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LIMITATIONS OF PURE METALS AND NEED OF ALLOYING

In engineering, only few materials are used as pure materials.

Eg: Pure Copper-Used in electrical wire

- High electrical conductivity

Pure metals have the following limitations:

1.Poor properties: Generally pure metals are not strong enough for engineering applications
where stresses have to be withstood

2.High cost: Pure metals are very costly because of the need for extensive refining steps.

3.Lack of availability (scarcity)

These limitations are overcome by alloying. Pure metals are mixed or alloyed with other metals
to form alloys.

NEED FOR ALLOYING

 Atoms are of varying size, so the possibilit of slip is low.

 Alloys increase the hardenability
 Alloying also improve mechanical properties

Alloy or solid solution

Alloys or solid solutions are materials in which impurity atoms are added purposely to bring
some special properties to the material.

In the case of alloys, the terms solute and solvent are generally used.

“Solvent” means the element or compound that is present in large quantity; sometimes solvent
atoms are also called as host atoms. “Solute” is used to denote an element or compound present
in a minor concentration.

In alloys, the crystal structure is maintained, and no new structures are formed.

SOLID SOLUTIONS

Most of the alloys are formed as solid solutions. Like liquid solution, solid solution also contains
a solute and solvent. Solution in a solid state that consist of two or more elements dispersed in a
single phase structureis called a solid solution.

Solid solutions are of 2 types (a) substitutional and (b) interstitial.

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SUBSTITUTIONAL SOLID SOLUTION

In this solid solution there is a direct substitution of one type of atom for another. In a Cu-Ni
solid solution, solute atoms (Ni) takes the positions normally occupied by solvent (Cu) atoms.
When solute atoms are substituted randomly, it is called random (disordered) solid solution.
When solute and solvent atoms are arranged in a regular fashion, it is termed as an ordered
substitutional solid solution.

INTERSTITIAL SOLID SOLUTION

When solute atoms are much smaller than solvent atoms, they can occupy interstitial positions
between solvent atoms. C,H, N and B atoms are very small and can form interstitial solid
solutions. An example is steel containing carbon in iron. In some cases, substitutional and
interstitial solid solutions can coexist.

HUME ROTHERY’S RULES

Hume-Rothery proposed 4 conditions for forming substitutional solid solutions. These are known
as Hume-Rothery’s Rules.

1. Size factor:

Size difference between solvent and solute atoms must be less than 15%. For extensive solid
solubility, size difference should be within 8%.

2. Crystal structure factor:

The crystal structures of solvent and solute atoms must be same.

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3. Electro negativity factor:

Difference in electro-negativity of solvent and solute must be small.

4. Valency factor:

In general a metal has a tendency to dissolve a metal of higher valency. Hence a solvent must
have a lower valency than solute.

PHASE DIAGRAM

Diagram or map representing the relationship between phases in equilibrium in a system as a

function of any two among temperature, pressure and composition

Also called equilibrium diagram or constitutional diagram

Types of phase diagram

 Unary phase Diagram

 Binary Phase Diagram

Unary phase Diagram

If a system consists of just one component (e.g.: water), equilibrium of phases exist is depicted
by unary phase diagram.

Binary Phase Diagram

If a system consists of two components, equilibrium of phases exist is depicted by binary phase
diagram.

For most systems, pressure is constant, thus independently variable parameters are–temperature
and composition

DEFINITIONS (TERMS USED IN PHASE DIAGRAM)

Component

Components are pure metals and/or compounds of which an alloy is composed. For example, in
a copper–zinc brass, the components are Cu and Zn, Solute and solvent.

System

“System” refers to a specific body of material under consideration (e.g., a ladle of molten steel).
Or it may relate to the series of alloys consisting of the same components, but not to consider
alloy composition (e.g., the iron–carbon system).

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Solubility limit

In alloy systems and 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.

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.

E.g., consider the sugar–water (C12H22O11–H2O) system.

Phases

A phase can be defined as a homogeneous portion of a system that has uniform physical and
chemical characteristics.

Every pure material is considered to be a phase; so also is every solid, liquid, and gaseous
solution. For example, the sugar–water syrup solution is one phase, and solid sugar is another.

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Microstructure

Microstructure is subject to direct microscopic observation, using optical or electron

microscopes;

In metal alloys, microstructure is characterized by the number of phases present, their

proportions, and the manner in which they are distributed or arranged.

Phase equilibria

Equilibrium means that the characteristics of the system do not change with time but continue
indefinitely; that is, the system is stable.

A change in temperature, pressure, and/or composition for a system in equilibrium will result in
a spontaneous change to another state.

Phase equilibrium is reflected by constancy with time in the phase characteristics of a system.

GIBBS PHASE RULE

The constructions of phase diagrams as well as some of the principles governing the conditions
for phase equilibria are dictated by laws of thermodynamics. One of these is the Gibbs phase
rule.

This rule represents a relationship between the number of phases, number of components and
number of degrees of freedom that will coexist within a system at equilibrium, and is expressed
by the simple equation;

F=C-P+2

Where F is termed the number of degrees of freedom, P is the number of phases present, and C
represents the number of components in the system

Degrees of freedom or the number of externally controlled variables (e.g. Temperature, pressure,
composition) which must be specified to completely define the state of the system and these
variables that can be changed independently without altering the number of phases that coexist at
equilibrium.

Since pressure is ignored in the case of liquids and solids; and phase rule can be modified as

F=C-P+1

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LEVER RULE

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Coring
As an alloy of isomorphous type solidifies, the centre of a grain will be rich in the component
having higher melting point. The concentration of the element having high melting point
decreases (the component with lower melting point increases) progressively from centre of the
grain to grain boundary. This variation in composition from the centre of each grain to its grain
boundary is called coring (a type of segregation). Coring can be removed by homogenization
(keeping at elevated temperature for sufficient time).

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INVARIANT REACTIONS

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IRON –CARBON PHASE DIAGRAM

Fe-C equilibrium (phase) diagram can be divided into 2 parts. (a) iron rich portion containing up
to 6.67 weight %C and (b) other portion containing 6.67-100% C (known as graphite. At 6.67%
C, the entire structure is cementite (an intermetallic compound Fe3C). Hence the iron rich
portion of iron-carbon diagram can be called Fe- Fe3C phase diagram.

The other portion containing 6.67-100% C does not have any technical or commercial
importance. Hence Fe-Fe3C diagram is the iron-carbon diagram of practical importance. Refer
Figure

In Fe-C diagram there are 5 different phases and 3 invariant reactions under equilibrium cooling
condition (very slow rate of cooling).

The family of Fe-C alloys with carbon content up to 2.14% is called steels. When carbon content
is more than 2.14% up to 6.67 %, the alloys are called cast irons.

PHASES IN FE-C DIAGRAM

1.∂ Ferrite:

∂ Ferrite is a stable phase only in the temperature range of 1394- 15380C. Maximum solubility
of C in ∂ ferrite is only 0.09% at 14950C. This phase is not of much significance.

2.α Ferrite:

It is an interstitial solid solution of C in BCC iron. Maximum solubility is 0.022% C at 7270C.

At room temperature the solubility is only 0.008% C.

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3. Austenite

It is an interstitial solid solution of C in FCC iron. Solubility of C in austenite is much higher

(≈100 times) than in BCC iron. Maximum solubility is 2.14 % at 11470C .

Austenite is known as γ phase. It is stable in the temperature range of 912-13940C.

4.Cementite:

Cementite is an intermetallic compound. It is iron carbide (Fe3C).

It is formed when carbon content is more than the solubility limit in iron. It is an extremely hard
and brittle phase. Properties of steel can be controlled by controlling the amount, size and shape
of cementite. It is a metastable phase. That is, cementite can remain indefinitely at room
temperature even though it is not a completely stable phase.

5.Liquid phase:

It is the fifth phase in iron-carbon equilibrium diagram.

Apart from these 5 phases, there are 2 phase mixtures in the Fe-C diagram.

(a)Pearlite: It is a mixture of 2 phases, ferrite and cementite. It is formed by the eutectoid

reaction at 7270C. It has the structure of alternate lamellae of ferrite and cementite.

(b)Ledeburite: It is formed by eutectic reaction. It is a mixture of austenite and cementite.

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INVARIANT REACTIONS

A horizontal line always indicates an invariant reaction in binary phase diagrams

Peritectic reaction - at 1495˚C and 0.18%C, d-ferrite + L↔ g-iron (austenite)

Eutectic reaction - at 1147˚C and 4.3 %C, L ↔ g-iron + Fe3C (cementite) [ledeburite]

Eutectoid reaction - at 727˚C and 0.77%C, g-iron ↔ a–ferrite+Fe3C (cementite) [pearlite]

HEAT TREATMENT
 Heat Treatment process is a series of operations involving the Heating and Cooling of
metals in the solid state.
 Its purpose is to change a mechanical property or combination of mechanical properties
so that the metal will be more useful, serviceable, and safe for definite purpose.
 By heat treating, a metal can be made harder, stronger, and more resistant to impact, heat
treatment can also make a metal softer and more ductile.
 No one heat-treating operation can produce all of these characteristics. In fact, some
properties are often improved at the expense of others. In being hardened, for example, a
metal may become brittle.

Purpose

• Relieve Internal stresses developed during solidification, machining, forging, rolling or

welding,

• Harden and strengthen metals.

• Enhance Machinability,

• Increase, heat, wear and corrosion resistance of materials.

• Improve electrical and magnetic properties.

• Refrain grain size

Stages of Heat Treatment

• Stage l— heating the metal slowly to ensure a uniform temperature.

• Stage 2—Soaking (holding) the metal at a given temperature for a given period of time.

• Stage 3— cooling the metal to room temperature

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1. ANNEALING

Annealing involves heating the material to a predetermined temperature and hold the material at
the temperature and cool the material to the room temperature slowly.

When an annealed part is allowed to cool in the furnace, it is called a "full anneal" heat
treatment.

2. NORMALIZING

 It is a type of heat treatment applicable to ferrous metals only.

 It differs from annealing in that the metal is heated to a higher temperature and then
removed from the furnace for air cooling.
 The normalizing consists of heating steel to about 40-55 0C above critical temperature
and holding for proper item and then cooling in still air or slightly agitated air to room
temperature.
 The purpose of normalizing is to remove the internal stresses induced by heat treating,
welding, casting, forging, forming, or machining.
 The grain size is finer in normalized structure than in annealed structure.

DIFFERENCE BETWEEN ANNEALING AND NORMALIZING

Normalizing Full Annealing

Faster cooling rate, in air Slower cooling rate, in furnace
Fine grains, fine pearlite Coarse grains, coarse pearlite
Strength and hardness high Ductility very high
Used as finishing operation Used as intermediate operation to improve
ductility and machinability.

3. QUENCHING OR HARDENING

 Hardening and Hardness are two very different things. One is a process of heat treatment
and other is a extrinsic property of a material.
 It is done to increase the strength and wear properties. One of the pre-requisites for
hardening is sufficient carbon and alloy content.
 To harden by quenching, a metal (usually steel or cast iron) must be heated into the
austenitic crystal phase and then quickly cooled.
 The hardening temperature depends on chemical composition.

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 Hardening is applied to cutting tools and machine parts where high hardness and wear
resistance are important.
 One drawback of using this method by itself is that the metal becomes brittle. This
treatment is therefore typically followed by a tempering process.

4. TEMPERING

 Hardened steels are so brittle that even a small impact will cause fracture.
 Toughness of such steel can be improved by tempering.
 However there is small reduction in strength and hardness.
 Tempering is a sub-critical heat treatment process used to improve the toughness of
hardened steel.
 Tempering consists of reheating of hardened steel to a temperature below Lower critical
temperature and is held for a period of time, and then slowly cooled in air to room
temperature.

5. AUSTEMPERING

 Austempering is heat treatment that is applied to ferrous metals, most notably steel and
ductile iron.
 In steel it produces a bainite microstructure whereas in cast irons it produces a structure
of acicular ferrite and high carbon, stabilized austenite known as ausferrite.
 It is primarily used to improve mechanical properties or reduce / eliminate distortion.

6. MARTEMPERING (MARQUENCHING)

 To overcome the restrictions of conventional quenching and tempering, Martempering

process can be used.
 Martempering or marquenching permits the transformation of Austenite to Martensite to
take place at the same time throughout the structure of the metal part.
 Residual stresses developed during martempering are lower than those developed during
conventional quenching.
 Martempering also reduces or eliminates susceptibility to cracking.

7. AUSFORMING

Ausforming is a thermo mechanical process in which steel is plastically deformed in austenite

condition and then quenched below Ms temperature to form martensite. High strength is obtained
without affecting toughness. Plastic deformation (usually rolling) of austenite should be done
without transforming to pearlite or bainite. Thus there are four process steps namely

1. Austenitize steel

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2. Rapidly cool to a temperature such that the structure remains as austenite. Cooling
rate should be above critical cooling rate to achieve this.

3. Deform the austenite at this temperature

4. Quench from this temperature to obtain martensite.

HARDENABILITY
Hardness and hardenability are two different concepts. Hardness is the resistance of the material
to indentation or deformation. It is a basic material property.
Hardenability is the ability of the steel to develop a hardened layer across the cross section or
thickness.
Greater the depth of hardness below the surface, higher will be the Hardenability of steel.
Hardenability of steel depends on composition of steel, method of quenching and section of steel.
The addition of alloying elements in steel decreases the critical cooling rate.Thus the
Hardenability of alloy steels is more than that of the carbon steels.

JOMINY END QUENCH TEST

The most simple and convenient method of determining the Hardenability is the Jominy End
Quench Test.
The Jominy test involves heating a standard test piece of diameter 25 mm and length 100 mm to
the austenite state, fixing it to a frame in a vertical position and then quenching the lower end by
means of a jet of water.
The mode of quenching results in different rate of cooling along the length of the test piece.
Surface hardness (in Rockwell C, HRc) is measured along the length of specimen. A curve is
made with distance from quenched end on X axis and HRc on Y axis. This plot is known as
Jominy curve or hardenability curve.

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SURFACE HARDENING METHODS

A number of engineering applications require different properties for surface and interior of
components. For example, gears, cams, rolls etc. require a very hard and wear resistant surface
(case) and a ductile and tough interior (core). Chemical storage tanks require a surface of very
high corrosion resistance. Such combination of properties is obtained by various surface
treatments.

The various surface hardening treatments can be classified into two types:
No change in surface composition Methods
(i) Flame hardening (ii) Induction hardening (iii) Laser hardening (iv) Electron beam hardening
Change in surface composition methods
(i)Carburizing (ii) Nitriding

NO CHANGE IN SURFACE COMPOSITION METHODS

1. FLAME HARDENING
In flame hardening an ordinary oxy acetylene torch is used to heat the part at the regions to be
hardened. Flame is slightly oxidizing in nature. The flame is adjusted to achieve a temperature of
about 8500C. The torch is moved to heat the part uniformly. It is then quenched by the jet of
water from nozzle. Carbon content should be between 0.3-0.6 percent. Tempering is done after
flame hardening.

ADVANTAGES
1. Rapid and efficient method.
2. Small regions (zones) can be hardened. Hence low distortions.
3. Also suitable for large components that cannot be fitted in furnace and for heavy components
which cannot be transported.

DISADVANTAGES
1. Case depth is difficult to control. Hence thin cases are difficult.
2. Low carbon steel cannot be hardened.

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APPLICATIONS
Gear teeth, cylindrical pins, lathe beds, cam surface, engine push rods, pulleys and sprocket
teeth.

2. INDUCTION HARDENING
Induction hardening can produce a hard and wear resistant surface with a soft core. Job to be
hardened is placed within an induction coil of several turns of copper wire. A high frequency
current is passed. This sets up an induced alternating current which heats the job surface to a
temperature of 750-8000C. Heated surface is quickly quenched by water

ADVANTAGES
1. Very fast process.
2. Irregular shapes can be hardened easily.
3. Case depth can be controlled effectively by varying frequency, current and time.
4. Unskilled operators can be employed
5. Environment is clean.

DISADVANTAGES
1. Medium carbon steel containing 0.35 to0.60% can be hardened. Low carbon and low nitrogen
steels cannot be used.
2. Hardness depends on carbon content. If carbon content is low, high hardness is possible only
in expensive high alloy steels.

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APPLICATIONS
Cams, gear teeth, shaft splines, bearing surfaces, pump shafts, piston rods, chain links etc.

3. LASER HARDENING
It is a variant of flame hardening. A phosphate coating is applied over the steel surface to
facilitate laser absorption. Selected areas are exposed to laser energy. The surface gets heated to
900-14000C. Heat can be controlled by varying power of laser. Parts are then self -quenched
(transferring heat to cooler surface) and tempered. Case depth is usually 0.1 to 1.5 mm.

ADVANTAGES
1. Process is precise.
2. Useful for ferrous materials containing more than 0.2% carbon. Steels and cast irons can be
hardened.
3. Minimum distortion.
4. Core remains soft.
5. Process is environmentally clean. Work piece need not be cleaned.

APPLICATIONS
Process is primarily used in automobile industry for axle shaft housings, power steering gear
housings etc.

4. ELECTRON BEAM HARDENING

It is similar to laser beam hardening. Heat source is a high energy electron beam. Beam is
focused by electromagnetic coils. Quenching is through self quench process (heat transfer to
external cooler surroundings). Case depth is in the range of 0.1 to 1.5 mm.

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ADVANTAGES
1. Surface can be hardened precisely in terms of depth and location.
2. Extremely low energy consumption.
3. Very low distortion

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CHANGE IN SURFACE COMPOSITION METHODS

1. CARBURIZING

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2. NITRIDING

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WHAT IS MEAN BY SPHERODISING

SPHEROIDIZING

 It is used to improve machinability and ductility of hyper eutectoid steel.

 Steel is heated to about 300C below A1 line. It is held at this temperature for sufficient
time and then cooled very slowly in the furnace.
 A structure of spheroids of cementite in ferrite matrix is obtained. This is the softest state
of hyper eutectoid steels.

TTT DIAGRAM
 TTT diagram is a plot of temperature versus the logarithm of time for a steel alloy of
definite composition.
 It is also called isothermal transformation diagram.
 The TTT diagrams are for the isothermal (constant T) transformations (material is cooled
quickly to a given temperature before the transformation occurs, and then keep it at that
temperature).
 It shows what structures can be expected after various rates of cooling.
 It graphically describes the cooling rate required for the transformation of austenite to
pearlite, bainite or martensite.

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CCT DIAGRAM
Usually materials are cooled continuously, thus Continuous Cooling Transformation diagrams
are appropriate than TTT diagrams
For continuous cooling, the time required for a reaction to begin and end is delayed, thus the
isothermal curves are shifted to longer times and lower temperatures.
Main difference between TTT and CCT diagrams: no space for bainite in CCT diagram as
continuous cooling always results in formation of pearlite

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