Materials Science

Module 1

Prince Mattom
Mechanical Engg. Dept
 Crystal Structure
Solid materials can be classified according to the regularity with which
atoms are arranged.

Crystalline arrangement of atoms is in a repeating periodic array

over large atomic distances
Eg: metals, diamond, ice, graphite etc.

Amorphous long range atomic order is absent

Eg: glass, amorphous carbon, amorphous Si, most plastics

Space lattice 3 - dimensional network of imaginary lines connecting

the atoms such that every point has identical surroundings

Unit cell smallest unit having the full symmetry of the

crystal
 Crystalline material

Single crystal when the regular and repeated arrangements of

atoms is perfect in a material

Single crystals of silicon and other semiconductors are used in

electronic microcircuits

Most crystalline solids composed of many small crystals

called grains and such materials are called Polycrystalline.
 Unit cell
Unit cell geometry is completely defined by
6 parameters (lattice parameters) : the edges of the unit cell a, b, c and
the angles , and .

Only 14 possible types of space lattices (Bravis lattices) and they fall
in 7 crystal systems

Most of the important Metals crystallize in either cubic or hexagonal

systems and only 3 types of space lattices

Body centered cubic

Face centered cubic
Hexagonal close packing
14 Bravis lattices
 Very common crystal structures and their
relevant properties
Unit cell n CN a/R APF Eg:
Simple cubic 1 6 4/4 0.52
Body centered cubic 2 8 4/3 0.68 Cr, V, Mo, Na, Mn,
-Fe
Face centered cubic 4 12 4/2 0.74 Al, Cu, Ag, Pb, - Fe

Hexagonal close packed 6 12 0.74 Ca, Ti, Mg, Zn, Cd

 n, no. of atoms per unit cell. For an atom that is shared with m
atoms, we count only a fraction of the atom 1/m

CN, the coordination no., which is the number of the closest

neighbours to which an atom is bonded.

APF, the atomic packing factor, which is the fraction of the

volume of the cell actually occupied by the spheres
APF = Sum of the atomic volumes / Volume of the cell
No. of atoms per unit cell
(atoms are considered as spheres)

a) Simple cubic lattice

8 atoms at the corners = 1 atom

Body centered cubic lattice

8 atoms at the corners = 1 atom

1 center atom = 1 atom
Total = 2 atoms

Eg: chromium, tungsten, alpha () iron, delta

() iron, molybdenum, vanadium and sodium

Center and corner atoms touch one another along cube

diagonals
Face centered cubic lattice

8 atoms at the corners = 1 atom

6 face centered atoms = 3 atoms
Total = 4 atoms

Eg: Aluminium, nickel, copper, gold,

silver, lead, platinum and gamma () iron

Atoms (spheres) touch one another across a face diagonal

(corner and face atoms)
Hexagonal close pack structure

unit cell consists of 3 layers of atoms

12 atoms at the corners 1/6 = 2 atoms

2 face centered atoms = 1 atom
(up & down)
3 center atoms (middle layer) = 3 atoms

Total = 6 atoms
 Coordination Number

It is the number of atoms touching a particular atom or the number of

nearest neighbours.

In BCC coordination no is 8

In FCC coordination no is 12

In HCP coordination no is 12
Atomic Radius (r)
It is defined as half the distance between the nearest neighbours in the crystal
structure. It is expressed in terms of cube edge a.
the cube edge length a and the atomic radius R
a) Simple cubic lattice
One atom is there at each of the corners of a cube.
r = a/2

b) Body centered cubic lattice

BCC atoms touch along the diagonal of the cube.
r = 3 a
4
Face centered cubic lattice
In FCC atoms touch along the diagonal of the face of the cube.

(4 r)2 = a2 + a2
16 r2 = 2 a2
r = 2 a
4
c) HCP lattice
 Atomic Packing Factor (APF)

The APF is defined as the fraction of solid sphere volume in a unit cell, or
Class assignment

Computation of the Atomic Packing Factor for BCC

Crystallographic Points, Directions, and Planes

POINT COORDINATES
The position of any point located within a unit cell may be
specified in terms of its coordinates as fractional multiples of
the unit cell edge lengths.

q, r, and s where q is some fractional

length of a along the x axis, r is some
fractional length of b along the y axis,
and similarly for s.
 For the unit cell shown in the accompanying sketch (a), locate the
point having coordinates 1
Specify point coordinates for all atom positions for a BCC unit cell.
List the point coordinates for all atoms that are associated
with the FCC unit cell
Crystallographic Directions

A crystallographic direction is defined as a line between two

points, or a vector. The following steps are utilized in the
determination of the three directional indices:

1. A vector of convenient length is positioned such that it

passes through the origin of the coordinate system. Any vector
may be translated throughout the crystal lattice without
alteration, if parallelism is maintained.

2. The length of the vector projection on each of the three axes

is determined; these are measured in terms of the unit cell
dimensions a, b, and c.
 3. These three numbers are multiplied or divided by a common
factor to reduce them to the smallest integer values.

4. The three indices, not separated by commas, are enclosed in

square brackets, thus: [uvw]. The u, v, and w integers
correspond to the reduced projections along the x, y, and z axes,
respectively.
 The [100], [110], and [111] directions within a unit cell.
 For each of the three axes, there will exist both positive
and negative coordinates.

Thus negative indices are also possible, which are

represented by a bar over the appropriate index.

For example, the [] direction would have a

component in the y direction.

Also, changing the signs of all indices produces an

antiparallel direction; that is, [] is directly opposite
to [].
 Draw a [0] direction within a cubic unit cell.
 Within a cubic unit cell, sketch the following directions:
Determine the indices for the directions shown in the
following cubic unit cell:
 For some crystal structures, several nonparallel directions
with different indices are actually equivalent;

this means that the spacing of atoms along each direction

is the same.

For example, in cubic crystals, all the directions

represented by the following indices are equivalent:

[100], [00], [010], [00], [001], and [00].

As a convenience, equivalent directions are grouped

together into a family, which are enclosed in angle
brackets, thus: <100>.
 Hexagonal crystals

a four-axis, or MillerBravais, in the coordinate system as shown

The three a1, a2 and a3 axes are all contained within a single plane
(called the basal plane) and are at 120o angles to one another.
The z axis is perpendicular to this basal plane.
 Conversion from the three-index system to the four-
index system,
[u v w] [u v t w]
is accomplished by the following formulas
 Miller Indices
Crystallographic planes

The layers of atoms or the planes along which atoms are

arranged are known as atomic or crystallographic planes.

The relation of a set of planes to the axes of the unit cell is

designated by Miller Indices
One corner of the unit cell is assumed to be the origin of the
space coordinates - and any set of planes is identified by the
reciprocals of its intersections with these coordinates.

If a plane is parallel to an axis, it intersects it at infinity.

All parallel planes have the same indices.

An infinite number of planes may be taken through the crystal

structure.
 Crystallographic planes are specified by three Miller indices as (hkl).

Any two planes parallel to each other are equivalent and have identical
indices.

The procedure employed in determination of the h, k, and l index numbers

is as follows:

1. If the plane passes through the selected origin, either another parallel
plane must be constructed within the unit cell by an appropriate
translation, or a new origin must be established at the corner of another
unit cell.

2. At this point the crystallographic plane either intersects or parallels

each of the three axes; the length of the planar intercept for each axis is
determined in terms of the lattice parameters a, b, and c.
 3. The reciprocals of these numbers are taken. A plane that
parallels an axis may be considered to have an infinite
intercept, and, therefore, a zero index.

4. If necessary, these three numbers are changed to the set of

smallest integers by multiplication or division by a common
factor.

5. Finally, the integer indices, not separated by commas, are

enclosed within parentheses, thus: (hkl).
 Reversing the directions of all indices specifies another
plane parallel to, on the opposite side of and equidistant
from, the origin.

Unique characteristic of cubic crystals is that planes and

directions having the same indices are perpendicular to one
another
Representations of a series each of (a) (001), (b) (110), and (c) (111)
crystallographic planes.
Determine the indices for the plane shown in the following cubic unit cell:
 Construct a (0 1) plane within a cubic unit cell:
Determine the Miller indices for the planes shown in the
following unit cell:
 Sketch within a cubic unit cell the following planes:
 Atomic Arrangements
atomic arrangement for a crystallographic plane
depends on the crystal structure.

(a) Reduced sphere

FCC unit cell with
(110) plane.

(b) Atomic packing of

an FCC (110) plane.
Corresponding atom
positions from (a)
are indicated
 (a) Reduced-sphere
BCC unit cell
with (110) plane.

(b) Atomic packing

of a BCC (110)
plane.
Corresponding
atom positions
from (a) are
indicated.

A family of planes contains all those planes that are crystallographically

equivalentthat is, having the same atomic packing;
and a family is designated by indices that are enclosed in bracessuch as
{100}.

For example, in cubic crystals the (1 1 1), ( ), ( 1 1), (1 ), (1 1 ), ( 1), ( 1

), and (1 1) planes all belong to the {111} family.
Each complete set of parallel planes must account for all the
atoms, the most important planes are the ones of high atomic
population and largest interplanar distance.

Packing of atoms in a particular plane

Plane B.C.C F.C.C

100 4 5
110 5 6
111 3 6
120 2 3
221 1 1
 Interplanar distance

The magnitude of the distance between two adjacent and

parallel planes of atoms
 Polymorphism and Allotropy

Materials may exist in more than one crystal structure, a

phenomenon known as polymorphism,
It is observed in metals, non metals and compounds

Allotropy is also the same phenomenon, but reserved for pure

elements.

It is the ability of a substance to exist in more than one physical

form

Eg : iron, titanium. Pure iron has a BCC structure at room

temperature, which changes to an allotropic form having FCC
structure at 912oC, again it changes to BCC structure at 1394oC.
 Carbon allotropic forms diamond and graphite.

Diamond very hard, transparent and electrical insulator

Graphite electrical conductor and lubricating characteristics

These differences arise from the difference in bonding and

crystal structure.

Ceramic materials like silica (SiO2), zirconia (ZrO2) are also

polymorphic.
 Deformation of metals

When a material is subjected to an external load, the

material suffers a change in shape, which is called
deformation.

If the deformation is temporary, it is elastic deformation

and if permanent, it is called plastic deformation

 Deformations takes place due to adjustments or
displacement in atomic arrangement within the crystal.

Mechanical behaviour relationship between its response

or deformation to an applied load or force

Factors considered while evaluating the properties are

Nature of the applied load and its duration
Tensile, compressive or shear, magnitude may be constant
with time or it may fluctuate, application time
Environmental conditions
Temperature, corrosive atmosphere
 Elastic deformation

When a solid material (bar) is loaded axially in tension, it

elongates longitudinally and shortens in lateral direction.

This elongation produced in the tensile direction, and

small contraction at right angles to tensile force and vice-
versa is called Poisson effect

On removal it returns to its original dimensions

Thus elastic deformation is reversible.

 As the applied load increases, a point reaches such that
deformation is no longer elastic inelastic region

2 possible ways to end elastic stage

by fracture

When elastic range is immediately followed by fracture, the material

is Brittle

by yielding
 Stress strain behaviour

For most metals that are stressed in tension and at elastic

limit, stress and strain are proportional to each other
through the relationship

This is known as Hookes law, and the constant of

proportionality E (GPa or psi) is the modulus of
elasticity, or Youngs modulus
 Plastic deformation

As the material is deformed beyond

elastic limit, the stress is no longer
proportional to strain (Hookes law, ceases
to be valid), and permanent,
nonrecoverable, or plastic deformation
occurs
 Yielding (plastic deformation) corresponds to the breaking
of bonds with original atom neighbors and move to new
equilibrium positions.

The atoms form new bonds in their new positions, there is

no tendency for the atoms to return to their original
positions (also material is not weakened)

Thus the deformation is inelastic and permanent and known

as plastic deformation.

There are two common mechanisms of plastic deformation

by slip
by twinning
 Plastic deformation by slip

Metals are significantly weaker in shear force than in

tension or compression
Hence yielding or plastic deformation occurs under the
action of a shear force

Under the influence of applied force, layers of atom

occupying an equilibrium position in the crystal, starts
sliding to another position of equilibrium
Since atoms occupies a position of equilibrium, it has no
tendency to move back to its original position.
 This displacement is permanent, so shear force causes a
permanent (plastic) deformation.

Here some atoms are said to have slipped past the other
atoms on a certain plane in a certain direction.

This process is called Slip.

Slip do not move with the same degree of ease on all

crystallographic planes of atoms and in all crystallographic
directions

A preferred plane, and in that plane there are specific

directions along which dislocation motion occurs.
 The plane in which slip takes place is known as Slip plane
The direction along which the atoms move is known as Slip
direction

A set of such favoured plane and direction together is

called a Slip system

For a particular crystal structure, the slip plane is the plane

that has the most dense atomic packingthat is, has the
greatest planar density.

The slip direction corresponds to the direction, in this

plane, that is most closely packed with atomsthat is, has
the highest linear density.
 Commonly observed Slip systems in metals

Crystal structure Slip plane Slip Direction

FCC {111} <110>

BCC {110} <111>

HCP {0001} <1120>

Slip occurs along <110> -type directions within the {111} planes, as indicated by
arrows in Figure.
Hence, {111} <110> represents the slip plane and direction combination, or the
slip system for FCC. Figure b demonstrates that a given slip plane may contain
more than a single slip direction.

For face-centered cubic, there are 12 slip systems: four unique {111} planes and,
within each plane, three independent <110> directions.

(a) A {111} <110> slip system shown within an FCC unit cell. (b) The (111) plane from
(a) and three <110> slip directions (as indicated by arrows) within that plane comprise
possible slip systems.
Slip Systems for Face-Centered Cubic, Body-centered Cubic, and
Hexagonal Close-Packed Metals

Metals with FCC or BCC crystal structures have a relatively

large number of slip systems (at least 12). These metals are
quite ductile because extensive plastic deformation is normally
possible along the various systems. Conversely, HCP metals,
having few active slip systems, are normally quite brittle.
SLIP IN SINGLE CRYSTALS

Even though an applied stress may
be pure tensile (or compressive),
shear components exist at all but
parallel or perpendicular alignments
to the stress direction. These are
termed resolved shear stresses

is the applied stress

 Schmids Law

Consider a single crystal of metal having

the shape of a cylindrical bar to which a
unidirectional force F is applied.

Let the angle between slip direction and

applied force be .

Inclination of the normal to slip plane
with the applied force be .

Sum of these two angle and need not

be 90o
 For a dislocation to move along its slip system, a shear force
acting along the slip direction must be produced by the
applied force

The shear force Fr is obtained by resolving the applied force

F along the slip direction as Fr = F cos

If the area of cross section of the cylindrical bar is A0,

area of the slip plane is A = A0 / cos

Resolved shear stress along the slip direction

r = Fr / A = F cos / (A0 / cos ) = F cos cos / A0
 Since
normal stress applied to the bar, = F / A0

r = cos cos

This equation is known as Schmids law.

 A metal single crystal has a number of different slip systems
that are capable of operating.

The resolved shear stress normally differs for each one

because the orientation of each relative to the stress axis
(and angles) also differs.

However, one slip system is generally oriented most

favorablythat is, has the largest resolved shear stress,
(max):
r max = ( cos cos ) max

In response to an applied tensile or compressive stress, slip in

a single crystal commences on the most favorably oriented
slip system when the resolved shear stress reaches some
critical value, termed the critical resolved shear stress
 The critical shear stress cr , is the shear stress
required to break enough metallic bonds in order
for slip to occur.

Plastic deformation occurs only when the applied

stress, produces a resolved shear stress r which is
equal to the critical resolved shear stress r = cr .,
minimum value to initiate slip along slip plane.

and the magnitude of the applied stress required

to initiate yielding is

The minimum stress necessary to introduce yielding
occurs when a single crystal is oriented such that

under these conditions,

 Slip occurs along a number of equivalent and most favorably oriented planes
and directions at various positions along the specimen length.

This slip deformation forms as small steps on

Slip lines in a zinc single crystal.
the surface of the single crystal that are
parallel to one another and loop around the
circumference of the specimen.
On the surface of a polished single crystal
specimen, these steps appear as lines, which
are called slip lines
Plastic Deformation Of Polycrystalline Materials

Deformation and slip in polycrystalline materials is more

complex.

Because of the random crystallographic orientations of the

numerous grains, the direction of slip varies from one grain
to another.

For each, dislocation motion occurs along the slip system

that has the most favorable orientation.
Polycrystalline metals are stronger than their single-crystal
equivalents, which means that greater stresses are required
to initiate slip and yielding as a result of geometrical
constraints that are imposed on the grains during
deformation.
 Plastic deformation by Twinning

In addition to slip, plastic deformation in some metallic

materials can occur by the formation of mechanical twins, or
twinning.

The concept of a twin was, a shear force can produce atomic

displacements such that on one side of a plane (the twin
boundary), atoms are located in mirror-image positions of
atoms on the other side.
 Planes parallel to which atomic movement takes place are
known as Twinning plane

The differently oriented region within the crystal and

between the twinning planes is known as the Twinned
region

Twinning is produced suddenly (within few microseconds)

and is accompanied with sound.
 The displacement magnitude within the twin region (indicated by
arrows) is proportional to the distance from the twin plane.

Twinning occurs on a definite crystallographic plane and in a specific

direction that depend on crystal structure.
For example, for BCC metals, the twin plane and direction are (112)
and [111], respectively

open circles represent atoms that did not move, and dashed and solid circles represent
original and final positions, respectively, of atoms within the twinned region.
 Mechanical twinning occurs in metals that have BCC and
HCP crystal structures
at low temperatures,
and at high rates of loading (shock loading), conditions
under which the slip process is restricted
(few operable slip systems)

amount of Plastic deformation from twinning is normally

small relative to that resulting from slip

the real importance of twinning lies with the

accompanying crystallographic reorientations;
twinning may place new slip systems in orientations that
are favorable relative to the stress axis such that the slip
process can now take place
 Differences
For slip, the crystallographic orientation above and below the
slip plane is the same both before and after the deformation; for
twinning, there will be a reorientation across the twin plane.
In addition, slip occurs in distinct atomic spacing multiples,
whereas the atomic displacement for twinning is less than the
interatomic separation.

Mechanical twinning occurs in metals that have BCC and HCP crystal structures, at
low temperatures, and at high rates of loading (shock loading), conditions under
which the slip process is restricted; that is, there are few operable slip systems.
 The amount of bulk plastic deformation from twinning is
normally small relative to that resulting from slip.

However, the real importance of twinning lies with the

accompanying crystallographic reorientations;

twinning may place new slip systems in orientations that

are favorable relative to the stress axis such that the slip
process can now take place.
 During / in slip During / in twinning

crystallographic above and below reorientation happens

orientation the slip plane is the across the twin plane
same both before
and after the
deformation
size Multiples of inter Fractions of inter atomic
atomic distances distances
Occurence On many slip On a particular plane for
systems each crystal
simultaneously
stress Lesser stress Occurs when slip is
restricted
stress necessary for
twinning is higher
Module 2
 Crystal Defects
Types

Point defects / Zero dimensional

Linear defects / Dislocations / One dimensional

Surface defects / Grain Boundary / Two dimensional

Volume defects
 I. Point defects localised imperfections

a) Vacancy
formed when atoms are missing from a lattice leaving a hole

The number of
vacancies increases
exponentially with
temperature

may be created by
local disturbances during the crystal growth
thermal vibrations causing individual atoms to jump
atomic arrangements in an existing crystal
plastic deformation, rapid cooling
bombardment with energetic particles
b) Substitutional
Alloying elements can dissolve in 2 ways
replace or substitute host atoms in the lattice

impurity atoms fill the voids or interstices among

the host atoms
c) Interstitial
Self interstitial
Self interstitial produces
Interstitial atoms much greater distortions
of the surrounding lattice
Interstitial impurity

Self interstitial Interstitial atoms

 Substitutional a foreign atom substitutes for or
replaces a parent atom in the crystal at a regular site

Interstitial a small sized impurity atom occupying

the void space between the parent atoms on regular
sites.

Impurity atoms cause local distortions in the lattice,

promote atomic diffusion and phase transformations.

Thermal and electrical conductivities also affected by

impurity atoms.
Schematic representation
of different point defects:

(1) vacancy;
(2) self-interstitial;
(3) interstitial impurity;
(4,5) substitutional impurities

The arrows show the local

stresses introduced by the
point defects.
d) Frenkel and Schottky Defects
In ionic crystals, existence of point defects is subjected to
charge neutrality (should be maintained)

Frenkel defect or Frenkel pair forms when an atom or ion

leaves its place in the lattice, creating a vacancy, and becomes
an interstitial by lodging in a nearby location not usually
occupied by an atom

Cations are generally the smaller ions, it is possible for them to get
displaced into the void spaces. (generally anions do not get displaced)

Frenkel defect occur due to thermal vibrations

No defects in the crystal at 0 K

Eg : NaCl crystal structure

 Schottky imperfection

two oppositely charged ions are missing form an ionic crystal

a cation-anion divacancy
Schottky defects facilitate Atomic Diffusion

the presence of these defects in ionic crystals increases their electrical

conductivity
II. Line defects (dislocations)
defects that cause lattice distortion centered around a line
formed by plastic deformation, vacancy condensation, and
atomic mismatch
A dislocation is a linear or one-dimensional defect around
which some of the atoms are misaligned

Two types of dislocations

a) Edge dislocation created by the insertion of an extra half plane

of atoms above

Edge dislocations are termed positive or negative depending upon

the position of the extra plane of atoms
top half positive denoted by
bottom half negative denoted by
 Presence of extra plane of atoms causes a distortion within
the crystal.

The region of the crystal where the extra plane is present

will be in compression and the other region will be in
tension.

Slip occurs in the direction of slip vector and slip plane is

parallel to the slip vector.

The region of the crystal above the slip plane will be

displaced in the direction of slip.

Dislocation is characterised by a vector known as Burgers

vector
Burgers vector is perpendicular to the edge dislocation line
 Within the region around the dislocation line there is
some localized lattice distortion.

The atoms above the dislocation line are squeezed

together, and those below are pulled apart.

The magnitude of this distortion decreases with

distance away from the dislocation line; at positions far
removed, the crystal lattice is virtually perfect.
 Plastic deformation corresponds to the motion of large numbers of
dislocations.
An edge dislocation moves in response to a shear stress applied in a
direction perpendicular to its line

(a) The extra half-plane of atoms is labeled A.

(b) The dislocation moves one atomic distance to the right as A links up to the lower
portion of plane B; in the process, the upper portion of B becomes the extra half-
plane.
(c) A step forms on the surface of the crystal as the extra half-plane exits.
 Let the initial extra half-plane of atoms be plane A.

When the shear stress is applied, plane A is forced to the right;

this in turn pushes the top halves of planes B, C, D, and so on,
in the same direction.

If the applied shear stress is of sufficient magnitude, the

interatomic bonds of plane B are severed along the shear plane,
and the upper half of plane B becomes the extra half plane as
plane A links up with the bottom half of plane B .

This process is subsequently repeated for the other planes, such

that the extra half-plane, by discrete steps, moves from left to
right by successive and repeated breaking of bonds and shifting
by interatomic distances of upper half-planes.
 Before and after the movement of a dislocation through
some particular region of the crystal, the atomic
arrangement is ordered and perfect;

it is only during the passage of the extra half plane that the
lattice structure is disrupted.

Ultimately this extra half-plane may emerge from the right

surface of the crystal, forming an edge that is one atomic
distance wide.
 The formation of a step on the surface of a crystal by the motion of an
edge dislocation.

Note that for an edge, the dislocation line moves in the direction of the
applied shear stress or parallel to the direction of the applied shear stress
 Glide of
an Edge
Dislocation

 Glide of crss
an Edge
Dislocation

crss is
critical
resolved
shear
stress on
the slip
plane in
the
direction
crss of b.
 Glide of crss
an Edge
Dislocation

crss is
critical
resolved
shear
stress on
the slip
plane in
the
direction
crss of b.
 Glide of crss
an Edge
Dislocation

crss is
critical
resolved
shear
stress on
the slip
plane in
the
direction
crss of b.
 Glide of crss
an Edge
Dislocation

crss is
critical
resolved
shear
stress on
the slip
plane in
the
direction
crss of b.
 Glide of crss
an Edge
Dislocation

A surface
step of b
is created
if a Surface
dislocation
step, not a
sweeps
over the dislocation
entire slip
plane

crss
 1 2 3 4 5 6 7 8 9

1 2 3 4 5 6 7 8 9
 1 2 3 4 5 6 7 8 9

Burgers vector
b Slip plane

slip no slip

boundary = edge dislocation

1 2 3 4 5 6 7 8 9
 Edge Dislocation

432 atoms
55 x 38 x 15 cm3
Dislocation Line:
A dislocation line is the boundary between
slip and no slip regions of a crystal

Burgers vector:
The magnitude and the direction of the
slip is represented by a vector b called
the Burgers vector,

Line vector
A unit vector t tangent to the dislocation
line is called a tangent vector or the line
vector.
 S 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
F 1
9
2
8
3
7 A closed
6 Burgers 4

5 Circuit in an 5

4 ideal crystal 6
7
3
8
2
1 9

16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1
F b
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

9 S 1
2
8
3
7
Map the same 4
6
5
Burgers circuit on a 5

4 real crystal 6
7
3
8
2
1 9

16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1

RHFS convention
b is a lattice translation

Surface defect

If b is not a complete lattice translation then a surface

defect will be created along with the line defect.
 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
F
9 S 1
2
8
3
7 4
6
5
5
6
4
7
3
8
2
1 9

16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1
Elastic strain field associated with an
edge dislocation
N+1 planes

Compression
Above the slip plane

Tension
Below the slip plane

N planes
A dislocation line cannot end
abruptly inside a crystal
T

It can end on a free surface

A dislocation line cannot end
abruptly inside a crystal

F
 Screw dislocation
formed by applying a shear stress (upward and downward ) that is
applied to a perfect crystal to produce the distortion that have been
separated by a cutting plane

The upper front region of the crystal is shifted one atomic distance
to the right relative to the bottom portion.

The atomic distortion associated with a screw dislocation is also

linear and along a dislocation line

The slip vector is parallel to the dislocation line

 The symbol is used to designate a screw dislocation.
Burgers vector is parallel to the line of the dislocation (SS) and
perpendicular to the direction of motion of this line
For a screw, the dislocation line motion is perpendicular to the stress
direction.

Crystalline materials contain some dislocations that

were introduced during solidification, during plastic
deformation, and as a consequence of thermal
stresses that result from rapid cooling.
 t

b
b || t

3
2
1
Screw Dislocation (another view)
 Positive Negative

Extra half Extra half

Edge plane above plane below
Dislocation the slip plane the slip plane

Left-handed Right-handed
spiral ramp spiral ramp
Screw
Dislocation b parallel to t b antiparallel to t
most dislocations are of the mixed type
 Movement of dislocations or displacement distance of atoms
around the dislocation : Slip or Burgers vector

Dislocations are characterized by Burgers vector, b.

The direction of motion of dislocations is usually parallel to a

direction of close packing (slip plane) in the structure
III. Planar defects 2 Dimensional defects

regions of distortions that lie about a surface having a

thickness of few atomic diameters

a) External surface the most common type of planar defect,

the atoms on the surface are bonded to other atoms only

on one side, the higher energy associated with these atoms
makes the surface susceptible to reaction.

The bonds of these surface atoms that are not satisfied

give rise to a surface energy,
To reduce this energy, materials tend to minimize, if at
all possible, the total surface area. (in liquids, not for
solids)
b) Grain boundaries

A narrow region between two grains of about 2~5 atomic

diameters in width and a region of atomic mismatch
between adjacent grains

During solidification of metals, when growing crystals

(grains) having different orientations meet each other,
The atomic packing between the adjacent grains get
distorted and a region of imperfection is formed.

This transition zone that is not aligned with either of the grains
is known as grain boundary
 There is a grain boundary energy similar to the surface energy.

The magnitude of this energy is a function of the degree of

misorientation, being larger for high-angle boundaries.

Grain boundaries are more chemically reactive than the grains

themselves as a consequence of this boundary energy.

Furthermore, impurity atoms often preferentially segregate along

these boundaries because of their higher energy state.

The total interfacial energy is lower in large or coarse-grained

materials than in fine-grained ones, since there is less total
boundary area in the former.

Grains grow at elevated temperatures to reduce the total boundary

energy
 c) Twin or Twin boundary

a region in which a mirror image of the structure exists

across a plane or a boundary

Twin boundaries occur in pairs resulting in a region of

different orientation in a crystal.

Twin boundaries are formed during crystal growth,

mechanical deformation or heat treatments

Twinning occurs on a definite crystallographic plane and in a

specific direction, both of which depend on the crystal
structure.
The higher energy of grain boundaries and more open
structure make them more favorable for nucleation and
growth of precipitates
d) Small-angle tilt boundary or Small-angle twist boundary

misorientation angle is generally < 10o

small-angle boundaries are regions of high energy and tend to
strengthen a metal

Tilt boundaries are formed when arrays of parallel edge dislocations

of the same sign get arranged one above the other.
Formed in mechanically deformed materials during the process of
recovery

Twist boundaries are formed by the arrays of parallel screw

dislocations
 a tilt boundary having an angle of
misorientation results from
analignment of edge dislocations.
e) Stacking faults or Piling-up faults

one or more of the stacking planes may be missing, give

rise to another two dimensional defect

Observed in closely packed crystal structures like FCC or

HCP

eg. ABCABAACBABC in FCC crystal

ABAABBAB in HCP crystal
 Surface Defects on crack initiation

Atoms located near the grain boundaries have distorted

or non-equilibrium surroundings and at higher energy
levels similar to exterior surfaces.

Exterior surfaces is usually rough and contains tiny

notches.

These notches initiate cracks and the cracks propagate

along the grain boundaries and lead to inter-granular
fracture.
IV. Volume defects

a cluster of point defects join to form a three-dimensional

void or a pore
a cluster of impurity atoms join to form a three-
dimensional precipitate
the size from a few nm to cm
 Sources of dislocation

Very large number of dislocations are necessary in a crystal

to facilitate plastic deformation.

Dislocations originate through different sources.

Principal source as a natural consequence of crystal
formation and growth, plastic deformation

Even in nearly perfect crystals, there is an equilibrium

concentration of imperfections including dislocations
(only a minor source of supply of dislocations actually needed for
plastic deformation)
 Dislocation multiplication can also arise -
From condensation of vacancies by the cross slip
mechanism
Creation of new dislocations from high angle grain
boundaries
Process of deformation

During plastic deformation, the dislocation density in the

crystals increased by 2 to 6 times depending on the amount
of deformation undergone by the crystal.

This indicates that there is a mechanism of generating

dislocations.
One such mechanism by which dislocation can be generated
from existing dislocation is known as Frank Read source
 Frank-Read source
Consider a segment of dislocation AB lying in a slip plane
(A and B are end points of dislocation on this plane)

If a shear stress acts on this slip plane, the dislocation

bulges out and produces slip

For a given stress, the dislocation line will assume a

certain radius of curvature and the loop continues to
expand under increasing stresses.

When the loop reaches a stage as the segments p and q

will meet, annihilate each other to form a large loop and a
new dislocation segment AB is formed.
 The loop can continue to expand and the segment AB is in
a position to repeat the process.

Frank-Read source can operate continuously and produce

an infinite number of loops, provided the loops disappear
at the surface of crystal.

If the loops are piled up against an obstacle such as grain

boundary, back stress begins to build up at the source and
the source gradually dies out.
 Movement of Dislocations

Motion of a large number dislocations within a crystal

Plastic deformation

Edge dislocation moves in response to a shear stress applied

in a direction perpendicular to the dislocation line Slip

Dislocations also move by processes of

Cross Slip
Climb

When movement of dislocations intersect each other

Jogs and Kinks are formed
 Slip

During slip, atomic bonds at one point are broken and

re-established at another point.

A crystalline solid material may contain many

dislocations of different types which may have
different orientations

The presence of dislocation makes slip easier than in a

perfect crystal
 In slip, only the configuration of dislocation is moving.

The configuration is shifted from one position to the

next by small variations of bond length in the
dislocation region.

This requires lesser force than what is required for

moving atoms by breaking normal bonds in perfect
crystals.
 Cross slip

When a screw dislocation moving along a slip plane encounters an

obstacle, it is blocked from further movement along the plane.

The dislocation can now shift to another intersecting slip plane

and continue to move along this plane.

This is called Cross Slip.

Cross slip can occur only with screw dislocation because a screw
dislocation only can shift to different intersecting slip planes.
(edge dislocations can move along parallel slip planes only)

This is due to the reason that Burgers vector in screw dislocation is

parallel to its dislocation line.
 Intersecting slip planes are present
in FCC and BCC crystals.

Hence cross slip occurs in such

crystals and ductility of metals
having these crystal structures are
better than HCP metals.

In HCP metals, the slip planes are

parallel and no cross slip can occur.

Hence HCP metals tend to be brittle

ones.
 Dislocation climb

An edge dislocation can move out of its slip plane to another parallel
slip plane just above or below it.

This type of dislocation movement is called dislocation climb.

If the slip plane shifts up in a positive edge dislocation(), it is called

positive climb.
For a negative edge dislocation, the upward shift of slip plane is
negative climb.
 The positive climb occurs by diffusion of vacancies to the site of
dislocation.

A row of atoms from the complete plane of atoms are absorbed

by nearby vacancies, thereby reducing the size of the incomplete
plane of atoms and hence shifting the slip plane.

In negative climb, some nearby atoms from normal atomic sites

move to dislocation site and form an additional row of atoms to
the incomplete plane of atoms.

This results in creation of a number of vacancies in the vicinity of

dislocation.
 The process of dislocation climb is due to self diffusion and is
controlled by the temperature level.

At higher temperatures, diffusion and hence climb occurs faster.

Dislocation climb is an important mechanism behind creep in

metals.

Climb is not possible in screw dislocations, as there is no

incomplete plane of atoms involved .

But, the screw dislocation can slip on any plane which contains
the dislocation line and Burgers vector.
 Jogs and Kinks

Figs. shows a cubic crystal in which edge dislocations of different

orientations are present.

A dislocation having Burgers vector b1 and dislocation line AB is

shown in fig (a). It slips along the slip plane PQRS.

Another dislocation in the same crystal having Burgers vector b2

and dislocation line CD as shown in the fig (b). This dislocation
slips along the slip plane WXYZ.

As these dislocations are in the same crystal, the slip planes are
represented together in fig (c).
 When the dislocation AB moves down, it intersects with the
other dislocation CD upon crossing the slip plane WXYZ.

This intersection produces a sharp break called jog in the

dislocation, moving it out of the slip plane.

Fig (d) shows the intersection of two edge dislocations with

Burgers vector at right angles to each other.
 A jog is formed when the Burgers vector of the intersecting
dislocation is normal to the other dislocation line.

Here, b1 is normal to CD and a jog is formed in CD, while b2 is

parallel to AB and no jog is formed in AB.

The resulting jog is parallel to b1 and its length is equal to b1.

The jog JJ also is having the features of edge dislocation and slips
along with the dislocation CD.
 When Burgers vectors of intersecting dislocations are parallel to
each other, jogs are formed on both the dislocations.

These jogs will lie on the original slip planes itself and they will
have features of screw dislocation.

Such jogs are known as Kinks

 Consider the edge dislocation EF having Burgers vector b3 and
moving along the slip plane PQRS as in fig (e).

Another dislocation GH having Burgers vector b4 is moving along

the slip plane WXYZ.

The two slip planes are normal to each other, but the Burgers
vectors are parallel.

Intersection of these dislocation leads to formation of kinks as

shown in fig(f).
 These kinks lie on the same slip planes and move along the same
slip planes.

These kinks are unstable, because they can line up and annihilate
during further slip.
 Forest of Dislocations

The dislocations moving one behind the other along an

active slip plane are called a forest of dislocations

When a dislocation forest intersects with other

dislocations, jogs are formed which restrict further
movement of dislocations.
 Dislocation density is defined as the total length of
dislocation lines per unit volume.

Changes in temperature below recrystallisation

temperature do not have any effect on dislocation density.

But cold working and annealing directly affect dislocation

densities

Completely annealed material contain dislocations of about

104 to 106 mm-2

While cold worked one will have density of 108 to 1010mm-2

 Correlation of Dislocation Density with Strength
and Nano concept

Usually, all crystalline materials will have a certain level of

initial dislocation density.

Cold working increases dislocation density, but leads to

strain hardening.

Strength of a material is inversely related to mobility of

dislocations

Even though cold working increases dislocation density,

strain hardening imposes barriers on mobility which leads
to an increase in strength.
 The yield of nanomaterials is also determined by the ease
with which dislocations can move through the material to
develop plastic strain.

Nanocrystalline metals can be considered as special cases

of polycrysatlline metals in which the grain size is very
small.

This reduction in grain size leads to considerable degree of

strengthening.

Additional strengthening generated through strain

hardening is relatively small.
 All the strengthening mechanisms that are active in
conventional grain size materials are also active in
nanocrystalline materials.

The primary mechanism for Strain hardening is the

increase of dislocation density with increasing plastic
strain, and the subsequent interaction of a moving
dislocation with this increased array of dislocations
 Mechanism of crystallization
(Phase transformation)
2 distinct stages
Nucleation
Growth

Nucleation
Homogeneous
Hetrogeneous
 Nucleation involves the appearance of very small
particles, or nuclei of the solid 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 the parent phase
(liquid phase).

The transformation reaches completion if the growth

of these new phase particles is allowed to proceed until
the equilibrium fraction is attained.
Schematic diagrams of the various stages in the solidification of a polycrystalline material; the
square grids depict unit cells. (a) Small crystallite nuclei. (b) Growth of the crystallites; the
obstruction of some grains that are adjacent to one another is also shown. (c) Upon completion of
solidification, grains having irregular shapes have formed. (d) The grain structure as it would
appear under the microscope; dark lines are the grain boundaries.
 Homogenous and hetrogenous nucleation

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 inhomogeneities, such as
container surfaces, insoluble impurities, grain
boundaries, dislocations, and so on.
 Solidification of metals also known as crystallization - is the
transformation from liquid state to solid state.

When the temperature of the molten metal is brought down,

some atoms may group together in positions exactly
corresponding to the space lattice they assume when
solidified.

These aggregations are not permanent; but continually, break

up and regroup at other points.
 The duration of aggregation depends on the size of the
group and temperature of the liquid.

Lower temperature increases the life of the group and also

promotes the formation of more groups within the liquid.

Such groups are known as EMBRYOS

 Undercooling

As the temperature of the liquid metal drops, a stage is

reached where embryos and the liquid coexist.

This temperature is called solidification or freezing

point.

At this point, both states are at same temperature and

hence the same kinetic energy. But there is significant
difference in the potential energy.
 Atoms in the solid are much closer together resulting in
lower potential energy.

Thus solidification occurs with release of energy.

The difference in potential energy between the liquid and

solid states is known as latent heat

At the freezing point - energy required to establish a

surface between the solid and liquid.

Hence at freezing point, energy is released by the heat of

fusion to create a stable boundary surface.

Hence undercooling is given to form a stable solid region.

 Homogeneous Nucleation

At sufficiently low temperatures, nucleation occurs by the

grouping of a few atoms from the liquid.

Nucleation originated with the support of undercooling is

known as Homogenous nucleation.

This kind of nucleation occurs uniformly throughout the liquid.

The nucleus grows further by adding more and more atoms to

it which leads to a small solid region.

Such stable solid regions within the liquid are called Nuclei.
 Subsequent to the formation of nuclei, release of heat of fusion
takes place and the temperature will be raised to the freezing
point again.

But loss of heat to the surroundings lowers the temperature

again making more atoms to freeze.

These atoms may attach themselves to already existing nuclei

or form a new nuclei of its own.

Thus process of solidification continues apparently at constant

temperature till the entire liquid is transformed into solid.
 Homogenous nucleation

involves thermodynamic parameter called Gibbs free

energy, G

a transformation will occur spontaneously only when G

has a negative value.
Eg : Solidification of a pure material

two contributions to the total free energy change that accompany

a solidification transformation

1. free energy difference between the solid and liquid phases, or

the volume free energy, Gv

(Its value will be negative if the temperature is below the

equilibrium solidification temperature (freezing temp.), and
the magnitude of its contribution is the product of Gv and
the volume of the spherical nucleus (i.e. 4/3 r3))

2. formation of the solidliquid phase boundary

 Associated with solidliquid
phase boundary is a surface free
energy, ,

which is positive whose

magnitude is the product of and
the surface area of the nucleus
(i.e., 4r2 ).

Total free energy change is equal to the sum of these two

contributions
(a)Schematic curves for volume free energy and surface free energy
contributions to the total free energy change attending the formation
of a spherical embryo/nucleus during solidification.

(b) Schematic plot of free energy versus embryo/nucleus radius, on

which is shown the critical free energy change (G*) and the critical
nucleus radius (r*).
 volume, surface, and total free energy contributions
are plotted schematically as a function of nucleus
radius

the volume free energy, Gv (which is negative)

decreases with the third power of r

for the curve resulting from the second term in

equation, energy values are positive and increase with
the square of the radius.
 The curve associated with the sum of both terms (Fig. b) first
increases, passes through a maximum, and finally decreases.

This means that as a solid particle begins to form as atoms in the

liquid cluster together, its free energy first increases.

If this cluster reaches a size corresponding to the critical radius

r*, then growth will continue with the accompaniment of a
decrease in free energy.

A cluster of radius less than the critical radius will shrink and
redissolve.

This subcritical particle is an embryo, whereas the particle of

radius r* greater than is termed a nucleus.
 A critical free energy, occurs at the critical radius and, consequently,
at the maximum of the curve in Fig. b.

This G* corresponds to an activation free energy, which is the free

energy required for the formation of a stable nucleus.
It may be considered as an energy barrier to the nucleation process.

Since r* and G* appear at the maximum on the free energy-versus-

radius curve
 This volume free energy change Gv is the driving force for the
solidification transformation, and its magnitude is a function of
temperature.

At the equilibrium solidification temperature Tm, the value of Gv is

zero, and with diminishing temperature its value becomes increasingly
more negative.

where Hf is the latent heat of fusion (i.e., the heat given up during
solidification)

Thus, both the critical radius r* and the activation free energy
G* decrease as temperature T decreases.
Schematic free energy-versus-embryo/nucleus radius curves for
two different temperatures.
This means that with a lowering of temperature at temperatures
below the equilibrium solidification temperature (Tm), nucleation
occurs more readily. Furthermore, the number of stable nuclei n*
(having radii greater than r*) is a function of temperature as
 critical nucleus size mainly determined by GV

amount of undercooling increases, the critical nucleus size decreases

Schematic diagrams of the various stages in the solidification of a polycrystalline material; the
square grids depict unit cells. (a) Small crystallite nuclei. (b) Growth of the crystallites; the
obstruction of some grains that are adjacent to one another is also shown. (c) Upon completion of
solidification, grains having irregular shapes have formed. (d) The grain structure as it would
appear under the microscope; dark lines are the grain boundaries.
 Heterogeneous nucleation

Nucleation is facilitated by the presence of some impurity atoms, an

inoculant (grain refiner), an imperfection or a grain boundary
Addition of grain refiners to molten metal can produce fine grained
grains. The grain refiners solidify earlier and form large number of
small solid particles in the liquid. Solidification of liquid is initiated
by heterogenous nucleation around these solid particles.

This type of preferential nucleation is called heterogenous nucleation.

A much lower level of undercooling is sufficient for this type of

nucleation to occur.

Even walls of the container promotes heterogenous nucleation

 In heterogenous nucleation, the activation energy (i.e.,
energy barrier) for nucleation is lowered when nuclei form
on pre existing surfaces or interfaces, since the surface free
energy is reduced.

In other words, it is easier for nucleation to occur at

surfaces and interfaces than at other sites.

Again, this type of nucleation is termed heterogeneous.

 Heterogeneous nucleation

occurs in a liquid on the surface of its container, insoluble

impurities and other structural materials that lower the
critical free energy required to form a stable nucleus
the surface energy to form a stable nucleus on the nucleating
agent is lower
much smaller amount of undercooling is required to form a
stable nucleus
 three interfacial energies (represented as vectors) that
exist at two-phase boundariesSL,na-S and na-Las
well as the wetting angle ,

na-L = na-S + SLCos

 Free energy- versus-embryo/nucleus radius plot on which are presented
curves for both homogeneous and heterogeneous nucleation.
 The critical radius for heterogeneous nucleation is the
same as for homogeneous, in as much SL as is the
same surface energy as

the activation energy barrier for heterogeneous

nucleation is smaller than the homogeneous barrier by
an amount corresponding to the value, S() function
 Nucleation rate versus temperature for both homogeneous and
heterogeneous nucleation. Degree of supercooling (T)
 Dendritic growth

During the process of solidification, each nucleus grows by

attracting atoms from the liquid into the space lattice.

Crystal growth continues in three dimensions

This gives rise to the characteristic tree-like structure

which is called a Dendrite

Since each nucleus is formed by chance, the crystal axes are

pointed at random, and dendrites growing from them will
grow in different directions in each crystal.
Crystal growth and grain formation

nuclei crystals grains

polycrystalline solidified metal containing many crystals

grains crystals in solidified metal
A grain is a portion of the material within which the
atomic arrangement is nearly identical
grain boundaries the surfaces between the grains

Two major types of grain structures:

equiaxed grains crystals grow about equally in all directions,

commonly found adjacent to a cold mold wall
columnar grains long, thin, coarse grains, created when
metal solidifies rather slow in the presence of a steep
temperature gradient,
columnar grains grow perpendicular to the mold surface
 Grains

The randomly formed nuclei will have different

crystallographic orientations.

All the neighbouring grains will be oriented differently due

to its independent formation.

As these nuclei grow, the outer arms of the neighbouring

grains meet

Finally, further growth becomes impossible, the remaining

liquid is used up in thickening the existing dendrite arms
and solidification will be completed.
 Grain size

The microstructure of single phase materials can be varied

by the changes in size, shape and orientation of grains.

Both shape and size of grains are related to the prevailing

conditions during grain growth.

The rate at which molten metal is cooled when it reaches the

freezing point affects the size of the crystal which forms.

A small fall in temperature, which leads to a small degree of

undercooling for solidification, promotes the formation of
relatively few nuclei, so that the resultant crystal size will be
large.
 Rapid cooling on the other hand, leads to high degree of
supercooling, and the solidification results in the
formation of a large number of nuclei and hence large
number of crystals or grains smaller in size will be formed

Grain size in materials can also be controlled by the

combination of controlled deformation and heat
treatments called Thermo mechanical treatments

A well designed thermomechanical process gives a

microstructure with a preferred orientation of grains and
tailored material properties.
 Grain size determination

Grain size and number of grains are quantified by the standard by

American society for testing of materials (ASTM).

Grain size is specified by an index called ASTM grain size number

N=2 (n-1)

N = average number of grains per square inch at a magnification of 100x

n is the grain size number

A large ASTM grain size number indicates large number of grains of a

fine grain size implies high strength of material.
 Effect of grain size on material properties

In a fine grained material there is more grain boundaries

Grain boundaries are obstructions to movement of

dislocations

Moving dislocations pile up near the grain boundaries

More stress needs to be applied in order to deform the

material.

So, a fine grained material is having more strength and

hardness, at the same time it will have poor ductility
 Grain shape

Nature of the container in which liquid solidifies will also

affect the shape and number of grains.

The mould is cold and has a chilling effect. This results in

the formation of a large number of nuclei and consequently
large number of fine grains along the surface.

As the mould is warmed up, chilling effect is reduced, so

that nuclei formation retarded.

Thus crystals formed towards the centre of the mould will

be larger in size.
 Latent heat of crystallization, liberating from the crystallizing metal,
decreases the undercooling of the melt and depresses the fast grains
growth.

At this stage some of small grains, having favorable growth axis, start
to grow in the direction opposite to the direction of heat flow.

As a result columnar crystals (columnar grains) form.

Length of the columnar grains zone is determined by the

constitutional undercooling.

When the temperature of the melt, adjacent to the solidification

front, increases due to the liberation of the latent heat,
constitutional undercooling will end and the columnar grains
growth will stop.
Further cooling of the molten metal in the central zone will
cause formation of large (Coarse) equiaxed grains.
 If the mould is narrow or longer, the equiaxed zone (at centre)
may be absent

Metallic mould tends to produce a fine grained structure,

while sand mould, a Coarse grained structure (at mould wall).

Thin sections are subjected to relatively larger rate of cooling

resulting in fine grains.
 Effects on Dislocation and Creep

A high angle grain boundary represents an area of lattice

disorder between neighbouring grains.

This can be viewed as a group of immobile dislocations

which forms a step or grain boundary ledge.

As the angle of mismatch increases, density of ledge

increases.
 Moving dislocations tend to pile up at grain boundaries.

These pile ups introduce stress concentration ahead of the

slip planes and generate new dislocations in adjacent
grains.

As more slip planes operate near the grain boundaries,

hardness will be higher near the boundary than the centre.

When the grain size is reduced, the behaviour near the

boundary will also be felt at the centre of grain and the
grains will have uniform hardness.

Creep (a grain boundary sliding phenomenon) becomes

prominent with increasing temperature and deformation
occurs by sliding along boundaries.
 Hall - Petch Equation

A fine-grained material (one that has small grains) is harder and

stronger than one that is coarse grained, since the former has a
greater total grain boundary area to impede dislocation motion.

For many materials, the yield strength varies with grain size
according to Hall - Petch equation. (not valid for both very large
and extremely fine grain materials)

Hall - Petch equation gives a relationship between the yield

stress and grain size of a material.

where y is the yield strength, d is the average grain diameter,

and 0 and ky are constants for a particular material
 Grain size may be regulated by
the rate of solidification from the liquid phase,
and also by plastic deformation followed by an appropriate
heat treatment.

It should also be mentioned that grain size reduction

improves not only strength, but also the toughness of many
alloys.

Small-angle grain boundaries are not effective in

interfering with the slip process because of the slight
crystallographic misalignment across the boundary.
 On the other hand, twin boundaries will also effectively
block slip and increase the strength of the material.

Boundaries between two different phases are also

impediments to movements of dislocations; this is
important in the strengthening of more complex alloys.

The sizes and shapes of the constituent phases significantly

affect the mechanical properties of multiphase alloys.
 The influence of grain size on the yield strength.

Note that the grain diameter increases from right to left and is not linear.
 Diffusion

Diffusion is the phenomenon of material transport by

atomic motion.

It is the process of mass flow by which atoms change its

position relative to their neighbours under the influence of
thermal energy and a gradient.

Simply it is the stepwise migration of atoms from lattice

site to lattice site.
 Rate of diffusion has a major role in achieving optimum
properties in a solid material

The carburisation of steel is controlled by diffusion rate of

atoms through the surface.

The diffusion phenomenon also assists introducing very

small concentration of impurities in semiconductors.
 The process by which atoms of one metal diffuse into
another is called inter diffusion or impurity diffusion.

Diffusion occurring in pure metals is called self diffusion,

where atoms of the metal exchange their positions.

Although self diffusion occurs continually in all materials,

it does not contribute any significant effects on the
properties of the material.
 Diffusion Couple

Many reactions and processes that are important in the

treatment of materials rely on the transfer of mass (or atom)
either within a specific solid or from a liquid/gas or another
solid phase.

This is necessarily accomplished by diffusion, the

phenomenon of material transport by atomic motion.

The phenomenon of diffusion may be demonstrated with the

use of a diffusion couple, which is formed by joining bars of
two different metals together so that there is intimate
contact between the two faces; this is illustrated for copper
and nickel in Figure
 Figure 1 includes schematic representations of atom
positions and composition across the interface.

This couple is heated for an extended period at an elevated

temperature (but below the melting temperature of both
metals), and cooled to room temperature.

Chemical analysis will reveal that, represented in Figure 2

concentrations of both metals vary with position as shown in
Figure 2(c).
Figure 1

(a) A coppernickel diffusion

couple before a high-
temperature heat treatment.

(b) Schematic representations of

Cu (red circles) and Ni (blue
circles) atom locations within
the diffusion couple.

(c) Concentrations of copper and

nickel as a function of position
across the couple.
Figure 2

(a) A coppernickel diffusion

couple after a high- temperature
heat treatment, showing the
alloyed diffusion zone.

(b) Schematic representations of

Cu (red circles) and Ni (blue
circles) atom locations within
the couple.

(c) Concentrations of copper

and nickel as a function of
position across the couple.
 This result indicates that copper atoms have migrated or
diffused into the nickel, and that nickel has diffused into
copper.

This process, whereby atoms of one metal diffuse into

another, is termed interdiffusion, or impurity diffusion.

There is a net drift or transport of atoms from high- to low-

concentration regions.
 Mechanisms of Diffusion

For an atom to move from its lattice site, two conditions are
to be satisfied :
(a) there must be an empty neighbouring site
(b) the atom must have sufficient energy to break bonds with
surrounding atoms

Vacancy Diffusion
Interstitial Diffusion
Interstitialcy Diffusion
Direct Interchange Diffusion
 Vacancy Diffusion

Interchange of an atom from a normal site to an adjacent

vacant site or a vacancy.

When this happens, a vacancy is created at another site, to

which another atom can move creating a vacancy elsewhere.

Hence, Vacancy diffusion can be viewed as a movement of

vacancies from site to site

This process necessitates the presence of vacancies within the

lattice of a material.
 Extent to which vacancy diffusion can occur is a function of
the number of vacancies

Significant concentration of vacancies may exist in metals

at elevated temperatures.

Both self diffusion and interdiffusion can occur by this

mechanism.
 Interstitial Diffusion

This involves migration of atoms from one interstitial

position to a neighbouring atom.

This mechanism is found commonly in interdiffusion of

smaller atoms of another species which can easily fit into the
interstitial positions.

In most metal interstitial diffusion occurs much more

rapidly than that by vacancy mode, since interstitial atoms
are smaller and thus more mobile.

Further, there are more empty interstitial positions than

vacancies
 Interstitialcy Diffusion

In this mechanism, an atom occupying an interstitial site

forces a regular atom to leave its site to an interstitial site.

Continuation results in interstitialcy diffusion.

 Direct interchange diffusion

In this case two or more adjacent atoms jump past each

other and exchange positions.

This may takes place between 2, 3 or 4 atoms.

When four atoms are involved it is also known as Ring

diffusion or Zenner ring diffusion.

This mechanism results in severe local lattice distortion,

requiring much more energy for the atoms to jump
 Kirkendal effect: In a diffusion couple, of metal A and B, the rate
at which A and B diffuse in each other are not necessarily be equal.
Usually the lower melting component diffuses more faster into the
other than vice-versa.

Diffusion flux (J). The quantity of mass diffusing through and

perpendicular to a unit cross-sectional area of material per unit
time. It is proportional to concentration gradient.

Diffusion coefficient (D). The constant of proportionality

between the diffusion flux and the concentration gradient in Ficks
first law. Its magnitude is indicative of the rate of atomic diffusion.

Concentration gradient (dC/dx). The slope of the concentration

profile at a specific position.
concentration(C) of the diffusing element is plotted v/s
position (or distance) within in the solid resulting curve -
concentration profile
 Steady-state diffusion. The diffusion condition for which there
is no net accumulation or depletion of diffusing species. The
diffusion flux is independent of time.

Nonsteady-state diffusion. The diffusion condition for which

there is some net accumulation or depletion of diffusing species.
The diffusion flux is dependent on time.

Activation energy (Q). The energy required to initiate a

reaction, such as diffusion.
 Ficks laws of Diffusion

Ficks first law. The diffusion flux is proportional to the

concentration gradient. This relationship is employed for steady-
state diffusion situations.

Diffusion is a time-dependent processthat is, the quantity of

an element that is transported within another is a function of
time.

It is necessary to know how fast diffusion occurs, or the rate of

mass transfer
 This rate is frequently expressed as a diffusion flux (J), defined
as the mass (or, equivalently, the number of atoms) M diffusing
through and perpendicular to a unit cross-sectional area of solid
per unit of time.

In mathematical form, this may be represented as

where A denotes the area across which diffusion is occurring and

t is the elapsed diffusion time.
(a) Steady-state diffusion across a thin plate. (b) A linear
concentration profile for the diffusion situation in (a).
 In differential form, this expression becomes

If the diffusion flux does not change with time, a steady-state

condition exists.

One common example of steady-state diffusion is the diffusion

of atoms of a gas through a plate of metal for which the
concentrations (or pressures) of the diffusing species on both
surfaces of the plate are held constant.
 When a steady-state diffusion in a single (x) direction, the flux is
proportional to the concentration gradient,

J dC/dx or

The constant of proportionality D is called the diffusion

coefficient.

The negative sign in this expression indicates that the direction

of diffusion is down the concentration gradient, from a high to a
low concentration.
 Ficks first law of diffusion is expressed as

=
 Ficks second law. The time rate of change of concentration is
proportional to the second derivative of concentration. This
relationship is employed in nonsteady-state diffusion situations.

Most practical diffusion situations are nonsteady-state ones.

That is, the diffusion flux and the concentration gradient at

some particular point in a solid vary with time.

The flux at a different cross sectional planes along the diffusion

direction are not equal.

Also the flux at a given cross section is a function of time.

 Under conditions of nonsteady state, use of Ficks 1st law Equation
is no longer convenient;

instead, the partial differential equation

known as Ficks second law, is used.

If the diffusion coefficient is independent of composition

 Factors affecting diffusion process

Nature of the diffusing species atomic diameter, bonding,

melting point etc..
Concentration of the medium into which diffusion takes place
Crystal structure atomic packing factor, atomic density along
diffusion direction, distortion of crystal lattice etc..
Presence of crystal imperfections provides path for diffusion
Grain size fine grains mean more grain boundaries and hence
more diffusion paths
Temperature higher the temperature faster the diffusion
Impurities presence of impurities slows down diffusion