2 d
0 
2 Dt  4Dt 

The final solution should be:

c'   x 
c( x , t )  1  erf  
2  2 Dt 
 When x=0, the
composition is always
kept at c=c’/2

c'   x 
c( x , t )  1  erf  
2  2 Dt 

  x 
c( x , t )  C s 1  erf   
  2 Dt 

erf(-z)=-erf(z)

  x 
c( x , t )  Cs 1  erf  
  2 Dt 
 Diffusion Mechanis

Interstitial mechanism Self Diffusion with Vacancy

These are the
two most
common
mechanisms

Ring Mechanism Interstitialcy

A Random Jump Process

1
J1  Bn1
6

1
J2  Bn 2
6

1
J B  J1  J 2  B ( n1  n 2 )
6

 C 
CB ( 1 )  CB ( 2 )   B 
 x 

1  C
J B   B 2  B
6  x
Diffusion by Vacancy mechanism
1
DA  B 2
6

 Gm 
B  zX v exp  
 RT 
  Gv 
X v  exp 
 RT 

1 2   S  S v   H m   H v 
DA   z exp m  exp  
6  R   RT 

 Q 
DA  D0 exp  
 RT 

1 2  S  S v 
D0   z exp m 
6  R 
Effeect of temperature on diffusion

 Q 
DA  D0 exp  
 RT 
Effect of defect on diffusion