Module 4

Contents
Phase diagrams: - need of alloying - classification of alloys - Hume
Rothery`s rule
Equilibrium diagram of common types of binary systems:
isomorphous (Cu- Ni) eutectic (Pb- Sn), lever rule and Gibb`s phase
rule.
Detailed discussion on Iron- Carbon equilibrium diagram with
microstructure and properties.
Heat treatment: - TTT, CCT diagram, applications - Tempering-
Hardenability, Jominy end quench test, applications-Surface
hardening methods.
Phase Diagrams
Alloys
An alloy is a homogeneous mixture of two or more metals. It may also
contain a metal and a non-metal.
Examples
• Stainless steel - Made of Iron, Chromium and Nickel-used for
manufacturing surgical instruments, utensils, etc.
• Solder – Made of Tin and Lead –Used for soldering
• Brass – Made of Copper and Zinc – Used in musical instruments,
decorative items, etc.
• Duralumin- Made of Aluminium, Copper, and Manganese- Used for
constructing wires, bars, aeroplane parts etc.
Need of Alloying
• An alloy has more tensile strength than its constituent elements. We
can increase the hardness of a metal by mixing it with another metal
or nonmetal.
• Metals melt at very high temperatures. When a pure metal is alloyed
with another metal or nonmetal, its melting point reduces
• Metals are extremely susceptible to chemical and weather attacks.
Alloys, on the other hand, are more resistant to corrosion. When a
metal is alloyed, it becomes inert, thereby enhancing its corrosion
resistance.
• Pure metals are ideal materials but due to higher cost, poor
properties and lack of availability, it is desirable to have a certain level
of impurity
Structure of Alloys

• Solid Solutions
➢Variation in composition possible
➢Has the crystal structure of one of the component
➢Examples-Austenite (Solid solution of C in ϒ-Iron), Ferrite (Solid solution of C
in α-Iron )
• Intermetallic Compounds
➢Fixed composition
➢Crystal structure different from either of the components possible
➢Examples-Cementite (Fe3C), Ni3Al
Solid Solutions
• Substitutional Solid Solutions
➢In the substitutional type,
solute or impurity atoms
replace or substitute for the
host atoms.
• Interstitial Solid Solutions
➢For interstitial solid solutions,
impurity atoms fill the voids or
interstices (vacant space
between atoms) among the
host atoms
Solubility Limit

• 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.
• It is the upper limit of the
solute content in the
solution.
Hume-Rothery’s Rule

Hume Rotherys rules are basic conditions for an element to

dissolve in a metal, to form a substitutional solid solution.
According to these rules, substitutional solid solutions may form
if the solute and solvent have:
• Same crystal structure
• Similar atomic radii (15% or less difference)
• Similar electronegativities
• Similar valency.
Cu –Ni Alloy/System

Cu
• FCC
• Melting point – 10850C
Ni
• FCC
• Melting point – 14530C

Phase Diagram-Tells us what phases are in equilibrium at what different

compositions and temperatures
Equilibrium Phase Diagrams/Equilibrium diagrams/Phase
Diagrams
• A diagram in the space of relevant thermodynamic variables (
temperature, pressure, composition) indicating phases in equilibrium.
• Three externally controllable parameters will affect phase structure—
temperature, pressure, and composition—and phase diagrams are
constructed when various combinations of these parameters are
plotted against one another.
Phases
• A homogeneous portion of a system that has uniform physical and
chemical characteristics.
• Phases are chemically homogeneous, physically distinct, and
mechanically separable.
• A single-phase system is termed a “homogeneous system” and a
system composed of two or more phases is termed a “mixture” or
“heterogeneous system”
• Three phases of matter- solid, liquid, and gas
• Solids-more than one phase (α-iron, ϒ-iron)
Component

• The independent chemical species (element or compound) in terms

of which the composition of a system is specified are called
components.
• In the Cu-Ni system the components are Cu and Ni.
• Phase diagrams are classified based on the number of components
➢Unary phase diagrams (single component)
➢Binary Phase diagrams (Two components)
➢Ternary Phase diagrams( Three components)
 Unary Phase Diagrams

• The simplest and easiest type

of phase diagram to
understand is that for a one-
component system, in which
composition is held constant.
• This one-component phase
diagram (or unary phase
diagram) [sometimes also
called a pressure-temperature
(or P–T) diagram]
Unary Phase Diagrams
• In the phase diagram for H2O, the regions for three different phases—
solid, liquid, and gas will exist under equilibrium conditions over the
temperature–pressure ranges.
• The three curves labeled aO, bO, and cO are phase boundaries; at any
point on one of these curves, the two phases on either side of the
curve are in equilibrium (or coexist) with one another.
• All three phase boundary curves intersect at a common point (at a
temperature of 273.16 K and a pressure of 6.04 *10-3 atm) at which
solid, liquid, and vapor phases are in equilibrium with one another.
This point is called a triple point or invariant point.
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.
• 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 Isomorphous Systems

• Isomorphous systems are the simplest form of binary phase diagrams.

• This type of systems shows a complete solubility of each other in solid
and liquid phases.
• These diagrams are called isomorphous because only a single type of
crystal structure is obtained at all possible compositions
• Examples
Cu-Ni, Au-Ag, Au-Cu, Mo-W, Mo-Ti Systems
Cu-Ni System
• For metallic alloys, solid
solutions are commonly
designated by lowercase Greek
letters (α,β,ϒ etc.)
• Liquidus Line- the line separating
the L And α + L phase fields is
termed the liquidus line. The
liquid phase is present at all
temperatures and compositions
above this line.
• Solidus Line – The solidus line is
located between the α and α+ L
regions, below which only the
solid phase exists.
Why phase diagrams?
• Constitution point- Any point (x,T) in the phase diagram that
represents an alloy of composition x held in equilibrium at
temperature T.
• Phase diagrams are used to answer these questions-

• At any constitution point,

➢What are the phases present?
➢What are the compositions of these phases?
➢What are the relative amounts of the phases?
Interpretation of Phase diagrams
Interpretation of Phase diagrams

What are the phases present?

Locate the temperature–composition point on the diagram and note the phase(s)
with which the corresponding phase field is labeled.
What are the compositions of Various phases ?
In a two-phase region
• Construct a tie line across the two-phase region at the temperature of the alloy.
• Note down the intersections of the tie line and the phase boundaries on either
side.
• Drop perpendiculars from these intersections to the horizontal composition axis,
from which the composition of each of the respective phases can be obtained.
Interpretation of Phase diagrams

What are the relative amounts of the phases?

Lever Rule
• Construct a tie line across the two-phase region at the temperature of the alloy.
• Note down the intersections of the tie line and the phase boundaries on either
side.
• The fraction of one phase is computed by taking the length of tie line from the
overall alloy composition to the phase boundary for the other phase, and dividing
by the total tie line length.
• The fraction of the other phase is determined in the same manner.
Example
The binary phase diagram
of metals P and Q is shown
in Fig. An alloy X
containing 60% P and 40%
Q is cooled from liquid to
solid state.
• What are the fractions of
liquid and solid at
12500C?
• Also find the
composition of Liquid
and solid phase at the
same temperature.
Equilibrium Cooling
Binary Eutectic Systems

Eutectic phase diagrams illustrate the behavior of two or more

immiscible solids and a liquid phase, showing the temperatures and
compositions at which different phases exist in equilibrium.
Examples
Cu-Ag, Au-Si, Pb-Sn Systems
 Pb-Sn Eutectic System

Lead
• FCC
• Melting point- 3270C
Tin
• BCT
• Melting Point -2320C
Pb-Sn Eutectic System

• Phases
• Solidus Line
• Liquidus Line
• Solvus line
• Invariant point
• Eutectic Point
Development of Microstructure
Development of Microstructure
Development of Microstructure
Gibbs Phase Rule

• This rule represents a criterion for the number of phases that will coexist within a
system at equilibrium, and is expressed by the simple equation

• where P is the number of phases present.

• F is the number of degrees of freedom ( the number of externally controlled variables (e.g.,
temperature, pressure, composition) which must be specified to completely define the state
of the system )
• C represents the number of components in the system
• N is the number of non compositional variables (e.g., temperature and pressure).
The Iron-Carbon System

• Of all binary alloy systems, the one that is possibly the most
important is that for iron and carbon
• Both steel and cast irons, primary structural materials in every
technologically advanced culture, are essentially iron-carbon alloys
Iron-Iron Carbide Phase Diagram
Invariant Reactions in Iron –Carbon Phase Diagram
• Eutectoid Reaction

• Eutectic Reaction

• Peritectic Reaction
Development of Microstructure
Development of Microstructure
Development of Microstructure
Isothermal Transformation Diagrams(T-T-T diagram)
Isothermal Transformation Diagrams
Isothermal Transformation Diagrams

Products
• Bainite
• Spheroidite
• Martensite
Continuous Cooling Transformation Diagrams
Continuous Cooling Transformation Diagrams
Tempered Martensite
Tempering is accomplished by heating martensitic
steel to a temperature below the eutectoid for a
specified time period.
Normally, tempering is carried out at temperatures
between 250 and 650C.
This tempering heat treatment allows, by
diffusional processes, the formation of tempered
martensite according to the reaction.
Heat Treatment of Steel-Products
Microstructures and Mechanical Properties for Iron–Carbon
Alloys
Hardenability

• Hardenability is a term that is used to describe the ability of an alloy

to be hardened by the formation of martensite as a result of a given
heat treatment.
• Hardenability is not “hardness,” which is the resistance to
indentation; hardenability is a qualitative measure of the rate at
which hardness drops off with distance into a specimen's interior due
to diminished martensite content.
• A steel alloy with a high hardenability hardens, or forms martensite,
not only at the surface but to a large degree throughout the entire
interior.
 The Jominy End-Quench Test
• One standard procedure that is widely utilized to
determine hardenability is the Jominy end-quench test.
• A cylindrical specimen 25.4 mm in diameter and 100 mm
long is austenitized at a prescribed Temperature for a
prescribed time.
• After removal from the furnace, it is quickly mounted in a
fixture and the lower end of the specimen is quenched by
a jet of water of specified flow rate and temperature.
• The cooling rate is a maximum at the quenched end and
diminishes with position from this point along the length
of the specimen.
• After the piece has cooled to room temperature, shallow
flats 0.4 mm (0.015 in.) deep are ground along the
specimen length and Rockwell hardness measurements
are made
Hardenability Plot
Surface hardening Techniques

• Surface hardening is a heat treatment process that reinforces the

surface of a metal, typically by altering its chemical composition or
through localized heating and cooling.
• These techniques create a harder, more wear-resistant surface while
maintaining a softer, more ductile core.

• Carburizing
• Nitriding
• induction hardening
Surface hardening Techniques

Carburizing:
Involves adding carbon to the surface of low-carbon steel, creating a hard, high-
carbon surface layer.
This process is often used for gears, shafts, and other components where wear
resistance is crucial.
Nitriding:
Diffuses nitrogen into the surface, forming a thin, hard layer that is highly resistant
to wear and corrosion.
Induction Hardening:
Uses a high-frequency electromagnetic field to rapidly heat the surface, followed
by quenching to create a hard, martensitic structure.