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
K3Fe(CN)6 10 grams Pre-mix KOH and water and alloys uses fresh and immerse; Ni-
Murakami's KOH 10 grams before adding Cu 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.
 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.
 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 self 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
 Diffusion - Mechanisms
1. Vacancy
2. Interstitial 2
3. Self-Interstitial 1
4. Direct Interchange

5 3

Zenner ring
4
Factors affecting diffusion
 Size of concentration gradient – More the
concentration gradient, higher the rate of
diffusion.
 Size of diffusing atoms – Smaller the size of
atoms, higher the rate of diffusion.
 Diffusing surface area – Diffusion rate increases
for larger surface areas.
 Temperature – Temperature increases the rate
of diffusion.
 Viscosity of the medium – More the viscosity
lesser will be the diffusion rate.
Factors affecting diffusion (high concentration
gradient)
Factors affecting diffusion (low concentration
gradient)
Factors affecting diffusion (low surface area)
 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 second 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.
Answer – 84 atoms / min