Professional Documents
Culture Documents
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
unstable
G
metastable
equilibrium state
26
P+F =C+2
F =CP+2
Gibbs
27
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
F=1
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:
dT v2 v1
H
S
T
dP H
dT TV
derived ~1834
dP H
dT TV
H
32
Gemesis,GE,SumitomoElectric,andDeBeers
33
2.93g/cm3
C2/c
2.65g/cm
2.65
g/cm3
P3121
4.287g/cm3
P42/mnm
OTHER EXAMPLES
Ice
35
OTHER EXAMPLES
CO2
36
OTHER EXAMPLES
Sulfur
37
P+F =C+1
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
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
40
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
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
44
keep cooling
more crystals of A
form, depleting melt
of A
P=2
F=1
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 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
49
cool more
note that liquid
becomes richer in B
Liq e + A A + B
Liq.
51
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
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
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)
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
61
62
BINARYSYSTEMSWITHIMMISCIBLELIQUIDS
upper
pp
consolute
temperature
T3
T2
A+L
immiscibility dome
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
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)
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)
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
P=1
F=2
CRYSTALLIZATION
the composition of the solid solution has to change continuously
during crystallization in order to maintain equilibrium
liquidus
L
T3
T2
tie line
T1
solidus
A x3
x2
s.s.
x1
s2 s1 B
The amount of s.s. and its A content continuously increases during cooling.
68
coring
onions
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.,
71
BINARYSOLIDSOLUTIONSWITHTHERMALMAX/MIN
BINARYEUTECTICWITHPARTIALSOLIDSOLUTION
very commonly crystalline phases have only partial solubility in
each other (immiscible solid solutions)
73
EXAMPLEOFPARTIALSOLIDSOLUTIONEUTECTIC
74
Ag in Cu
solubility
8%
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):
78
phase composition:
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
83
lamellar
globular
rodlike
acicular
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
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
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
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
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