Phase Diagrams

The accompanying graph is the phase diagram for pure H2O. Parameters
plotted are external pressure (vertical axis, scaled logarithmically) versus
temperature. In a sense this diagram is a map in which regions for the three
familiar phases—solid (ice), liquid (water), and vapor (steam)—are delineated.
The three red curves represent phase boundaries that define the regions. A
photograph located in each region shows an example of its phase—ice cubes,
liquid water being poured into a glass, and steam spewing from a kettle.
INTRODUCTION

The understanding of phase diagrams for alloy systems is extremely

important
Because there is a strong correlation between microstructure and
mechanical properties, and the development of microstructure of an
alloy is related to the characteristics of its phase diagram. In addition,
phase diagrams provide valuable information about melting, casting,
crystallization, and other phenomena.

This lecture presents and discusses the following topics: (1) terminology
associated
with phase diagrams and phase transformations; (2) pressure–
temperature phase diagrams for pure materials; (3) the interpretation
of phase diagrams; (4) some of the common and relatively simple
binary phase diagrams, including that for the iron–carbon system
 Definitions and Basic Concepts

Component: components are pure metals and/or compounds of which an

alloy is composed. For example, in a copper–zinc brass, the components
are Cu and Zn. Solute and solvent, which are also common terms
discussed earlier

System : which has two meanings. System may refer to a specific

body of material under consideration (e.g., a ladle of molten
steel); or it may relate to the series of possible alloys consisting
of the same components but
without regard to alloy composition (e.g., the iron–carbon
system).
 SOLUBILITY LIMIT

For many alloy systems and at some specific temperature, there is a

maximum concentration of solute atoms that may dissolve in the
solvent to form a solid solution; this is called a solubility limit. The
addition of solute in excess of this solubility limit results in the
formation of another solid solution or compound that has a distinctly
different composition.To illustrate this concept, consider the sugar–
water (C12H22O11–H2O) system. Initially, as sugar is added to water,
a sugar–water solution or syrup forms. As more sugar is introduced,
the solution becomes more concentrated, until the solubility limit is
reached, or the solution becomes saturated with sugar. At this time,
the solution is not capable of dissolving any more sugar, and further
additions simply settle to the bottom of the container. Thus, the
system now consists of two separate substances: a sugar–water syrup
liquid solution and solid crystals of undissolved sugar.
The solubility of sugar (C12H22O11) in a
sugar–water syrup.
PHASES:
Also critical to the understanding of phase diagrams is the
concept of a phase. A phase may be defined as a homogeneous
portion of a system that has uniform physical and chemical
characteristics. Every pure material is considered to be a phase;
so also, is every solid, liquid, and gaseous solution. For example,
the sugar–water syrup solution just discussed is one phase, and
solid sugar is another.When two phases are present in a system,
it is not necessary that there be a difference in both physical and
chemical properties; a disparity in one or the other set of
properties is sufficient. When water and ice are present in a
container, two separate phases exist; they are physically
dissimilar (one is a solid, the other is a liquid) but identical in
chemical makeup. Also, when a substance can exist in two or
more polymorphic forms (e.g., having both FCC and BCC
structures), each of these structures is a separate phase because
their respective physical characteristics differ.
Sometimes, a single-phase system is termed homogeneous.
Systems composed of two or more phases are termed
mixtures or heterogeneous systems. Most metallic alloys
and ,for that matter, ceramic, polymeric, and composite
systems are heterogeneous
Equilibrium is another essential concept; it is best described in
terms of a thermodynamic quantity called the free energy. In
brief, free energy is 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 is at a
minimum under some specified combination of temperature,
pressure, and composition. In a macroscopic sense, this means
that the characteristics of the system do not change with time,
but persist indefinitely—that is, the system is stable. A change in
temperature, pressure, and/or composition for a system in
equilibrium results in an increase in the free energy and in a
possible spontaneous change to another state by which the free
energy is lowered. The term phase equilibrium, often used in the
context of this discussion, refers to equilibrium as it applies to
systems in which more than one phase may exist
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. Three externally controllable parameters affect phase
structure— temperature, pressure, and composition—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 represented 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
Pressure–temperature phase diagram for H2O. Intersection of the dashed
horizontal line at 1 atm pressure with the solid–liquid phase boundary (point 2)
corresponds to the melting point at this pressure (T = 0°C). Similarly, point 3, the
intersection with the intersection with the liquid–vapor boundary, represents the
boiling point (T = 100°C).
As may also be noted from Figure , all three of the phase
boundary curves intersect at a common point, which is
labeled O (for this H2O system, at a temperature of 273.16 K
and a pressure of 6.04 × 10−3 atm). This means that at this
point only, all of the solid, liquid, and vapor phases are
simultaneously in equilibrium with one another.
Appropriately, this, and any other point on a P–T phase
diagram where three phases are in equilibrium, is called a
triple point; sometimes it is also termed an invariant point
inasmuch as its position is distinct, or fixed by definite values
of pressure and temperature. Any deviation from this point by
a change of temperature and/or pressure will cause at least
one of the phases to disappear.
Binary Phase Diagrams:

Another type of extremely common phase diagram is

one in which temperature and composition are
variable parameters and pressure is held constant—
normally 1 atm. There are several different varieties; in
the present discussion, we will concern ourselves
Possibly the easiest type of binary phase diagram to understand
and interpret is the type that is characterized by the copper–
nickel system (Figure). Temperature is plotted along the
ordinate, and the abscissa represents the composition of the
alloy, in weight percent of nickel. The composition ranges from
0 wt% Ni (100 wt% Cu) on the far left horizontal extreme to 100
wt% Ni (0 wt% Cu) on the right. Three different phase regions,
or fields, appear on the diagram: an alpha (𝛼) field, a liquid (L)
field, and a two-phase 𝛼 + L field. Each region is defined by the
phase or phases that exist over the range of temperatures and
compositions delineated by the phase boundary
lines.
Some comments are in order regarding nomenclature: First,
for metallic alloys, solid solutions are commonly designated
by lowercase Greek letters (𝛼, 𝛽, 𝛾, etc.). With regard to
phase boundaries, the line separating the L and 𝛼 + L phase
fields is termed the liquidus line, as indicated in Figure ; the
liquid phase is present at all temperatures and compositions
above this line. The solidus line is located between the 𝛼
and 𝛼 + L regions.
The copper–nickel phase diagram.
For a binary system of known composition and
temperature at equilibrium, at least Three kinds of
information are available:

(1) the phases that are present,

(2) the compositions of these phases, and
(3) the percentages or fractions of the phases. The
procedures for making these determinations will be
demonstrated using the copper–nickel system.
DEVELOPMENT OF MICROSTRUCTURE IN ISOMORPHOUS
ALLOYS

Schematic representation of the development of

microstructure during the equilibrium solidification of a 35
wt% Ni–65 wt% Cu alloy.
BINARY EUTECTIC SYSTEMS

The copper–silver phase diagram

The lead–tin phase
diagram
THE GIBBS PHASE RULE

The construction of phase diagrams—as well as some of the

principles governing the conditions for phase equilibria—are
dictated by laws of thermodynamics. One of these is the Gibbs
phase rule, proposed by the nineteenth-century physicist J. Willard
Gibbs. This rule represents a criterion for the number of phases that
coexist within a system at equilibrium and is expressed by the
simple equation
P+F=C+N

where P is the number of phases present . The parameter F is termed the

number of degrees of freedom or the number of externally controlled variables
(e.g., temperature, pressure, composition) that must be specified to define
the state of the system completely. Expressed another way, F is the number
of these variables that can be changed independently without altering the
number of phases that coexist at equilibrium. The parameter C represents
the number of components in the system. Finally, N is
number of non compositional variables (e.g., temperature and pressure)
The Iron–Carbon System

A portion of the iron–carbon phase diagram is presented in Figure .

Pure iron,
upon heating, experiences two changes in crystal structure before
it melts. At room temperature, the stable form, called ferrite, or 𝛼-
iron, has a BCC crystal structure. Ferrite experiences a polymorphic
transformation to FCC austenite, or 𝛾-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 𝛿-ferrite, which
finally melts at 1538°C (2800°F). All these changes are apparent
along the left vertical axis of the phase diagram. The composition
axis in Figure 9.24 extends only to 6.70 wt% C; at this concentration
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 , and the other (not shown)
for compositions between 6.70 and 100 wt% C (pure graphite).
The iron–iron carbide phase diagram.
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.
Figure 9.24 would be more appropriately labeled the Fe–Fe3C phase
diagram because 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.
Carbon is an interstitial impurity in iron and forms a solid solution with
each of
𝛼- and 𝛿-ferrites and also with austenite, as indicated by the 𝛼, 𝛿, and 𝛾
single-phase fields in Figure 9.24. In the BCC 𝛼-ferrite, only small
concentrations of carbon are soluble; the maximum solubility is 0.022 wt
% at 727°C (1341°F). The limited solubility is explained by the shape and
size of the BCC interstitial positions, which make it difficult to
accommodate the carbon atoms. Even though present in relatively low
concentrations, carbon significantly influences the mechanical properties
of ferrite. This particular iron–carbon phase is relatively soft, may be
made magnetic at temperatures below 768°C (1414°F), and has a density
of 7.88 g/cm3. Figure 9.25a is a photomicrograph of 𝛼-ferrite.

The austenite, or 𝛾 phase, of iron, when alloyed with carbon alone, is not
stable below 727°C (1341°F), as indicated in Figure . The maximum
solubility of carbon in austenite, 2.14 wt%, occurs at 1147°C (2097°F). This
solubility is approximately 100
times greater than the maximum for BCC ferrite because the FCC
octahedral sites are
larger than the BCC tetrahedral sites , and, therefore, the strains imposed
on the surrounding iron atoms are much lower. As the discussions that
follow demonstrate, phase transformations involving austenite are very
important in the heat treating of steels. In passing, it should be
Photomicrographs of (a) 𝛼-ferrite and (b)
austenite
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. Commercially pure iron
contains less than 0.008 wt% C and, from the phase diagram, is
composed almost exclusively of the ferrite phase at room
temperature. The iron–carbon alloys that contain between 0.008 and
2.14 wt% C are classified as steels . In most steels, the microstructure
consists of both 𝛼 and Fe3C phases. Upon cooling to room
temperature, an alloy within this composition range must pass
through at least a portion of the 𝛾-phase field; distinctive
microstructures are subsequently produced, Cast irons are classified
as ferrous alloys that contain between 2.14 and 6.70 wt% C.
On the basis of composition, ferrous alloys fall
into three classifications:
• Irons (<0.008 wt% C)
• Steels (0.008 to 2.14 wt% C)
• Cast irons (>2.14 wt% C)
The iron–iron carbide phase diagram.
Schematic representations of the microstructures for an iron–carbon alloy of
eutectoid
composition (0.76 wt% C) above and below the eutectoid temperature.
Schematic representation of the formation of pearlite from
austenite; direction of carbon diffusion indicated by arrows.
Photomicrograph of a
eutectoid steel showing the pearlite
microstructure consisting of alternating layers
of 𝛼-ferrite (the light phase) and Fe3C (thin
layers most of which appear dark).
Schematic representations
of the microstructures for an
iron–carbon alloy of
hypoeutectoid composition
C0(containing less
than 0.76 wt% C) as it is
cooled from within the
austenite phase
region to below the
eutectoid temperature.
Scanning electron
micrograph showing
the microstructure of
a steel that contains
0.44 wt% C. The
large dark areas are
proeutectoid ferrite.
Regions having the
alternating light and
dark lamellar structure
are pearlite; the
dark and light layers
in the pearlite correspond,
respectively,
to ferrite and cementite
phases.
Schematic
representations of the
microstructures for an
iron–carbon alloy of
Hypereutectoid
composition C1
(containing between
0.76 and 2.14 wt% C) as it
is cooled from within the
austenite-phase region to
below the eutectoid
temperature.
Photomicrograph of a 1.4 wt% C steel having a
microstructure consisting of a white proeutectoid
cementite network surrounding the pearlite colonies.
THE INFLUENCE OF OTHER ALLOYING
ELEMENTS

Additions of other alloying elements (Cr, Ni, Ti,

etc.) bring about rather dramatic changes in the
binary iron–iron carbide phase diagram, Figure.
The extent of these alterations of the positions of
phase boundaries and the shapes of the phase
fields depends on the particular alloying element
and its concentration. One of the important
changes is the shift in position of the eutectoid
with respect to temperature and carbon
concentration. These effects are illustrated in
Figures , which plot the eutectoid temperature
and eutectoid composition (in wt% C),
The dependence of eutectoid
temperature on alloy concentration for
several
alloying elements in steel.
The dependence of eutectoid composition (wt%
C) on alloy concentration for several alloying
elements in steel.
Thus, other alloy additions alter not only the
temperature of the eutectoid reaction, but also
the relative fractions of pearlite and the
proeutectoid phase that form. Steels are
normally alloyed for other reasons, however—
usually either to improve their corrosion
resistance or to render them amenable to heat
treatment .
Thank You!!