Module 2

Mechanism of crystallization: homogeneous and heterogeneous nuclei

formation, under cooling, dendritic growth, grain boundary irregularity.
Effects of grain size, grain size distribution, grain shape, grain orientation on
dislocation/strength and creep resistance - hall - petch theory, simple
problems
Classification of crystal imperfections: - types of dislocation – effect of point
defects on mechanical properties - forest of dislocation, role of surface defects
on crack initiation.
Burgers vector –dislocation source, significance of frank read source in
metals deformation - correlation of dislocation density with strength and
nano concept, applications.
Significance high and low angle grain boundaries on dislocation – driving
force for grain growth and applications during heat treatment.
Polishing and etching to determine the microstructure and grain size.
Fundamentals and crystal structure determination by X –ray diffraction,
simple problems –SEM and TEM.
Diffusion in solids, fick’s laws, mechanisms, applications of diffusion in
mechanical engineering, simple problems.
 Solidification/Freezing
 Freezing, or solidification, is a phase change
during which a liquid turns into a solid when its
temperature is lowered below its freezing point.
 For most of the substances, the melting and freezing
points are the same temperature; however, certain
substances possess differing solid–liquid transition
temperatures.
 The solidification of metallic, polymeric, and ceramic
materials is an important process to study because of
its effect on the properties of the materials involved.
 During solidification of molten/liquid crystalline
materials, formation of crystals take place and the
process is called as crystallization.
Solidification process
 Importance of solidification/Freezing
 Solidification is considered one of the most important
manufacturing processes.
 Several million pounds of steel, aluminum alloys, copper, and
zinc are being produced through the casting process.
 High-quality optical fibers and other materials, such as
fiberglass, also are produced from the solidification of molten
glasses.
 Many thermoplastic materials such as polyethylene, polyvinyl
chloride (PVC), polypropylene, and the like are processed into
useful shapes (i.e., fibers, tubes, bottles, toys, utensils, etc.)
using a process that involves melting and solidification.
 Crystallization

 Crystallization refers to the formation of solid crystals from

a homogeneous solution/melt.
 Crystallization is the process through which the atoms,
molecules or ions arrange themselves in a repeating
pattern.
 Crystallization is the (natural or artificial) process of
formation of solid crystals precipitating from a solution,
melt or more rarely deposited directly from a gas.
 The crystallization process consists of two major events,
nucleation and crystal growth
 The solubility of most compounds decreases as the
temperature is lowered thus produce crystals and rapid
cooling may cause the precipitation of amorphous solid or
microscopic crystals
 Nucleation
 In the context of solidification, the term nucleation refers to the
formation of the first stable nanocrystallites from molten
material.
 In a broader sense, the term nucleation refers to the initial stage of
formation of one phase from another phase.
 Aggregation of molecules/ions builds larger and larger and becomes a
nucleus at some point
 The materials solidify as the liquid cools to just below its freezing (or
melting) temperature, since the energy associated with the crystalline
structure of the solid is then less than the energy of the liquid.
 This energy difference between the liquid and the solid is the free
energy per unit volume Gv and is the driving force for solidification.
• When the solid forms, a solid-liquid
interface is created. A surface free
energy sl is associated with this
interface.
 Nucleation
 There are two types of nucleation: homogeneous and
heterogeneous.
 The distinction between nucleation 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.
 Undercooling/supercooling
 Just below the melting point of the solid, at freezing
point, atoms will cluster together called embryos,
an equilibrium state of solid and liquid exist.
 At this stage embryos can form and dissolve.
 An appreciable nucleation rate (i.e., solidification)
will begin only after the temperature, below the
equilibrium solidification (or melting) temperature.
 This phenomenon is termed supercooling (or
undercooling), and the degree of supercooling for
homogeneous nucleation is significant.
 Homogeneous nucleation
 At temperatures sufficiently below the solidification temperature,
nucleation occurs by grouping of few atoms from the liquid.
 In homogeneous nucleation, nucleation originates at the time of
undercooling.
 Homogeneous nucleation is uniform throughout the liquid.
 If the size of the nucleated atoms are sufficiently large enough to
be stable then the cluster of atoms is called as nuclei.
 During the formation nuclei, the kinetic energy of the atoms in
the liquid will be released as heat energy; which in turn increases
the local heat surrounding the nuclei.
 This heat energy is compensated by the heat loss to the
surrounding and freeze more and more atoms.
 Atoms can attach to existing nuclei or form their own nuclei.
 The process continuous till the entire fluid is transformed to a
solid.
 The theory of nucleation/Phase transformations involves a
thermodynamic parameter called free energy (or Gibbs free
energy), G.
 A transformation will occur spontaneously only when G has a
negative value.
 In solidification of a pure material, the nuclei of the solid phase
form in the interior of the liquid as atoms cluster together to form a
packing arrangement similar to that found in the solid phase.
 It is assumed that each nucleus is spherical in geometry and has a
radius r.

The total free energy is contributed by the

free energy difference between the solid
and liquid phases, or the volume free
energy, Gv, its value is negative and
energy associated with solid–liquid phase
boundary or surface free energy  .
 Nucleation
 The total change in
energy G,
G  43 r 3G v  4r 2
4
 r and 4r are the
3 2
3
volume and surface area
of sphere with radius ‘r’.
 Gv is the free energy
change per unit volume
  is the surface free
energy of the solid-liquid
interface
Gv negative since the phase transformation is assumed
to be thermodynamically feasible.
* and Gv are not a strong function of r
 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.
 On the other hand, a cluster of radius less than the critical will shrink
and redissolve. This subcritical particle is an embryo, whereas the
particle of radius greater than r* is termed a nucleus.
 A critical free energy, G*, occurs at the critical radius and G*
corresponds to an activation free energy, which is the free energy
required for the formation of a stable nucleus.
 It can 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
dG  4
dr
 
 3 Gv 3r 2  4 (2r )  0
 Which leads to the result

 Substitution of this expression for r* and results G*

 This volume free energy change Gv is the driving force for the
solidification transformation, and its magnitude is a function of
temperature.
 At the temperature at which the solid and liquid phases are predicted to be
in thermodynamic equilibrium (i.e., at the freezing temperature), the free
energy of the solid phase and that of the liquid phase are equal (Gv = 0),
so the total free energy change (G) will be positive.
 This means that with a lowering of temperature at temperatures below the
equilibrium solidification temperature (Tm), nucleation occurs more
readily.
 When the solid is very small with a radius less than the critical radius for
nucleation (r*), further growth causes the total free energy to increase.
 The critical radius (r*) is the minimum size of a crystal that must be
formed by atoms clustering together in the liquid before the solid particle
is stable and begins to grow.
 Heterogeneous Nucleation
 The activation energy (i.e., energy barrier) for nucleation is
lowered when nuclei form on preexisting 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, this type of
preferential nucleation is termed heterogeneous
nucleation.
 A low level of undercooling is required to initiate this type
of nucleation.
 Walls of the container promotes heterogeneous nucleation.
 Addition of grain refiner to molten metal produce fine
grains, since the grain refiner solidifies faster and act as
sites for heterogeneous nucleation thereby reducing the size
of the grains formed,
 In order to understand this phenomenon, let us consider
the nucleation, on a flat surface, of a solid particle from a
liquid phase.
 It is assumed that both the liquid and solid phases ―wet‖
this flat surface, that is, both of these phases spread out and
cover the surface.
 There are three interfacial energies (represented as vectors)
that exist at two-phase boundaries— SL, SI and IL—as well
as the wetting angle (the angle between the and vectors).
 Heterogeneous nucleation of a solid from a liquid.
The solid–surface (SI), solid–liquid (SL), and
liquid–surface (IL), interfacial energies are
represented by vectors. The wetting angle is also
shown.
 Dendritic growth
 If the nucleation in liquid is not initiated and the nucleation
is poor, the liquid has to be undercooled before the solid
forms.
 Under these conditions, a small solid protuberance called a
dendrite, which forms at the interface, is encouraged to
grow since the liquid ahead of the solidification front is
undercooled.
 Under the aforesaid conditions, the solid nucleus are grown
by attracting atoms from the liquid to form space lattice.
 As the crystal grows in three dimension, the attachment of
atoms take place only in preferred directions, mainly along
the axes of the crystal.
 The growth has tree like appearance and it is called as
dendrite (The word dendrite comes from the Greek word
dendron that means tree) .
Dendritic growth in 3D
 The final shape of the dendrite is in the form of a skeleton,
forms primary, secondary and tertiary arms, which will be
similar to the branches and twigs growing from the trunk of a
tree.
 As the solid dendrite grows, the latent heat of fusion is
conducted into the undercooled liquid, raising the
temperature of the liquid toward the freezing temperature.
Secondary and tertiary dendrite arms can also form on the
primary stalks to speed the evolution of the latent heat.
 Dendritic growth continues until the undercooled liquid
warms to the freezing temperature.
 The dendritic arms can grow longer/thicker till the space
between them is filled with solid.
 In pure metals, dendritic growth normally represents only a
small fraction and there wont be any evidence of dendritic
growth.
 If impurity is present it will solidify between the dendritic
arms
 (a) If the liquid is undercooled, a protuberance on the solid-liquid interface
can grow rapidly as a dendrite. The latent heat of fusion is removed by
raising the temperature of the liquid back to the freezing
 temperature. (b) Scanning electron micrograph of dendrites in steel.
Grain boundary irregularity
Cooling curve
 Grain boundary irregularity

 During solidification of liquid metals, when crystals

or grains with different atomic orientations meet
each other, as the grains are formed from different
nucleus.
 The atomic packing between the two adjacent grains
will be distorted and the region can be considered as
imperfection.
 The transition zone, where atoms are aligned neither
of the neighboring grains are called grain boundary.
 Atoms at the grain boundary had more energy than
the atoms at the interior of the grains.
 (a) The atoms near the boundaries of the three grains
do not have an equilibrium spacing or arrangement.
(b) Grains and grain boundaries in a stainless steel
sample.
 Grain size
 The microstructure of single phase materials can be varied by changes
in the size, shape and orientation of grains.
 The size and shape of the grains are associated with the prevailing
conditions during grain growth.
 The rate of cooling of the molten material can affect the grain growth.
 If the cooling rate is too slow (small degree of undercooling), at the
onset of nucleation, only a few nuclei will form and the growth
commences only from those nuclei, and the resultant crystal sizes will
be large.
 If the cooling rate is rapid (high degree of undercooling/supercooling) a
large number of nuclei will form and the resulting crystal will be small.
 The grain sizes can be adjusted with the help of thermo-mechanical
treatments.
 A well designed thermo mechanical process gives microstructure with
preferred orientation gives tailored material properties.
 Effect of grain size on material properties

 In a fine grained material, there are more grain

boundaries within the bulk of material.
 Grain boundaries are obstructions to dislocation
movements.
 Dislocations will pile-up at the grain boundaries.
 Therefore, more stress will be needed to deform such
materials.
 Thus, A fine grain material has more strength and
hardness.
 These materials will have poor ductility.
 Grain shape
 The nature of the container in which the liquid metal
cools also affect the shape and number of grains.
 Large number of fine grains will be formed at the
contact point of the mold and the solidifying metal.
 when the molten metal first strike the mold create a
chilling effect, which results in fine grained metal at
the surface.
 As the mol is warmed, the chilling effect will reduce
and the nuclei formation retards as the solidification
progresses.
Grain shape…..

 In the intermediate portion nature of cooling is

favorable to the formation of columnar grains.
 At the centre of the mold equi-axed grains can be
observed.
 The distinguished grains will be observed in large
molds, in narrow molds equi-axed grains will be
absent.
 A metallic mould can give fine grained structure and
a sand mold can give a course grained structure.
* equi-axed means equal length in all the three dimensions
 Orientation of grains

 Grains are formed are having random crystallographic

orientation.
 Grains can be grown in specified directions using
metallographic techniques.
 Grains of iron grown in [100] direction have a higher
magnetic permeability than any other orientation.
Effects of Grain size, shape and orientation on
dislocation and creep
 …
 Various degrees of crystallographic
misalignment between adjacent grains
are possible.
 When this orientation mismatch is
slight, on the order of a few degrees,
then the term small- (or low- )
angle grain boundary is used.
 One simple small angle grain boundary
is formed when edge dislocations are
aligned in the manner as in Figure, a
regular array. This type is called a tilt
boundary.
 When the angle of misorientation is
parallel to the boundary, a twist
boundary results, which can be
described by an array of screw
dislocations. tilt boundary having an angle of misorientation
results from an alignment of edge dislocations.
 When this orientation mismatch is large, on the order of a
appreciable degrees, then the term high angle grain
boundary is used.
 As the angle of mismatch increases the density of grain
boundary ledges will increase, and they are good sources of
dislocation.
 Moving dislocations can pile up at the grain boundary and
induce stress concentration ahead of the slip planes and can
create dislocation in adjacent grains.
 If the slip planes are more at grain boundaries, harness will
be high at grain boundaries than the center.
 As the grain size reduces, the grain boundary behavior will
be experienced at the center also, so grains will have
uniform hardness.
 Small grains barriers dislocation mobility lead to
higher strength and hardness.
 Strain hardening is grater in fine grained material
than the course grained material.
 Grain boundary sliding observe at temperatures
above o.5 Tm , this sliding is prominent with
increasing temperature and the deformation caused
by sliding of grain boundaries.
 This phenomenon is called as creep in materials.
 Hall-Petch equation
 One method of controlling the properties of a material is by
controlling the grain size. By reducing the grain size, we
increase the number of grains and, hence, increase the
amount of grain boundary area. Any dislocation moves only
a short distance before encountering a grain boundary, and
the strength of the metallic material is increased.
 The Hall-Petch equation relates the grain size to the
yield strength,

 where y is the yield strength (the level of stress necessary

to cause a certain amount of permanent deformation), d is
the average diameter of the grains, and 0 and K are
constants for the metal.
 The Hall-Petch equation is not valid for materials with
unusally large or ultrafine grains.
 The Hall-Petch constants of AZ31 Magnessium alloys
are K= 0.5 MPa.m1/2 and σ0 = 3 MPa, what is the
yield strength of the if the grain size is 4m.
 Crystal imperfections
 Point Defects or zero dimensional
 Vacancy

 Self interstitial or interstitialcy

 Interstitial impurity

 Substitutional Inpurity

 Frenkel defect

 Schottky defect

 Line defects- or one dimensional defect

 Edge dislocation

 Screw dislocation

 Surface defects or two dimensional defect

 Grain boundaries

 Tilt boundaries

 Twin boundaries

 Stalking fault

 Volume defects or 3-dimentional defects

 Vacancies

 If an atom is mission from the regular lattice site,

then it is called as vacancy.
 This defect arise due to imperfect packing of atom or
by the thermal vibrations at high temperature.

distortion
of planes

Vacancy
 Self interstitial or interstitialcy

 This is the inverse of vaancy, where atom squeezes into the

in the space between the normal lattice positions.
 Interstitial spaces are very small and such interstital
produces greater distortions to the surrounding lattice than
a vacancy.

distortion
of planes

self-interstitial
 Impurities
 Impurities are atoms of a foreign material.
A substitutional impurity refers to a forgein atom
substitutes/replaces a forgein atom in a regular crystal site.
An Interstitial impurity is a small sized atom occupying
the void space between the parent atoms on regular sites.
 Frenkel defect

 This defect is present in ionic crystal.

 In ionic crystals, even if the defects are present
overall electrical neutrality should be maintained.
 When an ion is displaced from a regular site to
another, then it is called as frenkel defect.
 The cations are smaller ions, therefore it is possible
for them to get displaced into the void spaces.
 Anions can’t occupy the void space, since the voids or
interstitial sites are too small to accomodate them.
 Schottky defect
 When a pair of cation anion is missing from the lattice of a
ionic crystal, the defect is known as Schottky defect.
 Schittky defect is similar to vacncy in normal crystals.
 Types of Dislocation

 The linear disturbances of atomic arrangements are

called line defects or dislocations
 Edge dislocation
 Screw dislocation
Effect of point defects on mechanical
properties -
forest of dislocation,
Role Of Surface Defects On Crack Initiation.
 Driving force for grain growth and
applications during heat treatment

 If the metal specimen is kept at the elevated temperature,

the grains will grow and the resultent grains become coarse.
 This phenomenon is called grain growth.
 Larger grains have lower free energy and it will result in the
reduction in amount of grain boundary.
 The lowest energy of the metal would be as that of a single
crystal.
 The driving force for grain growth is the reduction
in energy.
 The force opposing this driving force is the rigidity
of the lattice and it will decrease as the
temperature is increased, as a result grain growth will
be rapid.
 For any given temperature, there is maximum grain
size at which these forces are at equilibrium.
 The factors which favors slow nucleation can result
in rapid growth and it will result in a coarse grained
material.
 Factors that govern grain growth

1. Degree of prior deformation

 Amount of prior deformation favors nucleation and decreases
the final grain size.
 At critical deformation, the grain will grow to a very large size
upon annealing.
 If the deformation is low the lesser will be the distorted region
that can act as nucleation sites.
 Only a few few grains will be formed during crystallization,
resulting a coarse grained structure.
 With the increase in deformation, the number of
nucleationsites will be more and there by the number of grains.
 Time at temperature
 Increasing the time at any temperature above the
recrystallization temperature favors the grain growth and
increases the final grain size.
 Annealing temperature.
 The lower the grain size above the recrystallization
temperature, the finer will be the grain size.
 At low temperature diffusion rate will be slower thereby grain
growth.
 Insoluble impurities
 Greater the amount and finer the distribution of dissolvable
impurities, finer the grain size
 They not only act as nucleation sites, but also act as barriers to
grain boundary movements, results in finers grains
 Determination of microstructure
 Metallography is the part of metallurgy related to
the study of metals by microscopic examination
using optical or electron microscope.
 Metallographic examination reveals the structure of
grains, grain boundaries, presence of microphases,
line defects and surface defects.
 Optical microscope is used to study the features
and internal make up of the material at microscopic
level.
 The magification level of optical microscope is 2000x.
 For this purpose, the surface of the small sample is
prepared first.
Cu-Ni Alloy Steel

Tool Steel Heat treated Steel

 Selecting and cutting the specimen
 The specimen selected for the study should be a true
representative of the material being studied.
 In the case of casting, welding, case hardening etc., the
structure and composition of the material varies
considerably within a single component. In such cases,
specimens should be chosen from the area of interest.
 After selecting the particular region from the mass, the
specimen has to cut carefully using a saw or abrasive wheel.
 While cutting the specimen should not be heated to avoid
the further change in the microstructure.
 Speciments of sizes 10-15mm in diameter or square is
preffered and smaller samples should be mounted using
thermoplatic resin.
 Rough grinding

 First step in grinding is to make the surface

absolutely flat.
 It can be done using a file, rotating grinding wheel or
a motor diven emery belt.
 It is prefered to keep the file stationary and rub the
specimen against it.
 Again care must be taken to avoid heating.
 The specimen shold washed to remove the coarse
filings and abrasive particles.
 Intermediate and fine grinding
 This is carried out by emery papers of progressively
smaller grit sizes.

 The emery paper is kept on a flatsurface, such as

glass and the specimen is rubbed against it in a
single direcion.
 Once the grinding is completed, the specimen should
be washed thorouthgly.
 Intermediate and fine grinding
 If the specimen is first groung with emery paper with a
grit size of 220, the new scratches should be at 90o to the
previous grinding.
 The process should repeat with subsequent grit papers,
320, 400, 600 etc...
 While transfering the ginding papers, the specimen
should be turned 90o.
 The grinding should be continued till all the scratches
from the previous grinding disappears.
 Machine grinding is also possible by fixing the emery
paper on a rotating wheel.
 Fine grinding is done in a manner similar to the previous
grit sizes and the emery papers will be designated as 1/0,
2/0, 3/0, 4/0.
 Once the fine grinding is completed, the specimen surface
will be shining and scratch free on visual inspection
 Polishing
 During fine grinding a series of parallel groves will be left
on the sample surface by the last emery paper employed.
 Polishing is meant to remove these groves.
 Polishing is done by a polishing cloth pad impregnated with
suitable polishing medium.
 The cloth is wetted with distilled water and a small
quantity of polishing powder or paste is aplied.
 The specimen is pressed against the rotating wheel and
moved opposite to the direction of rotation.
 Harder specimens (Steel/iron) are generally given two
stage polishing.
 Diamond powder in the for of paste or slurry or alumina
are the common materials used (0.5-1.0 m).
 Non-ferrous materials are polished by magnessia
 Polishing...

 At the end of the polishing, the surface should be

scratch free with perfectly shining appearence.
 The surface should appear as a mirror.
 When the sample, after cleaning, is examined under
optical microscope at 100x, the surface should be
scratch free.
 Etching
 Before etching the specimen can be checked for
inclusions, slags, flakes etc.
 The mechanism of polishing is such that it leaves an
amorphous metal on the surface and true structure
will not be revealed.
 An etchent is used to dissolve this amorphous layer
so as to observe the microstructural features under
the microscope.
 In alloys, preferential etching is required to dissolve
the one or more phases.
 Etching is different for different phases, because of
the difference in chemical composition and
difference in the orientation of grains.
 Before etching the surface of the specimen should be
thoroughly cleaned.
 Surface can be cleaned by dipping the sample in
boiling alcohol.
 Once the sample in cleaned, the specimen is etched
by dipping the specimen into the etching reagent and
agitated for several second.
 One the sample is treated with etchents, the
specimen is very quickly transfered to water wash
away the etchent.
 During etching, the bright appearence of the sample
may be lost and it become dull and in some materials
grain structure may be visible.
Before etching

After etching
 Common etchents
chant Composition Conc. Conditions Comments
Copper ammonium chloride 9 grams
Hydrochloric acid 150 ml Immersion is recommended For etching 300 series stainless steel
Adler Etchant
Ferric chloride, hydrated 45 grams for several seconds and Hastelloy superalloys
DI Water 75 ml
CuCl2 5 grams For etching duplex and 400 series
Immersion or swabbing etch
Kalling's No. 2 Hydrochloric acid 100 ml stainless steels and Ni-Cu alloys and
at 20 degrees Celsius
Ethanol 100 ml superalloys.
Distilled water 190 ml
Nitric acid 5 ml 10-30 second immersion. Use Excellent for aluminum and titanium
Kellers Etch
Hydrochloric acid 3 ml only fresh etchant alloys.
Hydrofluoric acid 2 ml
Distilled water 92 ml
Kroll’s Reagent Nitric acid 6 ml Swab specimen up to 20 Excellent for titanium and alloys.
Hydrofluoric acid 2 ml seconds
Most common etchant for Fe, carbon
and alloys steels and cast iron -
Ethanol 100 ml Immersion up to a few
Nital Immerse sample up from seconds to
Nitric acid 1-10 ml minutes.
minutes; Mn-Fe, MnNi, Mn-Cu, Mn-Co
alloys.
CuSO4 10 grams For etching Ni, Ni-Cu and Ni-Fe alloys
Immerse or swab for
Marble's Reagent Hydrochloric acid 50 ml and superalloys. Add a few drops of
5-60 seconds.
Water 50 ml H2SO4 to increase activity.
Cr and alloys (use fresh and immerse);
iron and steels reveals carbides; Mo and
K3Fe(CN)6 10 grams Pre-mix KOH and water alloys uses fresh and immerse; Ni-Cu
Murakami's KOH 10 grams before adding alloys for alpha phases use at 75
Water 100 ml K3Fe(CN)6 Celcius; W and alloys use fresh and
immerse; WC-Co and complex sintered
carbides.
Recommended for microstructures
Seconds to minutes containing ferrite, carbide, pearlite,
Ethanol 100 ml
Picral Do not let etchant crystallize martensite and bainite. Also useful for
Picric acid 2-4 grams
or dry –explosive magnetic alloys, cast iron, high alloy
stainless steels and magnesium.
 Optical microscope

Biological Metallurgical
 Optical microscope

 Study of microstructure is carried out using reflected

light, as the light cannot penetrae the system.
 The major parts of the microscope are;
 Illuminating system
 Objective lens
 Eyepiece lens
 The maximum possible magnification is 2000x
 The objective lens convert the refleced light frm the
surface to an image, it also magnifies the image.
 In eyepiece the observer views the magnified image.
Optical microscope-Grains
X-ray Diffraction: Determination of
Crystal Structures
DIFFRACTION
 Diffraction occurs when a wave encounters a series of
regularly spaced obstacles that (1) are capable of scattering
the wave, and (2) have spacings that are comparable in
magnitude to the wavelength.
 Furthermore, diffraction is a consequence of specific phase
relationships established between two or more waves that
have been scattered by the obstacles.
 Waves 1 and 2 with the same wavelength are in phase.
 If both waves are scattered in such a way that they traverse
different paths.
 The scattered waves, have a difference in path length which
will be an integral number of wavelengths and they will
mutually reinforce or constructively interfere with one
another; and amplitudes are added.
 Other phase relationships are possible between scattered waves that
will not lead to this mutual reinforcement. The other extreme is
wherein the path length difference after scattering is some integral
number of half wavelengths.
 The scattered waves are out of phase—that is, corresponding
amplitudes cancel or annul one another, or destructively interfere (i.e.,
the resultant wave has zero amplitude).
X-Ray Diffraction and Bragg’s Law
 X-Ray Diffraction and Bragg’s Law
 X-rays are a form of electromagnetic radiation that
have high energies and short wavelengths—
wavelengths on the order of the atomic spacings for
solids.
 When a beam of x-rays impinges on a solid material,
a portion of this beam will be scattered in all
directions by the electrons associated with each atom
or ion that lies within the beam’s path.
 Necessary conditions for diffraction of x-rays by a
periodic arrangement of atoms.
 Consider the two parallel planes of atoms A-Aʹ and B-Bʹ in Figure, which
have the same h, k, and l Miller indices and are separated by the
interplanar spacing dhkl.
 Now assume that a parallel, monochromatic, and coherent (in-phase)
beam of x-rays of wavelength is incident on these two planes at an angle .
 Two rays in this beam, labeled 1 and 2, are scattered by atoms P and Q.
 Constructive interference of the scattered rays 1ʹ and 2ʹ occurs also at an
angle  to the planes, if the path length difference between 1-P-1 and 2-Q-2
(i.e., SQ+QT ) is equal to whole number, n, of wavelengths.
 That is, the condition for diffraction is
n= SQ +QT
n=dhkl sin+dhklsin
n=2dhklsin
 This equation is known as Bragg’s law; also, n is the order of
reflection, which
 may be any integer (1, 2, 3, . . . ) consistent with not exceeding unity.
 X-ray Diffraction Techniques

 Laue method
 A single crystal is held stationary on the path of the beam,
where is kept constant.
 A white radiation is directed to the crystal so that nemerous
values of the wavelength are available.
 The right combination lead to proper diffraction condition
 Rotating crystal method

 A monochromated X-ray beam is made to fall on a

single crystal of the material.
 The single crystal is rotated about an axis so that
various sets of lattice planes come successively into
reflecting positions.
 At some point the codition for diffraction will be
satisfied.
 Powder method

 The powder method is used to determine the value of

the lattice
 If a monochromatic x-ray beam is directed at a single
crystal, then only one or two diffracted beams may
result. parameters accurately.
 Powder method

 If the sample consists of some tens of randomly

orientated single crystals, the diffracted beams are
seen to lie on the surface of several cones. The cones
may emerge in all directions, forwards and
backwards.
 Powder method
 A sample of some hundreds of crystals (i.e. a
powdered sample) show that the diffracted beams
form continuous cones.
 A circle of film is used to record the diffraction
pattern as shown. Each cone intersects the film
giving diffraction lines. The lines are seen as arcs on
the film. Powder sample
Circular film strip

4
Incident rays
 The distance S=R4
 The camera radius=1rad = 57.3
Scanning electron microscope
 In SEM, the surface of a specimen to be examined is
scanned with an electron beam, and the reflected (or back-
scattered) beam of electrons is collected, and then
displayed at the same scanning rate on a cathode ray tube
(similar to a CRT television screen).
 The image on the screen, which may be photographed,
represents the surface features of the specimen.
 The surface may or may not be polished and etched, but it
must be electrically conductive; a very thin metallic surface
coating must be applied to nonconductive materials.
 Magnifications ranging from 10 to 50,000 times are
possible.
 Accessory equipment permits qualitative and semi-
quantitative analysis of the elemental composition of very
localized surface areas.
Transmission electron microscope
 The image seen with a transmission electron microscope
(TEM) is formed by an electron beam that passes through
the specimen.
 Details of internal microstructural features are accessible to
observation; contrasts in the image are produced by
differences in beam scattering or diffraction produced
between various elements of the microstructure or defect.
 Since solid materials are highly absorptive to electron
beams, a specimen to be examined must be prepared in the
form of a very thin foil; this ensures transmission through
the specimen of an appreciable fraction of the incident
beam.
 The transmitted beam is projected onto a fluorescent
screen or a photographic film so that the image may be
viewed. Magnifications approaching 1,000,000 are
possible with transmission electron microscopy, which is
frequently utilized in the study of dislocations.
 Replicas of materials made with polymer were used
in TEM earlier.
 Presently, the thin films of the material itself is used
for the analysis, wafers of 250 m were cut from the
bulk material using diamond cutter and then
thinning is done using grinding. Final thinning is
done by electrochemical process or ion milling.
 The features like dislocation, stalking fault,
formation of subgrains without crystallization etc.,
can be only observed in TEM.
 Diffusion
 Diffusion is the phenomenon of material transport by
atomic motion.
 It is the process of mass flow by which atoms change their
position relative to their neighbors under the influence of
thermal energy and a gradient.
 This process, whereby atoms of one metal diffuse into
another, is termed interdiffusion, or impurity
diffusion.
 Diffusion also occurs for pure metals, but all atoms
exchanging positions are of the same type; this is termed
self-diffusion. In self-diffusion, normally, no
compositional and property changes are observed.
 Diffusion in solids
 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;
 If the diffusion couple is heated for an extended period at
an elevated temperature (but below the melting
temperature of both metals), and then cooled to room
temperature.
 Chemical analysis will reveal that the concentrations of
both metals vary with position.
 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.
 Mechanism of Diffusion
 From an atomic perspective, diffusion is just the stepwise
migration of atoms from lattice site to lattice site.
 For an atom to diffuse, two conditions must be met:
 There must be an empty adjacent site
 The atom must have sufficient energy to break bonds with its
neighbor atoms and then cause some lattice distortion during
the displacement.
 The energy is vibrational in nature. At a specific temperature
some small fraction of the total number of atoms is capable of
diffusive motion, by virtue of the magnitudes of their
vibrational energies. This fraction increases with rising
temperature.
 Several different models for this atomic motion have been
proposed; there are two dominating models for metallic
diffusion, vacancy diffusion and interstitial diffusion.
 Vacancy Diffusion
 This mechanism involves the interchange of an atom from a
normal lattice position to an adjacent vacant lattice site or
vacancy and the mechanism is termed vacancy diffusion.
 This process necessitates the presence of vacancies, and the
extent to which vacancy diffusion can occur is a function of the
number of these defects that are present.
 Since diffusing atoms and vacancies exchange positions, the
diffusion of atoms in one direction results in the motion of
vacancies in the opposite direction.
 Both self-diffusion and inter-diffusion occur by this mechanism;
for the inter-diffusion, the impurity atoms must substitute for
host atoms.
 Interstitial Diffusion
 The second type of diffusion involves atoms that migrate from an
interstitial position to a neighboring one that is empty.
 Impurities such as hydrogen, carbon, nitrogen, and oxygen, which have
atoms that are small enough to fit into the interstitial positions.
 Host or substitutional impurity atoms rarely form interstitials and do
not normally diffuse via this mechanism.
 In most metal alloys, interstitial diffusion occurs much more rapidly
than diffusion by the vacancy mode, since the interstitial atoms are
smaller and thus more mobile.
 Furthermore, there are more empty interstitial positions than
vacancies; hence, the chances of interstitial atomic movement are
greater than for vacancy diffusion.
 Interstitialcy (Self interstitial) Diffusion
 In this mechanism an atom occupying an interstitial
site forces a regular atom to leave it site to an
interstitial site.
 Continuation of this results in interstitial diffusion.

Interstitialcy Diffusion
 Direct Interchange Diffusion
 In this case two or more adjascent atoms jump past each
other and exchange positions.
 This may take place between two, three or four 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
 Kirkendall Effect
 In a binary solution of A and B, the rates at which A and B
are not necessarily equal.
 Usually, the lower melting component diffuses much faster
than the other.
 Inert markers (thin rods of a high melting point substances
which is insoluble in the diffusion matrix) are placed at the
weld joint of the couple, prior to the diffusion anneal.
 These markers are found to shift during the anneal in the
slower moving species. The extent of this shift is found to
be proportional to the square root of the diffusion time.
 The kind of movement indicates that the net mass flow due
to the difference in diffusivities is being compensated by a
bulk flow of matter in the opposite direction within the
diffusion zone. Notice that the bulk flow occurs relative to
the ends of the diffusion couple.
 Fick’s Laws
Fick’s First Law of diffusion- steady-state diffusion
 Diffusion is a time-dependent process; i.e., the quantity of an element
that is transported within another is a function of time.
 This is necessary to know how fast diffusion occurs, or the rate of mass
transfer.
 The rate of mass transfer is frequently known as 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,

 The units for J are kilograms or atoms per meter squared per second
(kg/m2-s or atoms/m2-s).
 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 concentration C is plotted versus position (or distance)
within the solid x, the resulting curve is termed the
concentration profile; the slope at a particular point on
this curve is the concentration gradient:
 Fick’s first law states that, for a steady-state
diffusion process in a single (x) direction, the flux
is proportional to the concentration gradient.

C C
J or J   D
x x

 The constant of proportionality D is called the diffusion

coefficient, which is expressed in square meters per second.
The negative sign in this expression indicates that the
direction of diffusion is from a high to a low concentration.
 One example of steady-state diffusion is found in the
purification of hydrogen gas. One side of a thin sheet of
palladium metal is exposed to the impure gas composed of
hydrogen and other gaseous species such as nitrogen,
oxygen, and water vapor.
 The hydrogen selectively diffuses through the sheet to the
opposite side, which is maintained at a constant and lower
hydrogen pressure.
Fick’s secon Law of diffusion- Non-steady-state
diffusion
 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, with a net
increase or reduction of the diffusing species.
 Consider an elemental volume of length x along the
diffusion direction and a unit cross sectional area.
 The rate of accumulation or depletion of the diffusing
species is C
x
t

 The difference in flux in and out of the slab is;

 C   J 
 t  x  J x  J x  x  J x   J x  x x 
 C  J C J
 t  x   x x or t

x Unit Area

 Using first law; Flux in Jx

Flux out Jx+x

x
 C   C   2C
   D  D 2
t x  x  x
C x  2C x
or D
t x 2
 Cx concentration of the diffusing species at some distance x
from the surface.
 The diffusivity D, is independent of concentration
eventhough in actual situations D varies with
concentration.
 Applications of Diffusion
Determination of diffusion coefficient
 The diffusion coefficient D can be determined experimentally using a
diffusion couple (two bars of metals placed very close to each other Cu and
Ni). At room temperature the thermal energy is insufficient to cause an
appreciable diffusion. It the couple is heated to a higher temperature, near
melting point, the diffusion of species start from bar 1 to bar 2 and vice versa.
The effect of this diffusion is first at the interface, and it then proceed interior
to the bars.
Corrosion resistance in duralumin
 Duralumin is an alloy of aluminium with 4% copper. In the properly heat
treated condition, the alloy has the strength which is several times more than
that of aluminium and light in weight. Thus, it is widely used in aircraft
industries. The corrosion resistance of duralumin is poor compared to that of
aluminium, hence the sheets of duralumin is sandwiched between thin sheets
of pure aluminium and rolled to improve the corrosion resistance. This
sandwich like material is called alclad. This material is heated to 550C for
giving the appropriate heat treatment to increase the strength. The copper
from duralumin can diffuse into pure aluminium sheets and damage its
corrosion resistance. Therefore, the thickness of the aluminium sheet and
duration of elevated heating must be controlled.
Carburization of steel
 Surface hardening of steel objects (gears, cams etc.) to improve their
resistance against wear, indentation etc. is done by carburizing and
nitriding. When the steel object is annealed at an elevated temperature
in the carburizing medium, carbon diffuses into the steel from the
surface under a concentration gradient.
Decarburization of steel
 The opposite of carburization is decarburization. Here, the carbon is
lost from the surface layers of the steel, due to an oxidizing atmosphere
that reacts with carbon to produce CO and CO2. The fatigue resistance
in steel is lowered due to decarburization. The extent of decarburizing
can be estimated from the diffusion equation and post-machining
operations can be undertaken to remove the decarburized layer.
Doping in semiconductors
 Semiconductor devices are doped with small controlled quantities of
impurities for obtaining the desired electrical characteristics. The
dopant atoms may be diffused into the pure semiconductor crystal from
a gaseous atmosphere. The depth of penetration and the amount of
dopant in the crystal can be estimated following the same procedure as
given for the carburization problem.
Melting and Casting
 This is a widely used technique for the production of metals, alloys,
plastics and glasses.
 Diffusion plays an important role in the solidification of metals and
alloys,
Sintering
 Refractory materials like ceraamics and some metals are processed to
useful shapes by compacting the small powdered partcles, followed by
heating at high temperature. During heating diffusion take place and
the cavities between the parcle disappear.
Oxidation of aluminium
 Aluminium oxide acts as very thin protective coating on the surface of
aluminium. The oxide layer protects the diffusion of oxygen and thus
prevents the further oxidation.
Beverage bottles
 PET bottles used for carbonated beverages are suitable to minimize the
escape of CO2 by diffusion
 This ensures that the beverages will not loose their fizz for a reasonable
period of time.