High Temp. Mat. Proc.

Lecture 1
Dilute metallic solutions

Seshadri Seetharaman
Tel.: 08-790 83 55
Mobil.: 070 578 04 26
E-mail: raman@kth.se
What are we going to discuss?
 What are we going to discuss?

1. How to extrapolate interaction parameters as a function

of temperature?
 What are we going to discuss?

1. How to extrapolate interaction parameters as a function

of temperature?

2. How to correlate interaction parameter with solubility?

 What are we going to discuss?

1. How to extrapolate interaction parameters as a function

of temperature?

2. How to correlate interaction parameter with solubility?

3. How to estimate ε when you do not get the values in

literature?
 What are we going to discuss?

1. How to extrapolate interaction parameters as a function

of temperature?

2. How to correlate interaction parameter with solubility?

3. How to estimate ε when you do not get the values in

literature?

4. What happens when the solution is not dilute?

  i   i  RT ln ai
a i  xi   i

Standard states :
 i  1 when xi  1
 'i  1 when xi  0
 ' '  1 when atom% i  0
 ' ' '  1 when wt % i  0

For a detailed description of standard states:

G.K.Sigforth and J.F. Elliott Can. Met. Quart. 13 (1974), p. 455

7
Wagners equation
Richarson p. 154→

ln  2  ln  2  x 2 2( 2)  x3 2(3) ...

  ln  2 
 2( 2)    x  0
 x 2  x2  0 3
...

  ln  2 
 2(3)    x  0
 x3  x32  0
...

 B  when x B  1

8
 Central Atom Model
Lupis and Elliot
Acta Metall. Vol. 15, (1967) p. 265

1. Interatomic forces – only among nearest neighbours

2. Additivity rule applies

3. Z – constant
B: solute;
standard state: pure B
ln γB: Energy for a ”B” atom surrounded by ”Z” A atoms
compared to pure B

9
 Ternary Solution A – B – C

Situation 1:

very dilute solutions of “B” and “C” in “A”

• Probability of B and C to be nearest neighbours is very

small
• Ternary solution can be considered as consisting of Binary
Solutions

  
G E  RTx A ln  A   RTx B ln  B
 
 RTx C ln  C 
10
 Ternary Solution A – B – C
(Note: A= solvent)

Situation 2:
when the concentrations of B and C increase
(ex. xB and xC  0.05)

Wagner´s equation meaningful

• as B and C can participate in the same cluster

• Not the higher order terms!!

11
 Wagner´s equation
ln  2  ln  2  x 2 2( 2)  x3 2(3) ...

where
  ln  2 
 2(3)    x11
 x3  x2 0
x3 0
....

log  2  log  2 ( 0)  % wt 2e2( 2)  % wt 3e2(3) ...

where
  log  2  %1100
e (3)   
  %3  %2  0
2
%3  0 12
....
Richardson, p.154

13
 Ternary solution A – B – C
(A = solvent)

Situation 3:
with higher SOLUTE
concentrations

 NON-LINEAR variation
of lnγ

ρ terms have to be taken into account 14

 Solvent A
Solute B
Solute C

3 and 4

15
 MacLaurin Series applied to Dilute
Solution Interactions
A = solvent, B, C, D….solutes at
low conc.

  ln  B  ln  B
ln  B  ln  B  x B  xC  ...
x B xC

2 2
 x B   ln  B  xC   ln  B
2 2
      ...
 2  2
x B  2  2
xC

 2 ln  B  2 ln  B
 x B xC  xB xD ...
x B  xC x B  x D
16
 Extrapolation of ε as function of
temperature
Richardson, p.184-190
  ln  B 
  x 1   B(C )
 xC  x BA  0
xC  0

Define
G B(C )  RT  B(C )  xC  H B(C )  TS B(C )   B(C ) xC  T B(C ) xC

 B(C )  B(C )

1 T
R

 B(C )
 is slope for  B(C ) vs 1
R T 17
18
 Extrapolation of ε
η has been found to be a linear function of ε for various
alloying elements

S in Cu or N in Fe
Chipman and Corrigan

O in Cu
Jacob and Jeffes,Trans. Inst. Min. Metall.
vol. 80, 1971, p.c 181

19
 Richardson p. 187

N in Fe alloys at 1600C
Chipman and Corrigan 20
 Richardson, p.188

S in Cu alloys at 1400 C
Chipman and Corrigan
21
22
 Richardson, p. 189

O in Cu alloys at 1200C
Jacob and Jeffes
23
 Extrapolation of ε
RT  i( j )   i( j )  T i( j )

If  i( j )  0
 i( j )  linear function of  i( j ) and
 i( j ) 1

 i( j ) RT

But  i( j )  0
 i( j ) 1  1 1
 
 i( j ) R  T  

 : hypothetic al temperatu re

Lupis and Elliott,Trans. AIME vol. 236, 1966, p. 130 24

Extrapolation of ε
RT  i( j )   i( j )  T i( j )

 i( j ) 1  1 1
 
 i( j ) R  T  


 i( j )   i( j )

 i( j )  i( j )
Plot of vs
R R

for Cu - O.x solutions

 linear
25
Taskinen and Holappa, Calphad, vol. 6 (1982), p.293

i( j )
   1800  200 K
i( j)

26
27
28
29
30
31
 Interaction parameter → Solubility
limits
(Richardson p. 348-350)
Fe-Al-O system (deoxidation process)
Al3O3(s) = 2 Al + 3 O

ln K Al  2 ln a Al  3 ln ao  ln a Al 2 O3

Differenti ate with respect to x Al

Note
 d ln K Al d ln a Al 2 O3 
 and  0
 dx Al dx Al 

d ln a Al d ln ao
2 3 0
dx Al dx Al 32
 ε → Solubility limit
d ln a Al  1  ( Al )  dx 
     Al   (AlO )  O 
dx Al  x Al   dx Al 

d ln aO 1  dxO  ( Al )  dx 
     O   O(O )  O 
dx Al xO  dx Al   dx Al 

 2 
   2 (AlAl )  3 O( Al )
 dxO 

x Al 
 
 dx Al  Al 2 O3  3 
   3 O(O )  2 (AlO )
 xO  33
ε → Solubility limit contd.
 O( Al )   (AlO ) when x Fe  1

2
 2 (AlAl )  3 O
( Al )
0
x *Al


1
( x *Al ) Al 2 O3  
3
 (AlAl )   O( Al )
2

x *Al  minimum point  0.0066 

 0.31 wt% at 1600  C 34
35
ε → Solubility limit (contd.)
Cr3O4 ( S )  3Cr  4O

 3 
   4 O
(Cr )
dxO
  xCr 
dxCr  4 
   4 O(O ) (O )
 3 Cr
 xO 

dx O
For the min.point, 0
dx Cr

xCr* Cr O
2 3

1
(Cr ) 3 (Cr )
 Cr  O
4

(Cr ) (Cr)
 Cr  0 and  O  8.8

*
xCr  0.085  7.9 wt% 36
 ε → Solubility limit
FeCr2 O4 ( s )  Fe  2Cr  4O

*
xCr  *
1  xCr 
1
 1 *   (Cr )
 2 (Cr )
 1  x Cr  Cr O
 2 

 0.0568  5.5 wt%

Good agreement with the figure.

37
38
ε → Solubility limits (cont.)
Fe - x - O melts saturated with Fe x  O

 
x *x 1  x *x

1
   
1  1   x *x  x( x )    O( x )
   

Valid only for dilute solutions

If  Ox   x( x )

  
 
x *x 
( x) 

 O 
(  metal/oxyg en ratio in the oxide)
39
 ε → Solubility limit
Applications:

1. To estimate the amount of deoxidizer needed to

achieve a certain O content in the metal

40
 ε → Solubility limit
Applications:

1. To estimate the amount of deoxidizer needed to

achieve a certain O content in the metal

(x )
Estimate  O if you know x x
*
2.

41
 ε → Solubility limit
Applications:

1. To estimate the amount of deoxidizer needed to

achieve a certain O content in the metal

(x )
Estimate  O if you know x x
*
2.

3. Can be used for non-ferrous systems as well

42
 ε → Solubility limit
Applications:

1. To estimate the amount of deoxidizer needed to

achieve a certain O content in the metal

(x )
Estimate  O if you know x x
*
2.

3. Can be used for non-ferrous systems as well

4. Can also be used for non-oxygen systems like

nitrides, carbides, sulphides and so on
43
 Interaction Parameters ↔ Reg.
Soln. Model
Richardson p.155

G E  x A x B b AB  x B xC bBC  xc x AbCA

ln  A( ABC ) 
xB
 x B  xC 
ln  A( AB ' ) 
xC
x B  xC

ln  A( AC ' )   1  x A 2 
G(EB ' 'C ' ' )
RT 44
45
46
xB'  xC'  1  xS   xB  xC ...1)

xB'' xB
''
 (ratio between B and C is constant along SM)
xC xC

xB'' xC''
2) SBM and SNX are similar 
1
 
xB xC 1  xS 

G E  x xB b B  xB xC bBC  xC x bC

 xS x ' bAB  x xC ' bC  bBC xB'' xC'' 1  xS 

' xC
xB
' 2
B 3a)
xB xC

Gx x '   ' Gx x '   1  xS  GEx '' x '' 

xB E xC E

2
3b)
x B'  B xC S C B C
47
For regular solutions :

G E  bSB x B  x B  xC   bSC xC  x B  xC   x B xC bBC

We know that
x 'B  xC'  1  x S    x B  xC 

2 xB x x B xC
G SE  bSB x B'  bSC xC' C  bBC x B' ' xC' ' 
x B' xC' x B' ' xC' '


  G SE( SB' )
xB 


  G SESC '
 x B  xC   x x ' 
xC 

 x B  xC   x , x '

 1  x S 2 GEB ' 'C ' ' 
 S B S C

In terms of activity coefficien ts :

xB xC G(EB ' 'C ' ' )

ln  BC   ln  S ( SB' )  ln  S ( SC ' )  1  x S 2
x B  xC x B xC RT
48
 Ternary Soln ↔ Ref. Soln. Model
Richardson, p. 146
System B-S-C; S = solute in high dilution
Darken: Trans. AIME, vol. 239, (1967), p.90

G SE( SBC )  x B G SE( BS )  xC G SE(CS )  1  x S 2 G BE' 'C ' '

since
x S  0 ; 1  x S   1   x B  xC 

ln  S ( SBC )  x B ln  B ( B ' 'C ' ' )  xC ln  C ( B ' 'C ' ' )  x B ln  B ( B ' 'C ' ' )  xC ln  C ( B ' 'C ' ' )

G BE' 'C ' '  Redistribu tion of solvent atoms due to solution of S - breaking of B - C bonds

Alcock & Richardson: Acta Metall.vol. 6 (1958), p.385

49
 Richardson, p. 147

Std. state :  S  1 when x S  0

G(EB ' 'C ' ' )
Comments: d  1  x S 2
RT
• very little predictive value when s : O or S = strong interactions
50
• qualitative assessment
 Ternary Soln ↔ Ref. Soln. Model
Solution B - S – C where S is the solute in infinitive dilution
(Change A → S) Richardson, p. 155

  ln  S 
  x  0   S( B ) 
 x B  x SB  0
x C 1

 ln  S ( SB)  ln  S ( SC )  ln  B ( BC )

51
 Dilute Solutions
Quasi-chemical model
Richardson, p. 151-153
Alcock and Richardson: Acta Metall. vol.8 (1969) p. 882

• Modifies the regular solution model

• Accounts for non-random distribution of B and C around S

52
 Dilute solutions
Quasi-chemical model
ASSUMPTIONS:

1. Coordn. no. z is the same in pure S, B, and C

53
 Dilute solutions
Quasi-chemical model
ASSUMPTIONS:

1. Coordn. no. z is the same in pure S, B, and C

2. xS→0  S – S bonds negligible

54
 Dilute solutions
Quasi-chemical model
ASSUMPTIONS:

1. Coordn. no. z is the same in pure S, B, and C

2. xS→0  S – S bonds negligible

3. Bond energies are independent of composition

55
 Dilute solutions
Quasi-chemical model
ASSUMPTIONS:

1. Coordn. no. z is the same in pure S, B, and C

2. xS→0  S – S bonds negligible

3. Bond energies are independent of composition

4. Random mixing between B and C when S is not

involved
56
 Dilute solutions
Quasi-chemical model
W'
BS x B kT
 e
 C  S xC

W '  H for B  S  C  S

W' W  W
 W '  
k R  N 57
 Dilute solutions
Quasi-chemical model
S
Z
C  C   Z C  S ; G  GSE(C )
2

Z B  Z   S  B  B ;GSE( B)
Z
2

Z
B  B   Soln  BSoln G BEC  B 
2

C in Soln   C  C   Soln.  GCEC  B 

Z
2

ZW  G SE(C )  G SE( B )  GCE( B  C )  G BE(C  B )

C in Soln.   Z B  S   Z C  S   Bin Soln.  58

 Dilute solutions
Quasi-chemical model
ZW  G SE(C )  G SE( B )  GCE( B  C )  G BE( B  C )

GiE  RT ln  i

ZW  RT ln  S (C )  RT ln  S ( B )  RT ln  C ( B  C )  RT ln  B ( B  C )

ZW   S (C )   B ( B  C ) 
 ln  
RT   S ( B )   C ( B  C ) 
59
 Dilute solutions
Quasi-chemical model
W' W
 B  S  x x
 B e kT  B e RT
 C  S  xC xC

1
ZW   S (C )   B ( B  C )   ( B  S ) x B   s (C )   B ( B  C )  2
But  ln     
    S ( B )   C ( B  C ) 
RT   S ( B )   C ( B  C )   (C  S ) xC  
k
 xC
xC 
k  x B  xC

mole fraction of C around S

kxB
x B 
kxB  xC
60
 Dilute solutions
Quasi-chemical model
H   S
Z
2
E SS   S ZxC ECS   S x B

ZE BS   S
Z 
2
 
xC xC ECC  xC 

xB  xB 
xC ECB  x B 
xC E BB 

 
xC 
xB 
G S ( SCB)  H S ( SCB)  T S S ( SCB)  H S ( SCB)  T  ln s S  zxC

ln 
 Zx B ln 
 xC xB 
 
  
ideal conf. entropy Excess conf. entropy

due to x B  x B and
x C  xC

61
 Dilute solutions
Quasi-chemical model
Final equation

1 1 1
  C (C  B )  2   B (C  B )  2  1 2
xC    xB    
  S (C )    S ( B)    S (C  B ) 
     
x B  x C  1

Predictive when S is a metal eg. In in Cu - Au

Fails when S ia a non - metal, eg. S or O

Z  2  errors in assumption s

62
 Regular Approximation Model
Jacob and Jeffes
Trans. Inst. Min. Metall. vol. 80, (1971) p.c 32

Assumptions:

1. Solute forms a sepate species of the type B-S-B,

C-S-C, B-S-C

63
 Regular Approximation Model
Jacob and Jeffes
Trans. Inst. Min. Metall. vol. 80, (1971) p.c 32

Assumptions:

1. Solute forms a sepate species of the type B-S-B,

C-S-C, B-S-C

C  S xC
2.  (regular solution)
 B  S xB

64
 Regular Approximation Model
Jacob and Jeffes
Trans. Inst. Min. Metall. vol. 80, (1971) p.c 32

Assumptions:

1. Solute forms a sepate species of the type B-S-B,

C-S-C, B-S-C

C  S xC
2.  (regular solution)
 B  S xB

3. B and C involved in B-S and C-S bonds do not

react with other atoms
65
 Regular Approximation Model
H S ( SCB)  xC H S ( SC )  2 H C (CB )  x B H S ( SB)  2 H B (CB )

S S ( SC )  S S ( SB)

arises due to different bond strengths - inturn due to different vibrationa l frequencie s

M
G S(SCB)  x C G S(SC)  x B G S(SB) - 2H (CB)

  S ( SC ) 
   10  Model is good
  S ( SB) 

Explains Cu - Ni - O, Cu - Co - O, Sn - Pb - S, Cu - Ag - S, Cu - Ni - S

66
 Dilute Solutions
Quasi-Chemical Model with 3-bond numbers
Jacob and Alcock, Acta Metall. vol.20 (1972) p. 221
(Richardson, p. 197-198)
Features:
1. Solute makes smaller no. of bonds

67
 Dilute Solutions
Quasi-Chemical Model with 3-bond numbers
Jacob and Alcock, Acta Metall. vol.20 (1972) p. 221
(Richardson, p. 197-198)
Features:
1. Solute makes smaller no. of bonds
2. Different Z a) S
b) B, C bonded to S
c) B, C not bonded to S

68
 Dilute Solutions
Quasi-Chemical Model with 3-bond numbers
Jacob and Alcock, Acta Metall. vol.20 (1972) p. 221
(Richardson, p. 197-198)
Features:
1. Solute makes smaller no. of bonds
2. Different Z a) S
b) B, C bonded to S
c) B, C not bonded to S
3. Each S makes n bonds
B and C bonded to S make Z bonds of type B – B, B – C
or C – C

69
 Quasi-chem. – 3 bond numbers
Features (cont.)

• Rest of B and C atoms make Z bonds

• Strong S – B or S – C bonds distort B – B or C – C

bond energies  energy of the resulting bond E
is a fraction ( = (1-)) of normal bond energies.

ZE  ZE  ZE  Z  E
 
ZE ZE
70
 Quasi-chem. – 3 bond numbers
Features (contd.)
• Three different bond numbers, n, Z and Z
• S – S interactions neglicted

Final equation:
1 1 1
  n n   n n  n
 C ( BC )   B ( BC )  1
xC    xB    
  S ( SC )    S ( SB)    S ( SBC ) 
     

Very successful when n = 4, Z = 8 and  = ½

EMPERICAL
71
An example (Cu – O – Sn system) is given in fig. 2.

72
When you do not have the values of γS(SC) and γS(SB):


RT ln
 S ( SC )
 S ( BC )

  H f ,298 CS x   H f ,298 BS y 
per g. atom solute.

According to Richardson: I. Iron Steel inst. Oct (1950) p.

137-146

For liquid Fe solutions

 O ( Fe)
RT ln   H 298( wustite)   H 298( y O )
 O( y ) a b

per g. atom oxygen

73
 Quasi-chemical model – 3 bond
numbers
 1 
  S ( B ) n 
 S  n 
(C )
 
  C ( B )   1
  S (C ) 
 
 
1
n  4 and  
2

Comments:
1. Good predictive value in non-ferrous systems
2. Deviations when C is transition metal
3. When both C and S are non-metallic, the model seems
to fail

74
75
 Finite Concentrations
Richardson, p. 177-178
Can we use Wagner´s equ.?
Darken: Trans. AIME, vol. 239 (1967) p. 90

Thermodynamic consistency of Wagner´s equ.

Gibbs-Duhem:

dG  G1dx1  G 2 dx2  Gdx3

(T and P constant)
1  solvent; x1  1  x2  x3 
  
dG  G 2  G1 dx2  G 3  G1 dx3 
76
 Finite Concentrations (cont.)
dG  exact differenti al


 G 2  G1

 
 G 3  G1 
x3 x 2

GD:
1  x2  x3 d G1  x2 d G 2  x3 d G 3  0


1  x3  G 2  x3
G 3
 x2
G 2
 1  x 2 
G 2
x3 x3 x3 x 2

d G i  RTd ln  i
77
Finite Concentrations (cont.)
dG  exact differenti al


 G 2  G1

 
 G 3  G1 
x3 x 2

GD:

1  x2  x3 d G1  x2 d G 2  x3 d G 3  0

1  x3  G 2  x3
G 3
 x2
G 2
 1  x 2 
G 2
x3 x3 x3 x 2

d G i  RTd ln  i
78
 Finite Concentrations (cont.)
 ln  3  ln  3
1  x3   ln  2  x3  x2
 ln  2
 1  x2 
x3 x3 x 2 x 2

MUST BE SATISFIED BY RAOULTIAN AND HENRIAN SOLUTIONS

1-x3  2(3)  x3 3(3)  x2 2(2)  1  x2  3(2)

But x 2 and x3  0

 2(3)   3( 2)

79
Finite Concentrations (cont.)
1  x3  2(3)  x3 3(3)  x2 2(2)  1  x2  3(2)

When x 3 is finite but x 2  0

1 - x 3  2(3)  x3 3(3)   3(2)

 3( 2)   2(3)   3(3)

which is absurd.
80
 Darken´s quadratic representation
Trans. Met. Soc. AIME vol. 239 (1967) p. 90

Requirements:
1. Gibbs-Duhem equation must be satisfied
2. must reduce to appropriate formalism for binary solution
when x2 = 0 or x3 = 0
3. Raoult´s law is approached by the solvent when x1 → 1
Darken´s quadratic equation for ternary solutions:
GE
 x 2 ln  2  x3 ln  3  12 x 22  13 x32  12  13   23 x 2 x3
RT

 2 ,  3 , 12 and 13  obtained from binary solutions

 23 from ternary measuremen ts. 81

If 12  ln  2 and 13   3


GE
 12 x1 x 2  13 x1 x3   23 x 2 x3
RT
 23 for hypothetic al system 2 - 3

 G E 
RT ln  1  G1E G E
 1  x1  
 x1 x
  2
x3

ln  1  12 x 22  13 x32  12  13   23 x 2 x3


ln 2  212 x 2   23  12  13 x3  12 x 22  13 x32  12  13   23 x 2 x3

2


ln 3  213 x3   23  12  13 x 2  12 x 22  13 x32  12  13   23 x 2 x3

3

Set x 2 or x 3 to 0  equas. reduce to the binaries.

82
Fe - C - S at 1600  C.


ln 2  12 x 2 2  x 2   13 x32   23  12  13 x3 1  x 2 

2

Fe - C - S

ln S   FeS x S 2  x S    FeC xC2   SC   FeS   FeC xC 1  x S 
 
S I

Plot left - hand side expression as a fn. of I

Linear up to xC  0.1; beyond this deviation from linearity

Slope   SC   FeS   FeC

  
can be known known
calculated
from the slope
83
Comparison between Wagner´s
and Darkens equa.
 2( 2)  212
 3(3)  213
 3( 2)   2(3)   23  12  13
 
Wagner Darke : thermodyn. consistent
easy to use

Examples of applicatio n :

Fe - C - Si 

Fe - C - Al  xi 1  xC  up to 0.4
Fe - C - Mn 

and so on 84
85
86
 Finite Concentrations
Pelton – Bale modification of Wagner´s equ.
Metall. Trans. Vol. 17A (1986) p. 1211

ln  2  ln  2  ln  1   2(2) x2   2(3) x3 ...

This equa. is thermodyn amically sonsistent at finite concentrat ions.

87
 Pelton-Bale modification of ε
formalismen
Metall. Trans. Vol. 17A (1986) p. 1211
The problem of the thermodynamic
inconsistency of the ε formalism can be
overcome by simply adding ln γsolvent to
Wagner´s eqn.

ln 2  ln  solvent   i1 X 1   i 2 X 2

2
Compatible with Gibbs - Duhem at all concentrat ions

Ni  Cr  Fe system
1600 C
Fe as solute

88
Ni - Cr - Fe system at 1600 C Ni as solvent 89