CONTENTS:

Chapter 1: Binary phase diagrams

Chapter 2: Phase stability diagrams

(predominance area diagrams)

Chapter 3: Ternary phase diagrams

4
 Chapter 1 Binary phase diagrams
1.1 Introduction
A binary phase diagram gives the phases stability for a two-component (binary) system in two dimensions:
pressure-composition (T = constant - isobar diagram) or temperature-composition (P = constant - isotherm
diagram).
Phase rule: The degrees of freedom or variance () in a system are related to the number of phases
present () and the number of constituents (C) as follows:

 = C + 2 (T, P) -  = 4 - 
In condensed systems, modest variations in pressure does not appreciably alter phase relationship.
By convention, the isobar phase diagrams for condensed phases are given for P = 1 bar.
Th degrees
The d off freedom
f d for
f equilibriums
ilib i iin such
h systems
t then:  = 3 - 
are th
Figure 1

=1  =2 bivariant surface

=2  =1 monovarant li
line
=3  =0 invariant point

In binary diagrams, composition is generally

plotted on the abscissa (horizontal axis) ant
temperature is plotted on the ordinate
(vertical axis).
5

1.2 Lever rule

The overall composition of the Ge-Si binary system containing n0Si moles Si and n0Ge moles Ge
(n0 = n0Si + n0Ge) is given by x0Si = n0Si /n0.
Hyp: at equilibrium, at T = T0, the system consists in two phases and 
 
The compositions of each phase at two-phase equilibrium are: xSi and xSi
Calculate the molar fractions of phases  and  , f and f ?
n0 = nSi0 + nGe
0
= n + n  
 
xSi + xGe = 1 Figure
g 1
nSi
xSi + xGe = 1 nSi 


n n 
f =  = ? nGe Q
n + n n0 nGe P M
T0
n n
f = 
n +n  ==
n0
? 
n = ?
f + f =1 n = ?
xSi x0Si xSi.
M
Mass balance
b l for
f Si (or
( Ge):
G ) xSi
nSi0 = nSi + nSi = x Si n + x Si n  = ( n + n  )( x Si f  + x Si f  )
= n 0 {x Si f  + x Si ( 1 - f  )} = n 0 {( x Si - x Si ) f  + x Si }
MQ PM
f  f 
(n0
/ n0 - xSi) xSi0 - xSi MQ PQ PQ
f =
Si
= = 6
xSi - xSi xSi - xSi PQ
 1.3 Solutions, general considerations, immiscibility

Behavior of solutions - Gibbs energy of a phase ()

G

G  G 0  Gmix
id
 G xs  G mag
magnetic
excess energy contribution
before mixing in the case of
entropy of mixing non-ideal solution
in the case of an (regular for
ideal solution example)
(random mixing)

 disordered ideal binary A-B solution (liquid or solid)

* random mixing of A and B atoms on the lattice sites
* no interaction (attractive or repulsive) between dissimilar atoms
 Hmix = 0
* additional entropy of the solution associated to configurational
contribution  Smix  0

G  (T )  x A0 G A0 (T )  xB0 GB0 (T )  RT x A ln l xB 
l x A  xB ln
G0 (before mixing)  Gmix= -T Smix id

pure A pure B "ideal "solution

8
Expression for the entropy of configuration : Smix = k ln 
k : Boltzman constant

 : number of possible configurations for a solution containing (nA atoms of A) + (nB

atoms of B) ( n A  nB ) !

n A ! nB !

* in the initial state (before mixing) : only 1 configuration   = 1  S = 0

 Smix = Smix = k ln 
6

( N AV x A  N AV x B )!
S  k ln   k ln 5

N AV x A ! N AV x B !
4

Delta S(J)
Stirling : ln N !  N ln N  N 3

and
d N AV . k  R 2

 S mix
i   R ( x A ln x A  x B ln x B ) 0
0 .2 .4 .6 .8 1
x(A)
9

 disordered regular binary A-B solution (liquid or solid)

* random mixing of A and B atoms on the lattice sites
* interactions (attractive or repulsive) between dissimilar atoms
xs
 Gmix  H mix  0

H mix  l AB  l AB : number of A  B bonds per mole

A B
1
   AB  (  AA   BB )  ij : bonding energies  0
2
A B
l AB  N AV z x A x B ( z : coordinenc
di e  number
b off bondings
b di / atom
t )

xs
Gmix  H mix  N AV z  x A x B xs
Gmix  H mix   x A x B
 : interaction parameter
related to bonding energies

* attractive interactions A-B : AB < ½ (AA + BB) < 0  < 0

* repulsive interactions A-B : ½ (AA + BB) < AB < 0  >0 10

 nA (A) + nB (B) → (nA + nB ) moles ((A,B)) G = ?
G  H  TS
For nA + nB = 1 mole:
(a) (b)
H =  x A x B xB  xB 
S = - R(x A ln x A + x B ln x B ) A H  0
B A B
H  0
G  TS
G  RT  x A ln x A  x B ln x B    x A x B  T S
G
Gibbs free energy of mixing
for an ideal solution
Represents the non
ideality of the mixture H  0
H  0
xB  G
( ) id
(a): l i =
ideall solution  0 A B A B
xB 
G
(b):  < 0  T S
 TS
( )  >0
(c): ( )
(c) (d)
(d):  >> 0
(a), (b) and (c): G < 0 and d2G/d2xB > 0

(d): G curve presents a maximum (positive or negative value) 11

(a)-(c): Solution ((A,B)), global composition M’:

y decomposition
stable in relation with every p in two phases
p P’ and Q
Q’
NQ M' Q' G xB 
fP   P' M' Q'
Mass balance: PQ P' Q' f P
 f Q
1 A B
PN P' M'
fQ  
PQ P' Q' N
 G M  M' M P
NQ PN Q
G P Q  f P G P  f Q GQ  P' P  Q' Q  ....  M' N M
PQ PQ
G M  G P  Q

(d) : Solution ((A,B))M supersaturated: métastable in relation with solutions S1 et S2

Driving force of transformation: -G = NM > 0  Demixing (phase separation)
S S
 M → S1 + S2  two-phase equilibrium S1  S2:  A1   A2 and  B1   B 2
S S

G

 G M  M' M A
S'1 M' xB  S'2
B
G S 1  S 2  M' N M
 AS1   AS 2
S1 N
G S1  S 2  G M
12
S2  BS1   BS 2
1.4. Binary solution A-B : Gibbs energy - chemical potential - activity
Regular solutions:
G ( T ) = x0A GA0 ( T ) + xB0 GB0 ( T ) +  xA xB + RT {xA ln xA + xB ln xB }

Reference states  pure components A and B at the same state as the solution
xA + xB = 1 = classical reference state
 xA xB =  xA xB (xA + xB ) =  ( xA2 xB + xB2 xA )
=  xA2 xB +  xB2 xA =  ( 1 - xB )2 xB +  ( 1 - xA )2 xA

G ( T ) = xA0 GA0 ( T ) + xB0 GB0 ( T ) +  xA( 1 - xA )2 +  xB ( 1 - xB )2 + RT {xA ln xA + xB ln xB }

G0B
G( T ) = x A  A + xB  B
with G0A
 A = G +  ( 1 - x A ) + RT ln x A
0
A
2

=  0A + RT ln a A
and
 B = G B0 +  ( 1 - x B )2 + RT ln x B
=  0B + RT ln aB
13

* activity for solute (B)

aB = BxB
 B  G B0  RT ln a B a 
ln B  ( 1  x B )2 = lnB
 B  G B0   ( 1  x B )  RT ln x B
2 xB RT


 B = exp( ( 1 - x B )2 ) : activity coefficient
RT
• when A et B have the same crystallographic structure
• and in the case of extreme dilution
Dilute solutions (solvant A and solute B):
  
xB  0 B 
aB
 cte (Henry's law)  B   B  exp  
xB  RT 
  0   B  1  aB  xB
  0   B  1  aB  xB

aA aA
xA  1 ln  A  ln 0 A  1 ( Raoult's law : "ideal" solution)
xA xA

Reference states  pure components A and B at the same state as the solution
= classical reference state 14
 (1) Raoult's law :
ideal solution when xA  1

Henry's
e y s law
w:

(2) aB < xB  B < 1   < 0  Hmix < 0

(3) aB > xB  B > 1   > 0  Hmix >0

15

General case:
G ( T ) = x0A GA0 ( T ) + xB0 GB0 ( T ) + RT {xA ln xA + xB ln xB }+ Gmix
ex

ex ex ex
with: Gmix = xA G A + xB G B = xART ln  A + xB RT ln  B

Reference states  to be defined for A and B

G ( T ) = x0A GA0 ( T ) + xB0 GB0 ( T ) + RT {xA ln xA + xB ln xB }+ RT {xA ln  A + xB ln  B }

G ( T ) = x A  A + xB  B
with G0B
 A = G A0 + RT ln x A + RT ln A
=  A0 + RT ln aA G0A
and
 B = GB0 + RT ln xB + RT ln B
=  B0 + RT ln aB

ai = i.xi ((i = A,, B))

Reference states to be defined for A and B:
- pure liquid (or gas or solid A) and pure liquid (or gas or solid B)
- or anyy other real or hypothetical
yp reference states

Change of reference states for activities : 16

Example ai/<i> referred to pure solid i ai/(i) referred to pure liquid i
 1.5 Phase separation without structure change. Spinodal decomposition.

H   x A x B >0 miscibility gap (m, n)

T phase boundary
S   R x A ln x A  xB ln xB  TC
T2 m' n'
G  RT  x A ln x A  x B ln x B    x A x B T3 spinodal
Gibbs free energy of mixing
T4 curve
for an ideal solution xB 
Represents the non G
ideality of the mixture xm xn
T1  TC  T2  T3  T4 A B
T4
 2  G / x 2  0 T3
T  TC m n
T2
 3  G / x 3  0
TC
 G / x B  RT ln(
l ( xB / x A )   ( x A  xB ) T1
 G /
2
x B2  RT 1 / x A  1 / x B   2   0  x A x B  RT / 2 
 3 G / x B3  
 RT 1 / x A2  1 / x B2  0  x Bc  x Ac  0.5

Spinodal curve (line): 2G/ x2 = 0 (inflection points )  x(1-x) = RT/2

The top of the miscibility gap ():  3G/x3 = 0  TC = /2R 17

(critical mixing, critical temperature of mixing TC)

1) In the region limited by the spinodal curve where T miscibility gap

TC
the Gibbs free energy of mixing is concave downward:
spinodal
(  2  G / x 2  0 ) m' curve n'
T4
the decomposition is spontaneous (spinodal
xB 
decomposition) without necessity of large G
concentration fluctuation: xm xn
A B
In this region the solution may begin the process of
decomposition into the equilibrium phases by
T4
incremental changes in composition without
increasing the total Gibbs free energy of the system ((a))

2) In the region limited by the spinodal curve and the

phase boundary curve: (1)
(   G / x  0 )
2 2

the decomposition needs large concentration (2) spinodal point

fluctuations (discontinuous transformation) (inflection point)

Here, as the solution separates into two phases,

Here phases the
(b)
Gibbs free energy of the system must increase before it 18
can finally decrease
 2 different mechanisms of phase transformation :

spinodal discontinuous
decomposition precipitation





G

19

Fe30 Ni20 Mn25 Al25

TEM image of the as-cast microstructure

I. Baker and coll., Microsc. Microanal. 11 (suppl. 2), 2005

20
 1. 6 Liquid-solid phase equilibria
1.6.1 Introduction
a) Simple case: Ge-Si phase diagram (complete miscibility in liquid and solid states)
Liquidus, solidus, one phase region, two phase region,
Lenslike liq-sol phase region where liquid and solid coexist (1) (2)
T
Lever rule, solidification

liquid l l

C li curves
Cooling s
liquid + solid s
solid solution
- Cooling of a single phase:
 = Ah( T - Tf ) (J
(J.ss -11 )
t

dH = QP = dt = mC P dT = Ah( T - Tf )dt T

dT Ah dt
h : heat transfer coefficient T0
= dt =  mC P  T0 : initial sample temperature
( T - Tf ) mC P     Tf : fluid temperature
 Ah  A : surface exchange between the
sample and cooling fluid
T ( t ) = Tf + ( T0 - Tf ) exp(- t /  ) Tf
t
- Solidification (exothermic transformation): QP = HP = (Hs – Hl)P < 0 21

Exercise 1
The phase diagram of Ge-Si system is shown in figure 1.
1. Answer to the following question by using this phase diagram:
1.1 If a liquid solution containing 50at%Si is cooled from 1400°C, what is the composition of
the first solid to form? What is the composition of the last liquid to solidify?
1.2. For this 50at%Si solution, estimate the liquid and solid fractions at 1200°C. What is the
composition of each phase.

Figure 1

22
 b) Two phase equilibrium: general case

Two phase equilibrium: ((A,B))  <<A,B>>,  = 3 -  = 1

At fixed T = T0  the system is completely determined
 Compositions of liquid and solid phases are fixed
(( i ))    i  i  A or B Classical reference states:
(( i )) /( i )  (0i )  RT ln a(( i )) /( i ) a((i))/(i) : activity of i component in the liquid solution
with respect to pure liquid i (referred to the pure liquid i)
  i  /  i    0i   RT ln a i  /  i 
a<<i>>/<i>: activity of i component in the solid solution
with respect to pure solid i (referred to the pure solid i)
a(( i )) /( i )  Gim 
 exp  
a i  /  i   RT  ai   i xi

x(( i ))   i   Gim    i   ( H im  TSim )    i   H im  T 

 exp    exp    exp   1  m  

x i   (( i ))  RT   (( i ))  RT   (( i ))  RT  Ti  

Ideall solutions:
Id l ti a(( i )) /( i )  x(( i )) x(( i ))  H im  T 
(classical reference state)  exp   1  m  

a i  /  i   x i  x i   RT  Ti   23

Exercise 1 (continued)
2. Ge and Si are supposed to form ideal solutions in both liquid and solid phases.
2.1. Calculate the composition of the liquidus and solidus (of the liquid and solid solutions in
equilibrium) at T = 1200°C.

Figure 1

24
 1.6.2 Complete miscibility in liquid and solid states
A and B have the same crystal structures
structures, comparable atomic size
size,
similar electonegativities and valencies

1.6.2.1 Monotonous liquidus and solidus curves T liquid

a) Phase diagram (see 1.6.1) T0 liq  sol

b) The molar Gibbs free energy (free enthalpy) curves

solid
The molar Gibbs free energy of pure sol. and liq. A and B A xB 
B
The molar Gibbs free energy of mixing curves for liquid and G
solid phases T  T0
G(0A )
A double tangent can be drawn: one to the liquid and the
other to the solid curves which defines the composition of G0 A  0 G0 B   0
the solidus (m) and its conjugate liquidus (n) G(0B )
((A)) = <<A>> m n  =
((B)) <<B>>
Same chemical potential of A (or B) in the solid (m) and
liquid
q (n)
( ) xB 
A xm xn
B

Exercise 1 (continued)
2 Ge and Si are supposed to form ideal solutions in both liquid and solid phases
2. phases.
2.2. Sketch the Gibbs free energy-composition curves for the liquid and solid solutions 25
at T = 900°C, 1200°C and 1500°C.

c) Activity curves for ideal liquid and solid solutions

T liquid
Reference state solid <B> - metastable state at T0 > Tm,B: liq  sol
T0
Activities of B in solid solution a<<B)>> and liquid solution a((B)) are
referred to pure solid B (a<<B>>/<B> and a((B))/<B>) solid

A xB 
a<<B>>/<B> = x<<B>> B
Ideal solutions: a((B))/(B) = x((B)) (classical reference state) G
T  T0
a((B))/<B> = ? G(0A )

G0 A  0 G0 B   0
((B)) = °<B> + RTln a((B))/<B> = °(B) +RTln a((B))/(B) = °(B) +RTln x((B))
G(0B )
m n
 G 
m  H Bm  T 
a(( B )) /  B  x(( B )) exp B
  x(( B )) exp   1  0    x(( B )) xB 
  A B
 RT0   RT0  Tm ,B   xm xn
k1 < 1 (T0 > Tm,B) 1
a<<B>>/<B> = x<<B>>
T  T0
a((B))/<B> = k1.x((B)) < x((B))
aB

Reference state liquid (B) - stable state at T0 > Tm,B :

Demonstrate that:
a<<B>>/(B) = k2.x<<B>> > x<<B>>
xB  26
a((B))/(B) = x((B)) 0
 Exercise 1 (continued)
2 Ge and Si are supposed to form ideal solutions in both liquid and solid phases.
2. phases
2.3. Sketch the activity-composition relationship for Si in the liquid and solid
solutions at T = 900°C, 1200°C and 1500°C. In each case give the standard state you
have chosen.
chosen

27

1.6.2.2 Non monotonous liquidus and solidus curves

a) Phase diagram T liq T

liq  sol liq  sol
liq
x(( A ))  x A p'
azeotrope T1
m n o p T2
m' n' o'
x(( B ))  x B 
sol
sol
xB  xB 
A xm xn x0 x p B A x m' xn' xo' x p' B

 dT 
   0 (Gibbs-Konovalow theorem)
 dx B  azé

At the extremum (x((i)) = x<<i>> ) :

 Gim   m m   m 
 (( i ))    i  exp      i  exp  ( H i  TSi )     i  exp  H i  1  T  
    RT  Tim  
 RT   RT   

28
 s > l : minimum
If regular (solid and liquid) solutions :
s < l : maximum

Complementary work : Demonstration in the case of a minimum

Example: TA=Tm(A) < TB = Tm(B) TB

<<A B>> ֎ ((A,B))

<<A,B>> ((A B)) solvent
l t A and
d solute
l t B → x((B)) > x<<B>> TA

x(( i ))   i  Gim 

 exp  
x i   (( i ))  RT  x<<B)>> x((B))

A B

   
Regular and dilute liquid and solid solutions:  i  exp 
 RT 
x(( B ))    l  GBm ( TA ) 
Solvent A (T  TA):  exp s   1
x B  RT 

 TA  s > l
s  l  GBm ( TA )  H Bm  1  0
 TB  29

b) Gibbs free energy curves

T liq  sol liq T liq

liq  sol
T1 T2
sol

sol
xB  xB 
A B A B

T  T1 T  T2 G(0B )
G(0A )
G0 B 
G0 A
G0 A  0 G0 B
B  0

G(0A )  0 G(0B )  0

Two double tangents

30
 1.6.3 Complete miscibility in the liquid state and limited
(two terminal solid
miscibility in the solid state solutions:  and 
T
1.6.3.1 Eutectic phase diagram
T0 1 l1 l2 1
a) Phase diagram E

 a b
Solid solution , , solubility limit,
b0
liquidus, solidus, lever rule, solidification A a0 xa xE xb B

b)) Gibbs free energy

gy ((free enthalpy)
py) curves G T  T0
G0B 
G0 A 
G
 and  → different crystalline structure G(0A)  0 A
G
B G(0B )  0
G0 A
 and  → same crystalline structure Gliq G0B 
F F' H
H'

Examples of reference state: G T  T0

G(0A)  0 G(0B )  0
- pure liquids A and B 
G0A G G 0
GB
- pure solids A and B Gliq 

- stable constituents at considered temperature 31

two double tangents

d) Phase diagram calculation (role of interactions in liquid and solid solutions)

Strong repulsive interactions in solid solution

* Binary EUTECTIC phase diagram, pure A and B with same structure

* Eutectic reaction : LE  A + B

s from 10 to 15 kJ.mol-1

32
SfusA = SfusB = 20 J/mol.K
 Exercise 2
1. Using the Cd-Zn phase diagram (figure 2) answer the following questions involving an alloy of
80at%Zn which is cooled slowly:
80at%Zn,
1.1. At which temperature will the alloy start to solidify?
1.2. What is the composition of the last liquid to solidify.
1.3. How much eutectic structure will be there? Calculate the fraction of each phase in the
eutectic structure
1 4 Calculate the composition and fraction of each phase in equilibrium at room temperature.
1.4. temperature
2. Cd and Zn behave regularly liquid solution (regular solution). The enthalpy of mixing of Cd-
Zn liquid solutions can be approximately modelled with the following relation:
mixH = 10000xCdxZn (J.mol-11)
2.1. Calculate the activities of Cd (aCd) and Zn (aZn) in the eutectic liquid at TE = 266°C referred
to pure liquids Cd and Zn respectively. Calculate the activity of Zn in the eutectic liquid at TE =
266°C referred to pure solid Zn. Discuss this last result.
2.2. The Raoult law can be applied to  solid solution (low Zn solubility limit). Calculate the
solubility limit of Zn in  at TE = 266°C.
3. Sketch the Gibbs free energy-composition curves for the liquid and solid solutions ( and Zn)
at TE = 266°C.
Data :
Melting temperature: Tm (Zn) = 420°C, Tm (Cd) = 321°C .
Melting enthalpy: Hm (Zn) = 7320 J.mol-1, Hm (Cd) = 6192 J.mol-1. 33
Atomic structure of Cd and Zn: hexagonal.

Figure 2

420

321

266°C 266°C
 26.6
26,6

34
 1.6.3.2 Peritectic phase diagram
a)) Phase diagram
g T
At T = TP: three phase equilibrium (zero degrees of freedom)
liq  
Tm (A) < TP < Tm(B) l i
TP n 
p b
Peritectic transformation: liql + b →p liq   j

If xl < xi < xn:  k  

A xi xm B
at T = TP – : liq +  ( totally consumed)
If xp < xi < xb:
at T = TP – :  (liquid totally consumed) G

G T  TP
b) Gibbs free energy (free enthalpy) curves
G(0A)0 G
G(0B) 0
2500
T C
2447 liq
2300
liquide
2100
Gliq
1900
 l
1700
liquide  
a 
1500
lP b
1300
P 1138 P
1100
   Three double tangents
35
Cu 0,1 0,5 0,9 Ir

c) Phase diagram calculation (role of interactions in liquid and solid solutions)

Strong repulsive interactions

* Binaryy PERITECTIC p phase diagram,

g ,ppure A and B with same structure
* Peritectic reaction : LP + 2 → 1

 from 12 to 15 kJ.mol-1

SfusA = SfusB = 20 J/mol.K

36
 Complementary work : Evaluation of some thermodynamic properties
from experimental phase diagram
(( B ))   B 
(( B ))  (0B )   B  (0B )
T
TB
TM  TB
RTM ln a B ( x M )   B   (0B )   GBm  H Bm
TB  dT 
L  
TA  dx B L
M TM
aB : referred to pure liquid B

TE
 H Bm ( TM  TB )
a B  x ( T )  exp  
 A xE xM xL B
 RTM TB 

  ( 1  x B )2 
If regular liquid solution: a Breg  x B exp 
 RT 
In order to evaluate if a solution can be considered RT ln(( a B / x B )
f T ( x B ) 
as a regular solution → plot of the function: ( 1  x B )2

The constancy of f[T(xB)] along the liquidus curve ?  regular solution

37

dT / dxB  0
T liq

1.7. Intermediate compounds l 

 C l C l

T  T0 
Stoechiometric compound: AmBn  C  C
A B
Ax B y xB 
Not stoechiometric compound:
a wide composition range exists Am+xBn+y
G
G0 A  0 A  0
xj xk G0B   0B  0
 ( xi , j ) G G B ( xk ,l )
Congruent melting compound: the composition of the  A l
liquid in equilibrium with the compound is identical to i
the compound composition
 A ( xk ,l ) GC  B ( xi , j )
j k
T  T0
Peritectic decomposition (no congruent melting):
during heating the compound decomposes in a solid
phase and a liquid phase 1

Very sharp variation of chemical potentials

(activities) through intermediate phases aB

Note: The free Gibbs energy of each compound

is given in J/mole of atoms (A + B) 38
0
A xB  B
 3640
T C
3500 liquid

Mg2Pb: Stoechiometric 3000

l  ZrC
700
T C Congruent melting
660 2500
1805 ZrC
549,5
ZrC  C
2000
500 l  liquid
 liq  Mg 2 Pb
ZrC: not stoechiometric
ZrC   Zr
466,2 1500
l  Mg2 Pb 327,5
300   Mg 2 Pb 248,7 966
 ZrC   Zr
500
  Mg 2 Pb Zr 0,2 0,4 0,6 0,8 C
100
x Pb 
0
0, 2 Mg 2 Pb 0,6 0,8 Pb
Mg

T C Cd5Ni and CdNi: not stoechiometric

Cu13Ba: Stoechiometric
1455
Peritectic decomposition 1400 Peritectic decomposition

1200 Liquid

CuBa: Stoechiometric 1000

g
Congruent meltingg 800
l2 p2 690

600
l1 p1 495

400
318
x 10 x 0p2 x 20
1
0,2 0,4 0,8
Cd CdNi
0,6 Ni
Cd 5 Ni 39

1.8 Liquid immiscibility

a) Phase diagram

Miscibility
y ggap:
p liq
q1 + liq
q2
1000 T C liquid
During cooling of a liquid with global T0
C 876
composition
co pos t o xC, from
o T > TC :
800 L1 t wo liquids
T L1 L2
- for TP < T < TC: L
660 638
liq1 (C → M) + liq2 (C →N) 600 M B P N

400 liquid  Al
T = 638°C: Monotectic transformation:
liqM → <Al> + liqN 200
150 E
Al x1 xC x2 1In
0 0,2 0,6

40
b) Phase diagram calculation (role of interactions in liquid and solid solutions)

Strong repulsive interactions

* Relatively
y low melting
g points
p
* MONOTECTIC reaction : L1M  L2N + A

l from 20 to 17 kJ.mol-1

 

SfusA = SfusB = 20 J/mol

J/mol.K
K
41

Transforma tions
Designation
during cooling
liq
 
A E B liq E   A   B Eutectic

 P liq  A  liqB   P
A B Peritectic


liq 1
 liq 2 liq 1M   A  liq 2B Monotectic
A M B

liq 1 S liq 2 liq 1A  liq 2B   S Syntectic

A  B


 liq  M   A  liqB Metatectic
A M B

42
 1.9 Solid-solid transformations Transforma tions
Designatio
g n
d i
during li
cooling

   E  A  B Eutectoid
A E B

 P  A  B   P Peritectoid
A  B

1
2  1M   2 A   B Monotectoi d
A M B

T C
1600 1538
1.9.1 Eutectoid transformation  Liquid
1400
Liq  C g
1552
Liq  
1200
1163 Liq  Fe3C

Stable phase diagram (____): 1000
  Fe3C
Fe3C
T = TE’:   + Cg 800
E 740

600 E'
  Fe3C
Metastable phase diagram (_ _ _) :
T = TE:   + Fe3C (cementite) Fe
0 0,05 0,10
xC 
0,15 0,20 0,25
43

1900 T C
1.9.2 Peritectoid transformation 1700
Liquid
1500
E
 a   b  CrPd 1300

1100

 d  CrPd  Cr2 Pd 3 900

700 p
a 570 b
505 d
500
CrPd Cr2 Pd3
Cr 0,2 0,4 0,6 0,8 Pd
xPd 

T C
700
1.9.3 Monotectoid transformation
600
Liquid
Miscibility gap: 1 + 2 500  l

Same crystallographic structure (fcc) 400 


s1 361 s2 
300 277
a m b
200

T = Tm: 2,m → 1,a + b 100 

Al 0,2 0 0,4 0,6 0,8 Zn

xZn xZn 
44
 Exercise 3
Figure 3 gives the binary Ni-Ti diagram. At T = 882°C, Ti undergoes an allotropic
transformation Ti → Ti (: hexagonal structure and  c.c. structure). The stable structure
for Ni - fcc is noted . The Ni-Ti liquid solution is regular (= -84780J.mol-1).
The melting temperatures of Ni and Ti are 1455°C and 1670°C respectively. The melting
enthalpy of Ni and Ti are 17480 J.mol-1 and 14146 J.mol-1 respectively (T independent).
1. Calculate the Gibbs free energy of formation of TiNi compound at T = 1310°C from pure
liquids Ni and Ti at the same temperature.
xNi + (1-x)Ti →NixTi1-x G° in J/mole of atoms (Ni + Ti)
in the studied case x = 0,5 (Ni0,5Ti0,5 )
2. Calculate the Gibbs free energy of formation of TiNi compound at T = 1310
1310°C
C from pure
Ni-and pure Ti- at the same temperature.
3. At T = 1118°C, the liquid phase containing 60at%Ni is in equilibrium with Ni3Ti
compound. Evaluate the activity of Ni in this compound referred to pure Ni liquid at the
same T.
4. Sketch at T = 1200°C the Gibbs free energy-composition curves for the involved phases.
N t
Note:
0,75Ni + 0,25Ti →Ni0,75Ti0,25 G°1 in J/mole of atoms (Ni + Ti)
3Ni + Ti →Ni3Ti G°2 = 4G°1 in J/4 mole of atoms
or in J/mole of Ni3Ti compound
p

45

(Ni)

G°

G°<-Ti > G°<-Ni>

G 0Ni 0, 75 Ti 0, 25

Figure 3 G 0Ni 0,5 Ti 0,5

46
 Complementary work: Some rules concerning the binary phase construction
T T liq
q 
liq
liq   liq TD   n m
o
(a)
o Td   m n  p
TD d (b)
 Td d liq  D
p
D
liq  D
q
q
D
G G
xB  G(0B )  0
xB  G(0A )  0
G 0
( A)
0 G 0
(B)
0
Gliq
Gliq
 n' m'
m' n' d'
d' G
G T  TD   o' T  TD  
o'

At the peritectic temperature (T = TP), there are two ways

for extrapolating the liquidus curve at higher T region:

(a) At T = TP+ : metastable equilibrium o  D represented by the double tangent m’d’

situated above the o’n’ tangent (stable equilibrium: o  liqn)

(b) At T = TP+ : for the metastable equilibrium o  D it is impossible to plot a double

tangent m’d’ being above n’o’ tangent (due to the convexity of the liquid G curve) 47

Complementary work: Calculation of phase diagram

The calculation of phase diagrams is based on the knowledge of thermodynamic

properties of liquid and solid phases involved in the various equilibria.
As the diagrams are plotted for a constant pressure (in general for P = 1 bar), the
equilibrium conditions are obtained by minimizing, at each temperature, of the
potential thermodynamic global free enthalpy of the system Gsyst.
Of course, one must know, a priori, the nature and thermodynamic properties of
phases which are expected to form and coexist with other phases. Minimizing the
global free enthalpy of the system allows to define under what ranges of
composition and temperature these different phases can either exist only in internal
equilibrium or co-exist in equilibrium with one or more other phases.
The free enthalpy of a binary system A, B is described for each temperature by the
general relationship:

Gmsyst   f  Gm ( x  ,T )


Common reference state for are chosen for elements A and B in all phase. In most
cases, the Redlich-Kister formalism is applied to describe the free enthalpies of
mixing of different solutions and compounds.
compounds The minimization of the global free
enthalpy of system Gsyst for a given global initial composition x0 (closed system) in
relation with variables x and f leads to the compositions of phases in equilibrium
((x) as well as to their corresponding
p g molar fractions ((f)).

48
Topological Features of Binary Phase Diagrams

Principle of calculation of phase diagrams

Binary systems / solid-liquid equilibria

Usingg regular
g solution theory
y
Relationships between the characteristic features and the nature of the
interactions

Systematic variation of the parameters lambda

How changes in phase diagrams can be produced

Corresponding topological features

Gibbs energy of a liquid L and a solid solution 

Reference pure liquids

G (L,T) =  L xA xB + RT [xA ln xA + xB ln xB]

G (alpha,T) =   xA xB + RT [xA ln xA + xB ln xB] - xA fusG(A,T) - xB fus G(B,T)

with fusG(i,T)
G(i T) = fusS(i) (Tfusi – T)

(see also http://www.tms.org/journals/JOM/0312/Chang/Chang-0312.html)

Calculation of Phase Diagrams

Relationship between the characteristics of a phase diagram and the relative

stabilities of the phases involved : Considere the following thermodynamic
parameters to calculate the corresponding
p p gp
phase diagram
g with PANDAT

Same structure for A and B, AB-ProtoBin-ls.tdb database

Sfusi [J/mol.K], T [K],  [kJ/mol]

1. SfusA = SfusB = 20
TfusA = 800, TfusB = 1000
s = 10, 15 and l = 0

2. same as before with s = 12, 15 and l = 12, 15

3. SfusA = SfusB = 20
TfusA = 1173 andd TfusB = 673
s = l = 20
Calculation of Phase Diagrams with PANDAT

p y pp
Step-by-step procedure

1. Run the PANDAT program

2. Load a thermodynamic database : "Database" pull

2 pull-down
down menu
Move the chosen elements Available components windows -> Selected components
windows

3. Solution parameters given in a binary database :

To change the parameters
* Folder "Database" in the left column :Thermodynamic data displayed in plain
text format
* Change parameters (see next slide)
* Save "Database" menu, "Refresh Database" option

To check the parameters

* Folder "Components" and "Phases" in the left column, subfolder "Selected
Phases" : click the folder "Liquid" for example to have a complete thermodynamic
description of this liquid phase

4. Calculate the phase diagram : "Calculation" pull-down menu, Section 2D (or icon)
To customize the g
graph
p "Graph"p "Configure
g Graph"
p p pull-down menu or click the
mouse in the right part of the graph menu to activate the graph configuration option

Calculation of Phase Diagrams with PANDAT

Input window
 Exercises of chapter 1
Exercise 1
The phase diagram of Ge-Si system is shown in figure 1.
1- Answer to the following question by using this phase diagram:
1.1 If a liquid solution containing 50at%Si is cooled from 1400°C, what is the composition
of the first solid to form? What is the composition of the last liquid to solidify?
1.2. For this 50at%Si solution, estimate the liquid and solid fractions at 1200°C. What is
the composition of each phase.
2. Ge and Si are supposed to form ideal solutions in both liquid and solid phases.
2.1. Calculate the composition of the liquidus and solidus (of the liquid and solid solutions
in equilibrium) at T = 1200°C.
2.2. Sketch the Gibbs free energy-composition curves for the liquid and solid solutions at T
= 900
900°C,
C, 1200
1200°C
C and 1500
1500°C.C. Take G
G°(Si) = G
G°(Ge)
(G ) = 0.

2.3. Sketch the activity-composition relationship for Si in the liquid and solid solutions at T
= 900°C, 1200°C and 1500°C. In each case give the standard state you have chosen.

The following data are available:

Melting point: Tm,Ge =938°C Tm,Si =1412°C

Enthalpy of melting (supposed independent of T) :

53
Hm,Si = 50200J.mol-1 H°m,Ge = 36900J.mol-1

Figure 1

54
 Exercise 2
1. Using the Cd-Zn phase diagram (figure 2) answer the following questions involving an alloy of
80at%Zn, which is cooled slowly:
1.1. At which temperature will the alloy start to solidify?
1.2. What is the composition of the last liquid to solidify.
1.3. How much eutectic structure will be there?
1.4. Calculate the composition and fraction of each phase in equilibrium at room temperature.
2. Cd and Zn behave regularly liquid solution (regular solution). The enthalpy of mixing of Cd-
Zn liquid solutions can be approximately modelled with the following relation:
mix -1
mi H = 10000xCdxZn (J.mol )

2.1. Calculate the activities of Cd (aCd) and Zn (aZn) in the eutectic liquid at TE = 266°C referred
to pure liquids Cd and Zn respectively. Calculate the activity of Zn in the eutectic liquid at TE =
266°C
266 C referred to pure solid Zn. Discuss this last result.
2.2. The Raoult law can be applied to  solid solution (low Zn solubility limit). Calculate the
solubility limit of Zn in  at TE = 266°C.
33. Sketch
Sk t h the
th Gibbs
Gibb free
f energy-composition
iti curves for
f the
th liquid
li id and
d solid
lid solutions
l ti ( and
d Zn)
Z )
at TE = 266°C.
Data :
Melting temperature: Tm (Zn) = 420°C,
420°C Tm (Cd) = 321°C .
Melting enthalpy: Hm (Zn) = 7320 J.mol-1, Hm (Cd) = 6192 J.mol-1.
55
Atomic structure of Cd and Zn: hexagonal.

Figure 2

420

321

266°C 266°C
 26.6
26,6

56
Exercise 3
Figure 3 gives the binary Ni-Ti diagram. At T = 882°C, Ti undergoes an allotropic
transformation Ti → Ti (: hexagonal structure and  c.c. structure). The stable structure
for Ni - fcc is noted . The Ni-Ti liquid solution is regular ( = -84780J.mol-1).
The melting temperatures of Ni and Ti are 1455°C and 1670°C respectively. The melting
enthalpy of Ni and Ti are 17480 J.mol-1 and 14146 J.mol-1 respectively (T independent).
1. Calculate the free enthalpy formation of TiNi compound at its melting point T = 1310°C
from pure liquids Ni and Ti at the same temperature.
xNi + (1-x)Ti →NixTi1-x G° in J/mole of atoms (Ni + Ti)
in the studied case x = 0,5 (Ni0,5Ti0,5 )
2. Calculate the free enthalpy formation of TiNi compound at T = 1310
1310°C Ni-
C from pure Ni
and pure Ti- at the same temperature.
3. At T = 1118°C, the liquid phase containing 60at%Ni is in equilibrium with Ni3Ti
compound. Evaluate the activity of Ni in this compound referred to pure Ni liquid at the
same T.
4. Sketch at T = 1200°C the Gibbs free energy-composition curves for the involved phases.
N t
Note:
0,75Ni + 0,25Ti →Ni0,75Ti0,25 G°1 in J/mole of atoms (Ni + Ti)
3Ni + Ti →Ni3Ti G°2 = 3G°1 in J/3 mole of atoms
or in J/mole of Ni3Ti compound
p

57

(Ni)

G°

G°<-Ti > G°<-Ni>

G 0Ni 0,75 Ti 0, 25
Figure 3
G 0Ni 0,5 Ti 0,5 58
 Exercise 4 (Complementary work)
Figure 4 presents the binary Au-Sn diagram. At T = 13°C, Sn undergoes an
allotropic transformation Sn → Sn (: diamond structure and : tetragonal
structure). The stable structure for Au is fcc noted .
1. Indicate the single-phase regions and two-phase regions in this diagram.
2. Indicate if the intermediate phases are stoechiometric or not. Are they
congruent melting compounds or not.
3. This phase diagram involves a certain number of invariant transformations.
Indicate the temperature, the phases involved in these transformations as well
as the nature and the composition of these phases.
4. Two alloys containing 70at%Sn and 85at%Sn respectively are cooled from
the liquid state.
4 1 Sketch
4.1. S the cooling
i curves T(t)
( ) for
f both alloys.
4.2. Sketch at T1 = 700°C and T2 = 0°C the Gibbs free energy-composition
curves for the involving phases at each temperature.

59

G°(A )
G°(Au) G°(S )
G°(Sn)

Figure 4

60
 Chapter 2 Phase stability diagram (Predominance area diagrams)
2.1 Introduction
In practice, equilibria involving gas phase are often encountered. In these conditions,
the chemical composition of the gas determines the nature and composition of
condensed phases participating in each equilibrium.
For this type of equilibria, it is possible to establish a so called predominance area
diagram or  phase stability diagram which gives the stability area of different phase
in a two dimension diagram.
The lines delineating the stability area of each phase describe equilibria between
different involved phases.
p

When the gas phase contains only one component, the equilibria are described in a
coordinate system:
y Pgas = f ((T).
) When the ggas p phase contains two chemical species
p 1 and
2, generally an isothermal diagram is constructed and the pressure of gas 1 is expressed
as a function of that of gas 2: Pgas,1 = f(Pgaz,2).
Such isothermal phase stability diagrams can be established also when the system
consists of condensed phases (liquid or solid solutions); in that case the variables used
for the establishment of phase stability diagram are the activities of chosen constituents.

In order to facilitate the p

presentation and avoid a formal p
presentation,, the p
phase
stability diagrams will be presented on the basis of concrete examples moving from
simple to more complex phase equilibria. 61

2.2 Binary systems; the gas phase contains only one species (Fe-O system)
TC
Reactions evolving 1 mole of O2 : liq  O2
1600 Feliq  oxliq oxyde liquide

2 Fe  O2  2 FeO (1) Fe  oxliq M  O2

 = 3 (O2 + 2 solids) 1400 Fe  oxliq

6 FeO  O2  2 Fe 3O4 (2) H  O2
Fe  W W W M
4 Fe 3O4  O2  6 Fe 2 O3 (3) 1200
M H

1000
l m n o p q
From the phase rule: FeO

 = C + 2 -  = 2 (Fe, O) + 2 (P, T) -  = 4 -  →  = 1 800

Fe  W
Fe3O4 Fe2O3

: the variance or the degrees of freedom of the system 600

Fe  M
22 24 26 28 30
For a fixed T = T0 (for example T0 = 1000°C):  = 0
 log PO2 (bar )
the system is completely determined 5.8
6 p' q'
G
G°i - RTlnPO2 = 0 → PO2 = f(T) 8

10

nr G°i(J) PO2 (bar) 12 n' o'

12.5
14
1 -362400 1,3.10-15 14.9 l' m'
mass%O
16
2 -305600 2,9.10-13 22 26 28 30
0,02 0,6 24

FeO : Wustite
3 -140600 1,7.10-6 Fe3O3 : Magnetite
62
Fe2O3 : Hematite
 T C g
1600 oxliq oxliq  O2
10-8
M  O2
f M
1400
Phase diagram Fe  W
e
10-8
Examples: 1200 d c
M H
W
m n o p
1000
"FeO"
 T = 1000°C b 10-8 a
875C
800 W H

nr PO2 (bar) 600

Fe  W

Fe  M

1 1,3.10-15 24 26 28 30

FeO Fe3 O4 Fe2O3

2 9 10-13
22,9.10 13 pds%O
p

3 1,7.10-6 T C
o x liq
Fe liq
1600 g

 PO2 = 10-8 bar

Fe  f
1400 e

Fe  d c
1200 W
nr T (°C)
l n p
 1600
1000
1 m o
b
M a

 1270
800 Fe 
2 H
Predominance
3  875 area diagram
600 Fe3O4 Fe2O3
8 63
400
 30  20  10 0 10
log 10 PO 2

2.2 Ellingham diagrams

The standard free energy of formation of a compound (G°f) varies with T. The variation of
G°f with T is usually presented by means of a table or some simple equations like:
G°f = A + BTlnT + CT or G°f = A + BT
Ellingham presented the variation of G°f of formation of an oxide (from one mole of O2) with
T in a simple graphical form:
 → MO2 G°f = A + BT
(The same for nitrides, carbides, sulphides,….)
TlnPO2

At equilibrium: M + O2 ֎ MO2 G 0f  RT ln POeq2q

RT

Different states for M and oxide: liq-sol-gas.

Example: In the considered temperature range
(see figure) oxide is in the solid state and M
transforms from solid to liquid (at T = Tm) and
from liquid to vapour state (at T = Tv).
Tm Tv T(K)
Phase stability diagram in PO2 – T coordinates

64
 65

2.3 Ternary system; the gas phase contains two components

2 3 1 Fe-C-O
2.3.1 F C O system
 = C (Fe,O,C) + 2 –  = 5 -  Condensed phases: Fe, FeO, Fe3O4, Fe2O3
Gas phase: CO
CO, CO2, O2

The number of possible equilibrium involving 2

solid phases ( amongst 4) and a gas phase: C42 = 4 ! /( 2!.2! ) = 6

Fe/FeO, Fe/Fe3O4, Fe/ Fe2O3, FeO/Fe3O4, FeO/Fe2O3, Fe2O3/Fe3O4

FeO + CO ֎ Fe + CO2 (a)

Fe/ Fe2O3, FeO/Fe2O3
Fe3O4 + CO ֎ 3FeO + CO2 (b)
not studied here
Fe3O4 + 4CO ֎ 3Fe + 4CO2 ((c))
(metastable equilibrium)
3Fe2O3 + CO ֎ 2Fe3O4 + CO2 (d)

 = 3 (gas
( lid ) →  = 5 -  = 5 – 3 = 2
+ 2 solids)

One can vary the total pressure Ptot and temperature T (at least in a certain area of P-T
diagram) without destroying each of these equilibria.
66
%CO %CO b’ a
b’ FeO Fe a FeO
Fe3O4
FeO
Fe3O4
Fe c Fe c
Fe3O4

Fe3O4
Fe  FeO
c’ Fe3O4
Fe3O4 b c’ b
Fe FeO Fe
FeO
a’
d a’’ d’ T d d’ T
Fe2O3 Fe2O3
%CO b’
b a
Fe
Fe
y domain
The rule of continuity c
Fe  FeO
FeO

c’ Fe3O4 Fe3O4 b
Fe3O4
a’
d d’ T
Fe2O3
67

The different iron oxidation stages F  CO2  FeO

Fe F O  CO ,....
(until to form hematite phase) are
100
due to the oxidizing action of CO- Ptot  1bar

CO2 mixture
i t which
hi h iincreases with
ith a
xCO/(xCO+xCO2)

80 F
Fe
l
the CO2 content in this mixture: m
60

23,6

CO2 ֎ CO + ½ O2 FeO
100x

40 c 24

24,4
Fe3 O4
O2  O0 2  RT ln PO2 20
o
n
24,8
25,7

p
b
0
200 Fe O 600 1000 1400
 P  2 3 T ( C )
G  RT ln CO PO12/ 2   0
0

 PCO2 

For
o eexample,
p e, at T = 1000°C,
000 C, thee cchemical
e c po potential
e oof ooxygen
yge
O2, fixed by the gas mixture, varies significantly between
points m (1.3x10-15 bar) and n (2,9x10-13 bar).
→ some oxygen iso-percentages
iso percentages curves in the wustite FeO in
equilibrium with different gas mixtures and different T 68
 The gas mixture has a reducing capacity for high contents of
CO in the gas (i.e. stability area of Fe), but it has in the same area
of composition, a carburizing capacity due to the Boudouard
reaction:
CO2 + C ֎ 2CO G0
FeO  CO  Fe  CO2
( 1  xCO ) aC
2CO  CO2   C  Fe K(T )  2
Ptot
xCO
 G 0  e
K ( T )  exp  

100
 RT  C  CO2 ֎ 2CO 0,5
0,3
Fe

100xCOO/(xCO+xCO2)
80
0,1 0,04
0,02 a
The chemical potential of carbon, C = Fe3 C Fe
°C + RTlnaC = °C + RTln(CxC ),) fixed 60 d
by the gas mixture increases  FeO
c
significantly with CO content in the gas 40

Fe3O4
20
b
→ some carbon iso-percentages curves
in the Fe- in equilibrium
0
q with different 200 400 600 800 1000 1200 1400 1600
gas mixtures and different T T ( C )
69

Carburization of steel from a CO-CO2 mixture

2CO + 3 << Fe >> → Fe3C + CO2 Formation of Fe3C at /gas interface
Fe3C → 3 << Fe >> + << C >> D
Decomposition
iti off F
Fe3C iin F
Fe and
d C di l d iin  phase
dissolved h
2CO →<< C >> +CO2

11- Calculate the activity of carbon at equilibrium between the austenite phase and the metastable
Fe3C phase (3<<Fe>> + <<C>>  → Fe3C) : aC = f(T)
2- Calculate (PCO/PCO2) at equilibrium between the gaz CO-CO2 and the austenite phase at 1000°C

2CO →<< C >> +CO2 T C

1600 1538

G = 0 = G + RT ln( PCO2 / P .aC )
0 2
CO 1400
Liquide
Liq  C g
PCO + PCO2 = 1 Liq  
1552

 aC = f{PCO/PCO2 , G°(T)}
1200
1163 Liq  Fe3C

2CO → C + CO2 G°(T) 1000
b   Fe3C
a
When PCO  aC  800
E 740

 Fe   a 600 E'
  Fe3C Fe3C

b CO  CO2 0 0,05 0,10 0,15 0,20 0,25

CC
Fe xC 

xC (or CC)
Fe3C 70
z
Exercise 1 Fe-C-O system

Figure 1 presents, in xCO – T

coordinates, the equilibrium curve of
Boudouard reaction:
C + CO2  2CO
and the equilibrium curves of
reactions of reduction of some oxides
with COCO-CO
CO2 gas mixtures:
MO + CO  M + CO2
(Ptot = PCO + PCO2 = 1 bar).

Answer the following questions by using this figure: Figure 1

1. The reaction SnO2 + CO → Sn + CO2 is exothermic or endothermic?
2 A CO-CO
2. CO CO2 mixture
i t containing
t i i 30%CO can it reduce d att T = 1000°C:
1000°C Fe
F 3O4 into
i t
FeO? FeO into Fe?
3. Can carbon reduce FeO into Fe, SnO2 in Sn. If yes, in which temperature range?
4 Can
4. C SnS reduce
d F O into
FeO i t Fe,
F FeF 3O4 in
i FeO.
F O If yes, in
i which
hi h temperature
t t range??
71

2.3.2. Exercise 2: Cu-O-S system

Consider equilibrium in the ternary CuCu-O-S
O S system at T = 1000K
1000K. The solid phases
which can exist in this system are: Cu, Cu2O, Cu2S and CuSO4 and the gas phase is a
mixture of O2 and SO2.
The three phase equilibriums curves between gas and two solids are given in figure 2
(The metastable equilibrium gas/Cu/CuSO4 is not presented in this figure).
(1) gaz/Cu2O/CuSO4 4
(2) gaz/ Cu2S/CuSO4
(3) gaz/ Cu/Cu2O B
(4) gaz/ Cu2O/Cu2S 2
(5) gaz/ Cu/Cu2S
logP
g SO2

0
A

-2
-12 -10 -8 -6 Figure 2
logPO2

1 W
1. Write
it the
th reactions
ti (1) tto (5) with
ith avaluable
l bl stoechiometric
t hi t i coefficients.
ffi i t
2. Give the expressions of dependence PSO2 = f(PO2) for reaction (1) to (5) at equilibrium.
3. From the second question find which of lines plotted in figure 2 correspond to
equilibriums
q ((1)) to (5).
( )
4) Establish the phase stability diagram of Cu-O-S system at T = 1000K.
72
 2.3.3. Exercise 3: Si-C-O system
Consider equilibrium in the ternary SiSi-C-O
C O system at T = 1000°C.
1000°C The solid phases
which can exist in this system are: Si, SiO2, SiC and C and the gas phase is a mixture of
CO, CO2, O2. Here, we neglect SiO gaz.
1 Plot the phase stability diagram of Si-O-C system in logac - logPO2 coordinates.
1. coordinates
Note: take -30  logPO2  -25 and -4  logaC  0.
2. Trace in the same diagram the CO2 and CO isobars.

<Si> + O2 → <SiO2> G°1 = -683400 J

<Si> + <C> → <SiC> G°2 = -63300 J
<SiC> + O2 → <SiO2> + <C> G°3 = -620100 J
<C> + O2 → CO2 G°4 = -395200 J
2<C> + O2 → 2CO G
G°5 = -443600
443600 J

73

2.3.4 Zn-O-S system (Complementary work)

C d
Condensed
d phases
h (4)
(4): Z
ZnO,
O ZZnS,
S ZZnSO
SO4 ett Z
ZnO(ZnSO
O(Z SO4)2 (noted
( t d X)

Each solid component is alone in its own phase. Zn (liq. or sol.) is not taken into
account because it is oxidized for oxygen partial pressure as low as about 10-1515 bar

(not studied in the present application).

Components in gas phase: oxygen O2 and sulfur (sulphur) dioxide SO2. For the same
reason as before, S2 is not considered in the present application.
v  C  2   5 

The number of possible equilibrium involving

2 solid
lid phases
h ( amongstt 4) and
d a gas phase:
h C 42  4! / 2!  6

ZnS / ZnO (1) ZnO / ZnO( ZnSO4 )2 ((4))

ZnO / ZnSO4 (2) ZnS / ZnO( ZnSO4 )2 (5)
ZnS / ZnSO4 (3) ZnO( ZnSO4 )2 / ZnSO4 (6)

74
 T = 1200K

(4) (2) (6)

(1) ZnS/ZnO 100
(2) ZnO/ZnSO4
(3) ZnS/ZnSO4
(4) ZnO/ZnO(ZnSO4)2 10-2
(5) ZnS/ZnO(ZnSO4)2
(6) ZnO(ZnSO4)2/ZnSO4

The number of possible equilibrium 10-4

involving 3 solid phases ( amongst 4) (1)

PO2 (bar)
and a gas phase: C 43  4! / 3!  4 10 -6

C ( )
(5)
Z SZ OX
ZnS-ZnO-X A 1+4+5
A: (3)
10-8
ZnS-ZnSO4-X B: 3 + 5 + 6 B
A
ZnS-ZnO-ZnSO4 C: 1 + 2 + 3 10-10

ZnO-X- ZnSO4 ?: 2 + 4 + 6 (parallel lines)

10-12
10-4 10-2 100 102 104 106 108 1010
PSO2 (bar)
(b )

Plot the predominance area diagram of Zn-O-S system at 1200K 75

2.4 Stability phase diagram when only condensed phase are involved

In this example, the equilibrium between alumina (Al2O3) and titanium is studied. Ti is
dissolved in an chemically inert solvent (Ni) which may contain some Al content.
(Reactive brazing of alumina).
Al2O3
brazing
alloy
Al2O3

Liquid Ni does not wet alumina. The addition, to liquid Ni, of some Ti leads to a reaction
between alumina and dissolved Ti and the formation, at liquid alloy/alumina interface, of
wettable Ti oxide compounds. This makes possible the brazing of alumina by Ni-Ti alloys.

 > 90° M  < 90°

 M-Ti 

Al2O3 Al2O3

However, the formation of reaction compounds at metal/ceramic interfaces can lead to brittle
interfaces. The mechanical properties of such interfaces depend on the type of the reaction
compound formed at the interface as well as on the thickness and morphology of this reaction
layer. This way, the prediction of the reaction compounds formation at the interface and the
control of their thickness (of interfacial reactivity) are of very high importance
76
 Ti oxides: TiO, Ti2O3, Ti3O5, Ti4O7, TiO2. The reactions of alumina reduction by Ti can
be symbolised
y as:

y  Al 2 O3  3 z (( Ti ))  3  Ti z O y  2 y (( Al )) (1)

For such a system, the oxygen partial pressure is fixed by different equilibra (as for
example that of formation of Al2O3 (or TiO2,…) from Al (or Ti) and O2) and does not
appear explicitly in the expressions of the equilibrium constants of reaction of type (1)
3
2(( Al ))  O2  Al 2 O3
2
Ti  O2  TiO2

In order to study the equilibria between condensed phases:

 We can neglect (or not take into account) the gas phase. In that case the
variance
i (th
(the d
degrees off ffreedom)
d ) off th
the equilibriums
ilib i off type
t (1) becomes:
b
 = 4 (Ni, Ti, O, Al) + 1(T) – 3 (2 solids + 1 liquid) = 2
 We can take into account the gas phase but in that case we must fix a total
pressure via an inert gas (the number of independent constituent is then increased
by unity). In that case the general expression of the variance of equilibriums of
type (1) becomes:  = 5 + 2 – 4 = 3.
3 But with fixed total pressure Ptot = Pinert gas + PO2
+ …. = constant, the variance becomes  = 2.
77

Given the fact that, the number of Ti oxides is higher than unity, it is advantageous to
couple, with the previous equilibria, the equilibria between Ti oxides:
5  Ti 2 O3   3  Ti 3O5   (( Ti ))
7  Ti 3O5   5  Ti4 O7   (( Ti ))

2  Ti4 O7   7  TiO2   (( Ti ))
3  TiO    Ti 2 O3   (( Ti ))

The equilibria between Ti oxides can be schematized as:

a  Ti z O y    Ti( az  1 )Oay   (( Ti ))
 Gi0 
Th conditions
The di i for
f these
h reactions
i at equilibrium:
ilib i l K i  exp 
ln   ln
l aTi  C i ( T )
 RT 
ln aTi  C i ( T )

The conditions for reactions of alumina reduction by Ti at equilibrium:

y  Al 2 O3  3 z (( Ti ))  3  Ti z O y   2 y(( Al ))

 Gred
0

,i 
ln K red ,i 
 exp   2 y ln a Al  3 z ln aTi
 RT 

3z
ln aTi  C red ,i ( T )  ln a Al
2y 78
 ln aTi  C i ( T ) 10 0
xTi d TiO D'
3z c Ti2 O3 D
ln aTi  C red ,i ( T )  ln a Al 10 1
2y C
Ti3O5
10 2
If we consider that Ni-Ti-Al solution are b
diluted in Ti and Al (to be verified): 10 3 B
a Ti4 O7 q
ln xTi  ci ( T ) 10 4
A Al 2 O3
TiO 2
3z
ln xTi  cred ,i ( T )  ln x Al 10 5
2y T = 1500°C
10 6
A'
3
10 8 10 7
10 6
10 5
10 4
10 10 2 10 1 10 0
x Al

Two types of lines:

a)) Li
Lines corresponding
di to
t the
th equilibria
ilib i off Al2O3 reduction
d ti by b Ti (A’A
(A’A, AB
AB, BC
BC, CD and
d DD’)
DD’).
For DD’ a correction to the Henry’s law is necessary.
In the right side of A’….D’: stability domain of alumina - non reactive alloys

b) Lines Aa, Bb, Cc and Dd describe the equilibria of transformations between Ti oxides and
separate the stability domain of each oxide. For TiO/Ti2O3 equilibrium a correction Henry’s law is
necessary. In the right side of A’….D’ - reactive alloys

79

10 0
xTi d TiO D'
10 1 c Ti2 O3 D
m C
Ti3O5
10 2 o
p n
b
10 3 B
a Ti 4 O7 q
10 4
A Al 2 O3
TiO2
10 5
T = 1500°C
10 6
A'
3
10 8 10 7
10 6 10 5
10 4
10 10 2 10 1 10 0
x Al

Examples of reactive alloys (point o and m)

Initial composition m: reaction with alumina: 9(Ti) + 5Al2O3  3Ti3O5 + 10Al
evolution of alloy composition from m to n (xTi/xAl = -9/10 )
Initial composition o: evolution of alloy composition, for example, from o to p. At p,
formation of a new oxide Ti4O7: 12(Ti) + 7Al2O3 → 3Ti4O7 + 14Al , evolution of
composition from p to q (xTi/xAl = -12/14 ). Final equilibrium: point q

80
 References (Chapters 1 and 2)

[1] D.R. GASKELL, Introduction to the thermodynamics of materials, 4th edition,

Taylor & Francis,
Francis 2003.
2003

[2] P. DESRE, F. HODAJ, Thermodynamique des matériaux - équilibres de phases

et métastabilité, EDP Sciences, 2010.

[[3]] D. RAGONE,, Thermodynamics

y of materials,, Wiley,
y, 1995.

[4] H-G LEE, Chemical thermodynamics for metals and materials, Imperial
C ll
College P
Press, 2000
2000.

[5] M. HILLERT, Phase equilibria, phase diagrams and phase transformations,

their thermodynamic basis, Cambridge University Press, 1998.

81

82
 Chapter 3 : Ternary phase diagrams

3.1 Introduction

 Use of multi-component phase diagrams

 Design of new alloys
 Use of thermal treatments
 Prediction of behaviour of products
 Industrial point of view
 Binary alloys : Fe-C, Cu-Zn, Cu-Sn, Al-Si...
 Ternary alloys : Fe-Cr-Ni, Al-Ni-Co, Al2O3-CaO-SiO2
 Fundamentals
 How ternary systems are represented ?
 What are the reading rules and the main uses ?

 Extension to multicomponent systems

 Understanding of phase changes during heating/cooling (solidification …)

83

3.2 Phase equilibria

3 2 1 Gibb
3.2.1 Gibbs phase
h rule:
l Condition
C diti off equilibrium
ilib i i a heterogeneous
in h t system
t
variance : v = m + 2 − φ

m :number of components
2 :temperature and pressure of the system
φ :number of coexisting phases

P=Cste Condensed Phase Rule: v = m + 1 − φ

► Trivariant equilibrium: 3 degrees of freedom : one-phase region (three-dimensional space)

Φ Φ
Variables T − CA − CB
► Bivariant equilibrium: 2 degrees of freedom : two-phase
two phase region (space filled with tie
tie-lines,
lines
bounded by two surfaces)
Φ1 Φ1 Φ2 Φ1 Φ1
Variables T − CA or C A − CB or C A − CB
► Monovariant equilibrium: 1 degree of freedom : three-phase region (space bounded by three
surfaces and three curves, a tie-triangle at a fixed temperature)
Φ1
Variables T or C A
► Invariant equilibrium: no degree of freedom : four-phase region
84
3.2.2 Description of the state of a multicomponent system

Composition is expressed as:

► Number of moles

Number of moles of constituent i in each phase φ : ni φ

Total number of moles in all phases : n

► Atomic/mole or mass fractions

φ
n
xi
φ
= i linked with  x i φ =1
n i

Molar weight of constituent i: M i

φ
M i ni
wi
φ
=
 Mi n i φ
with  wi φ =1
i
i

► Atomic or mass percentage

φ φ
xi 100 wi 100
85

3.3 Representation of ternary systems

3 3 1 A three-dimensional
3.3.1 th di i l phase
h di
diagram

Maximum number of independent variables (P=Cste) :3

Temperature and two composition variables
Three-dimensional phase diagram : equilateral composition triangle as base
temperature as vertical axis

► Corners: pur components

p p
► Edges: binary compositions
► Prism edges: effect of T on the components
► Sides: binary T-x phase diagrams

Right triangular prism

Right-triangular

86
3.3.2 How to plot ternary compositions (T = Cste)

► Compositions represented in an equilateral triangle: Gibbs triangle

 Length of each side generally divided into 10 equal parts

representing 10% on the composition scale or 0.1 atomic/mass fraction

 The triangle
g mayy be ruled with lines p
parallel to its sides

content of A in alloy X : oB = pC = Xr = Xn
 draw a line parallel to the edge BC

content of B in alloy X : mA = nC = Xs = Xp
 draw a line parallel to the edge AC

content of C in alloy X : sA = rB = Xm = Xo
 draw a line parallel to the edge AB

content of A + content of B + content of C = 100

87

 Example: Plot of the composition point of an alloy Y containing 20% A – 50% B – 30 % C

 Starting from point A:

 M k outt along
Mark l AB a length
l th Ab = 50 % B

Draw a line from point b, parallel to side AC

 Mark out along AC a length Ac = 30 % C

Draw a line from point c, parallel to side AB

The composition point of the alloy Y lies at the

intersection of the two lines

88
► All points on a line drawn parallel to one side of
the triangle ABC contain a constant amount of
the component opposite to the edge.

► All points on lines drawn from a corner to the

opposite edge of the triangle contain a constant
ratio of the components along the edge

► Representation of the A-rich corner of the

system: small amounts of B and C

Right-angled triangle
89

3.4 Reading rules (T = Cste)

341A
3.4.1 Application
li ti off the
th lever
l rule:
l Tie-lines
Ti li and
d tie-triangles
ti t i l

► Ternary alloy M consisting of two phases α and β

( two
(or t alloys
ll mixed
i d together)
t th )
Lever rule : relative amounts of phases

f α M β
x A− x A
= M α
f β x A− x A

α Mβ
f =
αβ

Tie line: line which joins the composition points of conjugate phases, which coexist in
equilibrium at T and P, and the overall composition

Tie lines must not cross each other within any two phase region

Tie lines cannot intersect at a corner of the triangle

90
► Ternary alloy M consisting of three phases α, β and 
((or three alloys
y mixed together)
g )

Proportion of α Relative proportion of α

α MP fα MP
f = =
αP f β +f Mα

Tie triangle: triangle which joins the composition points of coexisting phase in a three
three-phase
phase
equilibrium at T and P. The overall composition is the fulcrum of the triangle.
91

3.4.2 Law of adjoining phase regions

Continuity between the three binary phase diagrams

and the ternary phase diagram.

diagram

Four lines meet at one point.

A tie
tie-triangle
triangle is in contact with one
one-phase
phase field at
its corner and two-phase areas on each side

Two boundaries of a one-phase field must

extrapolate
p

 outside the three-phase field

 or into the triangle
92
3.5 Systems containing two phases

Complete solubility of the components in both liquid and solid states

Liquidus: upper surface: surface representing the liquid in

equilibrium with a solid phase. The name of the primary
phase is given.
Above the liquidus, all alloys are molten.
Solidus: lower surface: surface representing the solid in
equilibrium with a liquid phase.
Below the solidus, all alloys are solid.

Between the two surfaces, all alloys are two-phase mixtures

(L + ))

 2 degrees of freedom: e.g. T − CA

Φ1 Φ1 Φ1
or C A − CB
 two-phase region:
* space bounded by two surfaces 3D representation (Space model)
* filled with tie-lines linking the composition points of with the composition triangle
liliquid
id (on
( the
th liquidus)
li id ) and
d solid
lid ((on th
the solidus)
lid ) as basis
co-existing at a given T.
93

However:

 Except for relatively simple cases, it is difficult to depict clearly by means of

perspective diagrams the complete ternary space model with its constituent spaces,
curves and points.

 Lines are not seen in true length

 Therefore, it is convenient to use:
- Projected views,
views 2D polythermal projection: e.g.
e g a projection of the liquidus or the
solidus surface on to the composition base of the space model
- Plane sections
 taken horizontally through the 3D space model: 2D isothermal diagrams
(isothermal plane intersections with various surfaces (liquidus, solidus…)
 or taken vertically through the 3D space model (vertical sections) 2D isopleth
diagrams

94
3.5.1 2D polythermal projection

► Liquidus projection: Projection of the liquidus surface on the base of the space model i.e.
ie
flat representation of the curved liquidus surface.
p case of a ternary
In the simple y system
y with continuous series of liquid
q and solid solutions,
everything shown is liquid add isothermal lines (isotherms) indicating the slope of the
relevant surface.
Isothermal lines (isotherms): constant temperature lines on the liquidus surface

_______
Liquidus projection (liquidus isotherms )
and solidus projection (solidus isotherms - - - - - )
on the composition triangle. 95

3.5.2 Isothermal sections

► Isothermal sections: Horizontal slices through the three dimensional diagram. All points on
the section are at the same temperature.

 Curved line l1-l2 generated by the

intersection with the liquidus
 Curved line s1-s2 generated by the
intersection with the solidus
 Two-phase field L +  between the liquidus
and solidus lines.
96
3.5.2 Isothermal sections

 Liquidus and solidus lines meet

at corner A


 Tie-lines rotate, as T falls, in the

direction from the highest melting
component to the lowest.
 Konovalov’s Rule: solid always
richer than the melt in that component
which raises the melting gp
point.
  

 One-phase fields: liquid phase region

or solid solution regions
 Two-phase fields: two phases will
coexist at this T.
T Some tie-lines can be
included

T = Tm(A) Tm(C) < T < Tm(A) 97

3.5.3 Vertical sections parallel to one of the binary system

► Isopleth
I l th sections:
ti V ti l slices
Vertical li th
through
h the
th three
th di
dimensional
i l diagram.
di

 Liquidus line: upper line, intersection of the vertical plane with the liquidus surface

 Solidus line: lower line, intersection of the vertical plane with the solidus surface
.
98
3.5.3 Vertical sections joining one corner to a point on the opposite binary

 Liquidus and solidus lines meet at the melting point of A

99

► Key points:
 For any alloy in the isopleth section
section, reading of the liquidus temperature and solidus
temperature
 In general tie-lines are NOT in the plane of a vertical section
 It is not possible to draw horizontal tie-lines across two-phase regions to indicate the
true compositions of the coexisting phases at a given temperature

100
Case of pseudo-binary section

section from a congruently melting compound of one of a binary systems to

the third component

Example: quasi-binary
quasi binary section between Al and the intermediate phase Mg2Si in the Al
Al-Mg-Si
Mg Si
ternary system = a truly binary section with tie-lines in that plane

101

102
 3.5.4 Crystallisation path: equilibrium freezing of alloy X

► Slow cooling assumed to allow equilibrium

conditions to be maintained at all T
F an alloy
For ll X:X
 Vertical line X-s3 or X-l: alloy composition at all T

 At point l: liquidus surface reached

 Point s: initial composition of the  phase

With further cooling:

 Curve l-l1-l2-l3: evolution of the liquid composition on
the liquidus surface: solidification path

 Curve s-s1-s2-s3: evolution of the solid composition on

the solidus surface

 Each point on the liquidus surface is connected through

the average alloy composition to a conjugate phase on the
solidus surface tie-lines l-s / l1-s1 / l2-s2 …
Course of solidification of alloy X
 Point s3: composition of the solid phase equal to the
average composition X
Point l3: composition of the last drop of liquid
103

Tie-lines for alloy

y X indicated in some isothermal
sections

 At any temperature application of the lever rule to the appropriate tie-line enables to calculate
the relative amounts of liquid and solid.
 Solidification
S lidifi ti / crystallisation
t lli ti path:
th extremities
t iti off tie-lines
ti li representing
ti the
th liquid
li id
compositions at sucessively lower T on the liquidus surface.
104
► In contrast to binaries it is impossible to make a convenient graphical representation of
the complete ternary phase diagram that can be utilized in all practically important cases.
Solution: employing a computer program which will compute the equilibrium composition in the
ternary system at any given temperature and composition.

 Diagplot 
Three components forming ideal solutions

105

3.6 Molar Gibbs energy diagram

F a two-phase
For t h equilibrium
ilib i α-β
β att given
i P and
dT

► Molar Gibbs energy curve of each phase

(as function of temperature and composition)
► Contact points of a common tangent line to
the curves
 Compositions of the two phases
in equilibrium
 Tie-line: connection of the composition
points
i t off conjuguate
j t phases
h

In a binary system

106
 ► Molar Gibbs energy surface of each phase
(as function of temperature and composition)

► Pair of contact points produced by a common

g
tangential plane ((in g
p green))
 Compositions of the two phases
in equilibrium
 Tie-line:
Tie line: line connecting two contact
points
 The two-phase field is created by the
common tangential plane rolling under
the two surfaces

In a ternary system
► A three-phase
three phase equilibrium for a ternary system
at a given temperature (tie-triangle) result from a
common tangential plane simultaneously touching
the molar Gibbs energy
gy surfaces of three pphases.

107

3.7 Systems containing three phases

Example: Liquid and two primary solid solutions giving a eutectic reaction
L+

3.7.1 Space model

Continuity between the three binary phase diagrams

and the ternary phase diagram
 Point  curve
 Curve  surface
 Surface  volume

Solvus: surface representing the solubility boundary of

one element in an other or of two elements in the third one

 Liquidus made of two surfaces AMNC and BMN

(primary solidification of  and )
These surfaces intersect along a curve or valley MN
108
 One-phase field (e.g. ):

indicates solubility of components B

and C in A

 The two-phase fields

(e.g. L+ in the binary AB and BC)

join to form a volume in the ternary

system.

 The three-phase field (L++:

pass continuously
ti l from
f one binary
bi eutectic
t ti
horizontal to the other :
stack of isothermal tie-triangles, the corners
represent the compositions of the phases
co-existing in equilibrium at a given T.
Exploded model
The three-phase space is enclosed by the three curved surfaces
DMNG MEFN
DMNG, MEFN, DEFG
DEFG:

The curves MN, DG and EF do not lie in the same plane 109

F the
For th eutectic ti L   +  with
t ti reaction ith falling
f lli T :

The liquid composition changes along curve MN

The composition
p of  changes
g along g curve DG
The composition of  changes along curve EF

abl: Position of a typical tie

tie-triangle
triangle at a given T

110
3.7.2 Projected views

Liquidus projection Solidus projection

Monovariant curve MN: eutectic valleyy Monovariant curve DG: limit of the 
from one invariant point in the binary AB solid solution region
to the invariant point in the binary BC Monovariant curve EF: limit of the 
Binary eutectic reaction L   +  solid solution region

Arrow: the curve slope in the direction

indicated, the arrow indicate direction of
decreasing gT

111

3.7.3 Plane sections

BC AB
a) T < T<T BC
b) T < T Eutectic
Eutectic Eutectic

 Isothermal sections  Isopleth section

From corner B to the

middle point of side AC

112
3.8 Systems containing four phases

381S
3.8.1 System
t containing
t i i a ternary
t eutectic
t ti reaction
ti L   + + 

Example: Three eutectic binary systems

Complete solubility of the components in the liquid state
Partial solid solubility of the components

 4 one-phase fields

 6 two-phase fields

113

 Eutectic reaction L   + : there is a three-phase region made of tie-triangles

Curve e1E composition of the liquid, curve a1a composition of , curve b1b
composition of 

Idem for the two other eutectic reactions L   + : and L   + 

 Ternary eutectic reaction: plane abc, composition of the four phases fixed
Ternary eutectic point E: meeting of the three eutectic valleys which run from the
binary
y systems
y to lower T within the triangle
g abc: 1 four-phase
p field

Involves 3 three-phase regions that approach

the ternary eutectic plane from higher T and
1 three-phase
three phase region existing below the plane
plane.

4 three-phase fields

Eutectic four-phase plane as the

junction of four tie-triangles

114
Liquidus projection

 Primary solid solutions ,  and 

 Ee1, Ee2, Ee3: monovariant lines, eutectic valleys

The arrows on the curves all points towards E

 Eutectic valley Ee1: composition of L for L   + 

115

Isothermal sections

 Two-phase field (e.g. L + )

- Stretches
St t h from
f one binary
bi (AB) tto an other
th (BC)
- Tie-lines gradually change their slope from one
side to the other
- Points representing the compositions of L:
generated a curved liquidus line
- Points representing the compositions of :
generated a curved solidus line
- These
Th t
two curved
d lines
li generate
t a volume
l when
h T
changes

T AB < T<TB
Eutectic Fus

116
Isothermal sections

 Three-phase field (e.g. L + )

- Starts
St t att the
th hhorizontal
i t l liline corresponding
di tot the
th
invariant eutectic reaction L   + in the AB system
- At a g
given T,, the three p
phases in equilibria
q form a
tie-triangle
- With decreasing T, positions of the tie-triangle
change and generate a volume.

AC AB
T <T<T Eutectic
Eutectic

117

Isothermal sections

 Relative positions of the tie-triangles

- TEut < T: Three tie-triangles
- TEut = T: Merging of the triangle formed by the
compositions of the three solid phases
ternary eutectic plane
- T < TEut : Three-phase region 

118
Development of the phase regions

 Diagplot
gp 
Ideal liquid solution, regular solid solutions

119

Solidification of alloys: Crystallisation path

► Slow cooling assumed to allow equilibrium conditions to be maintained at all T

Calculated path of solidification Solidification sequences

 Red points: extremities of the tie-lines representing the liquid compositions at successively
lower temperatures
 Each point is connected to one or two solid phase(s) on the solidus surface
120
  Alloy composition X in the three
three-phase
phase region
Primary solidification of 
Eutectic reaction L   + 

Ternary eutectic reaction L   + 

 Alloy composition Y in a two-phase region

Primary solidification of 
Eutectic reaction L   + 
Solidification completed when the  side of the tie-
triangle contains point Y

Projected view of the liquidus, solidus  Alloy composition Z in a one-phase region

and eutectic plane Primary solidification of . Ternary alloy consists of a
solid solution 

 The solidification path during primary stage can only be determined experimentally
121

Solidification of alloys: Crystallisation path – System without solid solubility

► Slow cooling assumed to allow equilibrium conditions to be maintained at all T

e.g. alloy m

Liquidus projection with eutectic

plane
122
  At Tliquidus: crystallisation of pure solid B

 When T decreases, liquid is depleted in B, change

of the liquid composition along mp
When the liquid composition reachs a point between points
m and p, what is the proportion of solid and liquid ?

 At p: the primary solidification ceases, the second

phase C appears, the liquid composition moves along
the binary eutectic valleys pE

The progress of this reaction can be represented by

tie-triangles at decreasing T
What is the composition of the solid precipitated out the
liquid between point p and q ?

 At E: the three solid phases crystallise according

to the ternary eutectic reaction
What is the proportion of the first crystalline phase (primary
phase) ?
 What is the pproportion
p of the eutectic structure of B and C
Solidification sequences
(formed when both B and C crystallise) ?

123

3.8.2 System containing a ternary quasi-peritectic reaction L +   + 

Example: Three eutectic binary systems

Complete solubility of the components in the liquid state
Partial solid solubility of the components

Ternary quasi-peritectic point Q:

meeting of two monovariant curves, with arrows

pointing towards Q, and the third valley running to
lower T
T, with arrow pointing away from Q

124
 Primary solid solutions ,  and 
 Qe1, Qe2, Qe3: monovariant lines, eutectic valleys
 Eutectic valley Qe1: composition of L for L   + 

Projected view of the liquidus,

solidus and quasi-peritectic plane

125

Development of the phase regions

 Diagplot
gp 
Three components forming regular solutions

126
 Relative positions of the tie-triangles
- TQP < T: Two tie-triangles L-- and L--
- TQP = T: The two triangles form a trapezium with
one common side
id LL-
Liq. composition point outside the triangle formed by the
compositions of the three solid phases isothermal
quasi-peritectic plane representing the invariant reaction
- T < TQP : The trapezium is divided across the
diagonal : two tie-triangles  and L–

127

3.8.3 System containing a ternary peritectic reaction L + +   

Example: One eutectic binary system, two peritectic binary systems

Complete solubility of the components in the liquid state
Partial solid solubility of the components

Ternary peritectic point P:

meeting of one monovariant curve, with arrow

pointing towards P, and two other valleys
running to lower T, with arrows pointing away
from P

128
 Primary solid solutions ,  and 

 Pp2 (L +   ) and Pp3 (L +   ): monovariant

lines, p
peritectic curves running
g to lower T

 Eutectic valley Pe1 (L   + runs down

 Point P: liquid composition in the invariant peritectic
reaction L  

Projected view of the liquidus, solidus

and quasi-peritectic plane

129

Development of the phase regions

 Diagplot
gp 
Three components forming regularl solutions

130
 Relative positions of the tie-triangles
- TP < T: Tie-triangle L-- associated with the

reaction and L +  

- TP = T:
T Liquid
Li id composition
iti point
i t ouside
id th
the
triangle formed by the compositions of the three solid
phases isothermal peritectic plane representing the
invariant reaction
- T < TP : The triangle is divided into three tie-
triangles , L- and L–

131

3.8.4 Summary: four-phase equilibria

► Transformation of one phase or interaction between two or three phases (P=Cste)

Temperature and phases compositions fixed invariant reactions

Ternary eutectic Ternary quasi-peritectic Ternary peritectic

L   + +  L +   +  L + +   

Liquid composition L within Liquid composition L outside Liquid composition L outside

th triangle,
the ti l i equilibrium
in ilib i th triangle,
the ti l opposite
it to th 
t the the triangle,
triangle opposite to the
with ,  and  corner  side

132
► Formation of a ternary eutectic: it is NOT necessary that the three binary systems are of
eutectic type. The binary systems may involve one or more peritectic type.

► Formation of a ternary quasi-peritectic / peritectic: the monaovariant reaction(s) which

precede(s) the invariant reaction can be either peritectic or eutectic

► Nature of the monovariant line:

 The
Th reaction
ti isi peritectic
it ti when
h the
th projection
j ti off the
th tangent
t t to
t the
th monovariant
i t line
li
lies outside the tie-triangle

 The reaction is eutectic when it lies inside the tie

tie-triangle
triangle

133

3.9 Formation of compounds between components

A bi
binary compound
d AB which
hi h melts
lt congruently
tl

► The composition of the compound lies within the corresponding primary field

► Straight line C-AB: join or Alkemade line

Divided the compositino triangle into sub-composition triangle

► The products of the crystallisation for any composition within a sub-triangle are those
indicated by the corner of the sub-triangle 134
A binary compound AB which melts incongruently

► The composition of the compound lies outside the corresponding primary field

135

Chapter 3 : Exercices

Exercice 1- Conversion atomic fractions/percentages - Exercice 3- Compositions and proportions in the ABC
mass fractions/percentages ternary system

Consider the AlAl-Bi-Cu

Bi Cu system. How many grams of Al, Bi a) Determine the composition of the mixture represented
and Cu should be used to elaborate 10g of an alloy by the point P.
containing 5 at. % Al and a ratio of Bi to Cu (atomic
fraction) of 24.

Data :MCu = 63,54

63 54 ; MAl = 26,97
26 97 ; MBi = 209.
209

Exercice 2- Determine the compositions of the points

represented by T, R and S.

T: 40%A - 40%B - 20%

R: 25%A - 20%B - 55%C
S: 65%A - 0%B - 35%C b) A mixture represented by the point P in figure above is to
be prepared by mixing the mixtures X and Y. Determine the
ratio of X to Y to obtain the right composition. The
composition of each point is given in the following table

A(%) B(%) C(%)

P 35 40 25
X 20 70 10
Y 40 30 30

136
Exercice 4- In a system ABC, a ternary alloy of
composition 30 mass.% B and 30 mass.%C consists at a
particular temperature of three phases of equilibrium
compositions as follows:
Exercice 5- Consider the Pb-Bi-Sn ternary system.
1- From the Gibbs phase rule,
1 rule determine the degrees of
freedom along the lines E1O, E2O and E3O?

Liquid phase : 50%A, 40 %B, 10 %C 2- Is there a ternary invariant point?

α solid solution : 85 %A, 10%B, 5%C
γ solid
lid solution
l ti : 10 %A,
%A 20%B,
20%B 70%C 3- Describe
3 D ib th
the crystallisation
t lli ti path
th off the
th li id
liquid
represented by the point A and draw the coresponding
a) Calculate the proportions by mass of liquid, α and γ curve on the ternary phase diagram.
present in this alloy
b) For the same temperature deduce the composition of 4- Determine the proportion of the solid which has
the alloy which will consist of equal proportions of α and crystallised when the second phase appears
γ phases of the compositions stated above, but with no
liquid phase. 5- What is then the proportion of Sn and Bi?

6- What is the p
proportion
p of liquid
q remaining
g jjust before the
ternary eutectic reaction?

7- Draw the isothermal sections for the Pb-Bi-Sn ternary

system at 150°C and 100°C making necessary
assumptions where relevant data are lacking.
lacking Give the
number and name of phases in equilibrium in each region.

137

Exercice 6- The following figure represents the vertical

section at 14 % Cr for the Fe-Cr-C system. Give the
number and the name of the phases coexisting in each
domain.

138
Exercice 7- Referring to the figure given below: Exercice 8- Describe crystallisation paths of liquid
compositions p, q and r
a) Determine whether binary compound δ and ternary
compounds  and φ melt congruently or incongruently.

b) Draw conjugation lines (joins) dividing the triangle into

sub-composition triangle.

c) Determine the crystallisation path of a liquid of

composition p.

139

Solidus projection
Exercice 9- The Fe-Cr-Ni

1) Describe the equilibrium solidification sequence of an

alloy containing 30 mass.% Cr and 15 mass.% Ni,
including a calculation of the proportions of the phases
present at 1400°C.

2) Describle
D ibl the
th changes
h th t occur in
that i an Fe-18Cr-12Ni
F 18C 12Ni
(mass.%) (austenitic stainless steel) during the
solidification and subsequent cooling to 650°C assuming
that equilibrium is attained. For this same alloy state what
structure would result from rapid cooling from 1000°C (Ms
is below room temperature).

3) Consider a series of Fe-Cr-Ni alloys containing 5

mass.% Ni and Cr contents ranging from 20 mass.% Cr
and 70 mass.% Cr annealed to equilibrium
q at 650°C.
Describe how the proportion of  phase varies with Cr
content.
Isothermal section
at 1400°C section
Isothermal
T = 1400
1400°C
C

140
 Liquidus projection

141

Isothermal section Isothermal section

at 1000°C at 650°C

142
 Vertical sections at increasing content of Cr

143

Chapter 3 : References

[1] A. Prince, Alloy phase equilibria, Elsevier, 1966

[2] D.R.F. West, Ternary equilibrium diagrams, Chapman-Hall, 1982.

[3] F.N Rhines, Phase diagrams in metallurgy, McGraw Hill Book Co., NY, 1956.

[4] H.G. Lee, Chemical Thermodynamics for metals and materials, Imperial College Press, 1999.

[5] M. Hillert, Phase equilibria,phase diagrams and phase transformations,their thermodynamic basis, Cambridge
University Press, 1998.

[6] K.
K Hack
H k ett al.,
l 3D3D-representation
t ti off phase
h and
d property
t diagrams
di i multi-component
in lti t systems,Int.
t I t J.
J Mat.
M t
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[7] ASM Handbook, Alloy phase diagrams, Vol. 3, ASm Int., 1993.

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