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2a Sim Am-Amis-fame Elaboration-1 Diagrams Antoni 2023-24
2a Sim Am-Amis-fame Elaboration-1 Diagrams Antoni 2023-24
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
n n
f = = ? nGe Q
n + n n0 nGe P M
T0
n n
f =
n +n ==
n0
?
n = ?
f + f =1 n = ?
xSi x0Si xSi.
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
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)
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
( 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
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
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
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
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:
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
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
spinodal discontinuous
decomposition precipitation
G
19
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
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
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
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.
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 )
G0 A 0 G0 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
27
dT
0 (Gibbs-Konovalow theorem)
dx B azé
Gim m m m
(( i )) i exp i exp ( H i TSi ) i exp H i 1 T
RT Tim
RT RT
28
s > l : minimum
If regular (solid and liquid) solutions :
s < l : maximum
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
sol
xB xB
A B A B
T T1 T T2 G(0B )
G(0A )
G0 B
G0 A
G0 A 0 G0 B
B 0
G(0A ) 0 G(0B ) 0
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
G(0A) 0 G(0B ) 0
- pure liquids A and B
G0A G G 0
GB
- pure solids A and B Gliq
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
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
from 12 to 15 kJ.mol-1
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
dT / dxB 0
T liq
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
G0 A 0 A 0
xj xk G0B 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
1200 Liquid
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
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)
* Relatively
y low melting
g points
p
* MONOTECTIC reaction : L1M L2N + A
l from 20 to 17 kJ.mol-1
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 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
45
(Ni)
G°
G 0Ni 0, 75 Ti 0, 25
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
with fusG(i,T)
G(i T) = fusS(i) (Tfusi – T)
1. SfusA = SfusB = 20
TfusA = 800, TfusB = 1000
s = 10, 15 and l = 0
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
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
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.
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 = 3G°1 in J/3 mole of atoms
or in J/mole of Ni3Ti compound
p
57
(Ni)
G°
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.
2.2 Binary systems; the gas phase contains only one species (Fe-O system)
TC
Reactions evolving 1 mole of O2 : liq O2
1600 Feliq oxliq oxyde liquide
1000
l m n o p q
From the phase rule: FeO
10
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
875C
800 W H
Fe M
1 1,3.10-15 24 26 28 30
3 1,7.10-6 T C
o x liq
Fe liq
1600 g
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
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
64
65
= 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
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
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
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
xC (or CC)
Fe3C 70
z
Exercise 1 Fe-C-O system
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.
73
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
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
74
T = 1200K
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
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.
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
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 ))
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
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
80
References (Chapters 1 and 2)
[4] H-G LEE, Chemical thermodynamics for metals and materials, Imperial
C ll
College P
Press, 2000
2000.
81
82
Chapter 3 : Ternary phase diagrams
3.1 Introduction
83
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
► Number of moles
φ φ
xi 100 wi 100
85
86
3.3.2 How to plot ternary compositions (T = Cste)
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
87
M k outt along
Mark l AB a length
l th Ab = 50 % B
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.
Right-angled triangle
89
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
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
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
A tie
tie-triangle
triangle is in contact with one
one-phase
phase field at
its corner and two-phase areas on each side
extrapolate
p
However:
perspective diagrams the complete ternary space model with its constituent spaces,
curves and points.
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
► Isothermal sections: Horizontal slices through the three dimensional diagram. All points on
the section are at the same temperature.
► 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
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
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
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
F a two-phase
For t h equilibrium
ilib i α-β
β att given
i P and
dT
In a binary system
106
► Molar Gibbs energy surface of each phase
(as function of temperature and composition)
► A three-phase
three phase equilibrium for a ternary system
at a given temperature (tie-triangle) result from a
In a ternary system common tangential plane simultaneously touching
the molar Gibbs energy
gy surfaces of three pphases.
107
Example: Liquid and two primary solid solutions giving a eutectic reaction
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 :
110
3.7.2 Projected views
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
111
BC AB
a) T < T<T BC
b) T < T Eutectic
Eutectic Eutectic
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 + +
4 one-phase fields
6 two-phase fields
113
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
4 three-phase fields
114
Liquidus projection
115
Isothermal sections
T AB < T<TB
Eutectic Fus
116
Isothermal sections
AC AB
T <T<T Eutectic
Eutectic
117
Isothermal sections
118
Development of the phase regions
Diagplot
gp
Ideal liquid solution, regular solid solutions
119
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 +
Primary solidification of
Eutectic reaction L +
Solidification completed when the side of the tie-
triangle contains point Y
The solidification path during primary stage can only be determined experimentally
121
123
124
Primary solid solutions , and
Qe1, Qe2, Qe3: monovariant lines, eutectic valleys
Eutectic valley Qe1: composition of L for L +
125
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
128
Primary solid solutions , and
129
Diagplot
gp
Three components forming regularl solutions
130
Relative positions of the tie-triangles
- TP < T: Tie-triangle L-- associated with the
131
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.
133
A bi
binary compound
d AB which
hi h melts
lt congruently
tl
► The composition of the compound lies within the corresponding primary field
► 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
136
Exercice 4- In a system ABC, a ternary alloy of Exercice 5- Consider the Pb-Bi-Sn ternary system.
composition 30 mass.% B and 30 mass.%C consists at a
particular temperature of three phases of equilibrium 1- From the Gibbs phase rule,
1 rule determine the degrees of
compositions as follows: freedom along the lines E1O, E2O and E3O?
6- What is the p
proportion
p of liquid
q remaining
g jjust before the
ternary eutectic reaction?
137
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.
139
Solidus projection
Exercice 9- The Fe-Cr-Ni
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).
140
Liquidus projection
141
142
Vertical sections at increasing content of Cr
143
Chapter 3 : References
[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
Res.,98 (10),pp. 918-925, 2007.
[7] ASM Handbook, Alloy phase diagrams, Vol. 3, ASm Int., 1993.
[9] Advanced Materials Processes, Vol. 165 n7, pp. 29-30, 2007.
[10] http//diagplot.net
[11] P. Desré, F. Hodaj, Thermodynamique des matériaux - équilibres de phases et métastabilité, EDP Sciences,
2010.
2010
144