Solid State Reactions

Phase Diagrams and Mixing

Prof Ken Durose,

Univ of Liverpool

Text book for this lecture:

Callister – Materials Science and Engineering
 Learning objectives
1.Solid state reactions
Recap: how Gibbs Free Energy
can be used to predict reactions
2 Phase diagrams
Be able to read a phase diagram
Be able to identify the phases
present at a given point
Be able to calculate how much
of those phases there are
Be able to predict the
microstructures from the phase
diagram
3 Mixing
Understand the thermodynamic
basis of mixing
Understand the origin of the
miscibility gap
Be able to use the phase
diagram to predict miscibility
phenomena
There will be worked
examples on this bit
for you to practice ….
 1. Prediction of reactions
e.g. solar cell contact – metal M to semiconductor AB

M stable M

AB AB
or
unstable M
MB + A

AB
M + AB  MB  A Will it happen at equilibrium?

keqm = [MB]*[A] /[M]*[AB] If keqm is large, the reaction goes from l to r

Find the Gibb’s free energy for the reaction. G   RT ln( k eqm )

If ∆G is large and negative, keqm is large and the reaction goes from l to r
 1. Prediction of reactions
G reaction  H reaction  T S reaction
G reaction  G final
 G initial
H reaction  H final
 H initial
S reaction  S final  S initial

M + AB  MB  A

G reaction  ( G MB  G A )  ( G M  G AB )
etc If ∆G is large and negative, keqm is large and the reaction goes from l to r

In this case the contact would be unstable to reaction with the solar cell
materials. The contact could become non-Ohmic, the series resistance
could increase, and the performance could become unstable.
 2. Equilibrium phase diagrams
ISSUES TO ADDRESS...
• When we combine two elements...
what equilibrium state do we get?
• In particular, if we specify...
--a composition (e.g., wt% Cu - wt% Ni), and
--a temperature (T )
then...
How many phases do we get?
What is the composition of each phase?
How much of each phase do we get?

Phase A Phase B

Nickel atom
Copper atom
 Components and Phases
• Components:
The elements or compounds which are present in the mixture
(e.g., Al and Cu)
• Phases:
The physically and chemically distinct material regions
that result (e.g.,  and ).

Aluminum-  (lighter
Copper
phase)
Alloy

 (darker
phase)
Adapted from
chapter-opening
photograph,
Chapter 9,
Callister 3e.
 Phase Equilibria
Simple solution system (e.g., Ni-Cu solution)

Crystal electroneg r (nm)

Structure
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278

• Both have the same crystal structure (FCC) and have

similar electronegativities and atomic radii (W. Hume –
Rothery rules) suggesting high mutual solubility.
• Ni and Cu are totally miscible in all proportions.
 Phase Diagrams
• Indicate phases as function of T, Co, and P.
• For this course:
-binary systems: just 2 components.
-independent variables: T and Co (P = 1 atm is almost always used).
T(°C)
• Phase 1600 • 2 phases:
Diagram L (liquid)
for Cu-Ni
1500 L (liquid)  (FCC solid solution)
system 1400 • 3 phase fields:
id us L
liq + s
1300 u
L lidu L+ 
so 
1200  Adapted from Fig. 9.3(a), Callister 7e.
(Fig. 9.3(a) is adapted from Phase
1100
(FCC solid Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park,
solution) OH (1991).
1000
0 20 40 60 80 100 wt% Ni
 Phase Diagrams:
number and types of phases
• Rule 1: If we know T and Co, then we know:
--the number and types of phases present.
T(°C)
• Examples: 1600
A(1100°C, 60): L (liquid)
1 phase:  1500

B (1250°C,35)
u s Cu-Ni
id
B (1250°C, 35): 1400 il qu us phase
2 phases: L +  olid diagram
s
1300 +  
L (FCC solid
1200 solution)
Adapted from Fig. 9.3(a), Callister 7e.
(Fig. 9.3(a) is adapted from Phase 1100 A(1100°C,60)
Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park,
OH, 1991). 1000
0 20 40 60 80 100 wt% Ni
 Phase Diagrams:
composition of phases
• Rule 2: If we know T and Co, then we know:
--the composition of each phase. Cu-Ni
T(°C) system
• Examples:
C o = 35 wt% Ni TA A
tie line dus
i qui
At T A = 1320°C: 1300 L (liquid) l

L +
Only Liquid (L) B us
TB l i d
C L = C o ( = 35 wt% Ni) so

At T D = 1190°C: 
1200 L+ D (solid)
Only Solid ( ) TD
C  = C o ( = 35 wt% Ni )
20 3032 35 4043 50
At T B = 1250°C: C LC o C  wt% Ni
Both  and L Adapted from Fig. 9.3(b), Callister 7e.
C L = C liquidus ( = 32 wt% Ni here) (Fig. 9.3(b) is adapted from Phase
Diagrams
of Binary Nickel Alloys, P. Nash (Ed.), ASM
C  = C solidus ( = 43 wt% Ni here) International, Materials Park, OH, 1991.)
 Phase Diagrams:
weight fractions of phases – ‘lever rule’
• Rule 3: If we know T and Co, then we know:
--the amount of each phase (given in wt%). Cu-Ni
• Examples: T(°C) system
C o = 35 wt% Ni TA A
tie line dus
i
At T A : Only Liquid (L) 1300 L (liquid) liq u

W L = 100 wt%, W  = 0 B L+
dus
At T D : Only Solid ( ) TB R S so l i

W L = 0, W  = 100 wt% 
L + (solid)
1200 D
At T B : Both  and L TD
S 43  35 20 3032 35 40 43 50
WL =   73 wt % C LC o C  wt% Ni
R +S 43  32
Adapted from Fig. 9.3(b), Callister 7e.
R (Fig. 9.3(b) is adapted from Phase Diagrams of
W = = 27 wt% Binary Nickel Alloys, P. Nash (Ed.), ASM
R +S International, Materials Park, OH, 1991.)
 e.g.: Cooling in a Cu-Ni Binary
• Phase diagram: T(°C) L (liquid) L: 35wt%Ni
Cu-Ni system. Cu-Ni
• System is: system
130 0 A 
--binary L: 35 wt% Ni L +
i.e., 2 components: : 46 wt% Ni
35 B
46
Cu and Ni. 32 C
43
--isomorphous 24
D L: 32 wt% Ni
36
i.e., complete
solubility of one +  : 43 wt% Ni
1200
L E
component in L: 24 wt% Ni
another;  phase : 36 wt% Ni

field extends from (solid)
0 to 100 wt% Ni.
• Consider 1100
Co = 35 wt%Ni. 20 30 35 40 50
Adapted from Fig. 9.4, Co wt% Ni
Callister 7e.
 Equilibrium cooling
• The compositions that freeze are a
function of the temperature
• At equilibrium, the ‘first to freeze’
composition must adjust on further
cooling by solid state diffusion
• We now examine diffusion processes –
how fast does diffusion happen in the
solid state?
 Diffusion
t=0
Fick’s law – for
steady state t=0
Co C
diffusion
J = flux – amount
of material per x
unit area per unit C
time 3Co/4
C = conc t=t
Co/2
Co/4
dC
J  D x
dx x
2
 Dt 2x
 Diffusion cont….
• Diffusion coefficient D (cm2s-1)

• Non-steady state diffusion

Fick’s second law
C C 2

D
t x 2

• Diffusion is thermally activated

 Qd 
D  D 0 exp   
 RT 
 L

Non –
α+L
equilibrium
α
cooling
 Cored vs Equilibrium Phases
• C changes as we solidify.
• Cu-Ni case: First  to solidify has C = 46 wt% Ni.
Last  to solidify has C = 35 wt% Ni.

• Fast rate of cooling: • Slow rate of cooling:
Cored structure Equilibrium structure
Uniform C :
First  to solidify:
46 wt% Ni 35 wt% Ni
Last  to solidify:
< 35 wt% Ni
Mechanical Properties: Cu-Ni System
• Effect of solid solution strengthening on:
--Tensile strength (TS) --Ductility (%EL,%AR)

60
Tensile Strength (MPa)

%EL for pure Cu

Elongation (%EL)
400 50 %EL for
TS for pure Ni
pure Ni 40
300
TS for pure Cu 30
200 20
0 20 40 60 80 100 0 20 40 60 80 100
Cu Ni Cu Ni
Composition, wt% Ni Composition, wt% Ni
Adapted from Fig. 9.6(a), Callister 7e. Adapted from Fig. 9.6(b), Callister 7e.

--Peak as a function of Co --Min. as a function of Co

 Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.
Cu-Ag
T(°C) system
Ex.: Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L,   ) 1000
• Limited solubility:  L+  L +
800 779°C
: mostly Cu TE 8.0 71.9 91.2 
: mostly Ag 600
• TE : No liquid below TE +
400

• CE : Min. melting TE
composition 200
0 20 40 60 CE 80 100
• Eutectic transition Co wt% Ag in Cu/Ag alloy

L(CE) (CE)  (CE) Adapted from Fig. 9.7,
Callister 7e.
 e.g. Pb-Sn Eutectic System (1)
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, find...
--the phases present:  +  Pb-Sn
--compositions of phases: T(°C) system
CO = 40 wt% Sn
C = 11 wt% Sn 300
L (liquid)
C = 99 wt% Sn
--the relative amount  L+ 
200 183°C L + 
of each phase: 18.3 61.9 97.8
W =
S
=
C - CO 150
R S
R+S C - C 100
99 - 40 59 +
= = = 67 wt%
99 - 11 88
C -C 0 11 20 40 60 80 99100
W = R = O  C Co
C, wt% Sn C
R+S C - C
Adapted from Fig. 9.8,
40 - 11 = 29 Callister 7e.
= = 33 wt%
99 - 11 88
 Microstructures
in Eutectic Systems: II
L: Co wt% Sn
• 2 wt% Sn < Co < 18.3 wt% Sn T(°C)
400
• Result: L
 Initially liquid +  L
300 
 then  alone L+
 : Co wt% Sn
 finally two phases
200

  poly-crystal TE
 fine -phase inclusions 

100
+  Pb-Sn
system
0 10 20 30
Adapted from Fig. 9.12, 2 Co Co , wt% Sn
Callister 7e. (sol. limit at Troom) 18.3
(sol. limit at TE )
 Microstructures
• Co =C
in Eutectic Systems: III
E
• Result: Eutectic microstructure (lamellar structure)
--alternating layers (lamellae) of  and  crystals.
Micrograph of Pb-Sn
T(°C) eutectic
L: Co wt% Sn microstructure
300 L
Pb-Sn
system
L+ 
200  183°C L 
TE

100 160 m
 : 97.8 wt% Sn
Adapted from Fig. 9.14, Callister 7e.
: 18.3 wt%Sn

0 20 40 60 80 100
18.3 CE 97.8
Adapted from Fig. 9.13, 61.9 C, wt% Sn
Callister 7e.
 Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister

7e.
 Intermetallic Compounds
Adapted from
Fig. 9.20, Callister 7e.

Mg2Pb

Note: intermetallic compound forms a line - not an area -

because stoichiometry (i.e. composition) is exact.
 Eutectoid & Peritectic
Peritectic transition   L 

Cu-Zn Phase diagram

Adapted from
Fig. 9.21, Callister 7e.
Eutectoid transition  
 Summary
• Phase diagrams are useful tools to determine:
--the number and types of phases,
--the wt% of each phase,
--and the composition of each phase
for a given T and composition of the system.
• Alloying to produce a solid solution usually
--increases the tensile strength (TS)
--decreases the ductility.
• Binary eutectics and binary eutectoids allow for
a range of microstructures.
 3)Thermodynamics of mixing
• Why do some things mix and others not?
• Why does heating promote mixing?
• Is an alloy of two semiconductors a
random solid solution, or is it just a
mixture of two phases?

Solid solution OR Mixture of phases ?

 Free energy of mixing

G mix  H mix
T S mix
• Enthalpy term – bond energies
• Entropy term – stats of mixing
 behaviour of mixtures 

consider the case: Pure A + Pure B 

mixture AxB1-x
Enthalpy term: Compare the energy in
bonds (VAB etc) before and after mixing
Heat of mixing Binding energy Binding ∆Hmix
in mixture compared energy
to average in change on
components mixing

Exothermic VAB > 1/2(VAA + VBB) Stronger -ve

Ideal VAB = 1/2(VAA + VBB) Same 0

endothermic VAB < 1/2(VAA + VBB) Weaker +ve

For reference only

∆Hmix derived
∆Hmix = (H for mixture AB) – (H for pure A + H for pure B)

• ∆Hmix = zNxA xB {1/2(VAA + VBB) – VAB}

NAA etc = number of bonds of type AA, AB

etc
NA, NB, number of atoms of A, B. NA + NB =
N
VAA, VBB, VAB, = binding energies of pairs A-A,
xA etc = NA/N = mole fraction of A
xB = NB/N = mole fraction of B.
For reference only

∆Smix derived
∆S = (Sfinal – Sinitial)

Sfinal from the statistical definition S = kBlnw

N !
∆Smix = kBln ( Nx )! ( Nx )!
A B

Using Stirling’s approximation lnn! = nlnn-n gives

• ∆Smix = -NkB[ xAlnxA + xBlnxB]
For reference only

∆Gmix - the formula

G mix  H mix
T S mix

• ∆Gmix = zNxA xB {1/2(VAA + VBB) – VAB}

+ NkBT[ xAlnxA + xBlnxB]

Binding energy term {...} may be +ve or –ve

Entropy term [...] is negative
Examples – changing ∆Hmix e.g. #1

T
• i) Negative
∆Hmix
• The free energy
curve is
concave
downwards at
all points at all
x.
• A mixes with B
in all  2
G
proportions. 0 for all x
x 2
 changing ∆Hmix e.g. #2
• ii) ∆Hmix = 0 T

• “ideal
solution”
• mixing is
entropy
driven.
• miscibility
over the
whole
composition
range.
 changing ∆Hmix e.g. #3
iv) ∆Hmix large T∆S
∆H
and positive ∆G
• Enthalpy
dominates
• miscibility Energy
gap exists
1
0 0.5
x’ x’’
• In gap, solid
segregates Miscibility
into xA’ and gap

xA’’ x
Low T
T
Moderate T
T
High T – mixing is promoted
T
 Binary
isomorphou
L
s
phase L + solid
T
diagram solid

Mole fraction x
 Phase
diagram with L
miscibility
L + solid
gap T
B solid

x’ x’’
locus
A
G
2

0
x 2

or ‘spinode’ Mole fraction x

Example phase diagram
CdTe-CdS
Worked example of earlier concept

Pb-Sn Eutectic System (2)

• For a 40 wt% Sn-60 wt% Pb alloy at 200°C, find...
--the phases present:  + L Pb-Sn
--compositions of phases: T(°C) system
CO = 40 wt% Sn
C = 17 wt% Sn 300
L (liquid)
CL = 46 wt% Sn L+ 
--the relative amount 220
200
 R S L + 
of each phase: 183°C
CL - CO 46 - 40
W = = 100
CL - C 46 - 17
+
6
= = 21 wt%
29 100
0 17 20 40 46 60 80
C Co CL
CO - C 23 C, wt% Sn
WL = = = 79 wt% Adapted from Fig. 9.8,
CL - C 29 Callister 7e.