ENGINEERING MATERIALS &

METALLURGY

UNIT I
CONSTITUTION OF ALLOYS AND PHASE
DIAGRAMS
INTRODUCTION

Ø Many metals are capable of having their atoms arranged in different patterns
depending on the temperature. This phenomenon of polymorphism is often
refereed to as allotropy.
Ø Allotropic changes involve volume changes and changes in mechanical
properties.
Ø A ferrous material is one which contains a majority of the allotropic element iron.
Ø They form the vast majority of engineering metallic materials since they are both
comparatively cheap and have high elastic module
Ø The allotropic behavior the ferrous materials could be heat treated to vary the
mechanical properties. Materials, when examined microscopically, may be
observed to be single phase, or to contain more than one phase.
Ø A phase may be defined as a portion of matter which is homogeneous
Ø An unsaturated solution of common salt in water is a single phase.
Ø The amount of salt is increased beyond the saturation limit the system will have
two phases, with a saturated solution of salt in water in equilibrium with excess
solid salt.
Ø The study of phase relationships plays an important role in the understanding of
the properties of materials.

SOLIDIFICATION OF A PURE METAL

In a crystalline material the atoms are vibrating about their lattice points at
any temperature above absolute zero.
The amplitude of vibration increases with temperature.
The temperature at which the thermal vibration is so intense that the bonds
between atoms are broken, melting occurs.
The atoms in the liquid are in a chaotic arrangement and possess both
vibrational and kinetic energy.
When the liquid is cooled, the way in which the liquid solidifies back into
a crystalline solid depends on its constitution.

FREEZING OF IMPURE METALS OR OF ALLOYS

v Temperature A marks the start of solidification and this

temperature would be about 1643K.
v It cannot be pure nickel which is freezing but will be a solid
containing mainly of nickel but carrying some copper. i.e., it will
be a solution of copper in nickel.
v Temperature B marks the end of freezing and will be about 1473K.
v The solid produced will therefore consist mainly of copper but will
carry some nickel,
v It will be a solid solution of nickel in copper.
v An alloy and melt over a range of temperature in which liquid and
solid exist together. This is the paste range of the alloy.
PHASE CHANGE AND ITS SIGNIFICANCE

Ø An alloy is a mixture of two or more metals,(OR)A mixture of metal and a non

metal, with the mixture exhibiting metallic properties.
Ø All commercial alloy systems are prepared mixing two liquid metals together.
Ø They dissolve in one another in all proportions, forming a homogeneous liquid
solution
Ø It is possible to determine the actual phase diagram by plotting temperature vs.
composition.
Ø The appropriate points are taken from the series of cooling curves and plotted on
the new diagram.
Ø For example in Fig, left axis represents the pure metal A and its cooling curve is
plotted. Similarly right axis represents metal B and its cooling curve is also
plotted. All intermediate compositions are presented as percentages of A and B as
shown.
Ø T indicates the beginning of solidification while T indicates the end of
solidification.
Ø The upper line obtained by connecting the points T on all curves is called the
Liquidus; The lower line determined by connecting the points T on all curves is
called solidus.
Ø The area above the liquidus line is a single-phase region, and an alloy in that
region consists of a homogeneous liquid solution.
Ø The area below the solidus line is a single-phase region, and an alloy in this
region consists of a homogenous solid solution.
 Ø These alloys are of industrial importance. The line CED is known as liquidus
since all alloys are liquid above this line, while the line CBD is called the solidus
since all alloys are solid below this line.
Ø The area between the solidus and liquidus represents “MUSHY” metal. Both
liquid and solid phases are present at temperatures and compositions within this
zone.
Ø Let us consider the cooling and solidification of an alloy of composition 40%
copper 60% nickel.
Ø Nickel is considered the solvent since it is present in greater proportion.

BINARY PHASE DIAGRAM OF COPPER 40% — NICKEL 60%

v Above the liquidus line a uniform liquid solution of the two metals exists.
v The 60/40 composition line intersects the liquidus at E and solidus at B
and the corresponding temperatures are ti and t respectively.
v When the temperature falls below 1455° C solidification begins with
nucleation and the growth of dendrites. At temperature ti, dendrites
formed contain about 79% nickel
v At the temperature, t the solid phase separating has the composition of
about 68% nickel and 32% copper while the residual liquid phase contains
only 44% nickel and 56% copper.
v When the temperature falls to t grain growth continues and more and more
metal solidifies around the original dendrites:
v The solidifying layers become progressively richer in copper as the
temperature falls.
v Solidification will be complete when temperature falls to t
v The remaining liquid solidifies at this temperature.
v To determine the composition, a horizontal line is drawn through B. It
intersects the liquidus at F. The liquid solidifying at this temperature will
have composition of about 34% nickel, and 66% copper.

v During the interval of cooling from t3 to room temperature nickel atoms

diffuse slowly from nickel-rich centers towards copper-rich outer zones.
4.4.1 Gibbs Phase rule
v A phase is a physically-distinct, chemically homogeneous and mechanically
separable region of a system.
v The gaseous, the liquid and the solid states of matter form separate phases.
v The gaseous state is always a single phase; liquid solution is also a single phase
while liquid mixture, such as oil and water, form two separate phases, as there is
no mixing at the molecular level.
v A solid solution has the atoms at the atomic level within the until cell and is
therefore a single phase.
v Instead in solid state if different chemical compositions and different crystal
structures are possible, the solid may consist of several phases.

The number of phases present in any alloy depends upon the

number of elements of which the alloy is composed. From
thermo dynamical considerations of equilibrium,

Gibbs derived the following phase rule:

F=C—P+2
Where
F = degree of freedom of system (temperature, pressure, concentration, composition of
phases)
C = number of compounds forming the system (i.e., elements or compounds)
P = number of phases in the alloys (in equilibrium state)
2 = number of external factors (temperature and pressure.)
METALLIC ALLOY SYSTEMS
An alloy is a mixture of two or more metals, or a mixture of metal and a non
metal, with the mixture exhibiting metallic properties.
All commercial alloy systems are prepared mixing two liquid metals together.
They dissolve in one another in all proportions, forming a homogeneous liquid
solution. There are few systems which are either partially or totally insolvable in
one another even in liquid phase. We are not considering those possibilities in this
volume.
Although two metals may be completely soluble in one another in the liquid phase
this does not assure that they will solidify to give a homogeneous solid phase, or
solid solution.
In solid phase the two metals may be:

1. Totally insoluble in one another

2. Totally soluble in one another
3. Partially soluble in one another
4. Forming an inter metallic compound combining with one another

METALS TOTALLY INSOLUBLE IN ONE ANOTHER WHEN SOLIDIFIED

• Let us consider the phase diagram drawn for case of two hypothetical metals, A
and B, which are completely soluble in one another in the liquid state, but are
totally insoluble in one another in the solid state.
• The melting point of pure metal A is marked off as point A on the left-hand
temperature axis.
• Point B on the right-hand axis rep-resents the melting point of pure metal B as
shown in Fig-
• When salt is dissolved in water, the freezing point of water decreases.
• In the same way the freezing point of a liquid metal decreases if the liquid metal
contains some other metal in solution.
• Line AL in Figure indicates the depression of freezing point of pure metal A
containing dissolved metal B. Similarly, line BM is the depression of freezing
point of pure metal B containing dissolved metal A. X percent of B dissolved in
liquid A depresses the freezing point of A by an amount ST.
• The liquid solution begins to solidify at a temperature of A — ST (point S on
curve AL in Figure) but it is crystals of pure A which begin to solidify.
• The two curves AL and BM intersect at point E. (The sections of curves EL and
EM are hypothetical as no liquid can exist at a temperature lower than that of
point E).

• The completed phase diagram for the alloy system of metals A and B.
• Let us consider an alloy containing X per cent of B.
• At a high temperature the alloy exists as a single phase liquid solution.
• On cooling, the liquid freezes at a point denoted by S on curve AE. Crystals of
solid pure A begins to form.
• When A crystallizes, the solution of the composition of the remaining liquid
becomes enriched in metal B, i.e., the freezing of metal A continues, the
temperature and composition of the remaining liquid follow the curve AR toward
point E. Point E is termed the eutectic point. At this temperature fine crystals of
grained mixture of both solid metals, A and B are formed, and this mixture is
termed the eutectic mixture.
• The final structure of the solid alloy containing X percent of B will be composed
of large crystals of pure metal A (primary crystals) and eutectic mixture of A and
B.
• If a liquid alloy containing V percent of metal B is allowed to solidify
solidification will follow a similar pattern, but in this case primary crystals of pure
metal B will solidify first.
• It must be noted that the composition of the eutectic mixture remains constant.
• In the phase diagram line AEB is termed the liquidus and line CED is termed the
Salk
• The alloy is always liquid at all points above the liquidus region
EFFECT OF ALLOY TYPE ON PROPERTIES

Ø In an alloy of two metals which are insoluble in solid state, the structure of solid
alloy is a mixture of two pure metals.
Ø Alloy composition the properties are expected to vary linearly but it is not so in
practice.
Ø This deviation is due to grain size effect. A eutectics finely divided mixture of
two metals.
Ø The dotted lines show the expected property variation, neglecting the grain size
effect.
Ø A fine crystal grained metal tends to be harder and stronger than a coarse grained
sample of the same material.
Ø A fine grain size causes a reduction in electrical and thermal conductivities.
Ø Since the primary crystals which solidify first on either side of the eutectic point
are much larger in size
Ø The deviation from expected behavior is more near eutectic point.
ALLOTROPY AND PHASE CHANGE OF PURE IRON
v Certain elements can exist in more than one crystalline form.
v The various separate forms of an element are called allotropes and the element is
said to exhibit allotropy.
v Carbon exists in two allotropic forms diamond and graphite.
v Iron can exist in two crystal forms, body-centered cubic and face-centered cubic.
v Pure iron is body-centered cubic in structure called α-iron at all temperatures up
to 908°C.
v At high temperatures between 1388°C and the melting point 1535°C also it exists
in b.c.c. form known as δ-iron.
v Between 908°C and 1388°C the structure is face-centered cubic and this form is
termed γ-iron.
v When the temperature reaches 908° C, another phase change occurs from f.c.c.
nonmagnetic γ iron to b.c.c. nonmagnetic α iron.
v Finally, at 768° C, the a-iron becomes magnetic without a charge in lattice
structure. Nonmagnetic a- iron was called fl-iron earlier until X-ray studies
revealed the fact that at 768° C there is no change in lattice structure
v The cooling curve for pure iron showing allotropic changes in shown in Fig

THE COOLING CURVE FOR PURE IRON SHOWING ALLOTROPIC CHANGES

PRESSURE-TEMPERATURE DIAGRAM FOR THE ONE COMPONENT SYSTEM OF IRON

Ø Pure iron is a single component system and there is no composition variable.

Ø The only other variables are temperature and pressure.
Ø Pressure is plotted on the x-axis and temperature on the y-axis as shown in the phase
diagram
Ø In phase diagrams, solid phases are denoted by Greek alphabets
Ø Let us first consider the single phase regions on the diagram such as gas, liquid and
several crystal forms of iron. Applying phase rule for C =1 and P = I, F = 2.
Ø In a single phase region within the limits prescribed by the boundaries of the region both
temperature and pressure can be varied.
Ø When two phases are in equilibrium, P = 2 and C = 1. Hence F = 1 i.e. either temperature
or pressure can be varied independently, but not both.
Ø Two phase equilibrium exists along the phase boundaries.
Ø Three phase equilibrium exists at points called triple points on the phase diagram, where
three phase boundaries meet. Two such points can be seen in Figure
Ø Applying phase rule for C = I and P = 3, F = 0; i.e. neither pressure nor temperature can
be varied arbitrarily.
Ø At only one particular combination of pressure and temperature, three phases will coexist.
If we change the pressure or temperature from the fixed triple-point value, one or two of
the phases will disappear.
Ø The equilibrium crystal form of iron at ambient temperature and pressure is b.c.c. (a). On
heating to908°C, a changes over to the f.c.c. (y) form. On heating to 1388°C, the γ iron
changes over to the b.c.c (α) form. When the pressure is increased, the transition
temperature is lowered,
MICROSTRUCTURE OF IRON AND STEEL (PHASE IN THE FE-C SYSTEM)

There are number of special names which are used to denote the various phases and types
of structure which occur in iron and steel.
Microstructure reveals the arrangement, size and shape of the grains and molecules.
It is observed through microscope of higher magnification.
Let us now see the names of these structures observed and their properties.

FERRITE

v BCC solid solutions and BCC allotropes of iron a and 8 are called ferrites.
v It is stable over the temperature range from —273° to 908°C in iron.
v The solubility of carbon is extremely limited. The maximum solubility is .002%, wt% at
723°C.
v It is soft, ductile and highly magnetic.
v It has low tensile strength and cannot be hardened.
v Its hardness is so low. It’s BHN is from 50—100.

AUSTEITE
v It is an interstitial solid solution of carbon in FCC (essentially y iron).
v It. is stable from 908 to 1388°C.
v The solubility is larger as compared to fer rite. The maximum solubility is 2.11 wt % at
1130°C.
v It is tough and non magnetic.
v It is ductile and denser than ferrite.
v Its BHN is around 200.
CEMENTITE
v It is interstitial compound formed between iron and carbon; it contains 6.7 wt % carbon
and is represented by the formula Fe It has a complex orthorhombic crystal structure.
v This is an extremely hard and brittle constituent.
v It is magnetic below 210°C.

PEARLITE
v It is eutectoid mixture of ferrite and cementite.
v It is formed when austenite decomposes during cooling below critical temperature
723°C.
v It has a fine to coarse lamellar structure consisting of alternate plates of ferrite and
cementite and contains about 87% ferrite.
 MARTENSITE
Ø It is formed when a steel is very rapidly - cooled from the austenite state.
Ø It is a ferrite highly super saturated with dissolved carbon.
Ø It is very hard and brittle.

BAINITE
Ø It is a decomposition product of austenite.
Ø It is formed when austenite decomposes by isothermal transformation
Ø Fast cooling of austenite results in formation of martensite while slow cooling result in
formation of pearlite. Intermediate cooling also results in formation of bainite. —

SORBITE AND TROOSTITE -

When martensite or bainite is heated at some temperature not exceeding 700°C to reduce
brittleness and hardness, these structures are produced.

IRON-CARBON EQUILIBRIUM (PHASE) DIAGRAM

The phase diagram for the iron-carbon system drawn with temperature as ordinate
and percentage of carbon as abscissa.
In this diagram we graphically represent the changes undergone by the iron with
change in the percentage of carbon (by weight) present in it at different
temperatures.
The crystal structure of pure iron at ordinary temperatures is cubic.
This form is known asα-iron.δ-iron is stable at all temperatures up to908°C
On heating further the crystal structure of iron changes to face-centered cubic.
This form is known as γ-iron. γ-iron changes into δ iron when heated through
1388°C. From then till the melting at 1535°C,
This δ -iron is stable. .
Fe-C alloys containing 0 to 1.4% carbon are called steels.
Most steels contain only iron carbide and not graphite.
Since Fe and iron carbide are the components in the Fe — Fe phase diagram,
it can be considered to be a metastable phase diagram.
Let us now consider the different transformation lines in the phase diagram.
The iron-iron carbide phase diagram
Curve ABCD

Ø This represents the solidification process of iron of different composition.

Ø The iron above this curve is in liquid state,
Ø This curve is known as liquidus.
Ø Pure iron starts solidifying at 1535°C (point A).
Ø Iron with 4.3% carbon the solidification temperature starts at 1130° (point C).
Ø The carbon content is about 6.7% the solidification temperature is greater 1535°C
(Point D).

Curve ANJECF

v This curve indicates that the iron below this curve exists in the solid state,
This curve is known as solidus.
v The line ECF at 1130°C indicates that the cast irons have common solidus
temperature.
v For the steel with increase of carbon content from 0 to 1.4%, the solidus
temperature decreases from 1535°C to 1130°C
v In triangle JEC, γ-iron is present with liquid iron. In the triangle CED, iron
carbide called cementite is present with liquid iron.

Curve GRE

The part GR represents the variation in temperature and composition at which the α
carbon transforms into γ+α while the part RE represents carbon transforms into γ and Fe

Curve GPQ

This part represents variation of carbon from 0 to 0.025 percent. With in this curve a-
form of iron is present.

Curve PSK

Ø This represents a constant temperature line (723°C).

Ø Cooling below this temperature γ decomposes into two phases, ferrite and
Cementite
Ø Thus Iron-carbon phase diagram is very important in understanding the changes
that iron undergoes with change in percentage of carbon content and temperature.
 T-T-T DIAGRAMS

Martensite and bainite are non- equilibrium phases of iron.

They do not appear in the iron- carbon phase diagram.
The transformation from one phase to another depends on the cooling rate
Depends on the variation of temperature with time. T-T-T i.e. time-temperature-
transformation diagram shows the influence of cooling rates on phase
transformations. Because of their shape these curves are also. Called ‘S curves’.
T diagram for plain carbon steel. It is seen that a slow cooling rate leads to
formation of coarse pearlite while a faster cooling rate leads to formation of fine
pearlite.
If the critical cooling velocity is exceeded, the non-equilibrium phase, martensite
is formed.
Bainite is formed by the isothermal transformation of under cooled austenite i.e.
by rapidly quenching steel to a temperature below the nose of the T-T-T curve
and maintaining the temperature constant until the transformation is complete
bainite formed.
The value of the critical cooling velocity is not constant for all steels.
An increase in the carbon content of the steel reduces the value of critical cooling
velocity, i.e. move the T-T-T curve towards the right.
HYPO-EUTECTOID STEELS
• These have carbon contents varying from 0.008% to just below 0.83%.
• They have microstructures consisting of grains of ferrite together with grains of pearlite.
• With increase of carbon content, the proportion of strong pearlite formed increases..

EUTECTOID STEELS
• These have carbon contents, ideally, of 0.83%.
• They consist entirely of lamellar pearlite.
• Many alloying elements influence the carbon contents of eutectoid steels; manganese if
added to the extent of about 1% reduces the % carbon in the eutectoid to about 0.7%.

HYPER-EUTECTOID STEELS

• If the carbon content is greater than 0.83%, hyper-eutectoid steels are formed.
• The steels consist of pearlite and cementite, the latter forming around the grain
boundaries of the pearlite.
• In practice, plain steels containing more then about 1.6% carbon are rare.

FERROUS ALLOYS AND THEIR APPLICATIONS

Iron is the prime constituent of ferrous alloys. They are produced in large quantities than
any other metal type because of the following factors:
1. Iron containing compounds exist in abundant quantities,
2. Ferrous alloys are produced with relative ease and cost effectiveness, and
3. Ferrous alloys are extremely versatile and hence they may be tailored to have a wide
range of mechanical and physical properties.
The only drawback of many ferrous alloys is that they are susceptible to corrosion. The
classification scheme of the various ferrous alloys is presented in Fig.
STEELS

Steels are iron-carbon alloys that contain appreciable concentrations of other

alloying element
The mechanical properties are sensitive to the content of carbon, which is
normally less than 1.0 wt %.Steels are classified according to carbon
concentration, namely, into low, medium, and high carbon types.
Plain carbon steels contain only residual concentrations of impurities other than
carbon. For alloy steels alloying elements are added.

Low Carbon Steels

Ø This is the greatest quantity produced steel and least expensive to produce.
Their properties are:
Ø Contain less than about 0.30 wt % C
Ø Microstructure consist of ferrite and pearlite constituents y strength “- 275
MPa -.tensile strength between 415 and 550 MPa
Ø Ductility of 25% EL
Ø Capable of withstanding a large amount of cold working
Ø Relatively soft and weak but ductile and tough machinable and weld able.

APPLICATIONS
Include manufacturing of automobile body components
Structural shapes (I-beams, channel and angle iron)
Sheets that are used in pipelines, buildings, bridges and tin cans.

HIGH STRENGTH, LOW ALLOY (HSLC) STEELS.

They contain other alloying elements such as copper, vanadium, nickel, and molybdenum
in combined concentrations as high as 10 wt %. There properties are:
• possess higher strengths than the plain low carbon steels.
• strengthened by heat treatment
• Ductile, formable and machinable
• More resistant to corrosion than the plain carbon steels
• yield strength ‘S-’ 480 MPa

APPLICATIONS

• Structures that are bolted or riveted such as bridges, towers, support columns in highrise
buildings.
• Truck frames and railway cars.
• Pressure vessels.
MEDIUM CARBON STEELS

Ø Contain carbon concentration between about 0.25 and 0.60 wt%

Ø May be heat treated by austenitizing, quenching and then tempering to improve
their mechanical properties.
Ø Have low harden abilities
Ø Can be heat treated in vary thin section with very rapid quenching rates ,/ yield
strength between 400 and 1000 MPa
Ø Tensile strength between 600 and 1400 MPA
Ø Ductility strength between 10 and 35% EL

Applications
Production of crankshafts, bolts and hammers .t chisels, knives, hacksaw blades

HIGH CARBON STEELS

v The high carbon steels have carbon contents between 0.60 and 1.4 wt %.
v They are hardest and strongest
v Least ductile of the carbon steels
v Normally used in a hardened and tempered condition
v Wear resistant
Typical applications are for making
• Blacksmith tools and
• Woodworking tools.

STAINLESS STEELS
v The stainless steels are highly resistant to corrosion (rusting).
v Their predominant alloying element is chromium; a concentration of at least 11 wt
% Cr is required.
v Addition of nickel and molybdenum enhances the corrosion resistance.

v They are magnetic

v Yield strength lies between 250 and 1700 MPa
v Tensile strength lies between 400 and 1800 MPa ductility varies between 5 and 30
% EL
Typical applications are in manufacturing of rifle barrels

CAST IRONS

Any materials made up primarily of iron with about 2% or more of carbon is considered
to be cast iron.
Most commercial alloys contain from about 2.5% to 3.8% carbon. There are four basic
types of cast iron that are usually produced.
GREY CAST IRON:

v This has a large amount of free carbon in the form of both flake and rosette
graphite in a matrix of, usually, pearlite and ferrite.
v Due to the weakening effects of the free graphite, this material exhibits
brittleness.
v This material exhibits a gray co lour on the fracture surface.
v Grey cast iron is typically weak in tension and fairly soft.
v It is brittle and strong in compression.
v It possesses excellent casting properties.

WHITE CAST IRON:

v Since a fractured surface is white in colour, it is named so.

v It has a structure composed of cementite and pearlite.
v Since the carbon is in the combined form (cementite), the iron is extremely hard
and virtually unmachinable.
v White cast iron is always low in silicon.
v Normally white cast iron is produced as an intermediate step in the production of
malleable irons.

MALLEABLE IRON:

v Malleable irons combine excellent casting qualities with a measure of strength

and ductility.
v They are produced by suitably annealing white iron castings
 GINEERING MATERIALS & METALLURGY
UNIT I
CONSTITUTION OF ALLOYS AND PHASE DIAGRAMS
PART A

1. What is a phase or equilibrium diagram? What information may be obtained from an

equilibrium diagram?
2. What is meant by a phase? State Gibbs’ phase rule.
3. State lever rule
4. What do you understand by allotropy? (April 2002).
5. What is meant by liquids?.
6. What is meant by solidus?
7. What is ferrite?
8. What are the possible microstructures of iron and steel? The possible microstructures
9. What is T-T-T diagram?
10. What are stainless steels and what are the possible classifications based on their
microstructure?
11. What are cast irons and what are their basic types?
12. How does the yield strength vary with grain size?
13. What is meant by heat treatment? What are the different methods of heat treatment?
14. What is age hardening or precipitation hardening?
15. What is over aging?
16. What is annealing and what is its purpose?
17. What is tempering?
18. Explain anstempering
19. Explain martempering (April 2002)
20. What is case hardening?

PART B

1. Two metals A and B are mutually soluble in one another in the liquid state and are
completely insoluble in one another in the solid state. Draw the equilibrium diagram for
the two metals A and B. Explain fully the mode of solidification of any one alloy of the
metals A and B.
2. Two metals A and B are mutually soluble in one another in both liquid state and solid
state. Draw the phase (equilibrium) diagram and explain the mode of solidification at
different compositions.
3. Draw the iron-carbon phase diagram and explain the various regions in it.
4. Discuss the transformation of austenite when cooled out various cooling rates based on
TTT diagram. Explain critical cooling rate. (April 2002)
5. What are various factors affecting mechanical properties of ferrous alloys? Explain the
process of heat treatment.
6. What are various ferrous alloys? List out their properties and applications.