ch1 - ch2 - Metallurgy - Materials Science - DAM

Introduction of Materials Science and Engineering
Classification of Materials
Solid materials have been conveniently grouped into three basic classifications:
(1) metals, (2) ceramics, and (3) polymers.
Metals
 Materials in this group are composed of one or more metallic elements (such as iron,
aluminum, copper, titanium, gold, and nickel), and often also nonmetallic elements (for
example, carbon, nitrogen, and oxygen) in relatively small amounts.
 Atoms in metals and their alloys are arranged in a very orderly manner.
 In comparison to the ceramics and polymers, are relatively dense.
 Mechanical Property- relatively stiff and strong, ductile (i.e., capable of large amounts of
deformation without fracture), and are resistant to fracture.
 Metallic materials have large numbers of non-localized electrons; that is, these electrons
are not bound to particular atoms. Many properties of metals are directly attributable to
these electrons.
 Example, metals are extremely good conductors of electricity, and heat, and are not
transparent to visible light; a polished metal surface has a lustrous appearance.
 Some of the metals (viz., Fe, Co, and Ni) have desirable magnetic properties.
Ceramics
 Ceramics are compounds between metallic and nonmetallic elements; they are most
frequently oxides, nitrides, and carbides.
 Examples-aluminum oxide (or alumina, Al2O3), silicon dioxide (or silica, SiO2), silicon
carbide (SiC), silicon nitride (Si3N4).
 Examples of traditional ceramics — clay minerals (i.e., porcelain), cement, and glass.
Properties-
 Relatively stiff and strong—stiffnesses and strengths are comparable to those of the metals,
very hard, extremely brittle (lack ductility), .highly susceptible to fracture.
 Thermal and electrical Properties- Insulative to the passage of heat and electricity low
electrical conductivities and are more resistant to high temperatures
 Optical characteristics-Ceramics may be transparent, translucent, or opaque.
D. A. Mhamane Metallurgy
Polymers
 Carbon-based compounds.
 Chain of H-C molecules. Each repeat unit of H-C is a monomer e.g. ethylene (C2H4),
Polyethylene – (–CH2 –CH2)n.
 Polymers include the familiar plastic and rubber materials.
 Many of them are organic compounds that are chemically based on carbon, hydrogen, and
other nonmetallic elements (viz. O, N, and Si).
 They have very large molecular structures, often chain-like in nature that have a backbone
of carbon atoms. Some of the common and familiar polymers are polyethylene (PE), nylon,
poly (vinyl chloride) (PVC), polycarbonate (PC), polystyrene (PS), and silicone rubber.
Properties
 Low densities, not as stiff nor as strong as ceramics and metals.
 Extremely ductile and pliable (i.e., plastic).
 Relatively inert chemically and unreactive in a large number of environments.
Limitations
 Tendency to soften and/or decompose at modest temperatures, which, in some instances,
limits their use.
 Low electrical conductivities and are nonmagnetic.
Composites
 A composite is composed of two (or more) individual materials, which come from the
categories discussed above—viz., metals, ceramics, and polymers.
 Objective-to achieve a combination of properties that is not displayed by any single
material
Examples
 Cemented carbides (WC with Co binder)
 Plastic molding compounds containing fillers
 Rubber mixed with carbon black
 Wood (a natural composite as distinguished from a synthesized composite)
Advance Materials
 Materials that are utilized in high-technology (or high-tech) applications are sometimes
termed advanced materials.
Examples
 Include electronic equipment (camcorders, CD/DVD players, etc.), computers, fiber-optic
systems, spacecraft, aircraft, and military rocketry, liquid crystal displays (LCDs), and
fiber optics.
 These advanced materials may be typically traditional materials types (e.g., metals,
ceramics, polymers) whose properties have been enhanced, and, also newly developed,
high-performance materials.
 Advanced materials include semiconductors, biomaterials, and what we may
term“materials of the future.
1.1.2 Biomaterials
Biomaterials are employed in components implanted into the human body for replacement
of diseased or damaged body parts.
 These materials must not produce toxic substances and must be compatible with body
tissues (i.e., must not cause adverse biological reactions).
 All of the above materials—metals, ceramics, polymers, composites, and
semiconductors—may be used as biomaterials.
Example-
Titanium and its alloy, Co-Cr alloy, stainless steel, zirconia, HA, TiO2 etc.
1.1.3 Semiconductors
 Semiconductors have electrical properties that are intermediate between the electrical
conductors (viz. metals and metal alloys) and insulators (viz. ceramics and polymers).
 The electrical characteristics of these materials are extremely sensitive to the presence of
minute concentrations of impurity atoms, for which the concentrations may be controlled
over very small spatial regions.
 Semiconductors have made possible the advent of integrated circuitry that has totally
revolutionized the electronics and computer industries (not to mention our lives) over the
past three decades.
The Materials Selection Process
 Pick Application and determine required Properties.

 Properties: mechanical, electrical, thermal, magnetic, optical, deteriorative.
 Properties- Identify candidate Material(s)
 Material: structure, composition.
 Material- Identify required Processing
 Processing: changes structure and overall shape
Example: casting, sintering, vapor deposition, doping forming, joining, annealing.
Crystal Structures
Fundamental concepts
Solid materials may be classified according to the regularity with which atoms or ions are arranged with
respect to one another.
 crystalline solids / material

 Non Crystalline material / amorphous solids
Crystalline solids / material

A crystalline material is one in which the atoms are situated in a repeating or periodic array over large
atomic distances; such that upon solidification, the atoms will position themselves in a repetitive three-
dimensional pattern, in which each atom is bonded to its nearest-neighbor atoms.
All metals, many ceramic materials, and certain polymers form crystalline structures
Unit cells
Unit cell is the basic structural unit or building block of the crystal structure and defines the crystal structure by
virtue of its geometry and the atom positions within.
Three relatively simple crystal structures are found for most of the common metals:
1. face-centered cubic (FCC)

2. body-centered cubic (BCC)
3. hexagonal close-packed (HCP)
1. The Body-Centered Cubic Crystal Structure (BCC)

The body-centered cubic unit cell is a cube with an atom at each corner of the unit cell and an atom in the center
of the unit cell.
E.g. Chromium, iron, tungsten
(a) a hard sphere unit cell representation, (b) a reduced-sphere unit cell, (c) an aggregate of many atoms
No. of Average atom/unit cell in BCC

There is one full atom at the center and one atom at each of the eight corners.
Therefore effective number of atoms inside each unit cell is,
=1 + [8 x (1/8)]
= 2 𝑎𝑡𝑜𝑚𝑠
2. Face-Centered Cubic Crystal Structure (FCC)

The crystal structure found for many metals has a unit cell of cubic geometry, with atoms located at each of the
corners and the centers of all the cube faces.
E.g.: copper, aluminum, silver, and gold
(a) atoms bonding (b) atoms as small spheres
No. of Average atom/unit cell in FCC

There are zero atoms completely enclosed by the FCC unit cell. Six face atoms that are each shared with an
adjacent unit cell. Eight corner atoms at the intersection of eight unit cells to give
Determination of FCC Unit Cell Volume
Calculate the volume of an FCC unit cell in terms of the
atomic radius R.
 The atoms touch one another across a face-diagonal the

length of which is 4R.
 Since the unit cell is a cube, its volume is a3
 Where ‘a’ cell edge length. From the right triangle on the
face,
3. Hexagonal Close-Packed Crystal Structure (HCP)

 The top and bottom faces of the unit cell consist of six
atoms that form regular hexagons and surround a single atom
in the center. Another plane that provides three additional
atoms to the unit cell is situated between the top and bottom
planes.
 The atoms in this mid plane have as nearest neighbors
atoms in both of the adjacent two planes.
No. of Average atom/unit cell in HCP

Three full atoms within the volume of each unit cell. The atoms at the center of the top face and base are shared
by only 2 unit cells. Each of the 12 atoms at the corner of the top face and the base are Shared by 6 HCP unit cells.
Atomic packing factor (APF)

The APF is the sum of the sphere volumes of all atoms within a unit cell divided by the unit cell volume. —that is,
FCC structure, the atomic packing factor is 0.74
Atomic Packing Factor for BCC
There is one full atom at the center and one atom at each of the eight corners.
Therefore effective number of atoms inside each unit cell is, =1 + [8 x (1/8)] = 2 𝑎𝑡𝑜𝑚𝑠
To find ‘a’ in terms of ‘r’
Atomic Packing Factor for FCC
The total atom and unit cell volumes may be calculated in terms of the atomic radius R.
The volume for a sphere is – (4/3)πR3
Since there are 4 atoms per FCC unit cell, the total FCC atom (or sphere) volume is
The total unit cell volume is
Therefore, the atomic packing factor is
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Defects in Solids
 The term “defect” or “imperfection” is generally used to describe any deviation from the
perfect periodic array of atoms in the crystal.
 The properties of some materials are extremely influenced by the presence of imperfections
such as mechanical strength, ductility, crystal growth, magnetic hysteresis, dielectric
strength, condition in semiconductors, which are termed structure sensitive are greatly
affected by the-relatively minor changes in crystal structure caused by defects or
imperfections.
 Crystal imperfections can be classified on the basis of their geometry as
Point Defects in Metals
It is a zero dimension defect, associated with one or two atomic positions.
(a) Vacancies -The simplest of the point defects is a vacancy, or vacant lattice site, one
normally occupied from which an atom is missing. All crystalline solids contain vacancies
and, in fact, it is not possible to create such a material that is free of these defects, vacant
atomic sites in a structure.
(b) Self-Interstitials- when an atom occupies an interstitial site where no atom would
ordinarily appear, causing an interstitials.
Point Defects in Ceramics

Vacancies- vacancies exist in ceramics for both cations and anions.
(a) Interstitials - interstitials exist for cations, interstitials are not normally observed for anions
because anions are large relative to the interstitial sites.
(b) Frenkel Defect To maintain the charge neutrality, a cation vacancy-cation interstitial pair occur
together. This is called a Frenkel defect. The cation leaves its normal position and moves to the
interstitial site. There is no change in charge because the cation maintains the same positive charge as
an interstitial.
Interstitial Frenkel and Schottky
(c) Schottky Defect

A cation vacancy–anion vacancy pair known as a Schottky defect. To maintain the charge
neutrality, remove one cation and one anion; this creates two vacancies.
Line Imperfections
 A dislocation is a linear or one-dimensional defect around which some of the atoms are
misaligned. The defects, which take place due to distortion of atoms along a line, in some
direction are called as ‘line defects, Line defects are also called dislocations.
 It is responsible for the phenomenon of slip by which most metals deform plastically.
The two types of dislocations are,

(a) Edge dislocation
 It is a linear defect that centers around the line that is defined along the end of the extra
half-plane of atoms.
 The distorted configuration extends all along the edge into the crystal.
 Thus as the region of maximum distortion is centered around the edge of the incomplete
plane, this distortion represents a line imperfection and is called an edge dislocation.
Edge dislocations are represented by ‘’ or ‘‘depending on whether the incomplete plane starts
from the top or from the bottom of the crystal.
 These two configurations are referred to as positive and negative edge dislocations
respectively.
(b) Screw dislocation:-

 In this dislocation, the atoms are displaced in two separate planes perpendicular to
each other.
 It forms a spiral ramp around the dislocation.
 The Burgers Vector is parallel to the screw dislocation line.
 Speed of movement of a screw dislocation is lesser compared to edge dislocation.
Mixed dislocations –
Most dislocations found in crystalline materials are probably neither pure edge nor
pure screw, but exhibit components of both types; these are termed mixed dislocations.
Burgers vector
 The magnitude and direction of the lattice distortion associated with a dislocation is
expressed in terms of a Burgers vector, denoted by a b.
 The Burger vector can be found by the gap in the Burger circuit which is obtained by
moving equal distances in each direction around the dislocation.
Surface imperfections
 Surface imperfections arise from a change in the stacking of atomic planes on or across a
boundary.
 The change may be one of the orientations or of the stacking sequence of atomic planes.
 In geometric concept, surface imperfections are two- dimensional. They are of two type’s
external and internal surface imperfections.
(a) External Surfaces

 They are the imperfections represented by a boundary. At the boundary the atomic bonds
are terminated.
 Surface atoms are not bonded to the maximum number of nearest neighbors, and are
therefore in a higher energy state than the atoms at interior positions. The bonds of
thesesurface atoms that are not satisfied give rise to a surface energy, expressed in units of energy
per unit area (J/m2 or erg/cm2).
(b) Grain Boundaries

The boundary separating two small grains or crystals having different
crystallographic orientations in polycrystalline materials.
(c) Twin Boundaries

 A twin boundary is a special type of grain boundary across which there is a specific mirror
lattice symmetry; that is, atoms on one side of the boundary are located in mirror- image
positions of the atoms on the other side.
 The region of material between these boundaries is appropriately termed a twin.
 Twins result from atomic displacements that are produced from applied mechanical shear
forces (mechanical twins), and also during annealing heat treatments following
deformation (annealing twins).
Volume Defects
These include pores, cracks, foreign inclusions, and other phases. They are normally
introduced during processing and fabrication steps.
Solidification
Solidification is basically phase transformation from liquid phase to solid phase. The progress of
a phase transformation takes place in two stages: nucleation and growth. Nucleation involves the
appearance of very small particles, or nuclei of the new phase (often consisting of only a few
hundred atoms), which are capable of growing. During the growth stage these nuclei increase in
size, which results in the disappearance of some (or all) of the parent phase.
Cooling Curve
Nucleation
There are two types of nucleation: homogeneous and heterogeneous. The
distinction between them is made according to the site at which nucleating events occur.
For the homogeneous type, nuclei of the new phase form uniformly throughout the parent
phase, whereas for the heterogeneous type, nuclei form preferentially at structural in
homogeneities, such as container surfaces, insoluble impurities, grain boundaries,
dislocations, and so on.
Homogeneous Nucleation
Nucleation without preferential nucleation sites is homogeneous nucleation.
Homogeneous nucleation occurs spontaneously and randomly, but it requires Superheating
or supercooling of the medium.
Fig.2.2: Schematic diagram showing the
Heterogeneous nucleation
Heterogeneous nucleation forms at preferential sites such as phase boundaries,
surfaces (of container, bottles, etc.) or impurities like dust. At such preferential sites, the
effective surface energy is lower, thus diminishes the free energy barrier and facilitating
nucleation. Heterogeneous nucleation occurs much more often than homogeneous
nucleation
Geometry of Solidification
The chill zone contains fine crystals nucleated at the mould surface. There is then selective
growth into the liquid as heat is extracted from the mould. If the liquid in the centre of the
mould is undercooled sufficiently there may also be equiaxed grains forming.
Geometry of solidification.
Phase Diagram
Introduction
 Phase diagrams are an important tool in the armory of an materials scientist
 In the simplest sense a phase diagram demarcates regions of existence of various
phases. (Phase diagrams are maps)
 Phase diagrams are also referred to as “equilibrium diagrams” or “constitutional
diagrams”. This usage requires special attention: through the term used is
“equilibrium”, in practical terms the equilibrium is not global equilibrium but
Microstructural level equilibrium.
 Broadly two kinds of phase diagrams can be differentiated*→ those involving time
and those which do not involve time.
 In this chapter we shall deal with the phase diagrams not involving time.
 This type can be further sub classified into:

 Those with composition as a variable (e.g. T vs. %Composition)
 Those without composition as a variable (e.g. P vs. T)
 Time-Temperature-Transformation (TTT) diagrams and Continuous-
Cooling- Transformation (CCT) diagrams involve time.
Components of a system
 Independent chemical species which comprise the system. These could be
Elements, Ions, Compounds
Example: Au-Cu system : Components →Au, Cu (elements) Ice-water system :
Component→H2O (compound)
Al2O3-Cr2O3 system : Components→Al2O3, Cr2O3
Phase
 A physically homogeneous and distinct portion of a material system (e.g. gas,
crystal, amorphous…)
 Gases : Gaseous state always a single phase → mixed at atomic or molecule level.
 Liquids: Liquid solution is a single phase → e.g. Nacl in H2O and Liquid
mixtures consists of two or more phases → e.g. Oil in water (no mixing at the
atomic level)
 Solids: In general due to several compositions and crystals structures many
phases are possible.
o For the same composition different crystal structures represent different
phases.
E.g. Fe (BCC) and Fe (FCC) are different phases
Phase transformation
 Phase transformation is the change of one phase into another. For example
 Water → Ice and α-Fe (BCC) → γ-Fe (FCC)
Grain
 The single crystalline part of polycrystalline metal separated by similar entities by
a grain boundary
Solute
 The component of either a liquid or solid solution that is present to a lesser or
minor extent; the component that is dissolved in the solvent.
Solvent
 The component of either a liquid or solid solution that is present to a greater or
major extent; the component that dissolves the solute.
System
 System has two meanings. First, ‘‘system’’ may refer to a specific body of material
or object. Or, it may relate to the series of possible alloys consisting of the same
components, but without regard to alloy composition.
Solubility Limit
 For many 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.
Microstructure
 (Phases + defects + residual stress) & their distributions
 Structures requiring magnifications in the region of 100 to 1000 times. (or) The
distribution of phases and defects in a material.
Phase diagram
 Map that gives relationship between phases in equilibrium in a system as a function
of T, P and composition. Map demarcating regions of stability of various phases
Solid solution and Compound
The element present in the alloy in the largest portion is referred as base metal or parent metal or
solvent and the other elements are referred as alloying element or solute. Solid solution is a type
of alloy in which the atoms of alloying element are distributed in the base metal and both have
similar crystal structure. The composition of alloying element may vary but the structure should
be similar to base metal.
Substitutional solid solution

In substitutional solid solution, atoms of alloying element occupy the atomic size of base metal.
They are further classified as:
(a) Regular or ordered substitutional solid solution:
In this type, the substitution of atoms of alloying element is in definite order in the base metal
matrix.
Examples: Ni-Al solid solution below 400 C.
Ordered Substitutional Solid Solution Random Substitutional Solid Solution

(b) Random or disordered substitutional solid solution:
In this type, substitution of alloying elements is in any random order in the base metal matrix.
Example: Alpha brass
Interstitial solid solution:
In Interstitial solid solution, the atoms of alloying elements occupy the interstitial sites of base
metal. This type of solution is formed when atomic size of alloying element is much smaller
compared to that of the base metal. Example: Fe-C
Interstitial solid solution
Hume - Rothery’s Rules for Solid Solubility

1. Atomic size:
Alloying elements having similar atomic size as that of the base metal matrix have better solid
solubility. For a favourable solid solution formation, the difference of atomic size of solute and
solvent should be less than 15 %.
2. Chemical affinity:
Element having lower chemical affinity have greater solid solubility. Element having higher
chemical affinity have the tendency of formation of compound and hence restrict formation of
solid solution.
3. Relative valency:
Metals having lower valency have more solubility for metals having higher valency. Hence, for
better solubility, the base metal selected should be one that has lower valency as compared to
that of alloying elements.
4. Crystal structure:
As mentioned earlier, solid solution is an alloy of element having similar crystal structure.
Difference in crystal structure limits the solid solubility of elements.
GIBB’S PHASE RULE
Gibbs phase rule establishes the relationship between the number of variable (F), the number
of element (C), and the number of phases (P). It is expressed mathematically as follows:
P + F = C + 2 ……….(I)
Where,
P = Number of phases in system
F = Number of variables that can be change independently without effecting number
of phases
C = Number of elements
2 = It represent any two variables amongst temperature, pressure and composition
In general all equilibrium diagram studied at constant pressure, hence Gibb’s phase rule is
modified to”
P + F = C + 1 ……….(II)
Phase rule helps to determine maximum number of phase present in an alloy system under
equilibrium conditions at any point in phase diagram. The phase rule can also be used to
determine the degree of freedom that can be changed
Cooling Curves
Cooling curve is the graphical plot of phases of element on temperature v/s time.
The resulting phase during solidification is different for various alloy composition.
The most common cooling curves are:
1. For pure metals
2. For binary solid solution (alloy)
3. For eutectic binary alloy
4. For off-eutectic binary alloy
1. For pure metals
Region AB represent liquid state, solidification starts at B and continue until C, region CD
represent solid state.
Application of Gibb’s phase rule in various regions:
(1) Region AB
P+F=C+1
1+F=1+1
Therefore, F = 1
Thus F = 1 means that only one variable i.e temperature can be varied without changing the
liquid phase of the system.
(2) Region BC
P+F=C+1
2+F=1+1
Therefore, F = 0
Thus F = 0 means that no variable amongst temperature and pressure can be varied with out
changing the Liquid + Solid phase of system. If the temperature is increased the metal goes
into liquid state and if the temperature is lowered it goes into solid state.
(3) Region CD
P+F=C+1
1+F=1+1
Therefore, F = 1
Thus F = 1 means that only one variable i.e temperature can be varied without changing solid
phase of system.
2. For binary solid solution (alloy)
Region AB represent liquid state, solidification starts B and continue until C, region CD
represent solid state.
(1) Region AB
P+F=C+1
1+F=2+1
Therefore, F = 2
Thus F = 2 means any two variables temperature and composition can be varied without
effecting liquid phase of the system.
(2) Region BC
P+F=C+1
2+F=2+1
Therefore, F = 1
Thus F = 1 means that only one variable i.e temperature can be varied without changing Liquid
+ Solid phase of system.
(3) Region CD
P+F=C+1
1+F=2+1
Therefore, F = 2
effecting solid phase of the system.
3. For eutectic binary alloy
Eutectic alloy is the one that undergoes eutectic reaction during cooling.
Eutectic reaction can be stated as:
Thus, eutectic alloy when cooled forms two different solid phases.
Fig. shows typically cooling curve for binary eutectic alloy. A binary eutectic alloy thus has
two element which are completely soluble in liquid state but entirely insoluble in the solid state.
Region AB represent liquid state, solidification starts at B and continue until C, region CD
represent solid state containing (A,B,C,D points as per previous diagram).

(1) Region AB
P+F=C+1
1+F=2+1
Therefore, F = 2
(2) Region BC
P+F=C+1
3+F=2+1
Therefore, F = 0
Thus F = 0 means that no variable amongst temperature and pressure can be varied without
changing the Liquid + Solid phase of system. If the temperature is increased the metal goes
into liquid state and if the temperature is lowered it goes into solid state.
(3) Region CD
P+F=C+1
2+F=2+1
Therefore, F = 1
Thus F = 1 means that only one variable i.e temperature can be varied without changing solid
state of system.
4. Cooling Curves for off-Eutectic binary alloy
Eutectic reaction occurs for a definite composition and definite temperature. In the composition
of alloy differs from the eutectic composition, it is referred as off-eutectic alloy. Off-eutectic
alloys with composition less than eutecti composition are called hypo-eutectic alloys and those
with composition more than eutectic composition are called hyper-eutectic alloys.
During cooling of off-eutectic alloy, either of the two solids separate out earlier depending on
whether the alloy is hypo or hyper eutectic alloy. The pre-separated solid referred as pro-
eutectic phase. Fig. shows typically cooling curve for off-eutectic binary alloy. Region AB
represent liquid state, solidification starts at B , region BC represent solidification either or,
region CD represent solidification of both and, region DE represent solid state of entire system.
(A,B,C,D,E points as per previous diagram).

(1) Region AB
P+F=C+1
1+F=2+1
Therefore, F = 2
(2) Region BC
In this region, either or start separating out by solidification.
P+F=C+1
2+F=2+1
Therefore, F = 1
Thus F = 1 means that only one variable i.e temperature can be varied without the solid state
of the system.
(3) Region CD
In this region, the other starts separating out by solidification
P+F=C+1
3+F=2+1
Therefore, F = 0
Thus F = 0 means that no variable amongst temperature and composition can varied without
changing the Liquid + Solid state of the system.
(4) Region DE
P+F=C+1
2+F=2+1
Therefore, F = 1
Thus F = 1 means that only one variable i.e temperature can be varied without changing the
Solid state of the system.
Construction of Phase Diagram

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.
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 T1,
which indicates the beginning of solidification, and the lower break at T2 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.
Since the left axis represents the pure metal A, TA 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 TA 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. It is common practice, in labeling of equilibrium
diagrams, to represent solid solution and sometimes intermediate alloys by Greek letters. In
this case, it is labeled the solid solution alpha (Î±). 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.
Specification of temperature and composition of an alloy in a two-phase region indicates that
the alloy consists of a mixture of two phases but does not give any information about the actual
chemical composition and the relative amounts of the two phases that are present. They can be
determined as under.
CLASSIFICATION OF EQUILIBRIUM DIAGRAMS

An equilibrium diagram has been defined as a plot of the com-position of phases as a function
of temperature in any alloy system under equilibrium conditions. Equilibrium diagrams may
be classified according to the relation of the components in the liquid and solid states as
follows:
 Components completely soluble in the liquid state,
1. and also completely soluble in the solid state,
2. but partly soluble in the solid state (EUTECTIC REACTION).
3. but insoluble in the solid state (EUTECTIC REACTION).
4. The PERITECTIC Reaction
 Components partially soluble in the liquid state,
1. but completely soluble in the solid state.
2. and partly soluble in the solid state.
 Components completely insoluble in the liquid state and completely insoluble in the solid
state.
A study of these diagrams will illustrate basic principles which may be applied to understand
and interpret more complex alloy systems
TWO METALS COMPLETELY SOLUBLE IN THE LIQUID AND SOLID STATES
– A system that illustrates an equilibrium diagram in which there is complete solubility in the
liquid and solid states is that of the Antimony- Bismuth system.
– Examples of other such systems are Ni-Cu, Au-Ag, Cr-Mo and W-Mo.
– Since the two metals (such as Sb and Bi or Ni and Cu, etc.) are completely soluble in the
solid state, the only type of solid phase formed will be a substitutional solid solution.
– The equilibrium diagram consists of two lines only— the liquidus and solidus.
– Above the liquidus there is a uniform liquid solution for any alloy in the series, while below
the solidus there is a single solid solution of any alloy.
– Between the liquidus and solidus, both liquid and solid solutions co-exist.
– Consider an alloy containing 30% Bismuth and 70% Antimony .As the liquid alloy cools, the
freezing starts at about 1080°F (582°C) (liquidus line).
– The composition of the solid formed and liquid at any point say 2(M) can be found from the
equilibrium diagram as explained under section.
– As cooling continues, a stage (i.e., point N) reaches when the whole mass is solid and further
cooling will bring the solid to the room temperature.
– Actually the solidification of a liquid alloy of this type consists of two processes:
I. a) Formation of crystals in the melt (at say point S),
b) Growth of crystals (just as at point M).
II. Homogenization of the composition in various parts of each crystal
a) By diffusion between core and encasement.
b) By diffusion between core and melt.
EUTECTIC SYSTEM
– In a eutectic reaction, when a liquid solution of fixed composition, solidifies at a constant
temperature, forms a mixture of two or more solid phases without an intermediate pasty stage.
This process reverses on heating.
– In eutectic system, there is always a specific alloy, known as eutectic composition that freezes
at a lower temperature than all other compositions.
– At the eutectic temperature, two solids form simultaneously from a single liquid phase.
– The eutectic temperature and composition determine a point on the phase diagram called the
eutectic point.
PERITECTIC REACTION:
– It is the reaction that occurs during the solidification of some alloys where the liquid phase
reacts with a solid phase to give a solid phase of different structure.
– Assuming very slow rates of cooling, the Peritectic reaction will occur only in those Pt-Ag
alloys that Contain between 12 and 69% silver (Ag).
– Consider a liquid (melt) of composition Z, i.e., containing 25% Ag.
Solidification commences at T1 and dendrites of α, initially of composition W, begin forming.
– Selective crystallization of α continues down to Tp, the Peritectic temperature; when the alloy
reaches. This temperature, it is composed of solid α-dendrites of composition B and liquid of
composition D in the proportion α : liquid = RD : RB.
EUTECTOID TRANSFORMATION:
– Eutectoid reaction is an isothermal reversible reaction in which a solid phase (usually solid
solution) is converted into two or more intimately mixed solids on cooling, the number of solids
formed being the same as the number of component in the system.
Iron–Iron Carbide (Fe–Fe3C) Phase Diagram
In their simplest form, steels are alloys of Iron (Fe) and Carbon (C). The Fe-C phase diagram is a
fairly complex one, but we will only consider the steel part of the diagram, up to around 7% carbon.
Phases in Fe–Fe3C Phase Diagram
 α-ferrite - solid solution of C in BCC Fe
• Stable form of iron at room temperature.
• The maximum solubility of C is 0.022 wt%.
• Transforms to FCC γ-austenite at 912 °C.
 γ-austenite - solid solution of C in FCC Fe.

• The maximum solubility of C is 2.14 wt %.
• Transforms to BCC δ-ferrite at 1395 °C.
• Is not stable below the eutectic temperature (727 ° C) unless cooled rapidly.
 δ-ferrite solid solution of C in BCC Fe.

• The same structure as α-ferrite
• Stable only at high T, above 1394 °C
• Melts at 1538 °C
 Fe3C (iron carbide or cementite)
This intermetallic compound is metastable, it remains as a compound indefinitely at room
T, but decomposes (very slowly, within several years) into α-Fe and C (graphite) at 650 -
700 °C.
 Fe-C liquid solution
A few comments on Fe–Fe3C system

 C is an interstitial impurity in Fe. It forms a solid solution with α, γ, δ phases of iron.
 Maximum solubility in BCC α-ferrite is limited (max. 0.022 wt% at 727 °C) - BCC has
relatively small interstitial positions
 Maximum solubility in FCC austenite is 2.14 wt% at 1147 °C - FCC has larger
interstitial positions
 Mechanical properties: Cementite is very hard and brittle - can strengthen steels.
Mechanical properties also depend on the microstructure, that is, how ferrite and
cementite are mixed.
 Magnetic properties: α -ferrite is magnetic below 768 °C, austenite is non-magnetic.
Classification. Three types of ferrous alloys:

• Iron: less than 0.008 wt % C in α−ferrite at room T
• Steels: 0.008 - 2.14 wt % C (usually < 1 wt % ) α-ferrite + Fe3C at room T .
• Cast iron: 2.14 - 6.7 wt % (usually < 4.5 wt %)
Eutectic and eutectoid reactions in Fe–Fe3C

Eutectoid: 0.76 wt% C, 727 °C
γ(0.76 wt% C) ↔ α (0.022 wt% C) + Fe3C
Eutectic: 4.30 wt% C, 1147 °C
L ↔ γ + Fe3C
Eutectic and eutectoid reactions are very important in heat treatment of steel.
Development of Microstructure in Iron
Carbon alloys Microstructure depends on composition (carbon content) and heat treatment. In
the discussion below we consider slow cooling in which equilibrium is maintained.
Microstructure of eutectoid steel (I)

Microstructure of eutectoid steel (II)
When alloy of eutectoid composition (0.76 wt % C) is cooled slowly it forms perlite, a lamellar or layered
structure of two phases: α-ferrite and cementite (Fe3C) The layers of alternating phases in pearlite are
formed for the same reason as layered structure of eutectic structures: redistribution C atoms between
ferrite (0.022 wt%) and cementite (6.7 wt%) by atomic diffusion. Mechanically, pearlite has properties
intermediate to soft, ductile ferrite and hard, brittle cementite. Microstructure of eutectoid steel (II) In
the micrograph, the dark areas are Fe3C layers, the light phase is α- ferrite
Microstructure of hypoeutectoid steel (I)
Compositions to the left of eutectoid (0.022 - 0.76 wt % C) hypoeutectoid (less than eutectoid -Greek)
alloys.
Ferrous Materials
Classification of Steels
The Society of Automotive Engineers (SAE) has established standards for specific analysis of
steels. In the 10XX series, the first digit indicates a plain carbon steel. The second digit
indicates a modification in the alloys. 10XX means that it is a plain carbon steel where the
second digit (zero ) indicates that there is no modification in the alloys. The last two digits
denote the carbon content in points. For example SAE 1040 is a carbon steel where 40 points
represent 0.40 % Carbon content. Alloy steels are indicated by 2XXX, 3XXX, 4XXX, etc.. The
American Iron and Steel Institute (AISI) in cooperation with the Society of Automotive
Engineers (SAE) revised the percentages of the alloys to be used in the making of steel, retained
the numbering system, and added letter prefixes to indicate the method used in steel making.
The letter prefixes are:
A = alloy, basic open hearth
B = carbon, acid Bessemer
C = carbon, basic open hearth
D = carbon, acid open hearth
E = electric furnace
If the prefix is omitted, the steel is assumed to be open hearth. Example: AISI C1050 indicates
a plain carbon, basic-open hearth steel that has 0.50 % Carbon content.
Another letter is the hardenability or H-value. Example: 4340H
General representation of steels:
Table 1. Classification of steels
SAE - AISI Classification
Number
1XXX Carbon steels

Low carbon steels: 0 to 0.25 % C
Medium carbon steels: 0.25 to 0.55 % C
High carbon steels: Above 0.55 % Carbon
2XXX Nickel steels

5 % Nickel increases the tensile strength without reducing ductility.
8 to 12 % Nickel increases the resistance to low temperature impact
15 to 25 % Nickel (along with Al, Cu and Co) develop high magnetic
properties. (Alnicometals)
25 to 35 % Nickel create resistance to corrosion at elevated
temperatures.
3XXX Nickel-chromium steels

These steels are tough and ductile and exhibit high wear resistance ,
hardenability and high resistance to corrosion.
4XXX Molybdenum steels

Molybdenum is a strong carbide former. It has a strong effect on
hardenability and high temperature hardness. Molybdenum also
increases the tensile strength of low carbon steels.
5XXX Chromium steels

Chromium is a ferrite strengthener in low carbon steels. It increases
the core toughness and the wear resistnace of the case in carburized
steels.
86XX Triple Alloy steels which include Nickel (Ni), Chromium (Cr), and
87XX Molybdenum (Mo).
93XX These steels exhibit high strength and also high strength to weight
94XX ratio, good corrosion resistance.
97XX
98XX
Table 2. The effect of alloying elements on the properties of steel
Element Effect
Aluminum Ferrite hardener

Graphite former
Deoxidizer
Chromium Mild ferrite hardener

Moderate effect on hardenability
Graphite former
Resists corrosion
Resists abrasion
Cobalt High effect on ferrite as a hardener

High red hardness
Molybdenum Strong effect on hardenability

Strong carbide former
High red hardness
Increases abrasion resistance
Manganese Strong ferrite hardener
Nickel Ferrite strengthener

Increases toughness of the hypoeutectoid steel
With chromium, retains austenite
Graphite former
Copper Austenite stabilizer

Improves resistance to corrosion
Silicon Ferrite hardener

Increases magnetic properties in steel
Phosphorus Ferrite hardener

Improves machinability
Increases hardenability
Red Hardness: This property, also called hot-hardness, is related to the resistance of the steel
to the softening effect of heat. It is reflected to some extent in the resistance of the material to
tempering.
Hardenability: This property determines the depth and distribution of hardness induced by
quenching.
Hot-shortness: Brittleness at high temperatures is called hot-shortness which is usually caused

by sulfur. When sulfur is present, iron and sulfur form iron sulfide (FeS) that is usually
concentrated at the grain boundaries and melts at temperatures below the melting point of steel.
Due to the melting of iron sulfide, the cohesion between the grains is destroyed, allowing cracks
to develop. This occurs when the steel is forged or rolled at elevated temperatures. In the
presence of manganese, sulfur tends to form manganese sulfide (MnS) which prevents hot-
shortness.
Cold-shortness: Large quantities of phosphorus (in excess of 0.12%P) reduces the ductility,
thereby increasing the tendency of the steel to crack when cold worked. This brittle condition
at temperatures below the recrystallization temperature is called cold-shortness.
Stainless Steels
Stainless steel is a generic term for a family of corrosion resistant alloy steels containing 10.5%
or more chromium. All stainless steels have a high resistance to corrosion. This resistance to
attack is due to the naturally occurring chromium-rich oxide film formed on the surface of the
steel. Although extremely thin, this invisible, inert film is tightly adherent to the metal and
extremely protective in a wide range of corrosive media. The film is rapidly self repairing in
the presence of oxygen, and damage by abrasion, cutting or machining is quickly repaired.
Benefits of Stainless Steel:

Corrosion resistance
All stainless steels have a high resistance to corrosion. Low alloyed grades resist corrosion in
atmospheric conditions; highly alloyed grades can resist corrosion in most acids, alkaline
solutions, and chloride bearing environments, even at elevated temperatures and pressures.
High and low temperature resistance
Some grades will resist scaling and maintain high strength at very high temperatures, while
others show exceptional toughness at cryogenic temperatures.
Ease of fabrication
The majority of stainless steels can be cut, welded, formed, machined and fabricated readily.
Strength
The cold work hardening properties of many stainless steels can be used in design to reduce
material thickness and reduce weight and costs. Other stainless steels may be heat treated to
make very high strength components.
Aesthetic appeal
Stainless steel is available in many surface finishes. It is easily and simply maintained resulting
in a high quality, pleasing appearance.
Hygienic properties
The cleanability of stainless steel makes it the first choice in hospitals, kitchens, food and
pharmaceutical processing facilities.
Life cycle characteristics
Stainless steel is a durable, low maintenance material and is often the least expensive choice in
a life cycle cost comparison.
Types of Stainless Steels:

In addition to chromium, nickel, molybdenum, titanium, niobium and other elements may also
be added to stainless steels in varying quantities to produce a range of stainless steel grades,
each with different properties. There are a number of grades to chose from, but all stainless
steels can be divided into five basic categories:
Austenitic
Ferritic
Martensitic
Duplex
Precipitation hardening
These are named according to the microstructure inherent in each steel group (a function of the
primary alloying elements). Austenitic and ferritic grades account for approximately 95% of
stainless steel applications.
Austenitic Stainless Steels:

When nickel is added to stainless steel in sufficient amounts the crystal structure changes to
"austenite". The basic composition of austenitic stainless steels is 18% chromium and 8%
nickel. Austenitic grades are the most commonly used stainless steels accounting for more than
70% of production (type 304 is the most commonly specified grade by far).
Basic properties of Austenitic Steels:

excellent corrosion resistance in organic acid, industrial and marine environments.
excellent weldability (all processes)
excellent formability, fabricability and ductility
excellent cleanability, and hygiene characteristics
good high and excellent low temperature properties (high toughness at all temperatures)
non magnetic (if annealed)
hardenable by cold work only (These alloys are not hardenable by heat treatment)
Common uses of Austenitic Steels:

computer floppy disk shutters (304)
computer keyboard key springs (301)
kitchen sinks (304D)
food processing equipment
architectural applications
chemical plant and equipment
Table 3. Chemical Composition of Austenitic steels
302 304 316
Carbon 0.15% max.. 0.08% max 0.08% max
Chromium 17.00 to 19.00% 18.00 to 20.00% 16.00 to 18.00%
Manganese 2.0% max 2.0% max. 2.0% max.
Silicon 1.0% max. 1.0% max. 1.0% max.
Nickel 8.00 to 10.00% 8.00 to 10.50% 10.00 to 14.00%
Molybdenum ---- ---- 2.00 to 3.00%
Table 4. Mechanical properties of Austenitic Stainless steels

302 304 316
Tensile strength 90 -185 84-185 84-185

(Ksi)
Yield strength (Ksi) 40-140 42-140 42-140
Elongation in 2 50 % 55 % 50 %
inches (Annealed)
Modulus of elasticity 28 x 10 6 28 x 10 6 28 x 10 6
(psi)
Hardness (Annealed) RB 75 - RB90 RB 75 - RB90 RB 75 - RB90
Hardness (Cold RC 25 - RC39 RC 25 - RC39 RC 25 - RC39

work)
Ferritic Stainless Steels:

This group of alloys generally containing only chromium, with the balance mostly Fe. These
alloys are somewhat less ductile than the austenitic types and again are not hardenable by heat
treatment. These are plain chromium stainless steels with varying chromium content between
12 and 18%, but with low carbon content.
Basic properties:
moderate to good corrosion resistance increasing with chromium content
not hardenable by heat treatment and always used in the annealed condition magnetic
weldability is poor
formability not as good as the austenitics
Common uses
computer floppy disk hubs (430)
automotive trim (430)
automotive exhausts (409)
colliery equipment (3CR12)
hot water tanks (444)
Martensitic Stainless Steels:

Martensitic stainless steels were the first stainless steels commercially developed (as cutlery)
and have relatively high carbon content (0.1 - 1.2%) compared to other stainless steels. They
are plain chromium steels containing between 12 and 18% chromium.
Basic properties
moderate corrosion resistance
can be hardened by heat treatment and therefore high strength and hardness levels
can be achieved
poor weldability
magnetic
Common uses
Knife blades
surgical instruments
shafts
spindles
pins
Precipitation-Hardening Steels:
These steels have been formulated so that they can be supplied in a solution treated condition,
(in which they are machinable) and can be hardened, after fabrication, in a single low
temperature "aging" process.
Basic properties
Moderate to good corrosion resistance
very high strength
good weldability
magnetic
Common uses
Shafts for pumps and valves.
Duplex Stainless Steels:
These are stainless steels containing relatively high chromium (between 18 and 28%) and
moderate amounts of nickel (between 4.5 and 8%). The nickel content is insufficient to
generate a fully austenitic structure and the resulting combination of ferritic and austenitic
structures is called duplex. Most duplex steels contain molybdenum in a range of 2.5 - 4%.
Basic properties:
high resistance to stress corrosion cracking
increased resistance to chloride ion attack
higher tensile and yield strength than austenitic or ferritic steels
good weldability and formability
Common uses
marine applications, particularly at slightly elevated temperatures
desalination plant
heat exchangers
petrochemical plant
Tool Steels
Plain carbon steels, if used for cutting tools, lack certain characteristics necessary for high-
speed production, such as red hardness and hot -strength toughness. The effect of alloying
elements in steel is of great advantage and yields tool steels that overcome many of the
shortcomings of the plain carbon steels.
Tool steels are defined by U.S. steel producers as "carbon or alloy steels capable of being
hardened and tempered". Many alloy steels would fit this loose definition. Tool steels usually
contain significantly more alloying elements than alloy steels. However, the real factor that
discriminates tool steels from carbon or allot steels is the manufacturing practice.
Approximately 70 types of tool steels are available in the United States. One reason for so
many types of tool steels is evolutionary development over a period of 80 years. The second
reason is the wide range of needs that they serve. Tool steels have properties that permit their
use as tools for cutting and shaping metals and other materials both hot and cold. The U.S. tool
steel classifications system is based on use characteristics. There are six major categories one
of which contains grades intended for special purposes. A prefix letter is used in the alloy
identification system to show use category, and the specific alloy in a particular category is
identified by one or two digits. For example:
S1 = Shock resistant tool steel
D2 = Cold-work tool steel
H11 = Hot work tool steel
M42 = High-speed tool steel
Tool Steel Type Prefix Specific Types
Cold Work W = Water Hardening W1, W2, W5

O = Oil Hardening O1, O2, O6, O7
A = Medium alloy Air A2, A4, A6, A7, A8, A9,
Hardening A10, A11
D = High Carbon, High D2, D3, D4, D5, D7
Chromium
Shock Resisting S S1, S2, S4, S5, S6, S7
Hot Work H H10-H19 Chromium types

H20-H39 Tungsten types
H40-H59 Molybdenum
types
High Speed M Molybdenum types (M1,

M2, M3-1, M3-2, M4, M6,
T M7, M10, M33, M34, M36,
M41, M42, M46, M50
Tungsten types (T1, T4, T5,
T6, T8, T15)
Mold Steels P P6, P20, P21
Special Purpose L and F series L2, L6
One problem that exists in discussing the metallurgy of tool steels is that, since there are six
major categories of tool steels, it is difficult to make statements that apply to all these steels.
The following are some of the characteristics of tool steels:
Composition and physical properties vary significantly (some tool steels have compositions
that fit into the composition ranges of carbon and alloy steels, but most tool steels have alloy
concentrations that are significantly higher than the carbon and alloy steels),
One important factor that should be kept in mind is that the alloy additions do not improve
corrosion resistance even though some grades have as much chromium as stainless steels. The
reason for this is that alloy elements are usually combined with carbon to form carbides.
The most significant metallurgical difference between tool steels and the other steels is their
microstructure. A fully hardened carbon steel or alloy steel would have only martensite as the
predominant phase. Most tool steels have a hardened structure of martensite and alloy carbides.
Require special heat treatment processes ,

Higher cost than alloy steels,
Better hardenability than most carbon and alloy steels,
High heat resistance
Easier to heat treat,
More difficult to machine than carbon and alloy steels
Most tool steels are sold as hot-finished shapes such as rounds and bars,
Cold-finished sheets are not available because it is difficult to cold roll or cold finish these
materials.
Cold Work Tool Steels (W, O, A, D-types):

Cold work tool steels are used for gages, blanking, drawing and piercing dies, shears, forming
and banding rolls, lathe centers, mandrels, broaches, reamers, taps, threading dies, plastic
molds, knurling tools.\
Water Hardening Oil Hardening Tool Medium High Carbon High

Tool Steels Steels Alloy Air Chromium Steels
(W series) (O-Series) Hardening (D-series)
Steels
(A-series)
Essentially these 0.90 to 1.45 % Carbon 5 to 10 % All D-series

are carbon steels with Mn, Si, W, Mo, Cr. alloying contain 12% Cr
with 0.60 to 1.10 They contain graphite in elements and over 1.5 % C.
% carbon. the hardened structure (Mn, Si, W, Air or oil quench.
along with martensite. Mo, Cr, V,
Lowest cost tool (Graphite acts as a Ni) to Low distortion,
steels. lubricator and also makes improve the high abrasion
Soft core(for machining easier. hardenability, resistance.
toughness) with Tungsten forms tungsten wear
hard shallow layer carbide which improves resistance,
(for wear the abrasion resistance toughness.
resistance). and edge retention in
Use of w-series cutting devices.
steels is declining.
Hot Work Tool Steels (H-series):

There are about 12 hot-worked tool steels. They are categorized by major alloying elements
into three subgroups.
Chromium types
Tungsten types
Molybdenum types
These steels are used in extrusion dies, forging dies, die casting, hot shear blades, plastic molds,
punches and dies for piercing shells, hot press, etc.
Shock Resisting Tool Steels (S-series):

These steels have 0.45 to 0.55 % carbon. The alloys, silicon, and nickel are ferrite
strengtheners. Chromium increases wear resistance and hardenability. The S-series of tool
steels were originally developed for chisel-type applications, but the number of alloys in this
category has evolved to include steels with a broad range of tool applications. This class of
steels has a very good shock resistant qualities with excellent toughness.
They are used in form tools, chisels, punches, cutting blades, springs, trimming, and swaging
dies, concrete and rock drills, bolt cutters.
Mold Tool Steels (P-series):

These steels have 0.10 to 0.35 % carbon. They show high toughness. The low carbon mold
steels cannot be quench hardened. The carbon and alloy content is low to allow hubbing of
mold details. The desired mold shape is pressed into the steel with a hub that is usually made
from a high-speed steel. Thus mold cavities can be made without machining. Hubbed cavities
are then carburized to make a production injection molding cavity.
High-Speed Tool Steels (M and T-series):

These are the classes of steel that deep harden, retain that hardness at elevated temperatures,
and have high resistance to wear and abrasion. The carbon content of these steels vary from
0.85 % to 1.50 %.
M-type:
The M-type tool steels are high in molybdenum content and are used for lathe centers, blanking
dies, hot forming dies, lathe cutting tools, drills, taps, etc. They are used in almost all cutting
tools.
T-type:
The T-type high speed tool steels with high carbon content have high wear resistance and very
high hardness. The ones with lower carbon content are tougher but not as hard as the former
group. As the amount of tungsten increases, the toughness decreases. This class of tool material
has a substantial amount of wear-resistant carbides in a very high heat resistant matrix. These
steels are used in machine cutting tools such as tool bits, milling cutters, taps, reamers, drills,
broaches. In some instances it is used where high temperature structural steel is needed.
Special Purpose Tool Steels (L and F series):

The L-type steels are low alloy steels with about 1 % Cr that makes them a good low cost
substitute for cold work steels. The F-type steels are high in carbon tungsten. They have high
wear resistance, good toughness, and medium hardenability. The L-type steels are used in
gages, broaches, drills, taps, threading dies, ball and roller bearings, clutch plates, knurls, files.
The F-type steels are used as finish machining tools.They have good wear resistance and will
maintain a sharp cutting edge. They may be used in dies, cutting tools, form tools, knives, etc.
Cast Iron
Cast irons may often be used in place of steel at considerable cost savings. The design and
production advantages of cast iron include:
Low tooling and production cost
Good machinability without burring
Ability to cast into complex shapes
Excellent wear resistance and high hardness (particularly white cats irons)
High inherent damping capabilities
The properties of the cast iron are affected by the following factors:
Chemical composition of the iron
Rate of cooling of the casting in the mold (which depends on the section thickness in the
casting)
Type of graphite formed (if any)
Types of Cast Iron:

Major types of cast iron are shown in Figure 1.
Figure 1. Types of Cast Iron

Gray Cast Iron:
Gray cast iron is by far the oldest and most common form of cast iron. As a result, it is assumed
by many to be the only form of cast iron and the terms "cast iron" and "gray iron" are used
interchangeably. Unfortunately the only commonly known property of gray iron- brittleness-
is also assigned to "cast iron" and hence to all cast irons. Gray iron, named because its fracture
has a gray appearance. It contains carbon in the form of flake graphite in a matrix which
consists of ferrite, pearlite or a mixture of the two. The fluidity of liquid gray iron, and its
expansion during solidification due to the formation of graphite, have made this metal ideal for
the economical production of shrinkage-free, intricate castings such as motor blocks.
The flake-like shape of graphite in Gray iron, see Figures 2 and 3, exerts a dominant influence
on its mechanical properties. The graphite flakes act as stress raisers which may prematurely
cause localized plastic flow at low stresses, and initiate fracture in the matrix at higher stresses.
As a result, Gray iron exhibits no elastic behavior but excellent damping characteristics, and
fails in tension without significant plastic deformation. The presence of graphite flakes also
gives Gray Iron excellent machinability and self-lubricating properties.
Figure 2. Graphite Flakes in Gray Cast iron
Figure 3. Photomicrograph of Gray Cast iron

Advantages of Gray Cast Iron:
Graphite acts a s a chip breaker and a tool lubricant.
Very high damping capacity.
Good dry bearing qualities due to graphite.
After formation of protective scales, it resists corrosion in many common engineering
environments.
Disadvantages:
Brittle (low impact strength) which severely limits use for critical applications.
Graphite acts as a void and reduces strength. Maximum recommended design stress is 1/4
of the ultimate tensile strength. Maximum fatigue loading limit is 1/3 of fatigue strength.
Changes in section size will cause variations in machining characteristics due to variation in
microstructure.
Higher strength gray cast irons are more expensive to produce.
Low Alloy Gray Cast Iron:
Enables gray cast iron to be used in higher duty applications without redesign or need for costly
materials.
Advantages:
Reduction in section sensitivity.
Improvement in strength, corrosion resistance, heat and wear resistance or combination of
these properties.
Disadvantages:
Higher cost.
Alloy additions can cause foundry problems with reuse of scrap (runners, risers, etc) and
interrupt normal production.
Increase in strength does not bring corresponding increase in fatigue strength.
Cr, Mo and V are carbide stabilizers which improve strength and heat resistance but impair
machinability.
White Cast Iron:

White cast iron is unique in that it is the only member of the cast iron family in which carbon
is present only as carbide. Due to the absence of graphite, it has a light appearance. The
presence of different carbides, depending on the alloy content, makes white cast irons
extremely hard and abrasion resistant but very brittle. An improved form of white cast iron is
the chilled cast iron.
Figure 4a. Photomicrograph of White Cast Iron

Chilled Cast Iron:
When localized area of a gray cast iron is cooled very rapidly from the melt, cast iron is formed
at the place that has been cooled. This type of white cast iron is called chilled iron. A chilled
iron casting can be produced by adjusting the carbon composition of the white cast iron so that
the normal cooling rate at the surface is just fast enough to produce white cast iron while the
slower cooling rate below the surface will produce gray iron. The depth of chill decreases and
the hardness of the chilled zone increases with increasing carbon content.
Chromium is used in small amounts to control chill depth. Because of the formation of
chromium carbides, chromium is used in amount of 1 to 4 percent in chilled iron to increase
hardness and improve abrasion resistance. It also stabilizes carbide and suppresses the
formation of graphite in heavy sections. When added in amounts of 12 to 35 percent, chromium
will impart resistance to corrosion and oxidation at elevated temperatures.
Figure 4b. Photomicrograph of Chilled Cast Iron
Fast cooling prevents graphite and pearlite formation. If alloys such as nickel, chromium, or
molybdenum are added, much of the austenite transforms to martensite instead of pearlite. The
hardness of chilled cast iron is generally due to the formation of martensite.
Chilled cast iron is used for railway-car wheels, crushing rolls, stamp shoes and dies, and many
heavy-duty machinery parts.
Ductile Cast Iron (Nodular Cast Iron):

This structure is developed from the melt. The carbon forms into spheres when cerium,
magnesium, sodium, or other elements are added to a melt of iron with a very low sulfur content
that will inhibit carbon from forming. The control of the heat-treating process can yield
pearlitic, ferritic, martensitic matrices into which the carbon spheres are embedded.
Figure 5. Nodular (Ductile) Cast Iron and the spherical carbon embedded into the
matrix.
Figure 6. Photomicrograph of Nodular Cast iron
The advantages of ductile cast iron which have led to its success are numerous, but they can be
summarized easily-versatility and high performance at low cost. Other members of the ferrous
casting family may have superior individual properties which might make them the material of
choice in some applications, but none have the versatility of ductile cast iron, which often
provides the designer with the best combination of overall properties. This is especially evident
in the area of mechanical properties where ductile cast iron offers the designer the option of
selecting high ductility, with grades guaranteeing more than 18% elongation (as high as 25 %),
or high strength, with tensile strengths exceeding 120 Ksi. Austempered ductile iron offers
even greater mechanical and wear resistance, providing tensile strengths exceeding 230 Ksi.
In addition to cost advantages offered by all castings, ductile cast iron, when compared to steel
and malleable cast iron, also offers further cost savings. Like most commercial cast metal, steel
and malleable cast iron decrease in volume during solidification, and as a result, require feeders
and risers to offset the shrinkage and prevent the formation of internal or external shrinkage
defects. Ductile cast iron offers significantly low shrinkage during casting. In the case of large
castings produced in rigid molds, it does not require feeders. In other cases, it requires feeders
that are much smaller than those used for malleable cast iron and steel. This reduced
requirement for feed metal increases the productivity of ductile cast iron and reduces its
material and energy requirements, resulting in substantial cost savings. The use of the most
common grades of ductile cast iron "as-cast" eliminates heat treatment costs, offering a further
advantage.
Ductile cast iron is used for many structural applications, particularly those requiring strength
and toughness combined with good machinability and low cost. The automotive and
agricultural industries are the major users of ductile iron castings. Because of economic
advantage and high reliability, ductile iron is used for such critical automotive parts as
crankshafts, engine connecting rods, idler arms, wheel hubs, truck axles, front wheel spindle
supports, disk brake calipers, suspension system parts, power transmission yokes, high
temperature applications for turbo housing and manifolds, and high security valves for many
applications. The cast iron pipe industry is another major user of ductile iron.
Malleable Cast Iron:

If cast iron is cooled rapidly, the graphite flakes needed for gray cast iron do not get a chance
to form. Instead, white cast iron forms. This white cast iron is reheated to about 1700oF for
long periods of time in the presence of materials containing oxygen, such as iron oxide. At the
elevated temperatures cementite (Fe3C) decomposes into ferrite and free carbon. Upon cooling,
the combined carbon further decomposes to small compact particles of graphite (instead of
flake -like graphite seen in gray cast iron). If the cooling is very slow, more free carbon is
released. This free carbon is referred to as temper carbon, and the process is called
malleableizing.
Figure 7. Malleable Cast Iron
Figure 8 shows ferritic malleable cast iron, which has a ferrite matrix and the tempered carbon
particles are embedded into the matrix.
Figure 8. Ferritic Malleable Cast iron
Figure 9 shows pearlite malleable cast iron, which has a pearlite matrix. By adding manganese
to the structure, carbon is retained in the form of cementite.
Figure 9. Pearlitic Malleable Cast Iron
A wide variety of physical properties can be obtained by heating and cooling through the
eutectoid temperature or by adding alloying elements. Slow cooling will cause the cementite
to decompose and release more free carbon (temper carbon). Fast cooling will retain some of
the cementite. The amount retained, will depend on the rapidity of cooling.
Malleable cast iron is used for connecting rods and universal joint yokes, transmission gears,
differential cases and certain gears, compressor crankshafts and hubs, flanges, pipe fittings and
valve parts for railroad, marine and other heavy-duty applications.
Advantages:
Excellent machinability
Significant ductility
Good shock resistance properties
Disadvantages:
The major disadvantage is shrinkage. Malleable cast iron decreases in volume during
solidification, and as a result, requires attached reservoirs (feeders and risers) of liquid metal
to offset the shrinkage and prevent the formation of internal or external shrinkage defects.

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Introduction of Materials Science and Engineering

The Materials Selection Process

 Pick Application and determine required Properties.

Example: casting, sintering, vapor deposition, doping forming, joining, annealing.

 crystalline solids / material

Crystalline solids / material

1. face-centered cubic (FCC)

1. The Body-Centered Cubic Crystal Structure (BCC)

No. of Average atom/unit cell in BCC

2. Face-Centered Cubic Crystal Structure (FCC)

(a) atoms bonding (b) atoms as small spheres

No. of Average atom/unit cell in FCC

Determination of FCC Unit Cell Volume

 The atoms touch one another across a face-diagonal the

3. Hexagonal Close-Packed Crystal Structure (HCP)

No. of Average atom/unit cell in HCP

Atomic packing factor (APF)

Atomic Packing Factor for BCC

The volume for a sphere is – (4/3)πR3

The total unit cell volume is

Therefore, the atomic packing factor is

Point Defects in Metals

It is a zero dimension defect, associated with one or two atomic positions.

Point Defects in Ceramics

Interstitial Frenkel and Schottky

(c) Schottky Defect

The two types of dislocations are,

(b) Screw dislocation:-

(a) External Surfaces

(b) Grain Boundaries

(c) Twin Boundaries

Fig.2.2: Schematic diagram showing the

 This type can be further sub classified into:

Substitutional solid solution

Ordered Substitutional Solid Solution Random Substitutional Solid Solution

Interstitial solid solution

Hume - Rothery’s Rules for Solid Solubility

Application of Gibb’s phase rule in various regions:

Application of Gibb’s phase rule in various regions:

Construction of Phase Diagram

CLASSIFICATION OF EQUILIBRIUM DIAGRAMS

TWO METALS COMPLETELY SOLUBLE IN THE LIQUID AND SOLID STATES

 γ-austenite - solid solution of C in FCC Fe.

 δ-ferrite solid solution of C in BCC Fe.

A few comments on Fe–Fe3C system

Classification. Three types of ferrous alloys:

• Steels: 0.008 - 2.14 wt % C (usually < 1 wt % ) α-ferrite + Fe3C at room T .

• Cast iron: 2.14 - 6.7 wt % (usually < 4.5 wt %)

Eutectic and eutectoid reactions in Fe–Fe3C

γ(0.76 wt% C) ↔ α (0.022 wt% C) + Fe3C

Eutectic: 4.30 wt% C, 1147 °C

Microstructure of eutectoid steel (I)

1XXX Carbon steels

2XXX Nickel steels

3XXX Nickel-chromium steels

4XXX Molybdenum steels

5XXX Chromium steels

Aluminum Ferrite hardener

Chromium Mild ferrite hardener

Cobalt High effect on ferrite as a hardener

Molybdenum Strong effect on hardenability

Manganese Strong ferrite hardener