Materials and Metallurgy

ME 3119

Md. Bakhtierkhalzi 1
Lecturer, Dept. of ME, RUET
 Constitution of Alloys

Alloy: An alloy is a substance that has metallic properties and is composed of two or more
elements, of which at least one is a metal.

If the system is made up of two elements, it is called a binary alloy system and if the system is
made up of three elements, it is called a ternary alloy system.

Alloys may be homogeneous or mixtures.

If the alloy is homogeneous it will consist of a single phase, and if it is a mixture it will be a
combination of several phases.

A phase is anything which is homogeneous (uniform) and physically distinct in nature or properties.
In the solid state there are three possible phases: A phase is a homogenous, physically distinct and
I. Pure metal mechanically separable portion of the material with
II. Intermediate alloy phase or compound a given chemical composition and structure.
III. Solid solution
Md. Bakhtierkhalzi 2
Lecturer, Dept. of ME, RUET
 Constitution of Alloys

If an alloy is homogeneous in the solid state, it can be only a solid solution or a compound.

If the alloy is a mixture, it is then composed of any combination of phases possible in the solid
state. It may be a mixture of two pure metals or two solid solutions or two compounds or a
pure metal and a solid solution and so on.

Pure metal: Under equilibrium condition all pure metals

exhibit a definite melting or freezing point.

Under equilibrium condition means extremely slow heating

or slow cooling.
If a cooling curve is plotted for a pure metal, it will show a
horizontal line at the melting or freezing point as shown in
figure.
Md. Bakhtierkhalzi 3
Lecturer, Dept. of ME, RUET
 Compounds
In many binary alloy systems, when the chemical affinity of elements is greater, their mutual
solubility becomes limited and compounds (also called intermediate phases) are formed
(rather than solid solutions)

When compound is formed, the elements loose their individual identity and characteristic
properties to a large extent. Water (H2O) is composed of elements that are normally gases at
room temperature, yet the compound is liquid at room temperature. The compound will have
its own characteristic physical, mechanical and chemical properties.

The crystal structure of a compound is different from its component.

Md. Bakhtierkhalzi 4
Lecturer, Dept. of ME, RUET
 Solution
A solution is a homogeneous mixture composed of two or more substances. In such a
mixture, a solute is a substance dissolved in another substance, known as a solvent.
The solvent is a chemical substance and can be in a solid, liquid or gaseous state. Thus
solution can exist in a gaseous, liquid or solid state.

The amount of solute that may be dissolved by the solvent is generally a function of
temperature (with pressure constant) and usually increases with increasing temperature.

There are three possible conditions for a solution: Unsaturated, saturated and supersaturated

Md. Bakhtierkhalzi 5
Lecturer, Dept. of ME, RUET
 Solution

If the solvent is dissolving less of the solute than it could dissolve at a given temperature and
pressure, it is said to be unsaturated.

If it is dissolving the limiting amount of solute, it is saturated.

If it is dissolving more of the solute than it should be, under equilibrium condition, the
solution is supersaturated.

The supersaturated solution may be accomplished by doing work on it, such as stirring or
preventing the equilibrium conditions by rapidly cooling the solutions.
The supersaturated solution is unstable and tends to become stable or saturated by rejecting
or precipitating the excess solute.

Md. Bakhtierkhalzi 6
Lecturer, Dept. of ME, RUET
 Solid Solution
• Variation in composition is possible
• Usually the crystal structure of the solution is that of one of the components.

Compound (Intermetallic)
• Fixed composition
• Crystal structure of the solution is different from either of the components.

Md. Bakhtierkhalzi 7
Lecturer, Dept. of ME, RUET
 Solid Solution
Solid solution, mixture of two crystalline solids that coexist as a new crystalline solid, or
crystal lattice. The mixing can be accomplished by combining the two solids when they have
been melted into liquids at high temperatures and then cooling the result to form the new solid.

Many metal alloys are solid solutions.

Example: Cu-Ni, Au-Ag etc.

In a solid solution, the metal in the major proportion is called the solvent (host or parent or
matrix) and the metal in the minor proportion is called the solute

Md. Bakhtierkhalzi 8
Lecturer, Dept. of ME, RUET
 Solid Solution
Examples
Austenite: Solid solution of C in gamma iron (FCC)
Ferrite: Solid solution of C in alpha iron (BCC)

Alpha brass: Solid solution of Cu (FCC) and Zn (HCP)

Solid solution of alpha brass has FCC structure

Md. Bakhtierkhalzi 9
Lecturer, Dept. of ME, RUET
 Solid Solution
There are two types of Solid Solutions:
i. Substitutional Solid Solution
ii. Interstitial Solid Solution

Substitutional Solid Solution

• In this type of solid solution, the solute atoms substitute the Example:
atoms of solvent in the crystal structure of the solvent. alpha brass (Cu in Zn)
• The substitutional solid solution are generally ordered at lower
temperatures and disordered at higher temperatures.
• Temperature is the deciding factor. rsolute rsolvent
 

Md. Bakhtierkhalzi 10
Lecturer, Dept. of ME, RUET
 Interstitial Solid Solution
 •These are formed when atoms of small atomic radii fit into the interstitial spaces of larger
solvent atoms.
• Atoms of elements such as carbon, nitrogen, boron, hydrogen, etc. which have radii less
than 1 A are likely to form interstitial solute atoms and may dissolve more readily in
transition metals such as Fe, Ni, Mn, Cr, etc. than in other metals.
Example
Austenite: C in voids of gamma iron

rsolute<< rsolvent

Md. Bakhtierkhalzi 11
Lecturer, Dept. of ME, RUET
 Solubility Limit

Md. Bakhtierkhalzi 12
Lecturer, Dept. of ME, RUET
Md. Bakhtierkhalzi 13
Lecturer, Dept. of ME, RUET
 RULES FOR FORMATION OF SOLID SOLUTION
HUME-ROTHARY RULES:
• These are the rules which govern the formation of Solid Solutions.
• In other words, only when these rules are satisfied, a substitutional solid solution is formed.

1. Crystal Structure Factor:

 For complete solubility of two elements, they should have the same type of crystal lattice.
 For example, Au-Ag solution, both should have FCC structure.

Md. Bakhtierkhalzi 14
Lecturer, Dept. of ME, RUET
 RULES FOR FORMATION OF SOLID SOLUTION
HUME-ROTHARY RULES:
• These are the rules which govern the formation of Solid Solutions.
• In other words, only when these rules are satisfied, a substitutional solid solution is formed.

1. Crystal Structure Factor:

 For complete solubility of two elements, they should have the same type of crystal lattice.
 For example, Au-Ag solution, both should have FCC structure.

Md. Bakhtierkhalzi 15
Lecturer, Dept. of ME, RUET
 RULES FOR FORMATION OF SOLID SOLUTION
2. Relative Size Factor:
 The atoms of the solute and solvent should have the same atomic size approximately.
 This factor is satisfied if the difference of atomic radii of two elements is less than 15%.

3. Chemical-Affinity Factor:
 For a substitutional solid solution to be formed, two metals should have less chemical
affinity.
 Greater is the chemical affinity, lesser is the chance of forming a solid solution.
 If two elements are farther apart in a periodic table, chemical affinity is more.

Md. Bakhtierkhalzi 16
Lecturer, Dept. of ME, RUET
 RULES FOR FORMATION OF SOLID SOLUTION
4. Relative Valence Factor:
 Among two metals, which have satisfied all the above rules, the metal of lower valence
tends to dissolve more of a metal of higher valence than vice-versa. For example, in the
aluminium-nickel alloy system, both metals are face centered cubic. The relative-size factor
is approximately 14 percent. However nickel is lower in valence than aluminum, and in
accord with the relative-valence factor solid nickel dissolves 5 percent aluminum, but the
higher valence aluminum dissolves only 0.04 percent nickel.

Md. Bakhtierkhalzi 17
Lecturer, Dept. of ME, RUET
 INTERMEDIATE PHASES
• Intermediate phases are those phases whose chemical compositions are intermediate
between the two pure metals and generally have crystal structure different from those of the
base (parent) metals.
• An alloy can be made up of a solid solution phase entirely or can exist along with an
intermediate phase.
• An intermediate phase here is nothing but a compound and is made up of two or more
elements of which at least one of them is a metal.

Md. Bakhtierkhalzi 18
Lecturer, Dept. of ME, RUET
  A compound is a chemical combination of positive and negative valence elements. i.e., atoms of different
elements are combined in different proportions and are expressed by chemical formulae like H2O, NaCl,
etc.

 When a compound or intermediate phase is formed, the elements lose their individual identity and
properties to a good extent and the compound will have its own characteristic physical,
mechanical and chemical properties.

Md. Bakhtierkhalzi 19
Lecturer, Dept. of ME, RUET
 There are three most common intermediate alloy phases:
i. Intermetallic or Valency Compounds
ii. Interstitial Compounds
iii. Electron Compounds

Intermetallic or Valence Compounds

• When alloy phase are exclusively metal-metal systems, they are called intermetallic
compounds.
• These are formed between chemically dissimilar metals and are combined by
following the rules of chemical valence.
• The combination is usually non-metallic and show poor ductility and poor electrical
conductivity and have complex crystal structure.
• Examples for intermetallic compounds: Mg2Pb, Mg2Sn, CaSe, Cu2Se

Md. Bakhtierkhalzi 20
Lecturer, Dept. of ME, RUET
 Interstitial Compounds
• These are similar to interstitial solid solutions except that they have more or less a
fixed composition.
• Example: Fe3C.
• The interstitial compounds are metallic in nature, have high melting points and are
extremely hard.

Md. Bakhtierkhalzi 21
Lecturer, Dept. of ME, RUET
 Electron Compounds
• These are of variable compositions and do not obey the valence law, but have a
definite electron to atom ratio.
• Example: Cu9Al4
• Each Cu atom has 1 valence electron and each Al atom has 3 valence electrons.
• So 13 atoms which make up the compound have 21 valence electrons with electron to
atom ratio being 21:13
• Electron compounds have properties same as those of solid solutions – wide range of
compositions, high ductility and
• low hardness.

Md. Bakhtierkhalzi 22
Lecturer, Dept. of ME, RUET
 Alloy

Homogeneous Mixatures

Solid Solution Intermediate

alloy structure
Intermetallic
Substitutional Interstitial
Interstitial

Electron Compound

Md. Bakhtierkhalzi 23
Lecturer, Dept. of ME, RUET