Phase Diagrams

1. Phases
A substance that has a fixed chemical composition throughout is called a
pure substance such as water, air, and nitrogen.A pure substance may exist in
different phases.

Defining Pure Substance:

A substance that has a fixed chemical composition throughout is called a

pure substance such as water, air, and nitrogen. A pure substance does not
have to be of a single element or compound. A mixture of two or more
phases of a pure substance is still a pure substance as long as the chemical
composition of all phases is the same.

Phases of a Pure Substance:

A pure substance may exist in different phases. There are three principle
phases solid, liquid, and gas.

A phase: is defined as having a distinct molecular arrangement that is

homogenous throughout and separated from others (if any) by easily
identifiable boundary surfaces.

A substance may have several phases within a principal phase, each with a
different molecular structure. For example, carbon may exist in as graphite
or diamond in the solid phase, and ice may exist in seven different phases at
high pressure. Molecular bonds are the strongest in solids and the weakest in
gases.

Solid: the molecules are arranged in a three-dimensional pattern (lattice)

throughout the solid. The molecules cannot move relative to each other;
however, they continually oscillate about their equilibrium position.

Liquid: the molecular spacing in liquid phase is not much different from that
of the solid phase (generally slightly higher), except the molecules are no
longer at fixed positions relative to each other.
 Phase Diagrams

Gas: the molecules are far apart from each other, and a molecular order does
not exist. Gas molecules move randomly, and continually collide each other
and the walls of the container they are in.

Molecules in the gas phase are at a considerably higher energy level than
they are in liquids or solid phases.
 Phase Diagrams

2. ONE COMPONENT OR UNARY PHASE

DIAGRAMS
Much of the information about the control of the phase structure of a
particular system is conveniently and concisely displayed in what is called
a phase diagram, also often termed an equilibrium diagram.

Parameters affecting phase structure:

 There are three externally controllable parameters that will affect

phase structure—viz. temperature, pressure, and com-position—
and phase diagrams are constructed when various combinations of
these parameters are plotted against one another.
 Perhaps the simplest and easiest type of phase diagram to understand
is that for a one-component system, in which composition is held
constant (i.e., the phase diagram is for a pure substance); this
means that pressure and temperature are the variables.
 This one-component phase diagram (or unary phase
diagram) [sometimes also called a pressure-temperature (or P-T)
diagram] is repre-sented as a two-dimensional plot of pressure
(ordinate, or vertical axis) versus temperature (abscissa, or
horizontal axis).
 Most often, the pressure axis is scaled logarithmically.
 Phase Diagrams

Phase diagram for H2O

Figure Pressure-temperature phase diagram for H2O

 Regions for three different phases—solid, liquid, and vapor—are

delineated on the plot.
 Each of the phases will exist under equilibrium conditions over the
temperature-pressure ranges of its corresponding area.
Furthermore, the three curves shown on the plot (labelled aO,
bO, and cO) are phase boundaries; at any point on one of these
curves, the two phases on either side of the curve are in equilibrium
(or coexist) with one another.
 That is, equilibrium between solid and vapor phases is along
curve aO—likewise for the solid-liquid, curve bO, and the liquid-
vapor, curve cO. Also, upon crossing a boundary (as temperature
and/or pressure is altered), one phase transforms to another.
 Phase Diagrams

 For example, at one atmosphere pressure, during heating the solid

phase transforms to the liquid phase (i.e., melting occurs) at the
point labelled 2 on Figure (i.e., the intersection of the dashed
horizontal line with the solid-liquid phase boundary); this point
corresponds to a temperature of 0°C. Of course, the reverse
transformation (liquid-to-solid, or solidification) takes place at the
same point upon cooling.
 Similarly, at the intersection of the dashed line with the liquid-vapor
phase boundary [point 3, at 100°C] the liquid transforms to the
vapor phase (or vaporizes) upon heating; condensation occurs for
cooling. And, finally, solid ice sublimes or vaporizes upon crossing
the curve labelled aO.

The isomorphous and eutectic phase diagrams are relatively simple, but
those for many binary alloy systems are much more complex.

Terminal and intermediate solid solution:

 Phase Diagrams

 The eutectic copper-silver and lead-tin phase diagrams have only

two solid phases, a and b; these are sometimes termed terminal
solid solutions, because they exist over composition ranges near
the concentration extremities of the phase diagram.
 For other alloy systems, intermediate solid solutions (or in-
termediate phases) may be found at other than the two composition
extremes. Such is the case for the copper-zinc system.
 Its phase diagram may at first appear formidable because there are
some invariant points and reactions similar to the eutectic.
 In addition, there are six different solid solutions—two terminal (a
and h) and four intermediate (b, g, d, and e). (The b' phase is
termed an ordered solid solution, one in which the copper and zinc
atoms are situated in a specific and ordered arrangement within
each unit cell.)
 Some phase boundary lines near the bottom of Figure are dashed to
indicate that their positions have not been exactly determined. The
reason for this is that at low temperatures, diffusion rates are very
 Phase Diagrams

slow and inordinately long times are required for the attainment of
equilibrium.
 Again, only single- and two-phase regions are found on the diagram,
and the same rules are utilized for computing phase compositions
and relative amounts.
 The com-mercial brasses are copper-rich copper-zinc alloys; for
example, cartridge brass has a composition of 70 wt% Cu-30 wt%
Zn and a microstructure consisting of a single α phase.

Intermetallic compound:

Figure The magnesium-lead phase diagram. [Adapted from Phase

Diagrams of Binary Magnesium Alloys,
 Phase Diagrams

 For some systems, discrete intermediate compounds rather than solid

solutions may be found on the phase diagram, and these
compounds have distinct chemical formulas; for metal-metal
systems, they are called intermetallic compounds.
 For example, consider the magnesium-lead system.
 The compound Mg2Pb has a composition of 19 wt% Mg-81 wt% Pb
(33 at% Pb), and is represented as a vertical line on the diagram,
rather than as a phase region of finite width; hence, Mg2Pb can
exist by itself only at this precise composition.
 Several other characteristics are worth noting for this magnesium-
lead sys-tem. First, the compound Mg2Pb melts at approximately
550°C (1020F), as indicated by point M .
 Also, the solubility of lead in magnesium is rather extensive, as
indicated by the relatively large composition span for the a-phase
field.
 On the other hand, the solubility of magnesium in lead is extremely
limited. This is evident from the very narrow b terminal solid-
solution region on the right or lead-rich side of the diagram.
 Finally, this phase diagram may be thought of as two simple eutectic
diagrams joined back to back, one for the Mg-Mg2Pb system and
the other for Mg2Pb-Pb; as such, the compound Mg2Pb is really
considered to be a component.
 This separation of complex phase diagrams into smaller-component
units may simplify them and, furthermore, expedite their
interpretation.
 Phase Diagrams

3.DETERMINATION OF PHASE MOUNTS

With regard to fractional phase amounts (e.g., mass fraction of the a or
liquid phase), when a single phase exists, the alloy is completely that
phase. For a two-phase alloy, on the other hand, the lever rule is utilized,
in which a ratio of tie line segment lengths is taken.

Determination of Phase Amounts

The relative amounts (as fraction or as percentage) of the phases present at
equilibrium may also be computed with the aid of phase diagrams. Again,
the single- and two-phase situations must be treated separately. The
solution is obvious in the single- phase region: Since only one phase is
present, the alloy is composed entirely of that Ge-Si phase; that is, the
phase fraction is 1.0 or, alternatively, the percentage is 100%.

Lever rule:
The tie line must be utilized in conjunction with a procedure that is often
called the lever rule (or the inverse lever rule), which is applied as follows:

1. The tie line is constructed across the two-phase region at the

temperature of the alloy.
2. The overall alloy composition is located on the tie line.
3. 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.
4. The fraction of the other phase is determined in the same manner.
5. If phase percentages are desired, each phase fraction is multiplied
by 100. When the composition axis is scaled in weight percent, the
phase fractions computed using the lever rule are mass fractions—
the mass (or weight) of a specific phase divided by the total alloy
 Phase Diagrams

mass (or weight). The mass of each phase is computed from the
product of each phase fraction and the total alloy mass.

In the employment of the lever rule, tie line segment lengths may be deter-
mined either by direct measurement from the phase diagram using a linear
scale, preferably graduated in millimeters, or by subtracting compositions
as taken from the composition axis.

 The problem is to compute the fraction of each of the a and liquid

phases.
 The tie line has been constructed that was used for the determination
of a and L phase compositions.
 Let the overall alloy composition be located along the tie line and
denoted as C0, and mass fractions be represented by WL and Wa for
the respective phases. From the lever rule, WL may be computed
according to

or, by subtracting compositions,

 Phase Diagrams

4. CONGRUENT PHASE TRANSFORMATION

Phase transformations may be classified according to whether or not there
is any change in composition for the phases involved.
Congruent transformation:

Figure: A portion of the nickel-titanium phase diagram on which is

shown a congruent melting point for the g-phase solid solution at
1310°C and 44.9 wt% Ti.
 Phase Diagrams

 Phase transformations may be classified according to whether or not

there is any change in composition for the phases involved.

 Those for which there are no compositional alterations are said to

be congruent transformations.

 Conversely, for incongruent transformations, at least one of the

phases will experience a change in composition. Examples of
congruent transformations include allotropic transformations and
melting of pure materials.

 Eutectic and eutectoid reactions, as well as the melting of an alloy

that belongs to an isomorphous system, all represent incongruent
transformations. Intermediate phases are sometimes classified on
the basis of whether they melt congruently or incongruently.

 The intermetallic compound Mg2Pb melts congruently at the point

designated M on the magnesium-lead phase diagram.

 Also, for the nickel-titanium system, there is a congruent melting

point for the g solid solution that corresponds to the point of
tangency for the pairs of liquidus and solidus lines, at 1310°C and
44.9 wt% Ti.

 Furthermore, the peritectic reaction is an example of incongruent

melting for an inter-mediate phase.
 Phase Diagrams

5. EUTECTOID AND PERITECTIC EACTIONS

In addition to the eutectic, other invariant points involving three different
phases are found for some alloy systems. One of these occurs for the
copper-zinc system at 560°C (1040°F) and 74 wt% Zn-26 wt% Cu.

Copper-zinc phase diagram:

A portion of the phase diagram in the vicinity appears enlarged in Figure.
Upon cooling, a solid d phase transforms into two other solid
phases (g and e) according to the reaction

Eutectoid reaction:
 The reverse reaction occurs upon heating. It is called a eutectoid (or
eutectic-like) reaction, and the invariant point (point E, Figure 1)
and the horizontal tie line at 560°C are termed
the eutectoid and eutectoid isotherm, respectively.

 The feature distinguishing “eutectoid” from “eutectic” is that 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 that is very

important in the heat treating of steels.
 Phase Diagrams

Figure1: A region of the copper-zinc phase diagram that has been

enlarged to show eutectoid and peritectic invariant points,
labeled E (560°C, 74 wt% Zn) and P (598°C, 78.6 wt% Zn),
respectively

Peritectic reaction:
The peritectic reaction is yet another invariant reaction involving three
phases at equilibrium. With this reaction, upon heating, one solid phase
transforms into a liquid phase and another solid phase. A peritectic exists
for the copper-zinc system (Figure 1, point P) at 598°C (1108°F) and 78.6
wt% Zn-21.4 wt% Cu; this reaction is as follows:
 Phase Diagrams

 The low-temperature solid phase may be an intermediate solid

solution (e.g., e in the above reaction), or it may be a terminal solid
solution.

 One of the latter peritectics exists at about 97 wt% Zn and 435°C

(815°F), wherein the h phase, when heated, transforms to e and
liquid phases.

 Three other peritectics are found for the Cu-Zn system, the reactions
of which involve b, d, and g intermediate solid solutions as the low-
temperature phases that transform upon heating.
 Phase Diagrams

6. The Iron–Iron Carbide (Fe–Fe3C) Phase Diagram

Ferrous alloys are those in which iron is the prime component, but carbon
as well as other alloying elements may be present. In the classification
scheme of ferrous alloys based on carbon content, there are three types:
iron, steel, and cast iron.
Ferrite and austenite:

 Pure iron,upon heating, experiences two changes in crystal structure

before it melts. At room temperature the stable form,
called ferrite, or a iron, has a BCC crystal structure.
 Ferrite experiences a polymorphic transformation to
FCC austenite, or g iron, at 912°C (1674°F). This austenite persists
to 1394°C (2541°F), at which temperature the FCC austenite
reverts back to a BCC phase known as d ferrite, which finally melts
at 1538°C (2800°F).
 All these changes are apparent along the left vertical axis of the
phase diagram.

Cementite:
 Phase Diagrams

Figure 1. The iron-iron carbide phase diagram

 The composition axis in Figure 9.24 extends only to 6.70 wt% C; at

this concen-tration the intermediate compound iron carbide,
or cementite (Fe3C), is formed, which is represented by a vertical
line on the phase diagram.
 Thus, the iron-carbon system may be divided into two parts: an iron-
rich portion, as in Figure 1, and the other (not shown) for
compositions between 6.70 and 100 wt% C (pure graphite).
 In practice, all steels and cast irons have carbon contents less than
6.70 wt% C; therefore, we consider only the iron-iron carbide
system. Figure1 would be more appropriately labelled the Fe-Fe3C
phase diagram, since Fe3C is now considered to be a component.
 Convention and convenience dictate that composition still be
expressed in “wt% C” rather than “wt% Fe3C”; 6.70 wt% C
corresponds to 100 wt% Fe3C.
 Phase Diagrams

 Carbon is an interstitial impurity in iron and forms a solid solution

with each of a and d ferrites, and also with austenite, as indicated
by the a, d, and g single-phase fields in Figure 1.
 In the BCC a ferrite, only small concentrations of carbon are soluble;
the maximum solubility is 0.022 wt% at 727°C (1341°F).

Eutectic reaction for the iron-iron carbide system

Eutectoid reaction for the iron-iron carbide system

 Phase Diagrams

7. Development of Microstructure In Iron–Carbon

Alloys
Several of the various microstructures that may be produced in steel alloys
and their relationships to the iron-iron carbon phase diagram are discussed,
and it is shown that the microstructure that develops depends on both the
carbon content and heat treatment.

Microstructures for an iron-carbon alloy:

 Initially, the alloy is composed entirely of the austenite phase having

a composition of 0.76 wt% C and corresponding microstructure,
also indicated in Figure .
 As the alloy is cooled, there will occur no changes until the eutectoid
temperature (727°C) is reached.
 Upon crossing this temperature to point b, the austenite transforms
according to Equation

Pearlite:
 The microstructure for this eutectoid steel that is slowly cooled
through the eutectoid temperature consists of alternating layers or
lamellae of the two phases (α and Fe3C) that form simultaneously
during the transformation. In this case, the relative layer thickness is
approximately 8 to 1.
 This microstructure, represented schematically in Figure, point b, is
called pearlite because it has the appearance of mother of pearl
when viewed under the microscope at low magnifications.
 The pearlite exists as grains, often termed “colonies”; within each
colony the layers are oriented in essentially the same direction,
which varies from one colony to another.
 The thick light layers are the ferrite phase, and the cementite phase
ap-pears as thin lamellae most of which appear dark. Many
cementite layers are so thin that adjacent phase boundaries are so
close together that they are indistinguishable at this magnification,
and, therefore, appear dark.
 Phase Diagrams

 Mechanically, pearlite has properties intermediate between the soft,

ductile ferrite and the hard, brittle cementite.

Figure 1:Schematic representations of the microstructures for an

iron-carbon alloy of eutectoid composition (0.76 wt% C) above and
below the eutectoid temperature.
 Phase Diagrams

Microstructural changes:

Figure 2: Schematic representation of the formation of pearlite from

austenite; direction of carbon diffusion indicated by arrows

Figure 2 illustrates schematically microstructural changes that accompany

this eutectoid reaction; here the directions of carbon diffusion are indicated
by arrows. Carbon atoms diffuse away from the 0.022 wt% ferrite regions
and to the 6.7 wt% cementite layers, as the pearlite extends from the grain
boundary into the unreacted austenite grain. The layered pearlite forms be-
cause carbon atoms need diffuse only minimal distances with the
formation of this structure
 Phase Diagrams

References:
W. D. Callister, Jr. D. G. Rethwis, (2014). MATERIALS SCIENCE and
ENGINEERING-An Introduction, 9th Ed.