Libyan Academy for Postgraduate Studies, Biomedical Engineering- Genetic Engineering

Phase Diagrams
BEM 603
Lecture 9

Feb 09, 2022

Fall 2021/2022
Outlines
➢ Introduction
➢ Definitions and basic concepts for phase diagrams and
phase transformations
➢ Pressure–temperature phase diagrams for pure materials
➢ One component phase diagram.
➢ Binary Phase Diagrams (isomorphous and eutectic
systems)
➢ Common examples of binary phase diagrams.
➢ The development of equilibrium microstructures, upon
cooling, for several situations.
Introduction
❑ The understanding of phase diagrams for alloy systems is extremely
important because there is a strong correlation between microstructure
and mechanical properties.
❑ In addition, phase diagrams provide valuable information about
melting, crystallization, and other phenomena.
❑ Some basic definitions:
➢ The term component is frequently used in this discussion; components
are pure metals and/or compounds of which an alloy is composed.
➢ Solute and solvent, which are also common terms, were defined in
previous sections.
➢ Solid solution, it consists of atoms of at least two different types;
the solute atoms occupy either substitutional or interstitial positions
in the solvent lattice, and the crystal structure of the solvent is
maintained.
Definitions and Basic Concepts
1. Solubility Limit
❑ Solubility Limit of a component in a phase is the maximum amount of the
component that can be dissolved in it (e.g. alcohol has unlimited solubility
in water, sugar has a limited solubility, oil is insoluble). The same concepts
apply to solid phases: Cu and Ni are mutually soluble in any amount
(unlimited solid solubility), while C has a limited solubility in Fe.
❑ 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 system, as in figure.
❑ The solubility limit increases slightly with rising temperature.
❑ The sum of the concentrations at any composition will equal 100 wt%.
The solubility
of sugar in a
sugar–water
syrup

❑ Question: What is the solubility limit for sugar in water at 20°C?

❑ Answer: 65 wt% sugar.
At 20°C, if C < 65 wt% sugar: syrup
At 20°C, if C > 65 wt% sugar: syrup + sugar
2. Phases
❑ A phase may be defined as a homogeneous portion of a system that
has uniform physical and chemical characteristics.
❑ For example, the sugar–water syrup solution is one phase, and solid
sugar is another. Each has different physical properties (one is a
liquid, the other is a solid); furthermore, each is different chemically
(i.e., has a different chemical composition); one is virtually pure
sugar, the other is a solution of H2 O and C12 H22 O11 .
❑ If more than one phase is present in a given system, each will have its
own distinct properties, and a boundary separating the phases will
exist.
❑ 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.
❑ For example, 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.

3. Microstructure
❑ Many times, the physical properties and, the mechanical behavior of a
material depend on the microstructure.
❑ In metal alloys, microstructure is characterized or specified by: (1) the
number of phases present, (2) their proportions, and (3) the manner in
which they are distributed or arranged.
❑ The microstructure of an alloy depends on such variables as the alloying
elements present, their concentrations, and the heat treatment of the alloy
(i.e., the temperature, the heating time, and the rate of cooling to room
temperature).
❑ For microscopic examination, after appropriate polishing and etching, the
different phases may be distinguished by their appearance, as in below
Figure.

Optical micrograph showing the ferrite and pearlite microstructure

4. Phase Equilibria
❑ 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 will result in an increase in the free energy and in a possible
spontaneous change to another state whereby the free energy is lowered.
❑ Phase equilibrium is reflected by a constancy with time in the phase
characteristics of a system.
❑ For example: suppose that a sugar–water syrup is contained in a closed vessel
and the solution is in contact with solid sugar at 20 ºC. If the system is at
equilibrium, the composition of the syrup is 65 wt% sugar–35 wt% water.
❑ Phase diagrame provide information about the equilibrium characteristics of
a particular system, which is important, but they do not indicate the time
period necessary for the attainment of a new equilibrium state.
❑ Sometimes, a state of equilibrium is never completely achieved because the
rate of approach to equilibrium is extremely slow; such a system is said to
be in a nonequilibrium or metastable state.
❑ Phase diagram can be defined as a graphical representation of all the
equilibrium phases as a function of temperature, pressure, and composition.
Interpretation of phase diagrams
For a given temperature and composition we can use phase diagram to
determine: (1) The phases those are present. (2) Compositions of the phases.
(3) The relative fractions of the phases.
One-Component (Unary) Phase Diagrams
❑ Phase diagram for a one-component system, in which composition is held
constant, pressure and temperature are the variables.
❑ For example phase diagram for H2 O, which is shown in Figure.
❑ There are three different phases delineated: solid, liquid, and vapor.
❑ 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 (labeled ao, bo, and co)
are phase boundaries.
❑ 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.

Pressure–temperature phase diagram for 𝐻2 𝑂

❑ It is noted that, from the Figure, all three of the phase boundary curves
intersect at a common point, which is labeled O (for this H2 O system, at a
temperature of 273.16 K and a pressure of 6.04 10−3 atm), which is called
a triple point.
❑ This means that at this point only, all of the solid, liquid, and vapor phases
are simultaneously in equilibrium with one another.
Binary Phase Diagrams
❑ It is common phase diagram, in which temperature and composition are
variable parameters, and pressure is held constant normally 1 atm.
❑ Binary phase diagrams are maps that represent the relationships between
temperature and the compositions and quantities of phases at equilibrium,
which influence the microstructure of an alloy.
❑ Binary phase diagrams are helpful in predicting phase transformations and
the resulting microstructures.
❑ The simplest binary system is the Cu-Ni (in below figure) which exhibits
complete solubility in liquid and solid state.
❑ The line above which the alloy is liquid is called the liquidus line. At
temperature just below this line crystals of α solid solution start forming.
❑ The line below which
solidification completes is
called solidus line. Hence,
only α solid solution exists at
any temperature below the
solidus line.
❑ The intermediate region
between liquidus and solidus
lines is the two-phase region
where liquid and solid
coexists.
❑ For metallic alloys, solid
solutions are commonly
designated by lowercase
Cu-Ni equilibrium phase diagram
Greek letters (𝛼, 𝛽, 𝛾, etc.)
❑ It can be noted that the two metals are soluble in each other in the entire
range of compositions in both liquid and solid state. This kind of system is
known as ‘Isomorphous’ system.
❑ Isomorphous systems contain metals which are completely soluble in each
other and have a single type of crystal structure.

Example: determination of Phase

compositions and amounts at point B.
Co = 35 wt. %, CL = 31.5 wt. %,
Cα = 42.5 wt. %
Mass fractions:
WL = S / (R+S)
= (Cα - Co) / (Cα- CL) = 0.68
Wα = R / (R+S)

= (Co - CL) / (Cα- CL) = 0.32

Development of microstructure in isomorphous alloys
(Under equilibrium cooling (very slow))
❑ Let us consider the copper–
nickel system, specifically an
alloy of composition 35 wt%
Ni–65 wt% Cu, as it is cooled
from 1300 ºC. Some
microstructural changes will
happen.
❑ Solidification in the solid +
liquid phase occurs gradually
upon cooling from the liquidus
line.
❑ At point C, 1250 ºC, the
compositions of the liquid phase
is 32 wt% Ni–68 wt% Cu [L(32
Ni)] and the composition of
𝛼 phase is 43 wt% Ni–57 wt%
Cu [(43 Ni)].
❑ Furthermore, the fraction of the 𝛼 phase will increase with continued
cooling. Note that the overall alloy composition (35 wt% Ni–65 wt% Cu)
remains unchanged during cooling process.

❑ Upon crossing the solidus line, the remaining liquid solidifies; the final
product then is a polycrystalline 𝛼-phase solid solution that has a uniform
35 wt% Ni–65 wt% Cu composition (point e). Subsequent cooling will
produce no microstructural or compositional alterations.
Development of microstructure in isomorphous alloys
(Under nonequilibrium cooling (Rapid cooling))
❑ In virtually all practical
solidification situations, cooling
rates are much too rapid to allow
equilibrium state to be achieved;
consequently, microstructures
other than those previously
described develop.
❑ For the same previous example
of 35 wt% Ni–65 wt% Cu alloy,
solidification in the solid+liquid
phase also occurs gradually. The
composition of the liquid phase
evolves by diffusion, following
the equilibrium values that can be
derived from the tie-line method.
❑ However, diffusion in the solid state is very slow. Hence, the new layers that
solidify on top of the grains have the equilibrium composition at that
temperature but once they are solid their composition does not change.
❑ This leads to the formation of layered (cored) grains (as in figure).
❑ For the example in the figure, the microstructure evolution during cooling
process for 35 wt% Ni–65 wt% will be as follows:
➢ At point aʹ, cooling from a temperature of about 1300 ºC. This is liquid
region with composition of 35 wt% Ni–65 wt%Cu [noted as L(35 Ni)].
➢ At point bʹ (approximately 1260 ºC), 𝛼-phase particles begin to form which,
from the tie line constructed, have a composition of 𝛼(46 Ni).
➢ Upon further cooling to point cʹ (about 1240 ºC), the composition of the
𝛼 phase that solidified is 𝛼[40 Ni]. However, because diffusion in the solid
𝛼 phase is relatively slow, the 𝛼 phase that formed at point bʹ has not
changed composition appreciably, it is still about 46 wt% Ni. The
composition of the grains has continuously changed with radial position,
from 46 wt% Ni at grain centers to 40 wt% Ni at the outer grain perimeters.
 ➢ Thus, at point cʹ, the average composition of the solid 𝛼 grains that have
formed would be the average composition, lying between 46 and 40 wt% Ni.
It can be considered as 42 wt% Ni–58 wt% Cu [(42 Ni)]. The average
compositions of the solid phase has been shifted to higher Ni contents, and is
represented by the dashed line in Figure.
➢ At point dˊ (~1220 ºC) and for equilibrium cooling rates, solidification should
be completed. However, for this nonequilibrium situation, there is still an
appreciable proportion of liquid remaining, and the phase that is forming has
a composition of 35 wt% Ni [(35 Ni)]; also the average -phase composition at
this point is 38 wt% Ni [(38 Ni)].
➢ Solidification finally reaches completion at point eˊ (~1205C). The
composition of the last 𝛼phase to solidify at this point is about 31 wt% Ni; the
average composition of the 𝛼 phase at complete solidification is 35 wt% Ni.
➢ The inset at point fˊ shows the microstructure of the totally solid material.
❑ The degree of displacement of the nonequilibrium solidus curve from the
equilibrium one will depend on: (i) the rate of cooling; (ii) the diffusion rate in
the solid phase.
❑ Example: For copper–nickel system, calculate the amount of each phase
present in 1 kg of a 50 wt.% Ni- 50 wt.% Cu alloy at (a) 1400°C, (b) 1300°C
and (c) 1200°C.
Solution
(a) For a 50 wt.% Ni- 50 wt.% Cu alloy at 1400°C, we are in the liquid (L) region of
the phase diagram. Therefore, we have 1 kg of liquid (L).
(b) For a 50 wt.% Ni- 50 wt.% Cu alloy at 1300°C, we are in the solid + liquid (α+L)
region of the phase diagram. Here we must use the lever rule to calculate the mass
fraction of each phase. If we draw a tie line across the α+L region at 1300°C, the
endpoints are at about 45 wt.% Ni and 60 wt.% Ni. Therefore, the mass fractions are:

(c) For a 50 wt.% Ni- 50 wt.% Cu alloy at 1200°C, we are in the solid (α) region of the
phase diagram. Therefore, we have 1 kg of solid (α).
Binary Eutectic Systems
❑ What happens when two materials are not completely soluble in each other,
the more typical situation? Another type of common phase diagram is
observed and called a binary eutectic phase diagram.
❑ A eutectic reaction is defined as the one which generates two solids from the
liquid at a given temperature and composition, L → α+ β.
❑ In addition to liquidus and solidus lines there are two more lines on A and B
rich ends which define the solubility limits B in A and A in B respectively.
These are called solvus lines.
❑ Example: Pd-Sn alloy phase diagram
➢ A number of features of this phase diagram are important and worth noting.
➢ First, three single-phase regions are found on the diagram: 𝛼, 𝛽 and liquid.
The 𝛼 phase is a solid solution rich in lead (Pb) and has tin (Sn) as the
solute component. The 𝛽-phase solid solution rich in tin (Sn) and has lead
(Pb) as the solute component.
 B E G

➢ Thus, the solubility in each of these solid phases is limited, in that at any
temperature below line BEG only a limited concentration of Sn will dissolve in Pb
(for the 𝛼 phase), and similarly for Pb in Sn (for the 𝛽 phase).
➢ The solid solubility limit line separating the 𝛼 and 𝛽 phase regions is termed a
solvus line.
➢ The maximum solubility of lead in the 𝛽 phase, point G (2.2 wt% Pb) occurs
at 183 ºC.
➢ The maximum solubility of tin in the 𝛼 phase, point B (18.3 wt% Pb) also
occurs at 183 ºC.
➢ Note that Pb-Sn materials were widely used as solders, since the melting
temperature (183°C) of the eutectic is considerably below that of pure Sn
(232°C) and pure Pb (327.5°C). Due to environmental concerns about Pb,
they are being replaced by other solder materials, such as Ag-Sn.

Development of the microstructure of Sn-Pb alloys upon cooling

❑ When a liquid of eutectic composition solidifies, a eutectic microstructure
is formed with alternating layers of α and β phases. These thin layers form
because the solidification reactions occur all at once, rather than gradually.
❑ The Figure (a) on the left side, illustrates phase changes for a Sn composition
below the solubility limit in Pb. The Figure (b) on the right side illustrates the
phase changes for a Sn composition below the solubility limit in the α phase at
elevated temperature, but above that solubility limit at room temperature.

(a) (b)
❑ Gradual cooling at the eutectic composition results in simultaneous
conversion from 100% liquid to 100% solid, which called eutectic reaction.

Schematic
representations of
the equilibrium
microstructures for a
lead–tin alloy of
eutectic composition
C3 above and below
the eutectic
temperature.
❑ Compositions of α and β phases are very different. In the eutectic reaction, the
simultaneous formation of α and β phases result in a layered (lamellae)
microstructure that is called eutectic structure (presented at point i in the
previous figure, and in below micrograph).

❑ During this transformation, there must necessarily be a redistribution of the

lead and tin components. This redistribution is accomplished by atomic
diffusion.

In the micrograph , the dark layers are α phase with lead-reach, the light
layers are β phase with tin-reach.
❑ The Gradual cooling at 𝐂𝟒 as in below figure: the Sn composition is 40 wt%,
higher than the solubility limit of Sn in the α phase, but less than the eutectic
composition. The final microstructure is shown in the figure below, which
illustrated ary α surrounded by stripes of the eutectic microstructure.

Schematic
representations of the
equilibrium
microstructures for a
lead–tin
alloy of composition 𝐶4
as it is cooled from the
liquid-phase region.
❑ The resulted microstructure is shown in the figure below, which illustrated
ary α surrounded by stripes of the eutectic microstructure.

Photomicrograph showing
the microstructure of a lead–
tin alloy of composition 50
wt% Sn–50 wt% Pb.

Example
Calculate the amount of each phase present in 1 kg of a 50 wt.% Pb- 50 wt.%
Sn alloy at (a) 300°C, (b) 200°C and (c) 100°C. Also calculate the amount of
each microstructure.
Sol.
(a) For a 50 wt.% Pb- 50 wt.% Sn alloy at 300°C, we are in the liquid (L)
region of the phase diagram. Therefore, we have 1 kg of liquid (L). The liquid
is also the microstructure.
(b) For a 50 wt.% Pb- 50 wt.% Sn alloy at 200°C, we are in the solid + liquid (α+L)
region of the phase diagram. Here we must use the lever rule to calculate the mass
fraction of each phase. If we draw a tie line across the α+L region at 200°C, the
endpoints are at about 17 wt.% Sn and 54 wt.% Sn. Therefore, the mass fractions
are:

The microstructures that exist here is two phases, liquid and α solid solution.
(c) For a 50 wt.% Pb- 50 wt.% Sn alloy at 100°C, we are in the α + β region of the
phase diagram. Drawing a tie line across this region of the phase diagram, the
endpoints are at about 98 and 5 wt.% Sn. Therefore, the mass fractions are:
Here the microstructure differs from the phase, and this is determined by what
happens just above the eutectic temperature, 183ºC. First, note that we on the left
side of the eutectic composition, 61.9 wt% Sn, so the primary phase is α.
Remember, the primary phase is the one that precipitates out prior to the eutectic
reaction. The remaining liquid is transformed into the eutectic microstructure.
Therefore:

0.73 kg

0.27 kg

𝜷 (98 wt% Sn)

(5 wt% Sn)