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MATERIAL SCIENCE

1 ENGINEERING MATERIAL

1. INTRODUCTION

(i) Solids exist in nature in two principal forms: crystalline and non-crystalline (amorphous),
which differ substantially in their properties.
(ii) Crystals are solids that possess long-range order. In long range order, as in crystalline
solids, there is a regular pattern of arrangement of particles which repeats itself periodically
over the entire crystal.
(iii) The arrangement of the atoms at one point in a crystal is identical, (excepting localised
defects that can arise during crystal growth), to that in any other remote part of the crystal.

2. SPACE LATTICES, BASIS AND CRYSTAL STRUCTURES

2.1. The Space Lattices

A space lattice is defined as an infinite array of points in three dimensions in which every
point has surroundings identical to that of every other point in the array.
2.3. UNIT CELL
It is discussed earlier that the atomic order in crystalline solids indicates that the
smallest groups of atoms form a repetitive pattern. Thus, in describing crystal
structures, it is often convenient to subdivide the structure into repetitive small repeat
entities called unit cells, i.e. in every crystal some fundamental grouping of particles
is re-peated.

Fig.1: Lattice parameters of a unit cell

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(ii) Careful measurement of mineral specimens allowed crystals to be classified in terms of

six crystal families, called anorthic, monoclinic, orthorhombic, tetragonal, hexagonal and
iso-metric. This classification has been expanded slightly by crystallographers into seven
crystal systems. The crystal systems are sets of reference axes, which have a direction as
well as a magnitude, and hence are vectors.

Fig.2: The reference axes used to characterise the seven crystals systems
The crystal families and classes are given in Table 1.1.
Table.1: The seven crystal systems
Crystal family Crystal system Axial relationships
Isometric Cubic a = b = c and α = β = γ = 90°
Tetragonal Tetragonal a = b ≠ c and α = β = γ = 90°
Orthorhombic Orthorhombic a ≠ b ≠ c and α = β = γ = 90°
Monoclinic Monoclinic a ≠ b ≠ c and α = γ = 90°; β = 90°
Anorthic Triclinic a ≠ b ≠ c and α ≠ 90°; β ≠ 90°; γ ≠ 90°
Hexagonal Hexagonal a = b ≠ c and α = β ≠ 90°; γ = 90°;
Trigonal A = b = c, α = β = γ; or
a’ = b’ ≠ c’ and α’ =β’ = 90°, γ’ = 120°
Rhombohedral
(Hexagonal axes)

Referring to Table.2:

Space lattice Abbreviation Effective number of lattice points in unit cell

Simple cubic SC 1

Body centred cubic BCC 2

Face centred cubic FCC 4

2.4. Atomic radius:

This is defined as half the distance between the nearest neighbours in the crystal structure
of a pure Atomic radius is denoted by r and expressed in terms of the cube edge element
a.
2.5. Atomic Packing Factor (APF):
This is defined as the ratio of total volume of atoms in a unit cell to the total volume of
the unit cell.

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This is also called relative density of packing (RDP). Thus

No. of atoms  Volume of one atom v …………….. (1)
APF = =
Volume of unit cell V

APF for Simple Cubic Crystal System (SCC) = 52%

APF for Body-centred Cubic Structure (BCC) = 68%

APF for Face-centred Cubic Structure (FCC) = 74%
APF for Hexagonal closed packed structure (HCP) =74%

3. DENSITY OF CRYSTAL

This is defined as:

Mass of unit cell
Density of the crystal (ρ) =
Volume of unit cell
Atomic mass
Mass of unit cell =  Number of atoms per unit cell
Avogadro number

M
Mass of unit cell = n
NA
Where:
n → number of atoms per unit cell and
NA → Avogadro's number
M → the atomic weight, and
a → side of a cubic unit cell).
nM
Density of the crystal (ρ) = ………………… (1)
a3NA
3.1. Linear density:
• This is defined as the number of atoms per unit length along a specific crystal direction.
3.2. Planar density:
• This is defined as the number of atoms per unit area on a crystal plane. This significantly
affect the rate of plastic deformation.

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4. DIRECTIONS, LATTICE PLANES AND MILLER INDICES

(i) In a crystal there exists directions and lattice planes which contain a large concentration of
atoms. Various properties of crystals, particularly mechanical are connected with the
structure of the crystal though the help of crystal directions.
(ii) A complete description of the crystal structure can be obtained from the study of atomic
positions in a unit cell. For crystal analysis it is necessary to locate directions and lattice
planes.

Fig.3: Crystal directions in an orthorhombic lattice

4.1. Crystallographic Planes:
(i) The crystal lattice may be regarded as made-up of an aggregate of a set of parallel
equidistant planes, passing through the lattice points, which are known as lattice
planes, or atomic planes.
(ii) The problem is that how to designate these planes in a crystal. Miller evolved a
method to designate a set of parallel planes in a crystal by three' numbers h, k and l
usually written within brackets thus (h k l) shown as Miller indices of the plane.
4.2. Determination of Miller Indices:
(a). Determine the coordinates of the intercepts made by the plane along the three
crystallographic axes i.e. x, y, z axes as shown in Fig.

Fig.4: Intercepts of plane on three crystallo-graphic axes and miller indices.

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x y z
2a 3b c
pa qb rc
Where: p = 2, q = 3, r = 1
(b). Now, express the above intercepts as multiples of the unit cell dimensions, or
lattice parameters along the axes, i.e. axes
x y z
2a 3b c
Intercept:
a b c
2 3 1
(c). Take the reciprocal of intercepts:
1 1 1
2 3 1
(d). Now, reduce these reciprocals to the smallest set of integral numbers and enclose
within a bracket
 1 1 1
6  2 6
3
6
1 
= (3 2 6)

These integers within the bracket are Miller indices. In general, it is denoted by [h k l].
Thus, we note that:
1 1 1
: : = h:k :l
P q r
1 1 1
: : = 3:2:6
2 3 1
4.3. Important Features of Miller Indices of Crystal Planes:
A few important features of Miller indices of crystal planes are:
(a). All the parallel equidistant planes have the same Miller indices. Obviously, Miller
indices define a set of parallel planes.
(b). A plane parallel to one of the coordinate axes has an intercept of infinity (∞) and
therefore the Miller index is zero.
(c). If the Miller indices of the two planes have the same ratio (i.e., say 844 and 422 or
211), then the planes are said to be parallel to each other. In other words, all equally
spaced parallel planes with an orientation have the same index number [h k l].
(d). Only the ratio of indices is important.
(e). Miller indices of planes are denoted by (h k l) i.e. the plane cuts the axes into h, k
and l equal segments. The directions in space are represented by square bracket [x y z].
(f). The common inside brackets are used separately and not combined. Obviously, (111)
is read as one-one-one and not 'one hundred eleven'.
(g). Miller indices may also be negative and negative indices are represented by putting

a bar over the digit, e.g. (0 1 0).

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4.4. Interplanar spacings

(i)These are the distances between planes and are represented by a number of parts of
the body diagonal of a unit cell.

1
dhkl = ………………. (1)
2
h k 2 l2
+ +
a2 b2 c2
dhkl gives the distance between two successive (h k l) places. For a cubic system: a = b
4.5. Angle between two planes or directions
The angle between these two planes is given by the relation
h1h2 + k1k 2 + l1l2
cos  =
h12 + k12 + l12  h22 + k 22 + l22

Similarly, the angle ϕ between the two directions having Miller indices (h 1, k1, l1) and
(h2, k2, l2) respectively is given by the relation
h1h2 + k1k 2 + l1l2
cos  =
h12 + k12 + l12  h22 + k 22 + l22

4.6. Representation of crystal planes in a cubic unit cell

(i) (100), (010) and (001) represent the Miller indices of the cubic planes ABCD, BFGC
and AEFB respectively in Fig.

Fig.5: Crystal a planes of a cubic unit cell

5. CO-ORDINATION NUMBER

(i) This is defined as the number of nearest atoms directly surrounding the given atom.
(ii) The value of co-ordination number is 6 for simple cubic, 8 for BCC and 12 for FCC In closely
packed structures this number is 12.

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6. DEFECTS OR IMPERFECTIONS IN CRYSTALS

(i) There are some properties of materials such as stiffness, density and electrical
conductivity which are termed structure—insensitive, are not affected by the
presence of defects in crystals while there are many properties of greatest technical
importance 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.
6.1. Classification of Crystal defects:
Crystalline defects can be classified on the basis of their geometry as follows:
(i). Point imperfections
(ii). Line imperfections
(iii). Surface and grain boundary imperfections
(iv). Volume imperfections
The dimensions of a point defect are close to those of an interatomic space. With
linear defects, their length is several orders of magnitude greater than the width.
Surface defects have a small depth, while their width and length may be several
orders larger. Volume defects (pores and cracks) may have substantial dimensions in
all measurements, i.e. at least a few tens of Å.

7. EFFECT OF ALLOYING ELEMENT ON IRON

7.1. CARBON
By increase in percentage of carbon in iron, ductility decreases and brittleness increases
and when carbon % increase from more than 2.1% in iron, iron convert into cast iron.
7.2. SULFUR
Sulphur is always present as impurity in iron, but it is very dangerous as after reacting
with iron, it produces FeS which gets accumulated at grain boundary. Melting point of
FeS is very low, so upon warm working FeS will melt out producing a cracks at grain
boundary. This leads to brittle fracture. Hence due to brittleness increase, this
phenomenon is called hot shortness or S embrittlement.To eliminate the ill effect of S,
small amount of manganese is added. Manganese reacts with sulphur before Sulphur
reacts with iron and produces manganese sulphate.

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(MP)MnS → High
The shear strength of manganese sulphide is less and hence power consumption
decrease.12% Mn is exceptionally strong steel known as had field steel, used in heavy
duty work like bulldoger.
7.3. PHOSPHORUS
(i) Phosphorus is generally kept below 0.4%.
(ii) This small quantity tends to dissolve in ferrite, increasing the strength and hardness
slightly. Large quantity of phosphorus tend to crack the steel when cold worked making
steel cold-short.
7.4. SILICON
It's amount generally varies in between 0.05% to 0.3%.
(i) It dissolves in ferrite, increasing the-strength of steel without gradually decreasing the
ductility.
(ii) By addition of Silicon, eutectic point shift towards left and graphite formation takes
place at much lower percentage of Carbon.
(iii) To produce steel, oxygen is passed through liquid iron, oxygen after combining with
carbon, produces CO2, So C is removed in form of CO2, it is an exothermic reaction. After
sometime, Fe pond turns to boil, this phenomenon is called steel boil. The moment we
stop the flow of oxygen a portion of oxygen will try to trap in material. Silicon is added
to remove this oxygen. Silicon after combining with oxygen produces S iO2 .When quantity
of silicon is such that oxygen is removed completly then material is called killed sheet.But
when removal of O2 is partial then material is called semi-killed sheet.

Element Effect(s)

Counteracts brittleness from S

Increase hardenability
Increase resistance
Mn
Reduces ductility and weldability
Increase hardenability significantly
Increase strength, toughness, red hardness, and hot When used with Cr, Mn, and V
Mo
Enhances corrosion and abrasion resistance
Ni Increases toughness and impact resistance
Increases strength in low carbon steel
P
Improves corrosion resistance

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Element Effect(s)
Strengthens low alloy steels
Increases hardenability
Si
Acts as deoxidizer
Improves magnetic properties when present in large percentage.
S Improves machinability of very low carbon steels
Increases austenitic hardenability
Ti
Reduces martensitic hardness in Cr steels
Increases strength while retaining ductility
V Produces fine grain size
Increases hardenability
Imparts hardness and wear resistance
W Significantly improves red hardness
Imparts strength temperature

8. IRON-CARBON PHASE DIAGRAM

(i) The Fe-Fe3C is defined by five individual phases and four invariant reactions. Five phases
are: α-ferrite (BCC) Fe-C solid solution, γ-austenite (FCC) Fe-C solid solution, δ-ferrite(BCC)
Fe-C solid solution, Fe3C (iron carbide) or cementite - an inter-metallic compound and liquid
Fe-C solution. Four invariant reactions are eutectoic, monotectic and peritectic.
(ii) As shown in figure by left axes, pure iron upon heating exhibits two allotropic changes. One
involves α -ferrite of BCC crystal structure transforming to FCC austenite, γ-iron, at 910C. At
1400°C, austenite changes to BCC phase known as δ-ferrite, which finally melts at 1536°C.
(iii) Carbon present in solid iron as interstitial impurity, and forms solid solution with
ferrites/taustenite as depicted by three single fields represented by α, γ and δ. Carbon dissolves
least in α -ferrite in which maximum amount of carbon soluble is 0.02% at 723°C.
(iv) This limited solubility give the shape and size of interstitial position in BCC (x_ferrite
However, carbon present greatly influences the mechanical properties of α-ferrite. α-ferrite can
be used as magnetic material below 768°C. Solubility of carbon in γ-iron reaches its maximum,
2.11%, at a temperature of 1147°C.
(V) Higher solubility of carbon in austenite a property FCC structure and corresponding
interstitial sites. Phase transformations involving austenite plays very significant role in heat
treatment of different steels. Austenite itself is non-magnetic. Carbon solubility in δ-ferrite is
maximum (00.1%) at 1495°C.
(vi) As this ferrite exists only at elevated temperature, it is of no commercial.
(vii) Out of these four solid phases, cementite is hardest and brittle that is used in different
forms to increase the strength of steels. α-ferrite, on the other hand is softest and act as matrix
of a composite material.

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(viii) Based on %C dissolved in it, a Fe-C solution is classified as: commercial pure irons with
less than 0.008%C: steels having %C between 0.008-2.11., while coat irons have Carbon in
the range of 2 11%-6.67%.

Fig.6: Iron-carbon phase diagram

(ix) Thus, commercial pure iron is composed of exclusively α-ferrite at room temperature.
(x) The presence of Si promotes the formation of graphite instead of cementite.
(xi) Fe-C system constitutes four invariant reactions:
(xii) Peritectic reaction at 1495°C and 0.16%C, δ-ferrite + L ↔ γ-iron (austenite)
(xiii) Monotectic reaction 1495°C and 0.51%C. L ↔ L+ γ-iron (austenite)
(xiv) Eutectic reaction at 1147°C and 4.3%C, L ↔ γ-iron Fe3C (cementite) [ledeburite]
(xv) Eutectoid reaction at 723°C and 0.8%C, γ-iron L ↔ α-ferrite + Fe3C (cementite) [pearlite]

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9. TIME-TEMPERATURE-TRANSFORMATION (TTT) DIAGRAMS

(i) The information on the change of phase with the cooling rate can be conveniently displayed
with the help of a time-temperature-transformation diagram (commonly known as the TTT
diagram).In such a diagram, the temperature is plotted along the vertical axis (using a linear
scale), whereas the abscissa represents the time on a logarithmic scale
(ii) Isothermal transformation diagram, also called as TTT diagram, measures the rate of
transformation at a constant temperature i.e. it shows time relationships for the Phases during
isothermal transformation. Information regarding the time to start the transformation and the
time required to complete the transformation can be obtained from set of TTT diagrams.
(iii) Consider austenite at temperature greater than 725°C. When this austenite is put in
quenching medium maintained at temperature below 725° C. For few time the austenite does
not change. After some time, the transformation begin. This time t i after which transformation
starts is known as incubation time.

Fig.7:Transformation-Time diagram

Fig.8: Temperature-Time diagram

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10. INTRODUCTION TO HEAT TREATMENT

(i) Heat treatment is a combination of heating and cooling operation and applied to a metal or
alloy in the solid state in a way that will produce desired properties.
(ii) All basic heat-treating processes for steel involve the transformation or decomposition of
austenite.
(iii) The nature and appearance of these transformation products determine the physical and
mechanical properties of any given steel.
(iv) The first step in heat treatment of steel is to heat the material to some temperature in or
above the critical range in order to form austenite.
(v) In most cases, the rate of heating to the desired temperature is less important than other
factors in heat-treating cycle.
(vi) Highly stressed materials produced by cold work should be heated more slowly than stress
free materials to avoid distortion.
10.1. ANNEALING
Annealing is a heat treatment process generally used to:
(i) Relieve internal stresses
(ii) Increase, softness, ductility and toughness
(iii) Produce a specific microstructure.
It consists of three stages:
(i) Heating to a desired temperature
(ii) Holding or Soaking' at that temperature
(iii) Cooling usually to room temperature.
10.2. NORMALIZING
(i) Normalizing is done to increase the strength of medium carbon steel.
(ii) The microstructure formed is fine grained Deanne with a proeutectoid phase.
(iii) Improve machinability of low carbon steel.
(iv) Improve structure of weld.
(v) Mechanical properties are better than annealing and process is of short duration
because of cooling in air.
(vi) The selection process of annealing, normalizing and spherodizing normalizing and
spherodizing depend on carbon content.
10.3. TEMPERING

It is done

(i) To relive residual stress (ii) To improve ductility (iii) Toughness is increased.

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10.4. CASE HARDENING

Here hard surfaces are produced with relatively soft core. Hard surface has good wear
resistance while soft core has good toughness. Hard surface is called case.There are
various treatments to impart surface hardness which are discussed below.
10.4.1 CARBURIZING
It is applied to low carbon steels having upto 0.18%C (Temp range is between (870-
950°C) and result in formation of Austenite phase, which has maximum solubility of
carbon.
Methods are as follows
PACK CARBURIZING
Piece is surrounded by a carburizing mixture and packed in a steel box. It is heated to
around (870-950°C)

Fig.9: Pack carburizing

GAS CARBURIZING
Here workpart is treated in a atmosphere of gases containing carbon and hydrocarbon
gases such as CH4, butane etc.
Part is heated to temperature of 950°C for 3-12 hrs (holding time). 2CO → CO2 + C
(atomic)
CH4 → 2H2 + C (atomic)
This atomic carbon diffuses into austenite and produced hard surfaces.
LIQUID CARBURIZING
Workpiece is heated to 950°C and dipped in a molten salt bath containing 20% NaCN,
which provides Carbon & Nitrogen. At this temperature Carbon and small amount of
Nitrogen diffuses into surface. The only disadvantage is that cost of carburizing salt is
very high. In carburzing operations carbon can be penetrated upto the depth of 0.3 mm
with hardness obtained around (55-65 HRC).
10.4.2 NITRIDING
(i) Here nitrogen content of the surface is increased.
(ii) It is done by heating steel in the atmosphere of NH 3 gas.
(iii) Piece to be nitrided are placed in an air tight container, workpieces is heated to a
temperature in range (500-600°C), at which NH3 dissociates into 2NH3 → 2N + 3H2
(iv) This atomic nitrogen diffuses to the surface making case hardened.
(v) This process makes the hardest case on steels.
(vi) Maximum thickness of case is around (0 — 0.5 mm).

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10.4.3 CYANIDING
(i) Here work part is immersed in molten salt bath containing sodium cyanide (NaCN).
which is heated to 820-860°C.
(ii) This is usually followed by water quenching.
10.4.4 CARBONITRIDING (GAS CYANIDING)
(i) A mixture of NH3 and a hydro carbon gas is used.
(ii) The work is heated to 850°C for 2-10hrs.
(iii) This is followed by quenching and low temperature tempering.
(iv) Carbon diffuses at a rate higher than nitrogen.
10.5. INDUCTION HARDENING
(i) Workpieces heated in an induction furnace surrounded by copper coils which are water
cooled. High frequency AC current is passed through Cu coils and thus alternate magnetic
field set up which induce eddy currents on the surfaces.
(ii) Heat is generated on the surface by eddy currents.
(iii) The surface of work piece is heated in austenitic range then quenched immediately
to form martensite.
(iv) The structure of core remain unchanged because it is not affected by heat.
10.6. FLAME HARDENING
(i) Process consists of heating the surface of high carbon steels by a high temperature
gas flame at 2400-3500°C, followed by immediate cooling is air or water.
(ii) Heat is suplied by oxy-acetylene torch. The heat is supplied so quickly to the surface
that the core remains unaffected.
(iii) The thickness of hardened layer is 2-4 mm and its structure is martensite.

Fig.10: Flame hardening

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