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?
Standard states :
i 1 when xi 1
'i 1 when xi 0
' ' 1 when atom% i 0
' ' ' 1 when wt % i 0
7
Wagners equation
Richarson p. 154→
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
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:
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
11
Wagner´s equation
ln 2 ln 2 x 2 2( 2) x3 2(3) ...
where
ln 2
2(3) x11
x3 x2 0
x3 0
....
where
log 2 %1100
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
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 1600C
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 1200C
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
i( j ) 1 1 1
i( j ) R T
i( j ) i( j )
i( j ) i( j )
Plot of vs
R R
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
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
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
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 )
If Ox x( x )
x *x
( x)
O
( metal/oxyg en ratio in the oxide)
39
ε → Solubility limit
Applications:
40
ε → Solubility limit
Applications:
(x )
Estimate O if you know x x
*
2.
41
ε → Solubility limit
Applications:
(x )
Estimate O if you know x x
*
2.
42
ε → Solubility limit
Applications:
(x )
Estimate O if you know x x
*
2.
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
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 SESC '
x B xC x x '
xC
x B xC x , x '
1 x S 2 GEB ' 'C ' '
S B S 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
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
52
Dilute solutions
Quasi-chemical model
ASSUMPTIONS:
53
Dilute solutions
Quasi-chemical model
ASSUMPTIONS:
54
Dilute solutions
Quasi-chemical model
ASSUMPTIONS:
55
Dilute solutions
Quasi-chemical model
ASSUMPTIONS:
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 BSoln G BEC B
2
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
Z 2 errors in assumption s
62
Regular Approximation Model
Jacob and Jeffes
Trans. Inst. Min. Metall. vol. 80, (1971) p.c 32
Assumptions:
63
Regular Approximation Model
Jacob and Jeffes
Trans. Inst. Min. Metall. vol. 80, (1971) p.c 32
Assumptions:
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:
C S xC
2. (regular solution)
B S xB
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.)
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 )
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.
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
Gibbs-Duhem:
G 2 G1
G 3 G1
x3 x 2
GD:
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
GD:
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
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)
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
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 2 212 x 2 23 12 13 x3 12 x 22 13 x32 12 13 23 x 2 x3
2
ln 3 213 x3 23 12 13 x 2 12 x 22 13 x32 12 13 23 x 2 x3
3
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
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
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