National Institute of Advanced Manufacturing Technology

(Formerly National Institute of Foundry and Forge Technology)

(Deemed to be University under distinct category under MoE, Government of India)
Ranchi- 834 003, Jharkhand India

Unit 3-Metallic Materials

Metals and alloys, ferrous materials- introduction to Iron -carbon Diagram, Steel and their Heat treatment,
properties and applications. Different types of heat treatment processes. Non-ferrous alloys: Copper based alloys,
Al based alloys, other important nonferrous alloys, properties and applications.

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1. Metals- alloys and ferrous materials

1.1 Alloys

An alloy is a material composed of a metallic base, usually the large majority component, and additional metal or
non-metal components that are added as property modifiers. Alloys are manufactured and carefully tuned by
experiment to deliver desirable properties that are not present in the primary material. Many alloys are made
purely of metals, but non-metal additions such as Silicon, Sulfur, Carbon, Nitrogen, and other light elements are
commonly used as property adjusters.

(a) Processing of alloys

Alloys are made by smelting and blending the base metal and additional elements (metals and/or non-metals) and
allowing them to cool. The admixing is often performed in the melt, but many non-metallic additives can be
worked in after initial solidification, by various methods. Two primary types of alloys are used; substitutional and
interstitial alloys.

 In substitutional alloys, like brass and bronze, the atoms of all of the alloying elements are similar in size.
The atoms of the alloying elements substitute for the same sites the atoms of the base material would occupy
in its lattice structure. This lends distributed property adjustments to the lattice that are intrinsic to the metals
involved. In most cases the substitution disrupts and stresses the lattice, reducing planar slip potential by
blocking.
 In interstitial alloys such as steel, the atoms of the alloying elements (Carbon, Silicon, Nitrogen) are smaller
and fit in between the atoms of the base metal. This placement also acts to disrupt slippage and fracture.
However, some non-metallic elements such as Silicon act as crystal growth triggers, altering the typical
crystal size to add strength and resilience as more and smaller crystals deliver a tougher material.

(b) Influence of alloying elements

 Carbon (C): The most important constituent of steel. It raises tensile strength, hardness, and resistance to
wear and abrasion. It lowers ductility, toughness and machinability.
 Chromium (CR): Increases tensile strength, hardness, hardenability, toughness, resistance to wear and
abrasion, resistance to corrosion, and scaling at elevated temperatures.
 Cobalt (CO): Increases strength and hardness and permits higher quenching temperatures and increases the
red hardness of high speed steel. It also intensifies the individual effects of other major elements in more
complex steels.
 Columbium (CB): Used as stabilizing elements in stainless steels. Each has a high affinity for carbon and
forms carbides, which are uniformly dispersed throughout the steel. Thus, localized precipitation of carbides
at grain boundaries is prevented.
 Copper (CU): In significant amounts is detrimental to hot-working steels. Copper negatively affects forge
welding, but does not seriously affect arc or oxyacetylene welding. Copper can be detrimental to surface
quality. Copper is beneficial to atmospheric corrosion resistance when present in amounts exceeding 0.20%.
Weathering steels are sold having greater than 0.20% Copper.

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  Manganese (MN): A deoxidizer and degasifier and reacts with sulfur to improve forgeability. It increases
tensile strength, hardness, hardenability and resistance to wear. It decreases tendency toward scaling and
distortion. It increases the rate of carbon-penetration in carburizing.
 Molybdenum (MO): Increases strength, hardness, hardenability, and toughness, as well as creep resistance
and strength at elevated temperatures. It improves machinability and resistance to corrosion and it intensifies
the effects of other alloying elements. In hot-work steels and high speed steels, it increases red-hardness
properties.
 Nickel (NI): Increases strength and hardness without sacrificing ductility and toughness. It also increases
resistance to corrosion and scaling at elevated temperatures when introduced in suitable quantities in high-
chromium (stainless) steels.
 Phosphorus (P): Increases strength and hardness and improves machinability. However, it adds marked
brittleness or cold-shortness to steel.
 Silicon (SI): A deoxidizer and degasifier. It increases tensile and yield strength, hardness, forgeability and
magnetic permeability.
 Sulfur (S): Improves machinability in free-cutting steels, but without sufficient manganese it produces
brittleness at red heat. It decreases weldability, impact toughness and ductility.
 Tantalum (TA): Used as stabilizing elements in stainless steels. Each has a high affinity for carbon and forms
carbides, which are uniformly dispersed throughout the steel. Thus, localized precipitation of carbides at
grain boundaries is prevented.
 Titanium (TI): Used as stabilizing elements in stainless steels. Each has a high affinity for carbon and forms
carbides, which are uniformly dispersed throughout the steel. Thus, localized precipitation of carbides at
grain boundaries is prevented.
 Tungsten (W): Increases strength, wear resistance, hardness and toughness. Tungsten steels have superior
hot-working and greater cutting efficiency at elevated temperatures.
 Vanadium (V): Increases strength, hardness, wear resistance and resistance to shock impact. It retards grain
growth, permitting higher quenching temperatures. It also enhances the red-hardness properties of high-
speed metal cutting tools.

(c) Designation systems

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 1.2 Ferrous metals

A metal with the descriptor “ferrous” means that it has iron in its composition. When the term ferrous metal is
used, it also usually implies that iron is a large percentage of the elemental composition. If it’s not the most
abundant element, it would probably be the second or third most prolific. If a metal only contains trace amounts
of iron, as many metals do, then that small amount is not considered enough to declare the metal ferrous.

(a) Steel

Based on the chemical compositions, Steel can be categorized into four (04) basic types:
 Carbon Steel
 Stainless Steel
 Alloy Steel
 Tool Steel

(i) Carbon Steel

Carbon steel is the most utilized steel in the industries and accounts for more than 90% of the total steel production.
Based on the carbon content, Carbon steels are further classified into three groups.
 Low Carbon Steel/Mild Steel
 Medium Carbon Steel
 High Carbon steel

Sl No. Type of carbon steel %C

1. Low carbon steel/ Mild steel Up to 0.25%
2. Medium carbon steel 0.25% to 0.60%
3. High carbon steel 0.60% to 1.5%

(ii) Stainless Steel

Stainless steel is an alloy steel that contains 10.5% Chromium (Minimum). Stainless steel exhibits corrosion
resistance properties, due to the formation of a very thin layer of Cr2O3 on its surface. This layer is also known as
the passive layer. Increasing the amount of Chromium will further increase the corrosion resistance of the material.
In addition to Chromium, Nickel and Molybdenum are also added to impart desired (or improved) properties.
Stainless steel also contains varying amounts of Carbon, Silicon, and Manganese.
Stainless steels are further classified as;
 Ferritic Stainless Steels
 Martensitic Stainless Steels
 Austenitic Stainless Steels
 Duplex Stainless Steels
 Precipitation-Hardening (PH) Stainless Steels

Ferritic Stainless Steel: Ferritic steels consist of Iron-Chromium alloys with body-centered cubic crystal
structures (BCC). These are generally magnetic and cannot be hardened by heat treatment but can be strengthened
by cold working.
Austenitic Stainless Steel: Austenitic steels are most corrosion-resistant. It is non-magnetic and non-heat-
treatable. Generally, austenitic steels are highly weldable.
Martensitic Stainless Steel: Martensitic stainless steels are extremely strong and tough but not as corrosion-
resistant as the other two classes. These steels are highly machinable, magnetic, and heat-treatable.
Duplex Stainless Steels: Duplex stainless steel consists of a two-phase microstructure consisting of grains of
ferritic and austenitic stainless steel (i.e Ferrite + Austenite). Duplex steels are about twice as strong as austenitic
or ferritic stainless steels.
Precipitation-Hardening (PH) Stainless Steels: Precipitation-Hardening (PH) Stainless Steels possess Ultra
high strength due to precipitation hardening.

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 (iii) Alloy Steel

In alloy steel, varying proportions of alloying elements are used, to achieve desired (improved) properties such as
weldability, ductility, machinability, strength, hardenability and corrosion resistance, etc. Some of the most used
alloying elements and their effects are as follows;
Manganese – Increases strength and hardness, decreases ductility and weldability
Silicon – Used as deoxidizers used in the steel making process
Phosphorus – Increases strength and hardness and decreases ductility and notch impact toughness of steel.
Sulfur –Decreases ductility, notch impact toughness, and weldability. Found in the form of sulfide inclusions.
Copper – improved corrosion resistance
Nickel – Increases hardenability and Impact strength of steels.
Molybdenum – Increases hardenability and enhances the creep resistance of low-alloy steels.

(iv) Tool Steel

Tool steels have high carbon content (0.5% to 1.5%). Higher carbon content provides higher hardness and strength.
These steels are mostly used to make tools and dies. Tool steel contains various amounts of tungsten, cobalt,
molybdenum, and vanadium to increase the heat and wear resistance, and durability of the metal. This makes tool
steels very ideal for use as cutting and drilling tools.

1.3 Allotropy

Allotropy, the existence of a chemical element in two or more forms, which may differ in the arrangement
of atoms in crystalline solids or in the occurrence of molecules that contain different numbers of atoms. The
existence of different crystalline forms of an element is the same phenomenon that in the case of compounds is
called polymorphism. Carbon Allotropes: Diamond, Graphite and Fullerene

2. Introduction to Iron -carbon Diagram

2.1 Cooling curves

(a) Cooling curve of pure metal

The melting temperature of any pure material (a one-component system) at constant pressure is a single unique
temperature. The liquid and solid phases exist together in equilibrium only at this temperature. When cooled, the
temperature of the molten material will steadily decrease until the melting point is reached. At this point the
material will start to crystallise, leading to the evolution of latent heat at the solid liquid interface, maintaining a
constant temperature across the material. Once solidification is complete, steady cooling resumes. The arrest in
cooling during solidification allows the melting point of the material to be identified on a time-temperature curve
as shown below.

A pure metal solidifies at a constant temperature equal

to its freezing point.

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 (b) Cooling curve of alloys

Most systems consisting of two or more components exhibit a temperature range over which the solid and liquid
phases are in equilibrium. Instead of a single melting temperature, the system now has two different temperatures,
the liquidus temperature and the solidus temperature which are needed to describe the change from liquid to solid.
The liquidus temperature is the temperature above which the system is entirely liquid, and the solidus is the
temperature below which the system is completely solid. Between these two points the liquid and solid phases are
in equilibrium. Figure below shows the cooling curve for alloy consisted from two components.
The result of running a series of cooling curves for various combinations or alloys between metals A and B, varying
in composition from 100 percent A & 0 percent B to 0 percent A & 100 percent B is shown in the diagram at LHS
in the figure given below.

It may be noted that each cooling curve is a separate experiment starting from zero time. The cooling curves for
the pure metals A and B show only a horizontal line because the beginning and end of solidification take place at
a constant temperature. However, since intermediate compositions form a solid solution, these cooling curves
shows two breaks or change in slope. For an alloy containing 80A and 20B, the first break is at temperature T 1,

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 which indicates the beginning of solidification, and the lower break at T 2 indicates the end of solidification. All
intermediate alloy compositions will show a similar type of cooling curve.

It is now possible to construct actual phase diagram by plotting temperature vs. composition. The appropriate
points are taken from the series of cooling curves and plotted on the new diagram as shown by the diagram at
RHS in the above figure. This figure is known as Isomorphous phase diagram.

Note:
The Isomorphous phase diagram is used when the
two alloying elements are miscible at solid state as
well as liquid state at any composition.
Some key Factors to occur such alloy are
 Same Crystal structure
 Valency
 Similar atomic radius
 Similar electronegativity
The diagram is very useful in finding the amount,
phase and composition of solutions.

Since the left axis represents the pure metal A, T A is plotted along this line. Similarly, TB is plotted. Since all
intermediate compositions are percentages of A and B, for simplicity the percent sign is omitted. A vertical line
representing the alloy 80A-20B is drawn, and T1 and T2 from cooling curve are plotted along this line. The same
procedure is used for the other compositions.

The phase diagram consists of two points, two lines, and three areas. The two points T A and TB represent the
freezing points of the two pure metals. The upper line, obtained by connecting the points showing the beginning
of solidification, is called the liquidus; and the lower line, determined by connecting the points showing the end
of solidification, is called the solidus line. The area above the liquidus line is a single-phase region, and any alloy
in that region will consist of a homogeneous liquid solution. Similarly, the area below the solidus line is a single-
phase region, and any alloy in this region will consist of a homogeneous solid solution. Upper case letters A and
B are used to represent the pure metals. Between the liquidus and solidus lines there exists a two-phase region.
Any alloy in this region will consist of a mixture of a liquid solution and a solid solution.

(c) Cooling curve of pure iron

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  Iron is relatively soft and ductile.
 It shows the property of allotropy (exist in
more than one crystal structure).
 Its melting point is 1539 ºC.
 At normal room temperature iron has BCC
structure and is called α-Fe or α-ferrite.
 Solubility of carbon in α-Fe is very low
(0.008% at room temperature and 0.025% at
its stable temperature.
 At 910 ºC it changes to FCC structure and is
called γ-Fe or austenite.
 Maximum solubility of carbon in γ-Fe is
2.04% at 1148 ºC.
 At 1401 ºC it again changes to BCC
structure and is called δ-Fe or δ-ferrite
 Maximum solubility of carbon in δ-Fe is 0.1
% at 1493 ºC
 At 768 ºC magnetic property of Fe
disappears and it becomes nonmagnetic
 Critical temperature of pure iron are 1401
ºC, 910 ºC and 768 ºC (curie point)

2.2 Gibbs Phase rule

The phase rule describes the possible number of degrees of freedom in an enclosed system at equilibrium, in terms
of the number of separate phases and the number of chemical constituents in the system. It was deduced by J.W
Gibbs in the 1870s. Today, the phase rule is popularly known as the Gibbs phase rule all over the world. Here, in
the article, we will be discussing the derivation of the phase rule.
Gibbs Phase Rule: Gibbs phase rule states that if the equilibrium in a heterogeneous system is not affected by
gravity or by electrical and magnetic forces, the number of degrees of freedom (F) is given by the equation
F=C-P+2
where, C is the number of chemical components,
P is the number of phases.
Basically, it describes the mathematical relationship for determining the stability of phases present in the material
at equilibrium conditions.

2.3 Iron-carbon (Fe3-C) diagram: Critical points in Fe–Fe3C equilibrium diagrams

The following phases are involved in the transformation, occurring with iron-carbon alloys:

 L - Liquid solution of carbon in iron;

 δ-ferrite – Solid solution of carbon in iron. Maximum concentration of carbon in δ-ferrite is 0.09% at 2719
ºF (1493ºC) – temperature of the peritectic transformation. The crystal structure of δ-ferrite is BCC (cubic
body centered).
 Austenite – interstitial solid solution of carbon in γ-iron. Austenite has FCC (cubic face centered) crystal
structure, permitting high solubility of carbon – up to 2.06% at 2097 ºF (1147 ºC). Austenite does not exist
below 1333 ºF (723ºC) and maximum carbon concentration at this temperature is 0.83%.
 α-ferrite – solid solution of carbon in α-iron. α-ferrite has BCC crystal structure and low solubility of carbon
– up to 0.025% at 1333 ºF (723ºC). α-ferrite exists at room temperature.
 Cementite – iron carbide, intermetallic compound, having fixed composition Fe3C.

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 Cementite is a hard and brittle substance, influencing on the properties of steels and cast irons.
The following phase transformations occur with iron-carbon alloys:

Alloys, containing up to 0.51% of carbon, start solidification with formation of crystals of δ-ferrite. Carbon content
in δ-ferrite increases up to 0.09% in course solidification, and at 2719 ºF (1493ºC) remaining liquid phase and δ-
ferrite perform peritectic transformation, resulting in formation of austenite.
Alloys, containing carbon more than 0.51%, but less than 2.06%, form primary austenite crystals in the beginning
of solidification and when the temperature reaches the curve ACM primary cementite stars to form.

Iron-carbon alloys, containing up to 2.06% of carbon, are called steels.

Alloys, containing from 2.06 to 6.67% of carbon, experience eutectic transformation at 2097 ºF (1147 ºC). The
eutectic concentration of carbon is 4.3%.
In practice only hypoeutectic alloys are used. These alloys (carbon content from 2.06% to 4.3%) are called cast
irons. When temperature of an alloy from this range reaches 2097 ºF (1147 ºC), it contains primary austenite
crystals and some amount of the liquid phase. The latter decomposes by eutectic mechanism to a fine mixture of
austenite and cementite, called ledeburite.
All iron-carbon alloys (steels and cast irons) experience eutectoid transformation at 1333 ºF (723ºC). The eutectoid
concentration of carbon is 0.83%.
When the temperature of an alloy reaches 1333 ºF (733ºC), austenite transforms to pearlite (fine ferrite-cementite
structure, forming as a result of decomposition of austenite at slow cooling conditions).

Critical temperatures:
 Upper critical temperature (point) A3 is the temperature, below which ferrite starts to form as a result of
ejection from austenite in the hypoeutectoid alloys.
 Upper critical temperature (point) ACM is the temperature, below which cementite starts to form as a result
of ejection from austenite in the hypereutectoid alloys.
 Lower critical temperature (point) A1 is the temperature of the austenite-to-pearlite eutectoid transformation.
Below this temperature austenite does not exist.
 Magnetic transformation temperature A2 is the temperature below which α-ferrite is ferromagnetic.

Phase compositions of the iron-carbon alloys at room temperature:

 Hypoeutectoid steels (carbon content from 0 to 0.83%) consist of primary (proeutectoid) ferrite (according
to the curve A3) and pearlite.
 Eutectoid steel (carbon content 0.83%) entirely consists of pearlite.
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  Hypereutectoid steels (carbon content from 0.83 to 2.06%) consist of primary (proeutectoid) cementite
(according to the curve ACM) and pearlite.
 Cast irons (carbon content from 2.06% to 4.3%) consist of proeutectoid cementite C 2 ejected from austenite
according to the curve ACM , pearlite and transformed ledeburite (ledeburite in which austenite transformed
to pearlite).

3. Steel and their Heat treatment

3.1 Time-Temperature-Transformation (TTT ) Diagram

Time-Temperature-Transformation (TTT) diagram or Isothermal transformation diagram or S-curve refers to only

one steel of a particular composition at a time, which applies to all carbon steels. This diagram is also called as C-
curve isothermal (decomposition of austenite) diagram and Bain’s curve. The effect of time-temperature on the
microstructure changes of steel can be shown by the TTT diagram. These diagrams are extensively used in the
assessment of the decomposition of austenite in heat-treatable steels. Further, iron-carbon phase diagram does not
show time as a variable and hence the effects of different cooling rates on the structures of steels are not revealed.

Fig. TTT diagram of eutectoid steel (i.e. steel containing 0.8% C)

Austenite is stable above eutectoid temperature 727 °C. When steel is cooled to a temperature below this eutectoid
temperature, austenite is transformed into its transformation product. TTT diagram relates the transformation of
austenite to time and temperature conditions. Thus, the TTT diagram indicates transformation products according
to temperature and also the time required for complete transformation.
Curve 1 is transformation begin curve while curve 2 is the transformation end curve. The region to the left of
curve 1 corresponds to austenite (A’). The region to the right of curve 2 represents the complete transformation
of austenite (F+C). The interval between these two curves indicates partial decomposition of austenite into ferrite
and Cementite (A’+F+C)

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 Fig. Detailed TTT diagram of eutectoid steel (i.e., steel containing 0.8% C)

Close to the eutectoid temperature, the undercooling is low so that the driving force for the transformation is small.
However, as the undercooling increases transformation accelerates until the maximum rate is obtained at the
“nose” of the curve. Below this temperature the driving force for transformation continues to increase but the
reaction is now impeded by slow diffusion. This is why TTT curve takes on a “C” shape with most rapid overall
transformation at some intermediate temperature.
Pearlitic transformation is reconstructive. At a given temperature (say T 1) the transformation starts after an
incubation period (t2, at T1). Locus of t2 for different for different temperature is called transformation start line.
After 50% transformation locus of that time (t3 at T1) for different temperatures is called 50% transformation line.
While transformation completes that time (t4 at T1) is called transformation finish, locus of that is called
transformation finish line. Therefore, TTT diagram consists of different lines of which 1%, 50% and 99%
transformation lines are shown in the diagram. At high temperature while underlooling is low form coarse pearlite.
At the nose temperature fine pearlite and upper bainite form simultaneously though the mechanisms of their
formation are entirely different.

On cooling of metastable austenite 1% martensite forms at about 230 °C. The transformation is athermal in nature.
i.e., amount of transformation is time independent (characteristic amount of transformation completes in a very
short time) but function of temperature alone. This temperature is called the martensite start temperature or MS.
Below MS while metastable austenite is quenched at different temperature amount of martensite increases with
decreasing temperature and does not change with time. The temperature at which 99% martensite forms is called
martensite finish temperature or MF. Hardness values are plotted on right Y-axis. Therefore, a rough idea about
mechanical properties can be guessed about the phase mix.

3.2 Continuous Cooling Transformation (CCT) Diagrams

Heat-treating operations are not carried out using isothermal process, but using continuous cooling. As a result,
the TTT curves representing the transformation of austenite are not strictly applicable to heat-treating operations.
The diagrams provide an estimate, but do not provide accurate microstructure information. Because of this
limitation, Continuous Cooling Transformation (CCT) diagrams were developed to overcome the limitations of
TTT curves.
The primary difference between TTT diagrams and CCT diagrams is that TTT diagrams examine the progress of
transformation as a function of time, at a fixed temperature. CCT diagrams examine the progress of transformation
as a function of changing temperature. In general, in CCT diagrams, the transformations of austenite are shifted
to lower temperatures and longer times. The CCT diagrams allow the prediction of microstructure and hardness,
which is not possible using a TTT curve.

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 Fig. CCT curve

 CCT diagram depends on composition of steel, nature of cooling, austenite grain size, extent of austenite
homogenising, as well as austenitising temperature and time.
 Similar to TTT diagrams there are different regions for different transformation (i.e., cementite/ferrite,
pearlite, bainite and martensite). There is transformation start and transformation finish line. However,
depending on factors mentioned earlier some of the transformation may be absent or some transformation
may be incomplete.
 In general for ferrite, pearlite and bainite transformation start and finish temperature moves towards lower
temperature and transformation time towards higher timing in comparison to isothermal transformation.
Transformation curve moves down and right.
 The bainite reaction can be sufficiently retarded such that transformation takes shelter completely under
pearlitic transformation in case of eutectoid plain carbon steel and therefore bainite region vanishes.
However, in other steel it may be partially sheltered. Therefore, bainitic region observed in non-eutectoid
plain carbon steel or alloy steels.
 C-curves nose move to lower temperature and longer time. So actual critical cooling rate required to avoid
diffusional transformation during continuous cooling is less than as prescribed by TTT diagram. Actual
hardenability is higher than that predicted by TTT.
 MS temperature is unaffected by the conventional cooling rate; however, it can be lowered at lower cooling
rate if cooling curves such that austenite enriches with carbon due to bainite or ferrite formation (in
hypoeutectoid steel). On the other, MS can go up for lower cooling rate such that austenite become lean in
carbon due to carbide separation (in hypereutectoid steel).
 Large variety of microstructure like ferrite/cementite/carbide +pearlite+bainite+martensite can be obtained
in suitable cooling rate. It is not feasible or limited in case of isothermal transformation.

3.3 Heat treatment of steel

It is defined as an operation involving the heating and cooling of a metal or an alloy in the solid-state to obtain
certain desirable properties without change composition. The process of heat treatment is carried out to change
the grain size, to modify the structure of the material, and to relieve the stresses set up the material after hot or
cold working.

 Process of controlled heating and cooling of metals

 Alter their physical and mechanical properties
 Without changing the product shape
 Sometimes takes place inadvertently due to manufacturing processes that either heat or cool the metal such
as welding or forming.

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 Heat treatment done for one of the following objectives:
 Hardening
 Softening
 Property modification.

Types of heat treatment processes

Types of heat treatment process

(i) Annealing

(a) Full Annealing

 The steel is heated above A3 (for hypo-eutectoid steels) and above A1 (for hyper-eutectoid steels) →(hold)
→then the steel is furnace cooled to obtain Coarse Pearlite.
 Coarse Pearlite has ↓ Hardness, ↑ Ductility.
 Not above Acm to avoid a continuous network of proeutectoid cementite along grain boundaries and restrict
for crack propagation

Fig. Heat treatment processes

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 (b) Recrystallization annealing

 It is also called intermediate annealing.


 Heat below A1 → Sufficient time → Recrystallization
 Cold worked strained grains converts to new stress-free, equal-axial grains.
 The lowest temperature of recrystallization of general metal is:
Trecystalization=0.4 Tmelting

(c) Stress-relief annealing

 The main sources of having internal stress in components are differential cooling, martensite formation,
machining or cold working and welding.
 Large castings or welded structures tend to possess internal stresses mainly caused during their
manufacturing and uneven cooling.
 No phase transformation takes place during stress relief annealing.
 This is also called recovery process: Heating below A1.

(d) Spheroidization annealing

 Heat below A1 and holding.

 Cementite plates → Cementite spheroids → ↑ Ductility
 Used in high carbon steel requiring extensive machining prior to final hardening and tempering.
 Low carbon steel is usually not spheroidized as this causes it to become soft and gummy.
 Medium-carbon steels are sometimes spheroidization annealed to obtain maximum ductility.
 It is important to check that the steel is kept too long at the spheroidized-annealing temperature, the cementite
particles will coalesce and become elongated thus reducing machinability.

(e) Diffusion annealing

 This process also known as homogenizing annealing, is employed to remove any structural non-uniformity.
 Dendrites, columnar grains and chemical inhomogeneities are generally observed in the case of ingots, heavy
plain carbon steel casting, and high alloy steel castings. These defects promote brittleness and reduce
ductility and toughness of steel.
 In diffusion annealing treatment, steel is heated sufficiently above A3 (say, 1000-1200°C), and is held at this
temperature for prolonged periods, usually 10-20 hours, followed by slow cooling.
 Segregated zones are eliminated and a chemically homogeneous coarse grain steel is obtained by this
treatment as a result of diffusion.

(f) Partial annealing

 Partial annealing is also referred to as inter-critical annealing or incomplete annealing.

 In this process, steel is heated between the A1 and the A3 or Acm followed by slow cooling. Applied on
hypereutectoid steels.
 Resultant microstructure consists of fine pearlite and cementite due to heating at about 10 to 30°C above A 1
for hypereutectoid steels.
 As low temperatures are involved in this process, so it is cost effective than full annealing

(g) Process annealing

 Steel heated below the lower critical temperature Holding for sufficient time  cooled.
 Since it is a subcritical annealing, cooling rate is of little importance.
 The purpose of this treatment is to reduce hardness and to increase ductility of cold-worked steel so that
further working may be carried out easily.
 It is an Intermediate operation.
 Less expensive than Recrystallization annealing.

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 Fig. Heat treatment processes

(ii) Normalizing

In hypo-eutectoid steels normalizing is done ⁓80 ºC above A3.

In hyper-eutectoid steels normalizing done above Acm.
The purpose is to refine grain structure prior to hardening, harden the steel slightly and reduce segregation in
casting or forgings.

(iii) Hardening

Heat above A3 | Acm → Austenization → Quench (higher than critical cooling rate)

The hardening process consists of four steps:

Step 1- 1st step- Heating above A3 temperature for hypoeutectoid steels and above A1 temperature for
hypereutectoid steels (⁓ 500 ºC).

Step 2- 2nd step- holding the steel components for sufficient socking time for homogeneous austenization.

Step 3- 3rd step- cooling of hot steel components at a rate just exceeding the critical cooling rate of the steel to
room temperature or below room temperature.

Step 4- 4th step- tempering of the martensite to achieve the desired hardness.

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 Fig. Hardening process

 Difference between Annealing and normalizing

Annealing Normalizing
Less hardness, tensile strength and toughness Slightly more hardness, tensile strength and toughness
Pearlite is coarse. Pearlite is fine and usually appears unresolved with
optical microscope
Heated metal is furnaced cooled. Heated metal is air cooled.

(iv) Tempering

 The hardened steel is not readily suitable for engineering applications. It possesses following three
drawbacks:
- Martensite obtained after hardening is extremely brittle and will result in failure of engineering
components by cracking.
- Formation of martensite from austenite by quenching produces high internal stresses in the hardened
steel.
 Structures obtained after hardening consists of martensite and retained austenite, both these phases are
metastable and will change to stable phases with time which subsequently results in change in dimensions
and properties of the steel in service.
 Tempering helps in reduce these problems. Tempering is the process of heating the hardened steel to a
temperature maximum up to lower critical temperature (A1), soaking at this temperature, and then cooling,
normally very slowly.

(v) Quenching and cooling rate in steel

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 Fig. Quenching and cooling rate in steel

a) Pearlite
It is a layered metallic structure of two-phases, which compose of alternating layers of ferrite (87.5 wt%)
and cementite (12.5 wt%) that occurs in some steels and cast irons. It is named for its resemblance to mother
of pearl.
b) Martensite
It is a very hard metastable structure with a body-centered tetragonal (BCT) crystal structure. Martensite is
formed in steels when the cooling rate from austenite is at such a high rate that carbon atoms do not have
time to diffuse out of the crystal structure in large enough quantities to form cementite (Fe3C).
c) Bainite
It is a plate-like microstructure that forms in steels from austenite when cooling rates are not rapid enough
to produce martensite but are still fast enough so that carbon does not have enough time to diffuse to form
pearlite. Bainitic steels are generally stronger and harder than pearlitic steels; yet they exhibit a desirable
combination of strength and ductility.

3.4 The Jominy end quench test

 A method to determine hardenability.

 A cylindrical specimen of diameter 25.4 mm and length 100 mm is austenized.
 After austenizing, it is quickly mounted to a fixture and at the lower end it is quenched by jet of water at a
specified flow rate and temperature.
 It causes the cooling rate to be maximum at the bottom end and diminishing along the specimen length.
 After, the specimen is cooled to room temperature, shallow flat of 0.4 mm deep are ground along the
specimen length.
 Rockwell hardness measurement are conducted for first 50 mm along the flat. For the first 12.8 mm, hardness
readings are taken at 1.6 mm intervals and for the remaining 38.4 mm, every 3.2 mm.
 A hardenability curve can be drawn when hardness is plotted in y-axis and the position from the quenched
end is x-axis.
 It can be seen that the quenched end is cooled most rapidly and exhibits the maximum hardness. 100 %
martensite is formed at the quenched end.
 Cooling rate decreases with the distance from the quenched end and hardness also decreases.

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 Fig. The Jominy end quench test
3.5 Case hardening

 Casehardening produces a hard wear resistant surface or case over a strong, tough core. Casehardening is
ideal for parts which require a wear resistant surface and at the same time, must be tough enough internally
to withstand the applied loads.
 The steels best suited to casehardening are the low carbon and low alloy steels. If high carbon steel is
casehardened, the hardness penetrates the core and causes brittleness.
 In casehardening, the surface of the metal is changed chemically by introducing a high carbide or nitride
content. The core is chemically unaffected.

The surface hardening by diffusion involves the chemical modification of a surface. The basic process used is
thermo-chemical because some heat is needed to enhance the diffusion of hardening species into the surface and
subsurface regions of part. The depth of diffusion exhibits time-temperature dependence such that:
Case depth ≈ K √Time

where the diffusivity constant, K, depends on temperature, the chemical composition of the steel, and the
concentration gradient of a given hardening species.

(i) Carburizing

 Carburizing is the most widely used method of surface hardening. Here, the surface layers of a low carbon
steel (<0.25%) is enriched with carbon up to 0.8-1.0%. The source of carbon may be a solid medium, a liquid
or a gas.
 In all cases, the carbon enters the steel at the surface and diffuses into the steel as a function of time at an
elevated temperature. Carburizing is done at 920-950°C. at this temperature the following reaction takes
place.
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 Fe+2CO→Fe(c)+CO2

Types of Carburizing:

 Gas carburizing
 Liquid carburizing
 Pack carburizing

(a) Gas carburizing

 Most widely used method of carburizing.

 It is carried out in retort type, sealed quench type, or continuous pusher type furnaces.
 These furnaces are either gas fired or are heated electrically. Gas carburizing temperature varies from 870°C
to 950°C.
 Gas atmosphere for carburizing is produced from liquid (methanol, isopropanol) or gaseous hydrocarbons
(propane and methane) using endothermic gas generator.
 A mixture of propane or methane with air is cracked in hot retort of an endogas generator to form carrier
gas, whose dew point is adjusted at about +4°C by proper gas/air ratio. The approximate composition of this
gas is 40% N, 40% H, 20% CO, 0.3% CO2, 0.5% CH4, 0.8% water vapor and oxygen in traces.

 The chemical equations are:

C3H8 → 2CH4 + C (cracking of hydrocarbon)
CH4 + Fe → Fe(C) + 2H2
CH4 + CO2 → 2CO + 2H2
2CO + Fe → Fe(C) + CO2

(b) Liquid carburizing

 Also known as salt bath carburizing.

 In this process, carburizing occurs through molten cyanide (CN) in low carbon steel cast pot type furnace
heated by oil or gas. Bath temperature is maintained between 815°C and 900°C.
 The bath surface is covered with graphite or coal to reduce radiation losses and excessive decomposition of
cyanide.
 Different salt mixtures used in this process are named according to their carbon potential activity.
 Besides sodium or potassium cyanide, cyanide, the bath contains contains (i) Sodium and potassium chloride
(ii) Barium chloride which acts as an activator.
 The chemical equations are:
BaCl2+2NaCN  Ba(CN)2+ 2NaCl
Ba(CN)2+Fe  Fe(C) + BaCN2
 Some beneficial nitrogen diffusion may also take place through oxidation of CN to CNO.
 In liquid carburizing, heating time is short and heat transfer is rapid. There is complete uniformity of the
carburized layer in the component.
 This process gives a thin and clean hardened layer of ⁓ 0.08mm thick.

(c) Pack or solid carburizing

 This method of carburizing is also known as solid carburizing.

 In this process, steel components to be heat treated are packed with 80% granular coal and 20% BaCO 3 as
energizer in heat resistant boxes and heated at 930°C in furnace for a specific time which depends on the
case depth required.
 Such a high temperature in furnace helps in absorption of carbon at the outer layer. The following reactions
takes place:
i. Energizer decomposes to give CO gas to the steel surface
BaCO3 → BaO +CO2
CO2 +C → 2CO
ii. Carbon monoxide reacts with the surface of steel:
2CO + Fe → Fe(c) +CO2
iii. Diffusion of carbon into steel
iv. CO2 formed in step (ii) reacts with “C” in the coal
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 CO2 +C ↔ 2CO
 Generally, carburizing time varies from 6 hours to 8 hours, and case depth obtained varies from 1 mm to 2
mm.

Fig. Pack carburizing

(d) Cyaniding and carbonitriding

In cyaniding and carbonitriding processes, the surface layer of steel (with 0.3-0.4%C) is hardened by addition of
both carbon and nitrogen.
In both the cases carbon and nitrogen are produced in liquid salt baths (in cyaniding) or by use of gas atmospheres
(in carbonitriding).
The temperatures used are generally lower than those used in carburizing ⁓750-900°C.
Exposure is for a shorter time, and thinner cases ⁓0.2 mm are made using cyaniding and ⁓0.6 mm with
carbonitriding.

- Cyaniding

 In Cyaniding is done in a liquid bath of NaCN, with the concentration varying between 30 and 97%. Both
carbon and nitrogen enter the steel via the following reactions:
2NaCN + O2 →2NaCNO
2NaCNO + O2 → Na2CO3 +CO + 2N
2CO → CO2 +C
 Carbon and nitrogen so formed in atomic form diffuse into the steel and give thin wear resistant layer of the
carbonitride ε-phase.
 The temperature used for cyaniding is lower than that for carburizing and in the range of 800-870°C. the
time of cyaniding is 0.5-3 hour to produce a case depth of 0.25 mm or less.
 Cyaniding process is not suitable for hardening those parts which are subjected to shock, fatigue and impact
because nitrogen addition has adverse effects on such properties of steels.

- Carbonitriding

 It is a case-hardening process in which a steel is heated in a gaseous atmosphere of such composition that
carbon and nitrogen are absorbed simultaneously.
 This process is also known as dry cyaniding or gas cyaniding. It is the gas carburizing process modified by
the addition of anhydrous ammonia.
 The decomposition of ammonia provides the nitrogen, which enters the steel along with carbon. A typical
gas mixture consists of 15% NH3, CH4, and 80% of neutral carrier gas.
 The temperature used is 750-900°C. With increasing temperature, a greater proportion of carbon enters the
steel.
 The presence of nitrogen in the austenite accounts for the major differences between carbonitriding and
carburizing.

(h) Nitriding

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  Nitriding is carried out in the ferrite region.
 No phase change occurs after nitriding.
 Pure ammonia decomposes to yield nitrogen which enters the steel: The solubility of nitrogen in ferrite is
small. Most of the nitrogen that enters the steel forms hard nitrides (e.g., Fe 3N).
 The chemical equation is:
2NH3 → 2[N]Fe + 3H2
 A typical nitriding steel contains alloying elements of 1%Al, 1.5%Cr and 0.2%Mo. Al, Cr, and Mo form
very hard and wear resistant nitrides.
 The temperature of nitriding is 500-590°C. the time for a case depth of 0.02 mm is about 2 hours.

Fig. Nitriding process

(e) Flame and induction hardening

- Flame hardening

 Flame hardening is the simplest form of surface hardening heat treatment.

 This process consists of heating the large work-piece, such as crank shaft, axle, large gear, cam, bending
roller, or any other complicated cross-section, by an oxy-acetylene, or oxyfuel blow pipe, followed by
spraying of jet of water as coolant.
 After hardening, reheating of the parts is carried out in furnace or oil bath at about 180-200 °C for stress
relieving.
 Normally, case depth up to 3mm can be achieved.

 Four methods are generally use for Flame Hardening

- Stationary (Spot): Torch and work is stationary
- Progressive: Torch moves over a work piece
- Spinning: Torch is stationary while work piece rotates
- Progressive-spinning: Torch moves over a rotating work piece.

Fig. Principle of flame hardening

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 - Induction hardening

 Used to surface harden crank shafts, cam shafts, gears, crank pins and axles.
 In this process, heating of the component is achieved by electromagnetic induction.
 Here, an alternating current of high frequency passes through an induction coil enclosing the steel part to be
heat treated.
 The induced emf heats the steel. the depth up to which the heat penetrates and rises the temperature above
A3 is inversely proportional to the square root of the AC frequency.
 Correspondingly, the hardened depth decreases with increasing frequency in induction hardening, the
heating time is usually a few seconds.
 Immediately after heating water jets are activated to quench the surface. Martensite is formed on the surface
which is hard and possess wear resistant properties.

Fig. Principle of induction hardening

4. Non-ferrous alloys: Copper based alloys

 Copper are essentially commercially pure copper, which ordinarily is very soft and ductile, containing up to
about 0.7% total impurities. These materials are used for their electrical and thermal conductivity, corrosion
resistance, appearance and colour, and ease of working. They have the highest conductivity of the
engineering metals and are very ductile and easy to braze, and generally to weld. Typical applications include
electrical wiring and fittings, busbars, heat exchangers, roofs, wall cladding, tubes for water, air and process
equipment.
 High copper alloys contain small amounts of various alloying elements such as beryllium, chromium,
zirconium, tin, silver, sulphur or iron. These elements modify one or more of the basic properties of copper,
such as strength, creep resistance, machinability or weldability. Most of the uses are similar to those given
above for coppers, but the conditions of application are more extreme.
 Brasses are copper zinc alloys containing up to about 45% zinc, with possibly small additions of lead for
machinability, and tin for strength. Copper zinc alloys are single phase up to about 37% zinc in the wrought
condition. The single phase alloys have excellent ductility, and are often used in the cold worked condition
for better strength. Alloys with more than about 37% zinc are dual phase, and have even higher strength, but
limited ductility at room temperature compared to the single phase alloys. The dual phase brasses are usually
cast or hot worked. Typical uses for brasses are architecture, drawn & spun containers and components,
radiator cores and tanks, electrical terminals, plugs and lamp fittings, locks, door handles, name plates,
plumbers hardware, fasteners, cartridge cases, cylinder liners for pumps.
 Bronzes are alloys of copper with tin, plus at least one of phosphorus, aluminium, silicon, manganese and
nickel. These alloys can achieve high strengths, combined with good corrosion resistance. They are used for
springs and fixtures, metal forming dies, bearings, bushes, terminals, contacts and connectors, architectural
fittings and features. The use of cast bronze for statuary is well known.
 Copper nickel are alloys of copper with nickel, with a small amount of iron and sometimes other minor
alloying additions such as chromium or tin. The alloys have outstanding corrosion resistance in waters, and
are used extensively in sea water applications such as heat exchangers, condensers, pumps and piping
systems, sheathing for boat hulls.
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  Nickel silvers contain 55 – 65% copper alloyed with nickel and zinc, and sometimes an addition of lead to
promote machinability. These alloys get their misleading name from their appearance, which is similar to
pure silver, although they contain no addition of silver. They are used for jewellery and name plates and as
a base for silver plate (EPNS), as springs, fasteners, coins, keys and camera parts.

Table. Classification of wrought copper alloys

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 5. Aluminium-based alloys
Aluminum alloys come in seven different categories, according to their chemical makeup, primary alloying
elements, and physical characteristics. These are:

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 1000 Series (Pure)

2000 Series (Copper)

3000 Series (Manganese)

4000 Series (Silicon)

5000 Series (Magnesium)

6000 Series (Magnesium and Silicon)

7000 Series (Zinc)

Here’s a more in-depth look at each of these alloy series.

1000 Series: Pure aluminum makes up at least 99% of the 1000-series alloys’ composition, with only traces of
other elements. The precise composition and impurity content of the various alloys in the 1000 series is what
differentiates them from one another. These alloys are very thermally conductive, highly ductile, and corrosion-
resistant, and are used in products like chemical tanks, conductive bus bars, and rivets.

2000 Series: The primary alloying element in the 2000 series is copper, which provides higher strength, but the
exact amount of copper and other trace elements vary from one 2000 series alloy to another. Copper alloys can be
machined, heat-treated, and withstand high temperatures. They’re often used in military, aerospace, and other
high-performance applications. For more information on this material, see our guide on Copper.

3000 Series: Manganese improves the metal’s corrosion resistance and formability. 3000 series alloys have
moderate strength but are not heat-treatable. They are used in cookware, automotive parts, and construction
materials, and also work well when welding and anodizing.

4000 Series: Silicon gives this aluminum alloy excellent molten fluidity and minimal shrinkage when it solidifies,
making it a great candidate for casting applications. It has good machinability and corrosion resistance and a
moderate amount of strength. It is usually used for engine blocks and other auto parts that need to disperse heat
efficiently. For more information on this material, see our guide on Silicone.

5000 Series: The main alloying element in the 5000 series is magnesium. These versions of aluminum can be
found in vehicles, pressurized vessels, and bridges. Specifically, aluminum 5052 is a very common choice among
our customers for bent sheet metal parts.

6000 Series: Featuring both magnesium and silicon as the main alloying elements, this series of metals offers
good strength, resistance to atmospheric corrosion, and are machinable. They are commonly used in structural
components for the aerospace, automotive, and construction industries. Aluminum 6061 is one of the most
commoditized materials available, making it a popular low-cost choice for machined components.

7000 Series: This is a heat-treatable alloy with zinc and smaller amounts of copper, magnesium, and other
elements. It has high strength, good toughness, and fatigue and corrosion resistance. These alloys are used in
aircraft and aerospace, as well as in high-performance sporting goods. They can be welded, but care is needed to
avoid cracking.

Table. Chemical Properties of Aluminum Alloys

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Sub: Materials Engineering Sub code: ESME2 Prepared by: Dr. Lokeswar Patnaik