Phase Equilibria

Reading: West 11-12

23

PHASE DIAGRAMS
Also called equilibrium or constitutional diagrams
Plots of temperature vs. pressure, or T or P vs.
composition, showing relative quantities of phases at
equilibrium
Pressure influences phase structure
y constant in most applications
pp
Remains virtually
Most solid-state phase diagrams at 1 atm
Note: metastable phases
p
do not appear on
equilibrium phase
diagrams

FeFe3Cphase
diagram
g

24

PHASES
A phase is a homogeneous portion of a system with uniform physical and
chemical characteristics, in principle separable from the rest of the system
Adifferenceineither physicalorchemicalpropertiesconstitutesaphase

gaseous state
seemingly only one phase occurs (gases always mix)
liquid state
often only one phase occurs (homogeneous solutions)
e.g., salt
lt water,
t
molten
lt N
Na2O-SiO
O SiO2
two immiscible liquids (or liquid mixtures) count as two phases
solid state
crystalline phases: e.g., ZnO and SiO2 = two phases
polymorphs: e
e.g.,
g wurtzite and sphalerite ZnS are different phases
solid solutions = one phase (e.g., Al2O3-Cr2O3 mixtures)

25

PHASE EQUILIBRIA
The equilibrium phase is always the one with the lowest free energy

G=H TS
Equilibrium state with
minimum
m
m m free
f
energy
gy under some
m
specified combination of

temperature, pressure, and

composition

The driving force for a phase

change
g is the minimization
m mz
of
f free
f
energy
e.g.,
g melting
g

unstable
G
metastable
equilibrium state

26

GIBBS PHASE RULE

1870s

P+F =C+2
F =CP+2

P: number of phases present at equilibrium

C: number of components needed to describe the system
F: number of degrees of freedom, e.g. T, P, composition

Gibbs

The number of components (C) is the minimum number of chemically

independent constituents needed to describe the composition of the
phases present in the system.
e.g.,
g , salt water. C = 2 ((NaCl and water))
solid magnesium silicates. C = 2 (MgO and SiO2)
solid MgAl silicates. C = 3. (MgO, Al2O3, SiO2)
The degrees of freedom (F) is the number of independent variables
that must be specified to define the system completely.

27

ONE COMPONENT PHASE DIAGRAMS

P+F =C+2

F=2

with C = 1

P+F =3

F 0
F=0

F=1

Composition is fixed,
Only
y T and P can vary
y

Three possibilities:
P = 1 F = 2 (bivariant phase field)
P = 2 F = 1 (univariant
( i i
phase
h
curve))
P = 3 F = 0 (invariant phase point)

28

EXAMPLE: BOILING WATER

P+F=C+2
C = 1 (water)
P = 2 (vapor + liquid)
F = 1 (either
( i h T or P,
P
but not both)
coexistence curve

F=1

*once we specify either T or P

of our boiling
g water,, the other
variable is defined as well
29

CLAUSIUS-CLAPEYRON EQUATION
Expresses the pressure dependence of phase transitions
as a function of temperature (gives slopes of coexistence curves)
From a to b, starting from Gibbs
Gibbs-Duhem
Duhem equation
equation:

dg1 s1dT v1dP

d 2 s2 dT v2 dP
dg
dg1 dg 2
dP s2 s1

dT v2 v1

H
S
T

dP H

dT TV
derived ~1834

Slope of the coexistence curves:

dP H

dT TV
H

positive along arrows

(melt, sublime, vaporize)

negative only for melting

*Ice less dense than water

31

ONE COMPONENT PHASE DIAGRAMS

Carbon

32

More than 100 tons of synthetic

y
diamonds are
produced annually worldwide by firms like Diamond
Innovations (previously part of General Electric),
Sumitomo Electric, and De Beers.

Gemesis,GE,SumitomoElectric,andDeBeers

33

ONE COMPONENT PHASE DIAGRAMS

SiO2

2.93g/cm3
C2/c
2.65g/cm
2.65
g/cm3
P3121

4.287g/cm3
P42/mnm

there are also many metastable phases

34
(not shown)

OTHER EXAMPLES
Ice

35

OTHER EXAMPLES
CO2

36

OTHER EXAMPLES
Sulfur

37

TWO COMPONENT (BINARY) DIAGRAMS

P+ F = C + 2
with C = 2

Composition is now variable: T, P, and

composition can vary

When vapor pressures

are negligible:

Condensed phase rule

P+F =C+1

Pressure is no longer a variable: only T and composition matter

P+F =3
Three possibilities (as before):
P = 1 F = 2 ((bivariant p
phase field))
P = 2 F = 1 (univariant phase curve)
P = 3 F = 0 (invariant phase point)

38

SIMPLE EUTECTIC SYSTEMS

simplest
p
binary
y diagram
g
for solids

P+F =3

(liquid)

P=1
F=2
P 2
P=2
F=1
(solid)

P 2
P=2
F=1
P=22
P
F=1
39

 no compounds/solid solutions in solid state

only single phase liquid at high temperatures
partial melting at intermediate temperatures

40

First, specify overall composition of the system

Second, pick a temperature.
The
he compos
compositions
t ons of the phases ((1 or 2)) are then fixed
f xed

e.g., start
with liquid
q
at a certain
composition

isotherm
Liquid
1490C
70% A
30% B

isopleth

41

now, slowly
cool liquid

crystals of A
begin to form

Liquidus curve: specifies the maximum temperature at which crystals

can co-exist with the melt in thermodynamic equilibrium
42

LIQUIDUS CURVE
Maximum T at which crystals can exist.
exist
aka Saturation Solubility Curve

Melting point
depression: the effect
off a soluble impurity
p
y
on the melting point of
pure compounds.

43

For example, consider salty ice:

add salt, freezing point falls

44

keep cooling
more crystals of A
form, depleting melt
of A
P=2
F=1

the system is now a mixture of crystals of pure A and the melt

45

Along the
Al
h isotherm
i h
XfY the
XfY,
h relative
l i amounts of
f the
h phases
h
A and
d melt
l
vary but the composition of the individual phases does not vary.
Along XfY, the two phases are pure A and melt of ~60% A & 40% B.

tie line
X

The relative
Th
l i amounts of
f the
h two phases
h
(phase
( h
composition)
i i ) can be
b
determined by using the level rule along the tie line XfY:
47
Amount of A = fY/XY and amount of liquid = Xf/XY.

PHASE COMPOSITION AND LEVER RULE

Lever rule:
L
l the
th fractional
f
ti
l amounts
t of
f two
t
phases
h
are inversely
i
l
proportional to their distances along the tie line (isotherm) from the
bulk composition axis
balance the teeter-totter

Phase 1

f1 L1 f 2 L2

Phase 2
X

f
L1 = Xf

f1
f1
L2

f 2 1 f1 L1

Y
L2 = fY

L2
fY
f1

L1 L2 XY

48

Ph
hase 1

Ph
Phase
2
X

Overall Composition
f
f
f
f

Y
f

Fraction of liquid (phase 2)

Xf /XY = 10%
Xf/XY = 60%
Xf /XY = 85%
Xf

49

cool more
note that liquid
becomes richer in B

We can use the phase diagram to determine the phase composition,

the relative amounts of A and melt at a certain T and bulk comp.
50

cool some more

last of the liquid
solidifies as crystals
of A and B

just above solidus:

fraction A: fe/Xe
melt fraction: Xf/Xe

passing through the

solidus is called the
eutectic reaction:

Liq e + A A + B
Liq.

Solidus curve: gives the lowest temperature at which liquids can

exist in equilibrium over a given compositional range

51

cool some more

sample is now
mixture of A and B
crystals

below solidus:
fraction A constant
at fY/XY
fraction
f
ti B constant
t t
at Xf/XY
X

P=2
F=1

not much interesting happens below the solidus line. The solid just
further cools with no change in composition.

52

crystals of A
precipitate first
(A primary)
crystals of B
precipitate first
(B primary)

~0%
0% B
~100% liq.

~0%
0% A
~100% liq.

53

slow heating is
the reverse of
slow cooling

54

EUTECTIC COMPOSITION (easily melted)

system with the eutectic composition will melt/freeze congruently
(i.e., completely, with no change in composition) and at the lowest T
composition with the
lowest melting point
eutectic point is invariant

P+F =3
F =0
-3p
phases present
p
(A, B, liquid e)

eutectic
point

55

56

Vapor--Liquid
Vapor
Liquid--Solid Nanowire Growth
800 deg. In-situ TEM
vapor
metal
catal sts
catalysts

nanowire

alloy
liquid

II

III

Alloying

Nucleation

II Growth
III

Unidirectional growth is the consequence of an anisotropy in solid

solid-liquid
liquid interfacial energy.
energy
Y. Wu et al. J. Am. Chem. Soc. 2001, 123, 3165
57

BINARYSYSTEMSWITHCOMPOUNDS
T
Type
1:
1 single
i l compound
d AB th
thatt melts
lt congruently
tl

AB melts congruently
(no change in composition)
two
t simple
i l eutectic
t ti systems
t
stitched together

58

BINARYSYSTEMSWITHCOMPOUNDS
T
Type
2:
2 single
i l compound
d AB that
th t melts
lt iincongruently
tl

AB melts incongruently
g
y at T2
(liquid composition is x,
liquid fraction is zy/zx)
x is a peritectic point
(3 phases: A, AB, liquid x)
AB melts completely at T3
liquid
li id compositions
ii
between
b
x and m precipitate AB first
Peritectic point: an invariant point (liquid & two solids) in which the
composition of the liquid phase is not between that of the two solids
59
(not a minimum in the intersection between two liquidus lines)

lets cool liquid of composition n:

1) crystal of A form at T3
2) more A forms
f
until
til liquid
li id
reaches composition x
3) At T2, peritectic reaction
occurs:

Liq. x + A Liq. x + AB
(crystalline phase changes from A
to AB, often very slowly)
4) Cooling to T1, more AB forms,
liquid composition moves to m
eutectic reaction occurs
5) below T1, we have AB and B

60

BINARYSYSTEMSWITHCOMPOUNDS
T
Type
3:
3 single
i l compound
d AB with
ith upper li
limit
it of
f stability
t bilit

AB decomposes before melting

(it disproportionates to A and B)

AB has upper limit of stability

simple eutectic system above T1

61

THECaO SiO2 BINARYDIAGRAM

11 compounds!
immiscible
liquids

Ca2SiO4 and CaSiO3 melt

congruently
y
Ca3SiO5 and Ca3Si2O7
melt incongruently
Ca3SiO5 has a lower limit
of stability
(decomposes to CaO and
Ca2SiO4 below 1250C)
liquid immiscibility dome
at the silica-rich end of
the diagram

62

BINARYSYSTEMSWITHIMMISCIBLELIQUIDS
upper
pp
consolute
temperature

Below T3, the liquid phase separates

into two liquids of different comp
comp.

T3
T2

A+L

immiscibility dome

cool this comp.

2 Liq.
a
A +L

L
invariant monotectic points
at points a and c

P+F =3

B +L

- 3 phases present
(liquid a, liquid c, A)

A +B
A

At T2, monotectic reaction occurs:

Liq a + Liq.
Liq.
Liq c Liq.
Liq c + A
63

THERMODYNAMICSOFLIQUIDIMMISCIBILITY
Enthalpy
Entha
py of mixing
m ng determines
t rm n s wh
whether
th r two liquids
qu s A an
and B m
mix

Gmix =H TS S>0formixing

ifH<0(strongerABattraction),the
(
g
),
liquidsaremiscibleatalltemps
ifH>0(strongerAA,BBattraction):
possiblymiscibleifH<TS(highT)
ibl i ibl if H < TS (hi h T)
immisciblewhenH>TS(lowT)

when a liquid enters the immiscibility dome

dome, the unmixing process
(phase separation) occurs by one of two major mechanisms:
1) nucleation and growth
(large compositional fluctuations
required for G<0)
2) spinodal
i d l d
decomposition
i i
(even infinitesimal compositional
fluctuations give G<0)

64

SOLID SOLUTIONS
a solid-state solution; a crystalline
y
material with variable composition
p

Two types:
substitutional
b tit ti
l ((solute
l t atom/ion
t /i replaces
l
solvent
l
t atom/ion)
t /i )
interstitial (solute atom/ion occupies interstitial site)

Formation of solid solutions favored by:

similar atomic/ionic radii (15%)
same crystal structure
similar
i il electronegativities
l t
ti iti
same valency

Ex m l s:
Examples:
Al2O3 Cr2O3 (substitutional, complete)
Si-Ge (substitutional, complete)
Fe-C
F C (interstitial,
(i
i i l partial)
i l)
65

BINARYSYSTEMSWITHSOLIDSOLUTIONS
simplest solid solution system has complete miscibility in both
solid and liquid states

P=1
F=2

copper melts at 1085 C

nickel melts at 1455 C
above liquidus: single phase liquid

P=1
F=2

between liq. and sol.: two phases

below solidus: single
g phase
p
solid

-phase is a substitutional solid

consisting of both Cu and Ni and
on an FCC lattice
66

CRYSTALLIZATION
the composition of the solid solution has to change continuously
during crystallization in order to maintain equilibrium

cool this comp.

liquidus

L
T3
T2

tie line

T1
solidus

A x3

x2

s.s.
x1

s2 s1 B

at T3, s.s. of composition

p
s1 forms
(lever rule shows ~100% liquid
of composition x1)
at T2, s.s. is composition s2, richer
in A, and liquid is composition x2,
depleted of B
(lever rule shows 33% s.s.
s s and
67% liquid)
at T1, s.s. is composition x1 and
the final liquid is composition x3
(lever rule shows ~100% s.s.)

The amount of s.s. and its A content continuously increases during cooling.

Equilibrium solidification requires very slow cooling

mi
microstructure
t
t
d
during
i cooling
li

No microstructural changes until the

liquidus line is reached at b
From b to d: -phase increases as
dictated by lever rule and composition
changes as dictated by tie lines and
their intersection with solidus/liquidus

maintaining equilibrium during

cooling results in a homogeneous
alpha phase

68

Somewhat faster cooling results in fractional crystallization

mi
microstructure
t
t
d
during
i cooling
li
diffusion in solids is very slow, requires time
non-equilibrium
q
(fast) cooling
g causes:
1) cored structures (inhomogeneous s.s.)
2) metastable phases
3) undercooled liquid
Consequences of non-equilibrium solidification:
segregation, cored structure.
upon reheating: grain boundaries will
melt first causing loss of structural integrity

coring
onions

coring in metals can be eliminated by heating

just below the solidus for sufficient time 69

CRYSTALLIZATION
Very slow cooling rate: crystallization to the same composition
Slightly
g y faster: fractional crystallization
y
Very fast (quenched): no time for crystallization, glass forms

A glass is a non-crystalline
(amorphous) solid, such as
glassy silica

70

METALLIC GLASSES
amorphous
h
metallic
t lli alloys
ll
smallsamplesoftenproducedbyrapid
cooling (millions of degrees a second) of
cooling(millionsofdegreesasecond)of
moltenmetal,e.g.,bymeltspinning
bulkmetallicglasses (BMG),1990s,often
f
formedfromalloyswithmuchlowercritical
df
ll
ith
hl
iti l
coolingrates.Thesealloyscontainmany
elements(Fe,Ti,Cu,Mg,Pd,etc.),thus
frustratingtheelementsintheirabilityto
formanorderedlattice.

properties:

e.g.,

better wear/corrosion resistance (no grain boundaries)

lower
l
thermal
h
l conductivity
d
(low
(l
phonon
h
mean free
f
path)
h)
higher strength (no line defects, no grain boundaries)
easy processing (they soften and flow with heating)

Ti40Cu36Pd14Zr10, believed to be noncarcinogenic, is about 3 times

stronger than titanium potential artificial bone

71

BINARYSOLIDSOLUTIONSWITHTHERMALMAX/MIN

Indifferent point (P = 2, F = 1), NOT invariant point

There are NEVER three phases.
phases
72

BINARYEUTECTICWITHPARTIALSOLIDSOLUTION
very commonly crystalline phases have only partial solubility in
each other (immiscible solid solutions)

3 two phase regions

one invariant point
compositional
iti
l range of
f
the two s.s. depends
on temperature
usually,
ll the
th m
maximum
xim m
solubility of B in A
(and vice versa) occurs
at solidus temp

73

EXAMPLEOFPARTIALSOLIDSOLUTIONEUTECTIC

74

Melting points of pure metals

FCC, copper iis solute,

FCC
l
rich
i h in
i Ag
A
max. 8.8% Cu
8.8% Cu
maximum

Ag in Cu
solubility
8%

Solid solution rich in copper

pp
silver as solute (FCC) max of
8% Ag at 779C

Solvus line line between single phase solid and

multi-phase solid
75

Eutecticisotherm

E t ti isotherm
Eutectic
i th

Eutectic reaction:
Liq E (71.9%
Liq.
(71 9% Ag)

cooling
heating

(8.0%
(8 0% Ag) + (91.2%
(91 2% Ag)
76

Pb-Sn (solder):

63/37 solder eutectic comp.

150C isotherm (40% Sn 60% Pb)

Given a 40% Sn 60% Pb alloy at 150C:

(a) What phase(s) are present?
((b)) What is ((are)) the composition(s)
p
( ) of the p
phase(s)?
()
(c) What is (are) the relative amount(s) of the phase(s)?

use tie line and Lever Rule!

77

composition of the two phases: use tie line

40% Sn 60% Pb alloy at 1500C

Ph
Phases
presentt
Temperature composition
point in + region ( and
will
ill coexist)
i t)
C (10% Sn 90% Pb)
C (98% Sn 2% Pb)

78

phase composition:

use Lever Rule

Relativeamountsof
eachphase(weight)

C C
C1

98 40
W

0.66
C C 98 10

C1 C 40 10

0.34
W
C C 98 10

79

MICROSTRUCTURALCHANGESINBINARYEUTECTICS
Pure element to maximum solubility at
room temperature
Cooling composition C1:
Alloy is liquid until it passes through
liquidus at b: -phase begins to form
More is formed while passing through
+L region compositional differences
dictated by tie lines and boundaries
All liquid crystallizes to -phase with C1
Results in p
polycrystalline
y y
solid with uniform
f
composition
Note crystal maintains -structure all the
way to room temperatures (at equilibrium).
equilibrium)
80

MICROSTRUCTURALCHANGESINBINARYEUTECTICS
Composition range between room
temperature solubility and max. solid
solubility at eutectic temperature
C li composition
Cooling
iti C2:
Changes are similar to previous case as
we move to solvus line
Just above solvus line, at point f,
microstructure consists of grains with
composition C2
Upon crossing the solvus line, the -solid
y is exceeded formation of
solubility
-phase particles
With continued cooling, particles will
continue to grow in size because the
mass fraction of increases slightly
with decreasing temperature
81

EUTECTIC
MICROSTRUCTURES

Solidification of eutectic composition:

L (61.9%
(61 9% Sn)
(18.3%
(18 3% Sn) + (97.8%
(97 8% Sn) redistribution of tin and
lead at eutectic temperature
Redistribution is accomplished by diffusion microstructure is lamellae or
columnar structure. This lamellae/columnar configuration: atomic diffusion
of lead and tin need only occur over relatively short distances
82

During the eutectic transformation

from liquid to solid ( + ), a
redistribution of and tin is necessary
because and and have different
compositions,
ii
neither
i h off which
hi h is
i the
h
same as the liquid. Redistribution is
through diffusion.
Liquid

83

lamellar

globular

rodlike

acicular

Each eutectic alloy has its own characteristic microstructure

spheroidal,nodular,orglobular;acicular(needles)or
spheroidal,
nodular, or globular; acicular (needles) or
rod;andlamellar(platelets,Chinesescriptor
84
dendritic,orfiligreed)

85

Compositions other than eutectic that, when cooled, cross the eutectic point
p
line is crossed,, liquid
q
p
phase,, which is of the eutectic
As eutectic temperature
composition, will transform to eutectic structure (often lamellae)
86

Anteater inclusion
u

87

cool this comp.

30
Relative amounts of microconstituents just below solidus:
Primary microconstitutent, f = Q/(p + Q) = (61.9 30)/(61.9 18.3) = 73% is primary alpha
Eutectic microconstituent, fe = same as liquid phase from which it was transformed, fe
fe = p/(p + Q) = (30 18.3)/(61.9 18.3) = 27% is liquid
The eutectic liquid fractionates into alpha and beta solid solutions:
f = R/(p + Q + R) = (97.8 61.9)/(97.8 18.3) = 45% alpha

Total = 73% + 27% 0.45 = 85% ; 73% is primary , 12% is eutectic , 15% is

89

longer time
available to
phase separate
yields larger
phase domains

90

BINARIESWITHSOLIDSOLIDPHASETRANSITIONS
in systems without solid solutions,
solutions solid-solid phase transitions are
indicated by isotherms

T1: B

T2: A

91

BINARIESWITHSOLIDSOLIDPHASETRANSITIONS
in systems with complete solid solubility
solubility, the solid-solid phase
transition temperature usually varies with composition

west 11.18

two phase region contains

one solid and one liquid phase
two phase region contains
two solid phases

92

ALLSOLIDINVARIANTPOINTS
Eutectic point E:

Liq. E A + B

Eutectoid point B:

B A + B

Peritectoid point Y:

A + B A

disproportionation
reactions

93

BINARIES:THEBIGPICTURE

94

Note: oid analogues of each these reactions may exist

95

96

THREECOMPONENTCONDENSEDSYSTEMS

P+F =C+1

with C = 3

P+F =4
If pressure iis constant,
t t th
three independent
i d
d t variables:
i bl
T & the concentrations of two components
The presence of four phases: F = 0, invariant point
(usually three crystalline phases and liquid)

97

EUTECTICSYSTEMWITHOUTCOMPOUNDS
Take 3 simple binary eutectic systems

98

 combine to form a triangular prism phase space

Temperature

Composition
p
(in plane)

projection onto
b
base
off ttriangle
i
l
(2D subliquidus diagram)
99

100

FINDINGCOMPOSITIONONATERNARYDIAGRAM
Two Line Method
Draw two lines through Composition 1
parallel to any two sides of the triangle
here AB and AC.
AC The intersection of
these two lines with the third side (BC)
divides this side into three line segments.
The lengths of the individual line
segments are proportional to the relative
amounts of the three components A, B,
and C.

101

subliquidus equilibria

102

CRYSTALLIZATIONPATHWAY
For a general composition:
1) start at primary phase field
2) proceed along univariant boundary curve
3) finish att eutectic
ut ti point
p int

103

CRYSTALLIZATIONPATHWAY EXAMPLE
Anorthite
Wollastonite
Sphene System
Anorthite CaAl2Si2O8
Wollastonite CaSiO3
Sphene CaSiTiO5

104

EUTECTICSYSTEMWITHONECOMPOUND
simplest case is one binary compound on a binary join

binary join A-BC

(only A and BC along this line)

two eutectic triangles

g
(A-B-BC and A-BC-C)

ternary diagrams with multiple compounds

compounds, solid solutions
solutions, etc.
etc
become very complicated very quickly
105