CHAPTER 8

Phase Diagrams
and
Microstructure
Development
1
8-I. Introduction
 There is a strong correlation between microstructure and
mechanical properties, microstructure is related to phase
diagram.
 Phase diagarms provide valuable information about
melting, casting, crystallization, and other phenomena.

8-II. DEFINITIONS AND BASIC CONCEPTS

Component ： pure metals and/or compounds
e.g., copper-zinc brass, the components are
Cu and Zn.
System ： A specific body of material under consideration or

series of possible alloys consisting of the same

2
components.
 Solute : atoms occupy either substitutional or
interstitial positions in the solvent lattice,
and the crystal structure of the solvent is
maintained.

A. SOLUBILITY LIMIT
Maximum concentration of solute atoms that may
dissolve in the solvent to form a solid solution;
Solubility limit depends on the temperature

F9.1

3
B. PHASES 90

 Phase:
A homogeneous portion of a system that has uniform
physical and chemical characteristics. Every pure
material is considered to be a phase. F10-11

 A single-phase system is termed “homogeneous” or “ a

homogeneous system.”
 Systems composed of two or more phases are termed
“mixtures” or “heterogeneous systems.”
 Most metallic alloys, ceramic, polymeric, and F9-2
composite are heterogenous materials .

4
C. MICROSTRUCTURE

 Microstructure is subject to direct microscopic

observation, using optical or electron microscopes
 In metal alloys, microstructure: number of phases
present, their proportions and the manner they are
distributed or arranged.
 Microstructure depends:
Elements present, their concentrations, heat treatment
(i.e., the temperature, the heating time at temperature,
and the rate of cooling to room temperature).
 Specimen preparation (polishing and etching):
different phases may be distinguished by their
appearance, light or dark,
5
D. PHASE EQUILIBRIA
 Equilibrium
 Free energy: A function of the Internal energy of a
system, and also the randomness or disorder of the
atoms or molecules (or entropy).
 A system is at equilibrium if its free energy Gibbs
energy, G is at a minimun

The characteristics of the system do not change

with time but persist indefinitely; that is, the
system is stable.
 Phase equilibrium
A constancy with time in the phase characteristics,
e-g., Sugar-water syrup at 20°C. 6
 65wt% C12H22O11–35wt% H2O
at 100°C : 80wt% C12H22O11 F9.1

 In materials systems,characteristics of the microstructure:

the phases present
their compositons F9-2
relative phase Amounts
their spatial arrangement or distribution.
 Free energy considerations and diagrams

 Phase diagrams are made with the assumption

that the systems are at equilibrium.
 In practical situations, systems are often not at
equilibrium. 7
  Phase diagrams do not indicate the time period
necessary for the attainment of a new equilibrium
state. It is often that a state of equilibrium is never
completely achieved because the rate of
approaching is slow.

 Nonequilibrium or metastable state.

Often, metastable structures are of more practical
sighinficance than equilibrium ones.
 The speed or rate at which they are established and
the factors that affect the rate must be considered.

8
E. (EQUILIBRIUM PHASE) DIAGRAMS
F10-12

 Phase diagram (equilibrium or constitutional diagram.) :

Relationships between temperature and the compositions and
the quantities of phases at equilibrium.
 at least three kinds of information are available (1)
the phases that are present, (2) the composition of
each of these phases, and (3) the percentages or
fractions of the phases
 Pressure is also a parameter that influences the phase
structure. However, pressure remains constant in most
applications F9-2(a F9-2
)
 Ordinary phase diagrams (and the ones presented here) are
for a constant pressure of one atmosphere (1 atm).
 Ordinate: temperture ; abscissa: composition (weight percent
and atom percent ) 9
8-III. Phase Diagram of Metallic Materials
 Isomorphous System (phase Diagram)
 Eutectic System (phase Diagram)
 Phase Diagram with Intermediate phases or
compounds

10
 8-III-1 BINARY ISOMORPHOUS SYSTEMS F9.2a

A. Binary: a system that contains two components.

B. Isomorphous ： the components can be F9-3a
dissolved into each other completely without
solubility limits.

Interpretation of Phase Diagram

(a). Number of phase fields

Three different phase regions, or fields:
An alpha ( ) field, a liquid (L) field, a two-phase
+L field
Liquid L : a homogeneous liquid solution
composed of both copper and nickel 11
α Phase : a substitutional solid solution consisting of
both Cu and Ni atoms and having an FCC crvstal
structure α , complete solublity : both Cu and Ni
have the same crystal structure (FCC) , nearly
identical atomic radij and electronegativities, similar
valences ⇒ Isomorphous
Isomorphous

Solid solutions: desinated by lowercase Greek letters

(   etc.).
Two-phase region
Liquidus line
Solidus line
12
(b) Melting temperatures
F9.3a
 Pure component
solid-to-liquid transformation takes place at the melting
temperature, and no further heating increase in
temperature is possible until this transformation has
been completed
 Solid solution
F9.3b
for any composition of solid solution, melting
phenomenon will occur over the range of temperatures
between the solidus and liquidus lines, both solid  and
liquid phases will be in equilibrium within this
temperature range

13
C. Phase Compositions

at least three kinds of information are available (1)

the phase that are present, (2) the compositions of
these phases, and (3) the percentages or fractions
of the phases

 PHASES PRESENT F9.2

For example : Figure 9.3

 60wt% Ni-40wt% Cu at 1100C : point A , single

 phase
 35wt% Ni-65wt% Cu alloy at 1250C : point B , 
and liquid phases at equilibrium.

14
 DETERMINATION OF PHASE COMPOSITIONS

(a) one phase region : same as the overall composition

e.g., point A ,α phase having a composition of 60wt%
Ni-40wt% Cu F9.3a
(b) two-phase region

 tie line : horizontal lines (isotherm) across the two-

phase region and terminate at the phase boundary
lines
 tie line-liquidus intersection : 31.5wt% Ni-68.5wt%
Cu composition of the liquid phase CL :
 solidus-tie line ntersection :C , 42.5wt% Ni-
57.5wt% Cu F9.3b
15
 DETERMINATION OF PHASE AMOUNTS
(a) single-phase region ： e.g., point A
only the  phase is present , 100% 
(b) two-phase region
The tie line must be utilized : lever rule (or the inverse
lever rule)
The fraction of one phase is computed by taking the
length of tie line from the overall alloy composition to
the phase boundary for the other phase , and dividing
by the total tie line length.
F9.3b
For example : point B in Figure 9.3b
35 wt% Ni-65 wt% Cu alloy
overall alloy composition ： C0
mass fractions WL and W 16
 S
wL 
RS (9.1a)

C  C0
WL  (9.1b)
C  C L

42.5  35
WL   0.68 (9.2a)
42.5  31.5

R C0  C L 35  31.5
W     0.32 (9.2b)
R  S C  C L 42.5  31.5

17
 D. Development of Microstructure in Isomorphous Alloys
Microstructure is developed during solidification ( cooling)
 Phase diagrams are constructed under the conditions of equilibrium
 Equilibrium Cooling: Cooling occurs very slowly, phase equilibrium
is continuously maintained  equilibrium microstructure
nonequilibrium cooling  nonequilibrium microstructure
 Process of Solidification

(1) Nucleation: the formation of initial solid phase

(very beginning step of phase transition) micro
 initial solid phase: in the form of small solid
particles  nuclei
(2) growth of the nuclei
structure
(3) maturity of microstructure:
grain, grain boundary (polycrystalline) 82 18
 Liquidus line
nucleation
liquidus line

nuclei

growth

maturity of
microstructure
solidus line
Compositional
Solidus line readustment
(by diffusion)
grain
boundary grains

Cu Ni 19

f04_09_pg265
Lever Rule
𝑅
𝑊 𝑆=
𝑅+ 𝑆

𝑆
𝑊 𝐿=
𝑅+ 𝑆 (9.1a) 20
 Nucleation ： nuclei Growth of nuclei
f17_03_pg65

melt

F3-17
Grains Grain boundarie
F3-17

21

f17_03_pg65
D-1.Equilibrium cooling
Example: copper-nickel system (Figure 9.3a), 35wt% Ni-
65 wt% Cu is cooled from 1300℃.
 at point b, ~1260℃, first solid  begins to form, 46wt%
Ni-54wt% Cu, noted as (46Ni) .
 The overall alloy composition (35wt% Ni-65wt% Cu)
remains unchanged during cooling.
 The solidification process is complete at about 1220℃,
point d, last remaining liquid: 24wt% Ni-76wt% Cu.
 The final product then is a polycrystalline -phase solid
solution .
Lever rule F9.4

22
 Nonequilibrium cooling

 Equilibrium solidification : readjustments in the

compositions of the liquid and solid phases must occur
(by diffusion) F9.5
 Nonquilibrium solidification:
In virtually all practical solidification situations, cooling
rates are much too rapid to allow compositional
readjustments in the solid phases: nonequilibrium
solidification (but assumed that diffusion rates in the
liquid phase are sufficiently rapid such that equilibrium is
maintained in the liquid).
F9.4
Example ： Fig.9.4

23
Nonequilibrium Cooling Equilibrium Cooling

24
 Point c’ (about 1240℃), liquid composition 29wt% Ni-
71wt% Cu;  phase that solidified is 40wt% Ni-60wt%
Cu [(40 Ni)]. The composition of the  grains has
continuously changed with radial position, from 46wt
% Ni at grain centers to 40wt% Ni at the outer grain
perimeters. Average composition : 42wt% Ni-58wt%
Cu [(42 Ni)].

 The solidus line has been shifted to higher Ni

contents-to the average compositions of the  phase.
At point e’ (~1250℃) , the last  phase: 31wt% Ni ,
average 35wt% Ni.

25
 The distribution of the two elements within the grains
is nonuniform:
nonuniform composition: segregation (concentration
gradients, the center of each grain, is rich in the high-
melting element: cored sturcture).
 Cored structure:
Grain boundary regions will melt first as they are richer in
the low-melting component cored structure has a lower
melting point. This produces a sudden loss in mechanical
integrity.
Furthermore, this melting may begin at a temperature
below the equilibrium solidus temperature of the alloy.
Coring may be eliminated by a homogenization heat
treatment at a temperature below the solidus point for the
particular alloy composition. 26
 Mechanical Properties Of Isomorphous Alloys F9-5

Solid-solution strengthening (Section 7.9): an increase

in strength and hardness by additions of the other
component. F9-6

8-III-2. Binary Eutectic Systems

For example: the copper-silver system.

 three single-phase regions , , and liquid.
  phase : a solid solution rich in copper, silver as the
solute FCC crystal structure.
 -phase ： solid solution FCC structure, copper is the solute
 The  and  phases are considered to include pure copper
and pure silver, respectively.
F9.7 27
 The solubility limit for the  phase has a maximum
[8.0 wt% Ag] at 779°C (1434 °F ), point B.

 Solubility limit line separating the  and + phase

regions : solvus line. Boundary AB between the  and
+L fields: solidus line.

 Maximum solubility in the  Phase: point G .

 Horizontal line BEG, a solidus line, the lowest

temperature at which a liquid phase may exist.

 Three two-phase regions:  + L,  + L and  + .

28
 The melting temperature of copper is lowered by silver
additions. The same may be said for silver.
 Point E is called an invariant point: the composition CE and
temperature TE; (71.9 wt% Ag and 779℃) (9-8)
cooling
L(CE) (CE) + (CE)
F 9.7
heating

 Eutectic reaction (eutectic means easily melted), CE and TE

the eutectic composition and eutectic temperature,
respetctively; (CE and CE)
cooling
L(71.9 wt% Ag) (8.0 wt% Ag) + (91.2 wt%
Ag) heating

 The horizontal solidus line at TE : eutectic isotherm

(eutectic phase diagrams , eutectic system) 29
A. Consturction of Binary Phase Diagrams F 9.7

 In general, one or at most two phases may be in

equilibrium within a phase field.
 for a eutectic system, three phases (, , and L) may
be in equilibrium, but only at points along the eutectic
isotherm.
 single-phase regions are always separated from each
other by a two-phase region.

B. Another common eutectic system: lead and tin F9.8

Low-melting-temperature alloys : having near-eutectic

compositions, example: 60-40 solder, 60 wt% Sn and 40
wt% Pb. F9.9
Rules 30
C. Development of Microstructure In Eutectic Alloys
(a) The first case : between a pure component and
the maximum solid solubility at room
temperature (0 – ~ 2wt% Sn) F9.9 F9.11

(b) The second case : between the room temperature

solubility limit and the maximum solid solubility at
the eutectic temperature. (2wt% Sn–18.3wt% Sn)
F9.12

Upon crossing the solvus line, the  solid solubility is

exceeded, which results in the formation of small -
phase particles (nucleation) , these particles will grow
in size because the mass fraction of the  phase
increases with decreasing temperature.
31
(c) The third case : the eutectic composition.
Upon crossing the eutectic isotherm, the liquid transforms to
the two  and  phases F9.13
cooling
L(61.9 wt% Sn) (18.3 wt% Sn) + (97.8 wt% Sn) (9.9)
heating

By atomic diffusion : alternating layers (lamellase )of the 

and  phases (eutectic structure) , atomic diffusion of short
distances
F9.14 F9.15
(d) The fourth case :
Eutectic α, primary α. microconstituent , two microconstituents :
primary  and the eutectic structure.
Fraction of the eutectic microconstituent w e and fraction of liquid wL
p
F9.16 F9.17 we  wL  (9-10)
pQ F9.18
C 4  18.3 C 4  18.3
  32
61.9  18.3 43.6
fraction of primary , W’

Q
w  
pQ
61.9  C4 61.9  C4
  (9.11)
61.9  18.3 43.6

Fraction of total , W (both eutectic and primary) , total , W

QR P
w  (9.12) w 
PQ R PQ R (9.13)

97.8  C4 97.8  C4 C4  18.3 C4  18.3

   
97.8  18.3 79.5 97.8  18.3 79.5
33
 W  fraction of primary  + fraction of eutectic 
Q P  R 
  
 

P Q P Q  P Q  R
QR

P Q  R

When, for case 4, conditions of equilibrium are not maintained :

(1) grains of the primary microconstituent will be cored ,
(2) the fraction of the eutectic microconstituent will be
greater than for the equilibrium situation.

34
8-III-3. Equilibrium Diagrams Having Intermediate
Phases or Compounds

 Terminal solid solutions: the solid solutions at each end.

 Intermediate solid solutions (or intermediate phases):
the solid solutions in between
Comparison
F9.19
For example: the copper-zinc system
 There are six different solid solutions-two terminal
( and ) and four Intermediate (, , , and ∈).
(the ’ phase: a specific and ordered
arrangement). Dashed phase boundary lines : not
determined.
 The commercial brasses are copper-rich copper-
zinc alloys. 35
 Intermetallic compounds.
F9.20

For example, the magnesium-lead system compound,

Mg2Pb (19wt% Mg-81wt% Pb): a vertical
line.

(1) Mg2Pb melts at 550℃ (M) ,

(2) The solubility :
(3) This phase diagram may be thought of as two simple
eutectic diagrams joined back to back: Mg-Mg2Pb
system and Mg2Pb-Pb; Mg2Pb is really considered to
be a component.
36
◆. Eutectoid and Peritectic Reactions
( eutectic reaction: L

eutectoid (or eutectic-like)

reaction: cooling
   
  F9.21 F9.19 (9.14
heating )
eutectoid isotherm
distinguishing “eutectoid” from “eutectic” : one solid
phase instead of a liquid transforms into two other solid
phases at a single temperature.
A eutectoid reaction is found in the iron-carbon system
(section 9.17) that is very important in the heat treating of
steels.

37
 Peritectic reaction (another invariant reaction):
one solid phasetransforms into a liquid phase and
another solid phase.


 +L  cooling
(9.15) F9.19
heating

◆. CONGRUENT PHASE TRANSFORMATIONS

Phase transformations without compositional alterations:

congruent transformations, e.g., melting of pure materials
and intermetallic compounds; with a change in
composition : incongruent tansformations ,e.g., eutectic
and eutectoid reactions.
38
 8-Ⅲ-4.THE IRON-CARBON SYSTEM

Both steels and cast irons, are essentially iron-carbon

alloys. F9.24

THE IRON-IRON CARBIDE (Fe-Fe3C)PHASE DIAGRAM

(a)Pure iron, upon heating, experiences two changes in

crystal structure before it melts. At room tempeature:
ferrite, or αiron, has a BCC crystal structure; At 912 ° C,
FCC austenite, or γ iron; at 1394 ° C, BCC phase,
δferrite; finally melts at 1538 ° C (2800 ° F ).

39
F13.1
The composition extends only to 6.70 wt% C, an intermediate
compound: iron carbide, or cementite (Fe3C)
F9.24
Carbon is an interstitial impurity in iron.

In the BCC α ferrite, only small concentrations of carbon are

soluble; (explained by the shape and size of the BCC
interstitial positions.)

Relatively soft, may be made magnetic.

The austenite, or γ phase of iron, solubility is approximately

100 times greater than for BCC ferrite since the FCC
interstitial positions are larger. Austenite is nonmagnetic.

Mechanically, cementite is very hard and brittle; the strength

of some steels is greatly enhanced by its presence. 40
(b). DEVELOPMENT OF MICROSTRUCTURE IN
IRON-CARBON ALLOYS

From the γ region into the α + Fe3C phase field with

eutectoid composition (0.76wt% C): lamellae, relative
layer thickness ( α to Fe3C): 8 to 1: pearlite ( because it
has the appearance of mother of pearl), with grains
termed “colonies”.
Pearlite has properties intermediate between the soft,
ductile ferriteand the hard, brittle cementite.
The alternating α and Fe3C layers in pearlite form by
carbon diffusion from the 0.022 wt% ferrite regions and to
the 6.7 wt% cementite layers.
F9.26 F9.27 F9.28 F12.15
41
HYPOEUTECTOID ALLOYS F9.29 F9.30

0.022 — 0.76 wt% C : hypoeutectoid (less than

eutectoid) alloy.
In cooling to point d, most of the small α particles
(proeutectoid ferrite) will form along the original γ grain
boundaries.
As the temperature is lowered just below the eutectoid, all
the γ (having the eutectoid composition) will transform to
pearlite (eutectoid ferrite ) ferrite. The fraction of pearlite, Wp:

Wp T
 T U

C '0  0.022 C ' O  0.022 (9.18)

 
0.76  0.022 0.74 F9.31
42
eutectic reaction (at 4.30 wt% C and 1147°C) :

cooling
L     Fe3C (9.16)
heating

eutectoid reaction ( at 0.76wt% C and a temperature of

727 °C) :

cooling
 (0.76 wt %C )    (0.22 wt %C )  Fe3C (6.7 wt %C ) (9.17)
heating

(fundamental to the heat treatment of steels)

Ferrous alloys are those in which iron is the prime
component, but carbon as well as other alloying elements
may be present. Based on carbon content, there are three
types: iron, steel, and cast iron. Pure iron: less than 0.008
wt% C, ferrite phase; Steels: between 0.008 and 2.14 wt%
C (rarely exceed 1.0 wt%) , consists of both α and Fe3C
phases ; Cast irons: 2.14 —6.70 wt% C( normally less
than 4.5 wt% C). 43
The fraction of proeutectoid α , W α,
W '  T
T U (9.19)
0.76  C '0 0.76  C ' O
 
0.76  0.022 0.74
Fractions of both total α ( eutectoid and proeutectoid) and
cementite are determined using the lever rule.
F9.32 F9.33
HYPEREUTECTOID ALLOYS
Containing between 0.76 and 2.14 wt% C.
Proeutectoid cementite as the temperatue is lowered
through the eutectoid to point i , all remaining austenite
of eutectoid composition is converted into pearlite ;
resulting pearlite and proeutectoid cementite as
microconstituents
F9.29 F9.30 44
Fractions of pearlite Wp and proeutectoid cementite WFe3C‘
W X
p  V X

6.7  C '1 6.70  C '1

 
6.70  0.76 5.94
(9.20)

W V
Fe 3C '  V  X
e3


C '10.76  C '10.76
6.70  0.76 5.94
(9.21) 45
(c). NONEQUILIBRIUM COOLING
In this discussion, it has been assumed that
conditions of metastable equilibrium have been
continuously maintained; thatis, sufficient time has
been allowed at each new temperature for any
necessary adjustment in phase compositions and
relative amounts as predicted from the Fe-Fe 3C
phase diagram. In most situations these cooling
rates are impractically slow and really unnecessary;
in fact, on many occasions nonequilibrium
conditions are desirable. F12.19
46
F12.21
 Two nonequilibrium effects of practical importance are (1)
the occurrence if phase changes or transformations at
temperatures other than those predicted by phase
boundary lines on the phase diagram, and (2) the existence
at room temperature of nonequilibrium phases that do not
appear on the phase diagram.

(d). THE INFLUENCE OF OTHER ALLOYING ELEMENTS

Alterations of the positions of phase boundaries and the
shapes of the phase fields
One of the important changes : shift in position of the
eutectoid with respect to temperature and to carbon
concentration
F9.34 F9.35 47
8-IV. Ceramic Phase Diagrams
Binary phase diagrams, frequently two components
share a common element, e.g., Oxygen in binary
oxide ceramics.
F12.24 F9.2

A. The Al2O3-Cr2O3 system

 Isomorphous, similar to copper-nickel phase

diagram (Figure 9.2a).
 The solid solution is a subsitiutional one: both
aluminum and chromium ions have the same
charge, similar radii (0.053 and 0.062 nm,
respectively,and both Al2O3 and Cr2O3 have the
same crystal structure(HCP). 48
 F12.25 F9.20
B. The MgO-Al2O3 System
 Similar to the lead-magnesium diagram (Figure9.20),
there exists an intermediate phase, or better a compound
called spinel( 尖晶石 ), which has the chemical formula
MgAl2O4 (or MgO-Al2O3) ( 鋁鎂尖晶石 )

 There is a range of compositions over which spinel is

a stable compound.
 Spinel is nonstoichiometric for other than the 50 mol%
Al2O3-50 mol% MgO composition.
 Limited solubility of Al2O3 in MgO due primarily to the
differences in charge and radii of the Mg2+ and Al3+
ions (0.072 versus 0.053 nm)
#88 49
 F12.26
C. The ZrO2-CaO system
 The compound CaZrO3 contains 31wt% CaO (50 mol%
CaO ).
 One eutectic(2250℃ and 23wt% CaO) and two eutectoid
(1000℃ and 2.5wt% CaO, and 850 ℃ and 7.5wt%
CaO) reactions are found for this system

 Three different crystal structures exist: tetragonal,

monoclinic, and cubic.

50
 Pure ZrO2 experiences a tetragonal-to-monoclinic
phase transformation at about 1150℃. A relatively
large volume change resulting in the formation of
cracks that render a ceramic ware useless. This
problem is overcome by ‘stabilizing’ the zirconia by
adding between about 3 and 7 wt% CaO: above
about 1000 ℃ both cubic and tetragonal phases will
be present. Upon cooling to room temperature
under normal cooling conditions, the monoclinic and
CaZr4O9 phases do not form (as predicted from the
phase diagram); consequently, the cubic and
tetragonal phases are retained, and crack formation
is circumvented. Partially stabilized zirconia, or PSZ.

51
  Yttrium oxide (Y2O3) and magnesium oxide are also
used as stabilizing agents.
 For higher stabilizer contents, only the cubic phase
may be retained at room temperture; such a material
is fully stabilized.

D. The SiO2- Al2O3 system

 The polymorphic form of silica at these temperatures:
cristobalite.
 Silica and alumina are not mutually soluble: absence
of terminal solid solutions
 Intermediate compound: mullite, 3Al2O3-2SiO2, mullite
melts incongruently at 1890℃. F12.27

 A single eutectic exists at 1587℃ and 7.7 wt% Al2O3 52

 53
f01_09_pg254
f02_09_pg257
54
Lever Rule
𝑅
𝑊 𝑆=
𝑅+ 𝑆

𝑆
𝑊 𝐿=
𝑅+ 𝑆 (9.1a) 55
 Liquidus line
nucleation
liquidus line

nuclei

growth

maturity of
microstructure
solidus line Compositional
Solidus line readustment
grain (by diffusion)

boundary grains

Cu Ni 56

f04_09_pg265
 Liquidus line
Equilibrium
solidus line

Nonequilibrium
solidus line

Cored
structure
(compositional 57
segregation)
f05_09_pg267
 Liquidus line
nucleation
liquidus line

nuclei

growth

maturity of
microstructure
solidus line Compositional
Solidus line readustment
grain (by diffusion)

boundary grains

Cu Ni
f04_09_pg265
Nonequilibrium Cooling Equilibrium Cooling

101