Kinetic processes in materials

Prof. Nguyen Hong Hai

Hanoi University of Science and Technology
Textbooks
 Kinetic processes in Materials

 Student Duties
Class attendance: ≥ 80%
Homework: 100%
Lab work: 100%

 Assessment
Mid-term grade (mid-term exam + class attendance +
home work): 0.3 (30%)
Final exam (test & exercises): 0.7 (70%)
 Kinetic processes in Materials

Content

 Review of thermodynamics (in what conditions phase

transformation occure?)
 Diffusion (how the phase transformation can occure?)
 Surfaces and interfaces (where the phase transformation can
occure?
 Phase transformation (how fast the phase transformation can
occure?)
 CLASSIFYING MATTER BY STATE

MATTER PLASMA

LIQUID SOLID GAS

Inogra
Organics
nics
MATERIALS

Metals Glass & Polymers Wood

Ceramics
 Twwo principal ways to make
materials are synthesis and
Materials cycle prosessing
Gas
Liquid Solid (Materials)
Solid
Relative position of MSE subjects

Fatigue, creep,
Kinetic
corrosion and wear Strongly related
resistances… processes in
with environment
materials
Strength, hardness,
ductility…
Size and
morphology of
grains, lattice
defects…
Melting
crystalisation,
solidification, 
deformation,
heat treatment 30%
…
Chemical 70%
composition
Physical space of materials MSE subjects
The difficulty increases toward
the center!
Role of Processing
 Kinetic processes in Materials

The outermost circle is the performance

circle, which characterizes how a material
behaves in given environments.

The performance is realized by a set of

properties, in the second circle, relevant to
those environments.

Those properties are achieved by an

agglomeration of phases with various
structures and their morphologies in the
third circle.

The structures are obtained through proper

processing in the fourth circle with accurate
chemical compositions in the fifth circle.

The physical space of materials

Kinetic processes in Materials

Kinetic
processes in
materials

The physical space of materials The key components in MSE

While the two outermost circles are environment-dependent, the three inner
circles can be directly related to the three key components in materials science
and engineering, crystallography, kinetics, and thermodynamics.

Thermodynamics and kinetics of materials are viewed as difficult subjects.

 Kinetic processes in Materials

Chapter 1 THERMODYNAMICS
 Kinetic processes in Materials

Chapter 1 THERMODYNAMICS

 The main use of

thermodynamics in physical
metallurgy is to allow the
prediction of whether an alloy is
in equilibrium.

 In considering phase
transformation we are
concerned with changes
towards equilibrium, and
thermodynamics is therefore
very powerful tool.

 However, the rate at which

equilibrium is reached cannot
be determined by
thermodynamics alone 
kinetic processes
Kinetic processes in Materials

1.1. Equilibrum

The main question of Thermodynamics is if a system is in equilibrium?

System: mixture of
one or more phases

Phase: a portion of the

system whose properties
Si
and composition are Al A356 A390
A413
homogeneous and which Eutectic
is physically distinct from
other part of the system.
 1.1. Equilibrum

Al Si
A390

Primary Si (coarse) Al-Si eutectic Primary Si (fine)

Processing

Microstructure of hypereutectic Al-Si alloy

desired
undesired
 Kinetic processes in Materials

1.1. Equilibrum T, 0C
Steel Cast iron
l+
1538
B 14870

 Components: the
different elements or 1394 l
N
chemical compounds
l+
which make up the l + Fe3C
 11480
system.
E C F
 The composition of a
phase or the system +
G  + Fe3C
can be described by 912
giving the relative
amounts of each P S 7270 K

component.
 + Fe3C (or  + graphit)
Fe3 C %C
500
Fe 1 2 3 4 5 6 7
Kinetic processes in Materials
1.1. Equilibrum

 Phase transformation: one or more phases in an alloy (the system)

change into a new phase or mixture of phases.

 - Al8Fe2Si (fishbone or chinese

-Al5FeSi (platelate form, very harmfull) script form, less harmfull)

Desired
Porosity

Stable Unstable

What determines the stability of phases?

 Kinetic processes in Materials
1.1. Equilibrum

 At constant temperature and pressure the relative stability of a system is determined

by its Gibbs free energy
G = H – TS (1.1)
 H: enthalpy, the measure of the heat content of the system
H = E + PV (1.2)
E : internal energy of the system, P: the pressure and V: the volume.
For the condensed phases (solids and liquids) the PV term is usually very small in
comparison with E, so H  E.
 T: absolute temperature
 S: entropy of the system, the measure of the randomness of the system.
 The intensive properties (independent on the size of the system): T and P
 The extensive properties (directly proportional to the quantity of material in the
system such as V, E, H, S, G)
 Kinetic processes in Materials
Unstable (dG  0)
Gibbs dG = 0
1.1. Equilibrum free
energy
G

dG = 0
A system is said to be in equilibrum
when it is in the most stable state;

At constant temperature and pressure a B

Arrangement of atoms
A

closed system (i.e. one of fixed mass and

composition) will be in stable equilibrum
if it has the lowest value of the Gibbs Metastable (diamond) Stable (graphite)

free energy, or in mathematical term:

dG = 0 (1.3)

From Equation G = H – TS: the state with

the highest stability will be that with low
enthalpy and high entropy.
 Kinetic processes in Materials
Gibbs Free
1.1. Equilibrum Energy G
dG = 0

G1
 Any transformation that results in a
decrease in Gibbs free energy is possible. dG = 0
G
Therefore a necessary criterion for any
phase transformation is: G2

G = G2 – G1  0 (1.4)
B A
Arrangement of atoms

 The answer to the question “How fast does a phase transformation occur?”
belong to the realm of kinetics
 The usual way of measuring the size of the system is by the number of moles of
material it contains (the extensive properties - V, E, H, S, G) are then molar
quantities, i.e. expressed in units per mole).
 The number of moles of a given component in the system is given by the mass
of the component in grams divided by its atomic or molecular weight.
 The number of atoms or molecules within 1 mol of material is given by
Avogadro’s number (Na) and is 6.0231023.
 Kinetic processes in Materials

1.2. Single component system

 Single component system: which

contains a pure element or one
type of molecule that does not
dissociate over the range of
temperature of interest.

 In order to predict the phases

that are stable or mixtures that
are in equilibrium at different
temperatures it is necessary to
calculate the variation of G with T

Carbon dioxide (CO2) pressure-

temperature phase diagram showing
the triple point and critical point of carbon
dioxide
 Kinetic processes in Materials

1.2.1. Gibbs Free Energy as a Function of Temperature

Specific heat: the quantity of

heat (in jouls) required to
raise the temperature of the  H 
substance by one degree
CP    (1.5)
 T  P
Kelvin

T
The variation of enthalpy H
with T can be calculated by
H
298
C P dT
intergrating equation 1.5

The variation of entropy

with temperature can also T
CP
be derived from the S dT
specific heat CP, taking 0 T
entropy at zero degrees
Kelvin as zero Fig. 1.2. Cp, H and S as
function of temperature
 1.2.1. Gibbs Free Energy as a Function of Temperature

Example 1: The specific heat of solid copper above 300K is given by

Cp = 22.64 + 6.28 x 10-3 T [J mol-1K-1]
By how much does the entropy of copper increase on heating from 300K to 1358 K?

CP
S  
T2
dT
T1 T
1358 22 , 64  6 , 28 . 10  3 T
 S 300  1358  300 T
dT


 22 , 64 ln T  6 , 28 . 10 3
T 
1358
300

1 1
 40 . 83 Jmol K

Answer: on heating from 300K to 1358 K the entropy of copper increases by 40.83 Jmol-1K-1
Kinetic processes in Materials

1.2.1. Gibbs Free Energy as a Function of Temperature

Finally the variation of G with temperature can be obtained by combining

Fig 1.2b and 1.2c using Equation (1.1): G = H - TS

H
H
Free energy slope = CP
curves for T(K)
different
phases, for TS
slope = -S
exemple
liquide and
G
solid, can be G
plotted.
G = H – TS

Fig. 1.3. G as function of absolute temperature

 G  G decreases with increasing T

   S
 T  P at the rate given by –S
 Kinetic processes in Materials

1.2.1. Gibbs Free Energy as a Function of Temperature

H H(liquid)

Note: d
H(solid)
c
1. At Tm both liquid and solid
phases have the same value of G L = H
b
and can exist in equilibrium.
 Tm is therefore the Tm
equilibrium melting temperature
298 T, (K)
at the pressure concerned.

2. At Tm the heat supplied to the a Liquid state

system will not raise its
temperature but will be
supplying the latent heat of
melting (L) that required to
convert solid into liquid (line bc
in Fig. 1.4)
G(solid) e
Solid state
f
G G(liquid)
Fig. 1.4. Variation of enthalpy (H) and free
energy (G) with temperature for the solid
and liquid phases of a pure metal.
 Kinetic processes in Materials

1.2.1. Gibbs Free Energy as a Function of Temperature

Molar
free
energy

G

GS

T
GL

T Tm Temperature

Fig. 1.4. Variation of entalpy (H) and free

energy (G) with temperature for the solid
and liquid phases of a pure metal.
 Kinetic processes in Materials

1.2.1. Gibbs Free Energy as a Function of Temperature

If a liquid metal is undercooled by T below Tm before it solidifies, solidification will

be accompanied by a decrease of free energy G (J mol-1). This free energy decrease
provides the driving force for solidification.

Molar
The free energies of the liquid and solid
free
at a temperature T are given by: energy Reversible
GL = HL - TSL transformation
Liquid  Solid
GS = HS – TSS
G
 G = GL - GS
GS
Therefore at a temperature T:
G = H - TS, [J.mol-1] (1.10)
T GL
H = HL – HS
Undercooling
S = SL - SS
T Tm Temperature
 Kinetic processes in Materials

1.2.1. Gibbs Free Energy as a Function of Temperature

Molar
At the equilibrium melting free
energy
temperature Tm the free energies of
solid and liquid are equal, i.e. G = 0.

Consequently: G

G = H - TmS = 0 GS

T
GL
And therefore at Tm

H L T Tm
S f   (1.11)
Temperature
Tm Tm

This is known as the entropy of fusion and for most metals is a constant  R (8.3 J mol-1 K-1).
 Kinetic processes in Materials

1.2.2. The driving Force for Solidification

Note: For small undercooling (T) the difference in the specific heats of the liquid and solid
(CLP – CSP) can be ignored.
 H and S therefore approximately independent of temperature.

Combining Equations (1.10) and

Molar
(1.11), with H = L thus gives:
free
energy
G = H - TS
(1.10)
G  ST
L G
G  L  T
Tm
H L GS
S  
(1.11) Tm Tm T
GL

T Tm Temperature

Conclusion: G is proportional to the T (driving force for

LT
G   S T solidification is proportional to the undercooling and
Tm proportional coefficient is S).
Kinetic processes in Materials

1.2.2. The driving Force for Solidification

How much is maximum undercooling? Tmax  (1/3) Tm

Metal Under- Metal Under- Metal Under-

cooling, cooling, cooling,
0C 0C 0C

Hg 77 Sb 135 Mn 308

Ga 76 Ge 227 Ni 319

Sn 118 Ag 227 Co 330

Bi 90 Au 230 Fe 295
Pb 80 Cu 236 Pd 332
Al 195 Pb 80 Pt 370

The maximum undercooling, T, is obtained by metal atomisation, which is

needed for homogeneous nucleation.
 How the pressure
Kinetic processescan influence on the undercooling?
in Materials
This effect is very small: the
Clapeyron  TP T V melting point of metal can be
equation:   M
P H increased only 10-2 0C/atm
 TP = 10-2 0C/atm

Example 2. Estimate the change in the equilibrium melting point of copper caused by a
change of pressure of 10 kbar (1bar = 0.98692 atm). The molar volume of copper is
8.010-6 m3 for the liquid and 7.610-6 m3 for the solid phase. The latent heat of fusion
of copper is: 13.05 kJ mol-1 . The melting point is 1085 0C at normal conditions.
H = HL – HS = L = 13050 J mol-1 Phase diagram is shifted
toward higher temperature
V = VL – VS = (8 – 7.6) . 10-6 = 0,4.10-6 m3
Tm = (1085 + 273) = 1358 K
P = 10 kbar = 109 Nm-2

About 0.0042 K/atm

The melting point is 1127 0C at 10 kbar instead of 10850

C at normal conditions
Influence of the pressure on the crystalisation of C
 Kinetic processes in Materials

1.3. Binary Solutions

 In practice the pure metals (single

component system) are rarely applied.
 In single component system all phases
have the same composition, and
equilibrium simply involves pressure
and temperature as variables
 In alloys composition is also variable
 Since pressure is usually fixed at 1atm,
most attention will be given to
changes in composition and
temperature
 Kinetic processes in Materials
1.3.1. The Gibbs Free Eneggy of Binary Solutions

 The Gibbs free energy of a binary solution

A
of A and B atoms can be calculated from
the energies of pure A and pure B
 Assumed that A and B have the same B
crystal structure , can be mixed in any
proportion to make a solid solution with
SS
the same crystal structure.
 Assumed that 1 mol of homogeneous solid
solution is made by mixing together XA mol
of A with XB mol of B. Free
energy
 XA and XB are the mole fraction of A and B per mole
in the alloy. befor
GB
mixing
Note: XA + XB = 1 (1.13) G1

The Gibbs free energy of the system GA

before mixing is given by:
0 XB 1
G1 = XAGA + XBGB J.mol-1 (1.14) A B
 Kinetic processes in Materials
1.3.1. The Gibbs Free Eneggy of Binary Solutions

 After mixing the free energy of the

solid solution, G2 will be:
G2 = G1 + Gmix (1.15)
where Gmix is the change in Gibbs
free energy caused by the mixing.

G1 = H1 - TS1
G2 = H2 - TS2
Hmix = H2 - H1
where Hmix is the heat absorbed or
Smix = S2 - S1 evolved during mixing, representing
the difference in internal energy (E)
before and after mixing.
It can be called heat of mixing.
Gmix = G2 – G1 = Hmix - TSmix (1.16)
Smix is the difference in entropy
between the mixed and unmixed states.
 Kinetic processes in Materials

1.3.2. Ideal solution

Gmix = Hmix - TSmix (1.16)

 If Hmix = 0, the resultant solution is said to be ideal and the free energy change on
mixing is only due to the change in entropy:
Gmix = -T Smix (1.17)

Smix can be found as follows: S = k ln (1.18)

where k is Boltzmann’s constant = R/Na = 1.380649×10−23 J⋅K−1

 is a measure of randomness or the number of distinguishable ways of
arranging the atoms in the solution.

N A  N B !
  (1.19)
N A!N B!

NA = X A N a ; NB = X B N a

NA and NB are number of A and B atoms, Na is Avogadro’s number

1.3.2. Ideal solution

Example 3.
(a) Assumed that there are 4 atoms (2 A-atoms and 2 B-atoms) in a simple cubic system.
How many distinguishable ways of arranging the atoms in the system?


N A  N B ! 
N A! N B !

(b) If there are 3 A-atom and 1 B-atom than how many ways?

The randomness is highest if NA = NB

 Kinetic processes in Materials

1.3.2. Ideal solution S = k ln N A N B !

  (1.19)
(1.18) N A!N B !

By substituting Equations (1.19) into (1.18),

using the Stirling’s approximation
(ln N!  N lnN – N)
and the relationship Nak = R
where R is universal gas constant,

Smix = -R (XAlnXA + XBlnXB) (1.19’)

Note: Since XA and XB are less than unity,

Smix is positive, i.e. there is an increase in 50%
entropy on mixing.
Gmix is function of composition
The free energy of mixing, Gmix = -TSmix and temperature
 Gmix is larger if temperature
is higher and amounts of
Gmix = RT (XAlnXA + XBlnXB) (1.20) component are equal
 Kinetic processes in Materials

1.3.2. Ideal solution Change

because
After mixing Before mixing of mixing Gmix
GB
G1
G2 = G1 + Gmix
G2
GA GB

GA
G2 = XAGA + XBGB + RT (XAlnXA + XBlnXB)

Note:
1. The actual free energy of the solution
G will also depend on GA and GB
2. As the temperature increases, GA and
GB decrease and the free energy
curves assume a greater curvature For ideal solution a random
arrangement of atoms is the
3. The free energy curves must end
equilibrum, or most stable
asymptotically at the vertical axes of
arrangement.
the pure components
Kinetic processes in Materials

1.3.3. Chemical Potential

 In alloy it is 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 at constant temperature and pressure,
the size of the system will increase by dnA and therefore the total free energy of
the system will also increase by a small amount dG’.
 If dnA is small enough, dG’ will be proportional to the amount of A added:
dG’ = A dnA (T, P, nB constant) (1.22)
 The proportionality constant A is called the partial molar free energy of A or the
chemical potential of A in the phase:

Note: G’ refers to whole system,

whereas G denotes the molar free
energy and is therefore independent
of the size of the system.
 Kinetic processes in Materials

1.3.3. Chemical Potential

 G ' 
 A   
Definition: chemical potential is the change of the free  n A T , P , n B
energy of whole system (G’) while a very small amount of
a component is added.  G ' 
Notes:
 B   
 nB T , P ,n A
 For binary solution at constant temperature and pressure
the separate contributions can be summed:
dG’ = A dnA + B dnB (1.24)
 If the solution contains more than 2 components and T and P change, Equation 1.24
must be added to give the general equation:
dG’ = -SdT + VdP + A dnA + B dnB + C dnC + …
o If A and B are added in the correct proportions (dnA : dnB = XA : XB, for example if
XA = 2/3, XB = 1/3, dnA : dnB = XA / XB = 2) , the size of the system can be increased
without changing A and B.
o So if Xamol A and XB mol B is added, the free energy of the system will increase by the
molar free energy. Therefore from (1.24) one can obtain:
G = A XA + B XB J mol-1 (1.25)
 Kinetic processes in Materials

1.3.3. Chemical Potential Molar

free
energy
A and B can be obtained by
extrapolating the tangent to the G
G
curve to the sides of the molar free B
energy diagram A
 Comparison of Equations 1. 21 and 1.25:
A XB B
G2 = XAGA + XBGB + RT (XAlnXA + XBlnXB) (1.21)

G = A XA + B XB (1.25)

G2 = XA(GA + RTlnXA) + XB(GB + RTlnXB) (1.21a)

A B
b
gives A and B for an ideal solution as:
a
A = GA + RT lnXA
B = GB + RT ln XB (1.26)
c d
 The difference between  and G is RT lnX
1.8. 15 g Au and 25 g Ag are mixed to form single-phase ideal solution.
a) How many mole of solution are there?
b) What are the mole fraction of gold and silver?
c) What is the molar entropy of mixing?
d) What is the total entropy of mixing?
e) What is the molar free energy change at 5000 C?
f) What are the chemical potentials of Au and Ag at 5000 C taking the free energies of pure
Au and Ag as zero?
g) By how much will the free energy of the solution change at 5000 C if one Au atom is
added? Express the answer in eV/atom
Given: atomic weight of Au is 197 and of Ag is 108

a) Number of mol of Au = 15/197 = 0.076

Number of mol of Ag = 25/108 = 0.231
Number of mole of solution = 0.307

b) Mole fraction of Au = 0,076/0,307 = 0.248

Mole fraction of Ag = 0,231/0,307 = 0.752

c) Molar Entropy of mixing

Smix = -R (XAlnXA + XBlnXB) = - 8,314 (0,248.ln0,248 + 0,752.ln0,752) = 4.66 JK-1mol-1
d) What is the total entropy of mixing?
e) What is the molar free energy change at 5000 C?
f) What are the chemical potentials of Au and Ag at 5000 C taking the free energies of
pure Au and Ag as zero?
g) By how much will the free energy of the solution change at 5000 C if one Au atom íis
added? Express the anwser in eV/atom

d) Total entropy of mixing = Molar entropy of mixing  number of moles of solution

= 4.66 . 0.307 = 1.43 J K-1
e) Molar free energy change at 5000 C
= Gmix = -RT (XAlnXA + XBlnXB)
= -TSmix = -773  4,66 = - 3,6 kJ mol-1
f) Au = GAu + RTlnXAu = 0 + (8.314  773  ln0.248) = - 8.96 kJ mol-1
Ag = GAg + RTlnXAg = 0 + (8.314  773  ln0.752) = - 1.83 kJ mol-1
g) For a very small addition of Au:
dG’ = A dnA (T,P,nB = const)
At 5000: Au = 8.96 kJ mol-1 , Avogadro number = 6.023  1023, 1eV = 1.6  10-19 J

 8,96.103
G '   Au  19 23
eV / atom  0.93.10 1
eV / atom
1,6.10 .6,023.10
 Kinetic processes in Materials

1.3.4. Regular Solutions

A regular solution is a solution whose entropy of mixing is equal to that of an ideal

solution with the same composition, but is non-ideal due to a nonzero enthalpy of mixing.

 In reality Hmix  0 (mixing is endothermic

(heat absorbed) or exothermic (heat
evolved).
 It is assumed that the heat of mixing,
Hmix, is only due to the bond energies
between adjacent atoms.
Necessary conditions: volumes of pure A
and B are equal and do not change during
mixing so that the interatomic distances
and bond energies are independent of
composition.
Three types of interatomic bonds are present:
o The structure of a binary solid solution
A-A (like-like) bonds each with an energy AA
is shown schematically in Fig.
B-B (like-like) bonds each with an energy BB
A-B (like-unlike) bonds each with an energy AB
 Kinetic processes in Materials

1.3.4. Regular Solutions

 The internal energy of the solution, E, will depend on the number of bonds of each
type PAA, PBB and PAB such that:
E = PAAAA + PBBBB + PABAB
 Before mixing pure A and B contain only A-A
and B-B bonds,
so the change in internal energy on mixing is given by:
Hmix = PAB  (1.27)
𝜺𝑨𝑨 𝜺𝑩𝑩
where 𝑨𝑩 (1.28)
𝟐
 If  = 0, Hmix = 0, the solution is ideal, the atoms are
completely randomly arranged and
PAB = NazXAXB bonds mol-1 (1.29)
where Na: Avogadro’s number, z is the number of bonds per atom.
 If  < 0 (like-unlike bond energy is smaller than that of like-like), the atoms in the
solution will prefer to be surrounded by atoms of the opposite type to reduce free
energy of the system and this will increase PAB  PAB > NazXAXB
 If  > 0, PAB will tend to be less than in a random solution: PAB < NazXAXB
 Kinetic processes in Materials

1.3.4. Regular Solutions Hmix = PAB  (1.27)

PAB = NazXAXB (1.29)

 In which case the following equation is

good approximation:
Hmix
Hmix = NazXAXB  =  XAXB (1.30) per
mol
where  = Na z  (1.31)

 Real solution that closely obey Equation 

1.30 are known as regular solutions.

 The variation of Hmix with composition

is parabolic and is shown in Fig. beside
A XB  B
for  > 0 ( > 0)

Hmix is max
(= 0,25  ) if
XA = XB = 0.5
Kinetic processes in Materials
1.3.5. Real Solutions

𝑨𝑨 𝑨𝑩
𝑨𝑩  = Na z  Hmix = NazXAXB  =  XAXB

 In alloys where the enthalpy of mixing, Hmix , is not zero ( and   0) the
assumption that a random arrangement of atoms is the equilibrum, or most
stable arrangement is not true,
and the calculated value for Gmix
Gmix = RT (XAlnXA + XBlnXB) (1.20)
will not give the minimum free energy.

Not most stable arrangement

if Hmix is not zero

 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.
G = H – TS
  
 Kinetic processes in Materials In systems where there is a size
difference between the atoms the quasi-
1.3.5. Real Solutions chemical model will underestimate the
change in internal energy on mixing
𝑨𝑨 𝑩𝑩 since no account is taken of the elastic
𝑨𝑩
strain fields which introduces a strain
energy term into Hmix.
In system with  < 0 the If  > 0 the internal
internal energy of system energy can be
is reduced by increasing reduced by increasing
the number of A-B bonds, the number of A-A
i.e. by ordering the atoms and B-B bonds, i.e. by
as shown in figure a. the clustering of the When the size difference is very large
atoms into A-rich and the interstitial solid solution are
B-rich groups (fig. b). energetically most favourable (Fig. c).

a) b) c)
 Kinetic processes in Materials

1.3.6. Ordered Phases

 If the atoms in a substitutional solid solution are completely

randomly arranged (each atom position is equivalent,  = 0)
then PAB, the number of A-B bonds, in such solution is given
by Equation 1.29:
PAB = NazXAXB bonds mol-1

 If  (= Na z  ) < 0 (or  < 0)

and the number of A-B bonds is 𝑨𝑨 𝑨𝑩
𝑨𝑩
greater than this, the solution is said
to contain short-range order (SRO).

 The degree of the ordering can be PAB  PAB ( random)

quantified by defining a SRO s
parameters such that: PAB (max)  PAB ( random)

where PAB (max) and PAB(random) refer to the maximum number of bonds
possible and the number of bonds for a random solution, respectively.
 Kinetic processes in Materials
1.3.6. Ordered Phases
PAB  PAB ( random) c) In solutions with
Example of orders s
PAB (max)  PAB ( random) compositions that are
close to a simple ratio of
A:B atoms another type
a) Random A_B b) Same alloy with short- of order as the long-
solution with a range order range one can be found.
total of 100 atoms PAB = 132, PAB(max) ~ 200, Now the atom sites are
and XA = XB = 0.5, S = (132 -100)/(200 – 100) no longer equivalent but
PAB ~ 100 (= PAB = 0.32 can be labelled as A-sites
(random), S = 0. (more PAB) and B-sites.

(c)
Kinetic processes in Materials

1.3.6. Ordered Phases

 Example: ordered substitutional structures in the Cu-Au system

a) high-temperature b) At low temperature solution c) Alloy with the

disordered with XCu = XAu = 0,5, i.e. 50/50 composition Cu3Au:
structure; atoms Cu Cu/Au mixture, form an ordered another superlattice
or Au can occupy structure in which the Cu and Au is found.
any site. are arranged in alternate layer;
each atom position is no longer
equivalent and the lattice is
described as a CuAu superlattice. Au-atoms
occupy the
corner site only

Alternative
layers of
Cu and Au
 Kinetic processes in Materials
1.3.6. Ordered Phases
Note:
 The entropy of mixing of structures with long–range order is extremly small
 With increasing temperature the degree of order decreases until some
critical temperature there is no long-range order at all.
 This temperature is a maximum when the composition is ideal required for the superlattice.
Critical
temperature  However, long-range order can
Critical temperatures is lower if the
composition still be obtained when the
deviates composition deviates from the
from ideal
ideal if some atom sites are left
vacant or if some atoms sit on
wrong sites.
 In such cases it can be easier to
disrupt the order with increasing
temperature and the critical
temperature is lower.

Note: The critical temperature for loss of long-range order increases with increasing ,
( = Naz ) or Hmix, and in many systems the ordered phase is stable up to the melting point
Kinetic processes in Materials

1.3.6. Ordered Phases

Some most common ordered lattices

 Kinetic processes in Materials

1.3.7. Intermediate Phases

 Often the configuration of atoms that has the minimum free energy after mixing
does not have the same crystal structure as either of the pure components (A or
B). In such cases the new structure is known as an intermediate phase.

(a) Intermediate phases of a solid solution.

(b) Intermediate phases of the Mg-Pb system.
 Kinetic processes in Materials

 Intermediate phases are

often based on an ideal
atom ratio that results in a
minimum Gibss free energy.
G
X

L+
+L Mg2Pb

Gmin

A B
Ideal composition

 For compositions that deviate  + Mg2Pb

+
from the ideal, the free energy Mg2Pb
Mg2Pb
is higher giving a characteristic
“U” shape to the G curve.

 The range of compositions (X) over which the free energy curve has a
meaningful existence depends on the structure of the phase and the
type of interatomic bonding.
 Kinetic processes in Materials
1.3.7. Intermediate Phases
G
o When small composition deviations cause
X
a rapid rise in G, the phase is referred to
as an intermetallic compound and is
usually stoichiometric, i.e. has a formula GA
Gmix
AmBn, where m and n are integers.

A B
a) Ideal composition

G
X
GB

o In other structure fluctuations in composition GA

can be tolerated by some atoms occupying
“wrong” positions or by atom sites being left
vacant, and in these cases the curvature of
A B
the G curve is much less (b). b) XB 
Kinetic processes in Materials
Kinetic processes in Materials
1.3.7. Intermediate Phases

-Al5FeSi  Si/Al = 1/5  - Al8Fe2Si  Si/Al = 1/8

Al5FeSi -  phase, platelete form, Al8Fe2Si -  phase, Chinese script form,

coarse very hamful, stable finer, less hamful, but metastable
As temperature decreases

   transformation involved Si
diffusion of Si from the melt into 

Preventing by:
1. Rapid solidification  no time for diffusion Si
2. Adding Mn to form intermetallic compounds such as Si19Mn11 ,

SiMn …or Al15(FeMn)3Si2  no more Si

3. Creating the protective layer

TEM picture showing a Si-rich zone
arrounding  in the presence of Sr
 Kinetic processes in Materials
G Before mixing
1.4. Equilibrum in Heterogeneous Systems
c
It is usually the case that A and B do not have the d
same crystal structure in their pure states at a given
temperature. In such cases two free energy curves a Gmix
must be drawn, one for each structure. b
After
e
The stable forms of pure A and B at a given mixing
A B
temperature and pressure can be denoted as  and
X
 respectively

Assumed  is fcc and  is bcc. The molar free energies

of fcc A and bcc B are shown as point a and b
 
The first step in drawing the free energy curve of the fcc
 is, therefore, to convert the stable bcc arrangement of
B atoms into an unstable fcc arrangement. This requires
an increase in free energy, bc

The free energy curve for the  phase can now be

constructed as before by mixing fcc A and fcc B. Note: A-rich alloys will have
the lowest free energy as a
Gmix for  of composition X is given by the distance
homogeneous  phase and
de as usual. B-rich alloys as  phase.
 Kinetic processes in Materials
1.4. Equilibrum in Heterogeneous Systems Consider alloy X0

 If atoms are arranged as a homogeneous

phase, the free energy will be highest as  and
lowest as , i.e. G0 per mole.

 However, the system can lower its free energy

if the atoms separate into two phases with
compositons 1 and 1, for example (Fig. a).
The free energy of the system will then
reduced to G1.
Futher reductions in free energy can be
achieved if the A and B atoms interchange
between the  and  phases until the
compositions e and e are reached (Fig b).

The free energy of the system Ge is now a

minimum and there is no desire for futher change.

Consequently the system is in equilibrium

and e and e are the equilibrium
compositions of the  and  phases.
 This results is quite general and applies to any alloy with an overal composition
between e and e: only the relative amounts of the phases change, as given by
the lever rule (compaire X0 and X1)

The denominator is the same but the

numerators are diffenent.
>
 When the alloy composition lies outside this
range, however, the minimum free energy lies
on the G and G curves and the equilibrium
state of the alloy is a homogeneous single
phase.
 From Fig. b) it can be seen that equilibrium
between two phases requires that the tangents
to each G curve at equilibrium compositions lie
on a common line.
 In the other words each component must have
x2 x1 X1
the same chemical potential in the two phases,
i.e. for heterogeneous equilibrium:
A = A, B = B
 Kinetic processes in Materials

Grain
1.5. The Influence of Interfaces on Equilibrium boundary

 In the free energy curves that have been drawn so

far the surfaces, grain boundaries and interphase
interfaces have been ignored.


 Interphase interfaces can become extremly
Atmos-
important in the early stages of phase  pheric
transformations (e.g. crystalisation) when one pressure
P
phase, , say, can be present as very fine particles
P
in the other phase.

 If the  phase is acted on by a pressure 1 atm, the  phase is subjected to an extra

pressure P due to the curvature of the / interface.

 If  is the / interfacial energy and the particles are spherical with radius r,
P is given appoximately by:
2/r: surface curvature
 : surface tension (energy)
 Kinetic processes in Materials

1.5. The Influence of Interfaces on Equilibrium


By definition, the Gibbs free energy contains a Atmos-
“PV” term: G = H – TS and H = E + PV so an  pheric
pressure
increase of pressure P therefore causes an
P
increase in free energy G: P
𝟐
G = V P ∆𝑷 =
𝒓
𝜸

Therefore the  cuvre on the molar free energy-composition diagram

in Fig. below will be raised by an amount:

2 Gr
G  VP  Vm G
r
G
Vm is the molar volume of the  phase G 

This free energy increase due to

interfacial energy is known as a
capillarity effect or the X Xr XB  X
Gibbs-Thomson effect.
 G
Gr
 An important practical consequence of
G
the Gibbs-Thomson effect is that the
G 
solubility of  in  is sentitive to the
size of the  particles.

 From the common tangent

construction it can be seen that the X Xr XB  X
concentration of solute B in  in
equilibrium with  across a curved 
interface (Xr) is greater than X, the
equilibrium concentration for a planar 
interface (or without interface). X
Xr > X
Xr
Taking the following typical values:
 = 200 mJ m2, Vm = 10-5 m3mol-1,
R = 8.31 J mol-1 K-1, T = 500 K gives: Xr 1
 1
X r nm 
For r = 10 nm Xr / X  1.1
For particles visible in the light microscope (r > 1 m) capillarity effects are very small:
for r = 1 m (1000 nm)  Xr / X = 1,001
 1.14. By how much liquid Cu be cooled below Tm before a solid particle of Cu can grow if
the particle diameter is:
a) 2 m
b) 2 nm (20 amstrons)?
Given for Cu: Tm : 1085 0C; Atomic weight: 63.5; Density 8900 kg m-3
Solid/liquid interface energy  = 0.144 J m-2
Latent heat of melting: L = 13.300 J mol-1

 If solid exists as a sphere of radius r within a liquid, then its free energy is increased by an
amount:
Grs is the molar free energy of the sphere

2 Vm
G  Gr  G 
S S
solid and Gs is the molar free energy in the
r absence of interface (or planar interface)

Growth of the sphere must lead to a

Gr
reduction of the total free energy of G
the system, i.e growth can occure
when GrS < GL, with G
G 
G = GL – GrS = S.T = (L/Tm).T

LT 2Vm

Tm r X Xr XB  X
 Increase in G 
Decrease in G
because of a because of the
volume unit of  formation of

liquid transforms liquid/solid
into solid interface
Molar LT 2Vm
free 
energy, Tm r
G 2VmTm
T 
rL
G = LT/Tm G rS
Substituting the
GrS - GS = 2Vm /r numerical values
given:
Tmin G S T (r = 1 m) > 0.2 K
GL T (r = 1 nm) > 200 K

Tm Temperature, T

Home exercise 1.1: do this example for Al.

Find yourself the properties of Al.
 Kinetic processes in Materials
G
1.6. The Kinetics of Phase
Transformations Metastable
Ga

The thermodynamics can be used G1

to calculate the driving force for a G: Decrease in
G because of a
transformation: G = G2 – G1, volume unit of G
liquid transforms
but it can not say how fast a Stable
into solid
transformation will proceed. G2

The study of how fast processes

occur belongs to the science of
kinetics.
Innitial Activated Final
state state state
Before the free energy of the atom
Molar
can decrease from G1 to G2 the GL
free
atom must pass through a so-called energy,
transition or activated states with a G G
free energy Ga above G1 GS
T

Temperature, T
 Kinetic processes in Materials How an atom can reach the
activated state?
1.6. The Kinetics of Phase Transformations
G
As a result of the random thermal motion of Metastable
Ga  activation free
the atoms the energy of any particular atom
G1 energy barrier
will vary with time and occasionally it may
be sufficient for the atom to reach the
activated state. This process is known as Thermal
G
activation
thermal activation. Stable
G2
The probability of an atom reaching
the activated state is given by
exp (-Ga/kBT), where kB is
Innitial Activated Final
Boltzmann’s constant (= R/Na) and
state state state
Ga is known as the activation free
energy barrier.
 G a 
 The rate at which a transformation occurs will rate exp  
depend on the frequency with which atoms reach  kT 
the activated state.
 H a 
Putting Ga = Ha - TSa and changing from atomic rate exp  
to molar quantities enables this equation to be  kT 
wrotten as Arrhenius rate equation
Arrhenius rate equation