FACULTY OF ENGINEERING & THE BUILT ENVIRONMENT

Department of Civil, Mining & Process Engineering

MATERIALS SCIENCE 124

Mrs J.T. Kurasha

Solid Solutions and phase diagrams
The main objectives of this discussion is:
(a) To understand solid solutions and how they
strengthen materials.
(b) To understand phase equilibria.
(c) To understand the relationship between
properties and the phase diagram.
 Thinking points
• Is it possible for solid, liquid and gaseous
forms of a material to coexist?
• Is it possible to have a solid solution?
• When alloys such as brass solidify, which
element solidifies first – copper or zinc? Why?
 Solid solutions
• A solid solution contains two or more types
of atoms or ions that are dispersed uniformly
throughout the material. In metallic materials,
it is also known as alloying.
• The ‘impurity’ atoms are known as the solute,
and the parent material are known as the
solvent.
• Solid solutions can be formed in metallic,
ceramics and polymer materials.
 Types of solid solutions
• The solute atoms/ions may either occupy
regular lattice sites, or interstitial sites.
(a) When the solute atoms occupy regular lattice
sites, a substitutional solid solution results.
This is a solid solution where solute atoms
replace/substitute solvent atoms, occupying
positions that are normally occupied by the
solvent atoms.
(b) When the solute atoms occupy interstitial sites, or sites
that are normally unoccupied, an interstitial solid solution
results.

• Controlling the amounts of solute atoms affects the

mechanical and other properties of the solid solutions.
• In metallic materials, solute atoms disturb the atomic
arrangement and interfere with dislocation movement,
such that the material is solid solution strengthened.
 Solubility and solid solutions
• How much solute material should be added to avoid
forming additional phases?
• This is defined by the solubility of the solute in solvent
atoms/ions.
• Unlimited solubility – the solute and solvent
atoms/ions form only one phase regardless of the
ratios in which they are mixed, e.g water and alcohol
form one phase when mixed in whatever ratios. Cu and
Ni also have unlimited solubility.
• Many semiconductor materials form solid solutions
with unlimited solubility, e.g. solid solutions of gallium
arsenide (GaAs) and aluminium arsenide (AlAs).
• Limited solubility – If too much solute is added to a solvent,
more than two phases can result. Hence the solute has limited
solubility in the solvent. For example, adding too much salt to a
glass of water results in the excess salt sinking to the bottom of
the glass.

• Another example is the Cu-Zn solution, in which Cu can only

from a homogeneous solid solution with a maximum of 30% Zn.
If there is more than 30% zinc, a CuZn compound is formed in
addition to the solid solution of Cu and Zn.

• P, B and As are used as dopants for Silicon, and they all have
limited solubility in Si.

• In polymeric systems, copolymers can be formed, which behave

similar to solid solutions. For example, the monomers
acrylonitrile (A), butadiene (B) and styrene (S) form a
copolymer called ABS.
 Conditions for unlimited solubility
• For unlimited solubility to take place, the following
conditions, known as the Hume-Rothery rules must be
satisfied.
1. Size factor – The solute and solvent atoms/ions must be of
similar size, with no more than 15% difference in atomic
radius in order to minimize lattice strain.
2. Crystal structure – the materials must have the same
crystal structure.
3. Valence – the ions must have the same valence, otherwise
differences may encourage the formation of compounds
rather than solutions.
4. Electronegativity – the atoms must have approximately
the same electronegativity, otherwise compounds form.
 Example 1
1. Consider the substitutional solid solution of Cu and
Ni.
-Pure Cu atoms are about 0.2551nm in diameter, and are
about 2% larger than those of Ni (0.2487nm). This
difference is small and only a slight distortion of the
lattice occurs when a Cu atom enters a Ni crystal, or vice
versa.
- Both Cu and Ni have the FCC crystal structure.
- Both Cu and Ni have a valence of +2.
- Cu and Ni have an electronegativities of 1.9 and 1.8
respectively.
- Hence Cu and Ni have unlimited solubility.
 Example 2
• Consider the substitutional solid solution of Cu
and Ag.
-Ag atom diameter is 0.2884nm, and is about 13%
larger than the Cu atom.
- Ag also crystallizes in the FCC structure like Cu.
- The valence of Cu is +2, while that for Ag is +1.
- Both Ag and Cu have electronegativities of 1.9.
• Due to a fundamental difference in size of the Cu
and Ag atoms the solubility of Ag in Cu is only 1%.
• In interstitial solid solutions, the solubility of the
interstitial solute atoms is always limited.

• This is because interstitial atoms are much smaller than

the solvent atoms, which violates the first Hume-
Rothery condition.

• Research shows that extensive interstitial solid

solutions occur only if the solute atom has an apparent
diameter smaller than 0.59 that of the solvent.

• The four most important interstitial solute atoms are

carbon, nitrogen, oxygen, and hydrogen, all of which
are quite small in size.
 Solid solution strengthening
• In metallic materials, solid solution formation
results in a strengthening mechanism known as
solid solution strengthening.
• The strengthening effect is caused by increased
resistance to dislocation motion as the solute
atoms act as barriers to dislocation movement.
• This explains why brass is stronger than pure
copper, or why steels are stronger and harder
than pure iron.
• The degree of solid solution strengthening depends on
two factors:

(a) A large size difference between the solute and solvent

atoms increases the strengthening effect because a
larger size difference produces a greater disruption to
the initial crystal structure, making slip more difficult.

(a) The greater the amount of alloying element added, the

greater the strengthening effect. E.g a Cu-20% Ni alloy
is stronger than a Cu-10% Ni alloy.
 Effect of solid solution strengthening
on properties
(a) The yield strength, tensile strength and hardness
of the alloy are greater than those of the pure
metal.

(b) The ductility of the alloy is in most cases always

less than that of the pure metal.

(c) Electrical conductivity of the alloy is much lower

than that of pure metal, because electrons are
more scattered by the atoms of the alloying
element.
• Hence solid solution strengthening of Cu and Al for
transmission of electrical power is not recommended
because of this enhanced/pronounced effect.

(d) The resistance to creep and strength at elevated

temperatures is improved in alloys than in pure metals.
E.g. high-temperature alloys like those used for jet
engines are extensively solid solution strengthened.
 Isomorphous Phase Diagrams
• A phase diagram shows the phases and their
compositions at any combination of
temperature and alloy composition.

• A Phase – is a portion of a system which is

physically homogenous within itself, and is
bounded by a surface that separates it from
any other portions/phases.
 Cont..
• A phase is characterised by:
(a) The same structure or atomic arrangement
throughout.
(b) Roughly the same composition and
properties throughout.
(c) A definite interface between the phase and
any surrounding phases.
 Example
• If you enclose a block of ice in a vacuum
chamber, the ice begins to melt, and at the
same time some of the water vaporises. This
happens at the triple point of water.
• Hence three phases of water coexist, and each
has a unique atomic arrangement, unique
properties, and a definite boundary between
each phase.
 Gibb’s phase rule
• Describes the relationship between the number of components and the number of
phases for a given system, and the conditions that may be allowed to change, for
example temperature, pressure, etc.

• This famous rule is used to determine the number of phases that can coexist in
equilibrium in a given system.

• The general form of the phase rule is:

2+C=F+P

Where
C = the number of chemically independent components, usually elements or
compounds, in the system.

F = the number of degrees of freedom, i.e. the number of variables that are allowed to
change without changing the number of phases in equilibrium, e.g. temperature,
pressure, composition.

P = number of phases present.

 Point to note
• Phases do not always have to be solid, liquid
or gas. Crystal structure can be different for a
given element.
• For example Fe can exist as BCC or FCC, and
these two solid forms are different phases of
Fe that will be stable at different temperature
and pressure.
 Example
Consider the triple point of water:
• One component, i.e., water.
• 3 phases present, i.e. vapor, liquid, and solid.
• F=1–3+2=0
• Hence no variable is allowed to change at this
invariant point.
Common terms

Fig 1 Typical phase

diagram
 Cont..
• Liquidus – the area above the liquidus line corresponds
to the region in which liquid phase only is stable.
Hence the liquidus temperature is the temperature
above which a material is completely liquid.
• Solidus – the area below the solidus line defines the
region in which only the solid phase is stable. Hence
the solidus temperature is the temperature below
which the alloy is 100% solid.
• The region between the solidus and liquidus lines is a
two-phase area where both phases coexist. The
temperature difference between the liquidus and the
solidus is known as the freezing range.
 Cont..
• Isomorphous alloy systems are systems in which
a single type of crystal structure is observed for
all ratios of the components, e.g. Cu-Ni system, or
NiO- MgO systems, only one solid phase forms.
• Binary systems – Two component systems, e.g.
mixture of two metallic elements.
• Ternary systems – three component systems,
mixture of three elements. Often encountered in
ceramic and metallic systems.
 The Lever Rule

C
 Lever rule cont’d…
• To calculate the amount of solid and liquid at a
given point within the two phase region, we
construct a tie line horizontally until it
intersects the liquidus and solidus lines, which
gives the desired compositions.
• The general form of the lever rule is:
𝑜𝑝𝑝𝑜𝑠𝑖𝑡𝑒 𝑎𝑟𝑚 𝑜𝑓 𝑙𝑒𝑣𝑒𝑟
phase percent = x 100
𝑡𝑜𝑡𝑎𝑙 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑡𝑖𝑒 𝑙𝑖𝑛𝑒
 Example
Determine the amount of solid and liquid phases at
point z in the Cu-Ni system shown below.
Cont…
 Example 2
A

Determine the amount of solid and liquid at points A and B in the above system.
Solution
 Three phase reactions
➢ Involve 3 separate phases (limited solubility!)
➢ Occur at a ‘single’ point.
➢ Often associated with special characteristics of the material
• Lets look at 5 of these common reactions which involve 3 separate
phases in binary systems.
 Eutectic system

Eutectic
L→α+β

• At eutectic temperature, two solid phases form

simultaneously from a single liquid phase.
• The eutectic temperature and composition determine a point
on the phase diagram called the eutectic point.