MMEE 210

Materials Science

Dr Enoch N., OGUNMUYIWA

 Phase Diagrams:
Equilibrium and Microstructural
Development
 Specific Learning Outcomes

 Describe component, mixture, phase, and equilibrium for a

materials system.
 Sketch and describe simple isomorphous binary phase diagrams.
 Identify the various phases and regions in a simple phase diagram.
 Determine and extract important parameters on a binary phase
diagrams.
 Be able to apply tie line and lever rule to determine phase
composition and phase fraction in a mixture.
 Define various invariant reactions.
 Compare non-equilibrium solidification of metals and explain the
general difference in microstructure when compared to
equilibrium solidification.
 Describe microstructural evolution during equilibrium cooling as
metal solidifies at various regions of the phase diagram.
 Issues to Address…

 Solubility and solubility limits.

 Components and mixtures; phase(s), equilibrium, phase
equilibria, and phase diagram; types of phase diagram –
unary, binary, tenary.
 Proportion of phases based on the lever rule and the
interpretation of phase diagrams;
 Invariant reactions: eutectic, eutectoid, peritectic,
peritectoid systems.
 Practical phase diagram: iron–iron carbide phase diagram.
 Phase Diagrams: Introduction
 From your basic chemistry and physics classes you are familiar
with the concept of states of matter.
 For example, water exists as a gas, liquid, or solid, and the
properties of water depend on which state of matter it is in.
 The same kind of situation occurs for engineering materials, but
our concept of “state of matter” needs to be expanded to deal with
their complexity.
 Consider three simple mixtures: water with a little bit of salt in it;
water with a lot of salt in it; and water mixed with oil.
 Phase Diagrams: Introduction
1. In the solution of salt completely dissolved in water, what
substances are present?
2. In the solution of salt completely dissolved in water, what states of
matter are present?
3. In the solution of salt partially dissolved in water, what substances
are present?
4. In the solution of salt partially dissolved in water, what states of
matter are present?
5. For a mixture, can you predict the number of states of matter
present by knowing the number of substances present? Explain
your answer.*
6. In the mixture of water and oil, what substances and states of
matter are present?
7. What is different about the mixture of water and oil compared to
pure water or pure oil?
8. Is listing the substances and states of matter present sufficient to
describe a mixture? Explain why or why not.
 Phase Diagrams: Introduction
 The term “state of matter” is insufficient to describe a mixture.
 After all, the mixture of water and oil has only one state of matter;
liquid, yet it is clearly different from pure water or pure oil.
 In the case of engineering materials we can have several different
types of mixtures, which vary in their properties.
 For example, pure aluminum is a very ductile metal. However,
high strength aluminum can be made by creating a material that
has particles of Ti3Al embedded in an Al/Ti mixture.
 Clearly we need some terms that more accurately describe a mixture.
 The terms we will use are component and phase.
 Salt completely dissolved in water has two components and one
phase.
 Salt partially dissolved in water has two components and two
phases.
 A mixture of oil and water has two components and two phases.
 Solid salt has one component and one phase.
 Pure water has one component and one phase.
 Phase Diagrams: Terminologies
 Pure metallic elements have engineering applications; e.g., ultra-high
purity Cu or Al is used to make microelectronic circuitry.
 In most applications, however, we use alloys – a material that exhibits
properties of a metallic material and is made from multiple elements.
These multiple elements are called, “component”.
 There are two types of alloys:
 Single-phase alloys (homogeneous systems) and
 Multiple-phase alloys (mixtures or heterogeneous systems).
 Components are elements or compounds needed to specify a
material system or an alloy.
 The components are determined by what we mix together to make the
material, e.g.,
 Brass – Cu and Zn
 Bronze – Cu and Sn
 Plain carbon steel – Fe and C.
 Corrosion resistant stainless steel – Fe, C, Ni and Cr.
 Component is a distinct chemical substance from which the phase is
formed.
 Phase Diagrams: Terminologies
 A phase is any portion, including the whole of a system, that is
physically homogeneous within it and bounded by a surface that
separates it from any other portions.
 A phase is a chemically and structurally homogeneous portion of
the microstructure.
 A single-phase microstructure can be polycrystalline, but each
crystal grain differs only in crystalline orientation, not in
chemical composition.
 A phase may be defined as a homogeneous portion of a material
system that has uniform physical and chemical characteristics.
 A phase has the following characteristics:
1. The same structure or atomic arrangement throughout;
2. Roughly the same composition and properties throughout; and
3. A definite interface between the phase and any surrounding or
adjoining phases.
 The properties of materials depend on the components and phases
that are present.
 Phase Diagrams: Terminologies
 A mixture contains more than one type of phase, and the
characteristics of each phase are retained when the mixture is
formed.

 A phase diagram shows the phases and their compositions at any

combination of temperature and alloy composition.

 Phase diagrams are maps/graphs that represent the relationships

between temperature and the compositions and quantities of
phases at equilibrium.
 Unary phase diagram – one component system, e.g., water, pure
metal undergoing phase changing as a result of changes in
temperature. Sometimes also called a pressure–temperature is
represented as a two dimensional plot of pressure against
temperature. Most often, the pressure axis is a log scale.
 Binary phase diagram – two components systems, e.g. Ni–Cu,
Cu–Sn, etc. This is widely use by materials engineers.
 Tenary phase diagram – three components systems, e.g., MgO–
Al2O3–SiO2, etc.
 Phase Diagrams: Terminologies
 Equilibrium – means the characteristics of the system do not
change with time but persist indefinitely; that is, the system is
stable. It is described in terms of a thermodynamic quantity called
the free energy.

 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.

 Phase equilibria – refers to equilibrium as it applies to systems in

which more than one phase may exist.

 Phase equilibrium is reflected by a constancy with time in the phase

characteristics of a system.
 (Equilibrium) Phase Diagram: Types - Unary

Schematic representation of the one-component

phase diagram for pure iron.
Schematic unary phase diagram for
magnesium, showing the melting and
boiling temperatures at one
atmosphere pressure. On this diagram,
point X is the triple point.

Schematic representation of the one-

Component phase diagram for H2O.
(Equilibrium) Phase Diagram: Types - Binary
(Equilibrium) Phase Diagram: Types - Tenary
 Phase Diagrams: Terminologies
 Isomorphous phase diagram – A phase diagram in which the
components display unlimited solid solubility, i.e., constituents
exhibit complete solid solubility, e.g. Cu–Ni system, Al2O3–Cr2O3
system, etc.

 Solvus line/curve – is a line/curve on a temperature-composition

diagram indicating the limits of solubility of one solid phase in
another.

 Solidus line/curve – is the line/curve below which the system has

completely solidified.

 Liquidus line/curve – is the line/curve above which a single liquid

phase will be present.

 Solubility limit – is the maximum concentration of a solute atom

that can dissolve in a solvent to form a solid–solution.
Phase Diagrams: Terminologies

(Solvus line/curve)

Phase diagram for sugar and water.

 Phase Diagrams: Terminologies

Binary phase diagram for

copper and nickel.
 Phase Diagrams: Solubility
Solubility can be:
Unlimited – complete dissolution of one phase into another, e.g. Ni–Cu
system.

Limited – excess amount of one phase leading to the formation of new

phase, e.g. excess Zn and Cu system.
 Phase Diagrams: Solubility

Salt–water Phase Diagram

Solubility Limit: 10 0
Maximum concentration for Solubility

Temperature (°C)
which only a single phase 80 Limit L
solution exists. (liquid)
60 +
L
40 (liquid solution S
i.e., syrup) (solid
20 salt)
Question:
What is the solubility limit for
0 20 40 60 65 80 100
salt in water at 20oC?
Water
C = Composition (wt% salt)

salt
Answer: 65 wt% salt.
At 20oC, if C < 65 wt% salt: syrup
At 20oC, if C > 65 wt% salt: syrup + salt
 Phase Diagrams: Solubility
Conditions for Unlimited Solid Solubility (The Hume–
Rothery Rule)

1. Size factor: The atoms or ions must be of similar size, with no more
than a 15% difference in atomic radius, in order to minimize the
lattice strain (i.e., to minimize, at an atomic level, the deviations
caused in interatomic spacing).
2. Crystal structure: The materials must have the same crystal
structure; otherwise, there is some point at which a transition occurs
from one phase to a second phase with a different structure.
3. Valence: The ions must have the same valence; otherwise, the
valence electron difference encourages the formation of compounds
rather than solutions.
4. Electronegativity: The atoms must have approximately the same
electronegativity. Electronegativity is the affinity for electrons. If the
electronegativities differ significantly, compounds form—as when
sodium and chloride ions combine to form sodium chloride.
 Binary Phase Diagrams: Information Contained
1. Phases present – The phase diagram can be treated as a road map; if
we know the coordinates—temperature and alloy composition—we
can determine the phases present (e.g. liquid, solid, liquid + solid,
etc.), assuming we know that thermodynamic equilibrium exists.

2. Phase(s) compositions and phase(s) amount(s) - For each phase, we

can specify a composition, expressed as the percentage of each element
in the phase. Usually the composition is expressed in weight percent
(wt%).
a. When only one phase is present in the solid solution, the
composition of the phase equals the overall composition of the
material. If the original composition of a single phase material
changes, then the composition of the phase must also change.
b. When two phases, e.g., liquid and solid coexisting, their
compositions differ from one another and also differ from the
original overall composition. In this case, if the original composition
changes slightly, the composition of the two phases is unaffected,
provided that the temperature remains constant.
 Binary Phase Diagrams: Examples

1. How many phase(s) are

present in the overall Ni–Cu
phase diagram shown?
2. Can you identify by listing the
phase(s) from question 1
above?
3. At a temperature of 1380oC
and at 40 wt% Ni, what
phase(s) is/are present?
4. For the given temp. above and
at a point A on the diagram,
determine the:
a. Composition of each
phase present.
Binary phase diagram for b. Amount of each phase
copper and nickel.
present.
Phase Diagram: Determination of Phase Composition
Step 1: Locate the temperature–composition point on the phase
diagram.
Different methods are used for single and two-phase regions.
If only one–phase is present, the procedure is trivial: the
composition of this phase is simply the same as the overall
composition of the alloy.
If it is a two - phase

Step 2: Draw a line parallel to the composition axis, starting at the

liquidus and stops at the solidus. This is the tie-line.

Step 3: The intersections of the tie line and the phase boundaries on
either side are noted.

Step 4: Perpendiculars are dropped from these intersections to the

horizontal composition axis, from which the composition of
each of the respective phases is read.
 Binary Phase Diagrams: Examples

1. The composition of the liquid

phase is read off the composition
axis from where the tieline hits
the liquidus, i.e., CL (at pt. A, the
composition of the liquid phase
is 28 wt% Cu and 72 wt% Ni).

2. The composition of the solid

phase is read off the composition
axis from where the tieline hits
the solidus, i.e., Cα (at pt. A , the
composition of the solid phase is
21 wt% Cu and 79 wt% Ni).
Enlarged Ni–Cu phase diagram
Phase Diagram: Determination of Phase Amounts
For phase amounts we also use the tie-line, but it is a little more
complicated. We need to use something called the lever rule. Here
is what we do:

Step 1: Figure out the length of the entire tie-line, i.e., this would
be:
𝑪𝜶 – 𝑪𝑳
Step 2: Figure out the length of the tie-line that goes from the
solidus to point the point of interest. This would be:
𝑪𝜶 – 𝑪𝟎
Step 3: The amount of the liquid phase is the fraction of the tie-
line that goes from the solidus to the point of interest. In
terms of steps 1 and 2, this becomes:
𝑪𝜶 − 𝑪𝟎
𝒘𝒕% 𝒍𝒊𝒒𝒖𝒊𝒅 𝑾𝑳 = × 𝟏𝟎𝟎
𝑪𝜶 − 𝑪𝑳
Step 4: The amount of solid present would = (100 – wt% liquid).
 Phase Diagram: Determination of Phase Amounts
Similarly for the α–phase,
𝑪𝟎 − 𝑪𝑳
𝒘𝒕% 𝒍𝒊𝒒𝒖𝒊𝒅 𝑾𝜶 = × 𝟏𝟎𝟎
𝑪𝜶 − 𝑪𝑳
The amount of liquid present would = (100 – wt% Solid).

Example Question

At a temperature of 1250oC, determine the phase compositions and

phase amounts at overall compositions of

1. 35 wt% Ni–65 wt% Cu, and

2. 40 wt% Ni–60 wt% Cu.
Phase Diagram: Determination of Phase Amounts

𝑪𝜶 − 𝑪𝟎
𝑾𝑳 =
𝑪𝜶 − 𝑪𝑳

𝑪𝟎 − 𝑪𝑳
𝑾𝜶 =
𝑪𝜶 − 𝑪𝑳
Ask that burning question now!