UNIT IV MATERIAL CHARACTERIZATION TESTING

Macroscopic and Microscopic observations, Optical and Electron microscopy (SEM and TEM) - Principles,

Types, Advantages and Limitations, Applications. Diffraction techniques, Spectroscopic Techniques,

Electrical and Magnetic Techniques- Principles, Types, Advantages and Limitations, Applications.
❑Committee on Characterization of Materials, Materials Advisory Board, National Research Council developed the
definition of Material Characterization: “ Characterization describes those features of composition and structure
(including defects) of a material that are significant for a particular preparation, study of properties, or use, and
suffice for reproduction of the material ”.

❑ Materials Characterization has 2 main aspects:

✓ Accurately measuring the physical and chemical properties of materials

✓ Accurately measuring (determining) the structure of a material (Atomic level structure & Microscopic level
structures)

❑ Mechanical, Electrical and magnetic properties of a material are strongly dependent on its structural
characteristics. Therefore, material characterization is very important part of any structure-property correlation
exercise.

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 SPACE LATTICE
A 3D network of imaginary lines connecting the atoms.

UNIT CELL

❑ Smallest unit having the full symmetry of the crystal is called the unit cell.
❑ The simplest portion of a lattice that can be repeated by translation to cover the entire
1-D, 2-D, or 3-D space.
❑ The specific unit cell for each metal is defined by its parameters, which are the edges
of the unit cell a, b, c and the angles α (between b and c), β (between a and c) and γ
(between a and b).
❑ There are 14 possible types of space lattices (Bravais lattice), and they fall into 7
crystal systems.

c
α
β b Replaces repeating element
γ ( atoms, molecule, base etc.)
a
3
 14 Bravais Lattices divided into 7 Crystal Systems

A Symmetry based concept ‘Translation’ based concept

Crystal System Lattice Parameters Bravais Lattices

P I F C
1 Cubic (a = b = c,  =  =  = 90)   
2 Tetragonal (a = b  c,  =  =  = 90)  
3 Orthorhombic (a  b  c,  =  =  = 90)    
4 Hexagonal (a = b  c,  =  = 90,  = 120) 
5 Trigonal (a = b = c,  =  =   90) 
6 Monoclinic (a  b  c,  =  = 90  )  
7 Triclinic (a  b  c,     ) 

P Primitive
Basis of definition of crystals is
I Body Centred
‘symmetry’ and hence the
classification of crystals is also based F Face Centred
on symmetry
C A/B/C- Centred 82
 Crystalline and Noncrystalline Materials

❑ Isotropic Materials: If the properties of the material are independent of the

direction in which they are measured, the material is categorized as isotropic.
❑ Anisotropy Materials: If the properties of the material are dependent of the
direction in which they are measured, the material is categorized as
anisotropic. Examples of these properties include: Periodicity of atoms in a
crystal structure, Density of a material of crystalline solids, Carrier velocity,
Phonon velocity etc.
❑ Allotropy: Elements that can exhibit more than one crystal structure are
allotropic.
❑ Polymorphism: Compounds that behave in the same manner as allotropic
materials are referred to as polymorphism.
❑ Single Crystal: A continuous periodic crystal structure only interrupted by the
boundaries of the solid
❑ Amorphous: Although short range periodicity may be present, long range
periodicity is absent. Hence, amorphous material is not crystalline.
❑ Polycrystalline: A material composed of from two to many single crystal
grains.

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7
❑ light is a stream of invisible particles or corpuscles wave length
❑ light is an electromagnetic wave

1m wave length in nm
amplitude
750
IR
650

600

visible light 550

UV 500
100nm
X-ray
380

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 Reflection of light Refraction of light

 1
air

 
1 2  =
1 2

 2
glass

 1

s p e e d o f light in air
Index of refractionof the substance =
s p e e d o f light in the substance

C0 = f   c0 n2 sin1
ns = =
speed of light in cs n1 sin 2
vacuum Frequency wave length
n (air) = 1.0 n (water) = 1.33 n(glass)=1.5
3 x 10^10 cm/sec.

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10
❑ Three basic ways by which image can be formed:
➢ Projection image- formation of a shadows when an object is placed in
front of a point source of illumination.
➢ Optical image- formed by conventional lens systems.
➢ Scanning image- each point of the picture is presented serially (e.g.-
television picture).

Magnification: Image size/Object size

❑ The fineness of detail that can be distinguished in an image.

❑ The smallest distance between two points that we can resolve with our eyes is
about 0.1- 0.2 mm → Resolution/Resolving power of human eye
❑ Any instrument that can show us pictures revealing detail finer than 0.1 mm
could be described as a microscope
❑ Shorter wavelength  greater resolution
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A microscope is an instrument to see small objects with naked eye.
Optical microscope; is a type of microscope which uses visible light and a system of
lenses to magnify images of small samples.
There are two basic configurations of the conventional optical microscope in use, the
simple (one lens) and the compound (many lenses).
Differences between biological microscope and metallurgical microscope
Essentially, a metallurgical microscope refers to a high power microscope used for the
purposes of viewing opaque objects (objects in which light cannot pass through) these
types of microscopes are different from the typical biological microscopes in that they use
the principle of reflected light microscopy. This makes them ideal for viewing
metallurgical samples as well as a variety of other opaque objects (ceramics, plastics,
rocks etc).
Optical Microscopes
➢ Optical microscopes are the oldest microscopes.

➢ Optical microscopes are the simplest and most used types.

➢ Optical microscopes use visible wavelengths of light.

History of optical microscopes

• Middle of the 15th centruies, one lens is used.

• Hans and Zacharias Janssen in 1600,in Holland. They realized that couple of lenses
zoom objects while he was manufacturing glasses.

• (1632-1723) Anton van Leeuwenhoek. He created microscope which zooms object 270
times and he started to researh the bacteria.
Basic Components
• Eyepiece Lens: the lens at the top that you look
through.
• Tube: Connects the eyepiece to the objective lenses
• Objective Lenses: Usually you will find 3 or 4 objective
lenses on a microscope. They almost always consist of
4X, 10X, 40X and 100X powers.
• Rack Stop: This is an adjustment that determines how
close the objective lens can get to the slide.
• Condenser Lens: The purpose of the condenser lens is
to focus the light onto the specimen.
• Stage: The flat platform where you place your slides.
Stage clips hold the slides in place.
• Revolving Nosepiece or Turret: This is the part that
holds two or more objective lenses and can be rotated
to easily change power.
• Illuminator: A steady light source (110 volts) used in
place of a mirror. If your microscope has a mirror, it is
used to reflect light from an external light source.
• Arm: Supports the tube and connects it to the base
• Base: The bottom of the microscope, used for support
 Microscope stand eyepiece

❑ Carrier of all changeable

components tube
❑ High mechanical stability
❑ High thermal stability
tube lens
❑ Precise focusdrive

Lampe house objective

❑ Integrated illumination for stage

transmitted light
❑ separate lampehouses for condenser
incident- and transmitted light.
❑ special lampehouses for
fluorescence
illumination

Microscope Stand41
 Condenser

❑ Collect illumination light rays and converge them to a focus

❑ Contains the aperture diaphragm for homogeneous illumination
❑ Increases resolution, enhances contrast, reduces glare

Condenser top

Condenser disc
 Specimen stages Objective

❑ Object guide ❑ Tubus length 160mm

❑ x/y - stage ❑ different objective classes
❑ Scanning stage ❑ Magnification (1,6x - 100x)
❑ Pol rotary stage ❑ 4x -red, 10x-yellow, 40x blue, 100x grey
❑ Heated stage ❑ Different apertures

Objective lens Cross section of a typical objective 44

 Objective

magnification
objective type

coverglass
Numerical
specification
aperture

Correction classes of objectives

Objectiv class Field of view Chromatic correction
C PLAN 20mm Achromat
N PLAN 22mm Achromat
PL >25mm Semi Apochromat
FLUOTAR
PLAN APO >25mm Apochromat
PL APO (CS) >25mm Apochromat, smaller
tollerances for
confocal applications
APO U-V-I 20mm Apochromat
UV, visual light, IR-
Transmission 22
 Tube

❑ monocular tube
L Plan 10x/20 L Plan 15x/20
❑ binocular tube
❑ binocular Phototube
❑ Ergonomy tube
❑ Special tubes
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V2

25
26
84% of Light

Abbe Equation

d 1.22
d r= =
2 2NA

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 Rayleigh Criteria

Two adjacent object points are defined as being resolved when the central diffraction
spot (Airy disk) of one point coincides with the first diffraction minimum of the other
point in the image plane

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 ΔI = 26.4%

Intensity distribution of two Airy disks with a distance d/2

d 1.22 0.61
Resolution (R) = = =
2 2 NA NA
Self Luminous Body

d 1.22
Resolution (R) = =
2 NA Con + NAObj Non Luminous Body
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Metallography:
✓ A systematic method to examine microstructure of materials (mainly metallic materials).
✓ Can also be used to examine ceramics, polymers and semiconductors.

(1) Sectioning

Why sectioning?
1. Size limitation of specimen to be examined under optical microscope.
2. Locate area needs to be selected from a large sample.

Abrasive Cutting: It is the most common sectioning method.

Electric Discharge Machining (EDM):

❑ Electrically conductive materials can be produced via EDM.
❑ Cutting is accomplished by an electric discharge between an electrode and the sample
submerged in a dielectric fluid.

Microtomy:
❑ Useful for preparing soft materials such as polymer samples.
❑ Steel, glass or diamond knives in a microtome can cut samples into very thin sections.
 (2) Mounting

Required when
(1) the sample is small or too oddly shaped to be handled.
(2) The sample edge area needs to be examined

Thermal Mounting:
The sample is encased in thermosetting or thermoplastic polymers at high temperature
and pressure

Cold Mounting:
The sample is encased in epoxy type materials. Type of epoxy depends upon material
being analyzed.

Adhesive Mounting: The sample is glued to a piece of a large holder

Clamp Mounting: The sample is fixed in mechanical clamping devices

 (3) Grinding

❑ Removes the damage from the surface produced by sectioning.

❑ Grinding also produces damage which must be minimized by subsequent grinding
with finer abrasives.
❑ At the end of grinding phase, the only grinding damage present must be from the last
grinding step.
❑ Such damage will be removed by polishing.

Grinding Materials: Abrasive paper (covered with silicon carbide grit).

Commonly a series of abrasive papers are used from coarse to fine.
Typical Grit Sequence: 120-, 240-, 320-, 400-, 600-, 1200-, 2400-, etc.

❑ The initial grit size depends on the surface roughness and depth of damage from
sectioning.
❑ Surfaces cut with abrasive cutoff saws generally start with 120- to 240- grit surface
finishes.
❑ Surfaces cut by EDM or diamond saws generally start with 320- to 400- grit surface
finishes.
 (4) Polishing

❑ After being ground to a 600-grit finish (or better), the sample is polished to produce
a flat and scratch-free surface with high reflectivity.
❑ Coarse polishing: abrasives in the range of 30 μm to ~3 μm using diamond grits of
the appropriate size.
❑ Fine polishing: abrasives in the range of 1μm or less using diamond grits of the
appropriate size.
❑ Final polishing: 0.25-0.05 μm diamond, silica, or alumina slurries.
 (5) Etching

❑ Using chemicals to selectively dissolve the surface of a material in order to reveal

microstructural details
❑ Grain boundaries are more susceptible to etching.
❑ May be revealed as dark lines.
❑ Due to change in crystal orientation across GB.

❑ Etching is basically a controlled corrosion process. Results from electrolytic action

between surface areas of different potential.
❑ Electrolytic activity results from local physical or chemical heterogeneities which
render some features anodic and others cathodic under the specific etching
conditions.
❑ Chemical Etchants produce contrast by
– Crystal faceting
– Selective phase dissolution.
❑ Common chemical etchants have three components:
– A corrosive agent (acids)
– modifier ( alcohol, glycerin…)
– An oxidizer (hydrogen peroxide, Fe3+, Cu2+…)
Reflected light micrographs
of Fe-1.0%C steel
 We can analyse with optical microscope
• Grain Boundaries

• Phase boundaries

• Microstructure

Some materials that can be determined in optical microscope

• carbides in steels.

• SiC particules in metals such as Ti orAl.

• Fiberglasses which glass fiber in epoxy resin.

 Applications
Optical microscopy is used extensively in;
• Microelectronics
• Material Science and Geology
Non-transparan objects(Ex:metals and alloys)
• Biotechnology (Analyzing transparanobject)
• Pharmaceutic Research
• Microbiology

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Views of Optical Microscope

Clinker of cement (x50)

37
 view of Al2O3

Grain boundaries and grain sizes of electrolytic iron

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 Advantages & Disadvantages

• Optical microscopes can enlarge only times of

1000,because of using light.
• Optical microscopes are not able to display details
that smaller than 250 nm which is the half wave
length of the light.
• On the light ways air is an accepteble thing so living
samples can analyse with optical microscope.
• In structure analyse generally light reflection is used
so optical microscopes are convenient to distiguish
some ranges,distributions,shifting bants and basic
properties in samples.

39
A scanning electron microscope (SEM) is a type of electron microscope that images a sample by scanning it
with a high energy beam of electrons in a raster scan pattern. The electrons interact with the atoms that
make up the sample producing signals that contain information about the sample’s surface topography,
composition and other properties

40
Need for Electron Microscope
1. Electron microscopes are scientific instruments that use a beam of energetic electrons to examine
objects on a very fine scale
2. Electron microscopes were developed due to the limitations of light microscopes which are limited by
the physics of light.
3. In the early 1930’s this theoretical limit had been reached and there was a scientific desire to see the fine
details of the interior structures of organic cells (nucleus, mitochondria etc,)
4. This required 10000x plus magnification which was not possible using current optical microscopes
5. The first scanning electron microscope (SEM) debuted in 1938 (Manfred Von Ardenne) with the first
commercial instruments around 1965. Its late development was due to the electronics involved in
“scanning” the beam of electrons across the sample
Characteristics that can be viewed on SEM
1. TOPOGRAPHY: The surface features of an object or “how it looks”, its texture; direct relation
between these features and materials properties
2. MORPHOLOGY: The shape and size of the particles making up the object; direct relation
between these structures and materials properties
3. COMPOSITION: The elements and compounds that the object is composed of and the relative
amounts of them; direct relationship between composition and material properties
4. CRYSTALLOGRAPHIC FORMATION: How the atoms are arranged in the object; direct
relation between these arrangements and material properties
❑ Electrons are used to create images
of the surface of specimen topology
❑ Resolution of objects of nearly 1
nm
❑ Magnification upto 500000X (250
times > light microscopes)
❑ secondary electrons (SE),
backscattered electrons (BSE) are
utilized for imaging
❑ specimens can be observed in high
vacuum, low vacuum and in
Environmental SEM specimens can
be observed in wet condition.
❑ Gives 3D views of the exteriors of
the objects like cells, microbes or
surfaces

45
46
 Optical SEM
Illumination Light Beam Electron Beam
Wave Length 2000-7000 Å 0.05Å
Lens Optical lenses for Electrostatic lens for demag
magnification crossover and electromagnetic
lens for magnification
Magnification 10X-20X 10X-2,00,000X
Depth of Focus 1 microns 30 μm at 1000X
Resolution Visible region on 50Å
2000Å
Focusing Mechanical Electrical
Obtainable Transmitted and Several
image Reflected
Contrast Color and brightness Shape and chemical property
controlled controlled

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o Electron source

o Electromagnetic Lenses

o Deflection coils

o Scanners

o Electron detectors

48
 Electron Source

We want many electrons per time

unit per area (high current density)
and as small electron spot as
possible.
Traditional guns: Thermionic
electron gun (electrons are emitted
when a solid is heated)
• W-wire, LaB6-crystal

Modern: Field emission guns

(FEG) (cold guns, a strong electric
field is used to extract electrons)
• Single crystal of W, etched to a thin
tip

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 Thermionic Electron Gun

❑ Commonly used electron source

❑ Cheap and does not require relatively high vacuum
❑ Electrons are emitted from a heated tungsten filament / LaB6 and then
accelerated towards an anode; a divergent beam of electrons emerges from
the anode hole

Single crystal of LaB6 Tungsten wire

W
LaB6
50
Functioning of Thermionic Electron Gun

❑ An positive electrical potential is applied to the anode.

❑ The filament (cathode) is heated until a stream of electrons is produced .
❑ A negative electrical potential (~500 V) is applied to the Whenelt Cap.
❑ A collection of electrons occurs in the space between the filament tip and
Whenelt Cap. This collection is called a space charge.
❑ Those electrons at the bottom of the space charge (nearest to the anode) can
exit the gun area through the small (<1 mm) hole in the Whenelt Cap .
❑ These electrons then move down the column to be later used in imaging

Spot Size:
30 μm for W
5 μm for LaB6

51
 (a) (b)
Scanning electron micrograph of W filament: (a) unused,
(b) failed 89
 Field Emission Gun (FEG)

❑ In recent years cold field-emission and thermally-assisted field emission guns have
become increasingly common.
❑ FEG requires a different gun design as well as much better vacuum in the gun area
(~10e-8 Pa instead of the ~10e-5 Pa)
❑ With field emission guns we get a smaller spot and higher current densities
compared to thermionic guns
❑ In these a very fine point on the pointed filament is formed.
❑ Electrons are emitted by tunnelling through the potential barrier at the tip surface
when a very high potential field gradient is formed at the surface.

A simple tungsten tip can be very sensitive

to surface contamination. More than any
other cathode design, the field emission tip
is extremely sensitive to the size, shape and
surface condition

Field Emission Tip 90

 Functioning of the Field Emission Gun

❑ Consists of a small single-crystal

tungsten needle that is put in a strong
extraction voltage (2-5 kV).
❑ In the case of a cold FEG, the needle is
so sharp that electrons are extracted
directly from the tip.
❑ In the case of a thermal FEG, the tip is
heated to 2000K for few seconds to
clean the adsorbed gas on tip. It also
stabilizes the emission of electron beam
at low vacuum

54
❖ Electron probes of sizes down to ~ 6 nm are attainable with conventional
thermionic emission sources, although smaller probes ~ 2 nm can be achieved using
field emission sources

❖ Unlike the thermionic gun, the FEG does not produce a small cross-over directly
below the emitter, but the electron trajectories seemingly originate inside the tip
itself, forming a virtual source of electrons for the microscope.

55
 Electron Lenses
❑ Magnetic Lenses are used because of less aberrations and good focus.
❑ As electrons are deflected by the electromagnets, the trajectories of electrons can
be adjusted by the current applied to the coils(electromagnets).
❑ Electron lenses can be used to magnify or demagnify ( SEM Lenses always
demagnifies) the electron beam diameter, because their strength is variable, which
results in a variable focal length
Condenser Lenses
❑ Hole at the center of pole pieces
❑ Coil of several thousand turns of wire
through which a current (0-1A) is
passed which creates a magnetic field
❑ To concentrate field further a soft iron
pole piece is inserted into the bore of
the objective lens
❑ Appropriate aperture size is chosen to
exclude inhomogeneous and scattered
electrons
❑ A second condenser lens is often used
to provide additional control on the
electron beam 93
❑ Electrons from a source interact with electrons in specimen yielding a variety of
photons and electrons via elastic and inelastic scattering processes.
❑ These are the “signals” that we use to make images and measure to characterize
the composition of our specimens.

Elastic and inelastic scattering of electron by sample

Elastic :
❑ Incident electron’s direction is altered
by Columbic field of nucleus
(Rutherford scattering), screened by
orbital electrons.
❑ Direction may be changed by 0-180°
but velocity remains virtually constant.
80-100% of beam energy is transferred. 1
p( )
❑ Ex: Backscattering of electrons (~high EO 2 sin 4 
energy)
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Inelastic:
❑ Incident electron transfers some energy (up to all, E0) to tightly bound inner-shell
electrons and loosely bound outer-shell electrons
❑ Examples:
✓ Secondary electron excitation
✓ Inner-shell ionization (Auger electrons, X-rays)
✓ Bremsstrahlung (continuum) X-ray generation
✓ Cathodoluminescence radiation (non-metal valence shell phenomenon)
✓ Photons & Plasmons

Monte Carlo simulation: Can

simulate the “interaction volume”
of scattered electrons for whatever
kV and whatever composition
material you may be interested in.
(in seconds)

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 Specimen – Electron Beam Interaction

Electron beam

Cathodoluminescence Auger electrons

Bremsstrahlung Secondary electrons

Characteristic x-rays Backscattered electrons

SEM
Heat

Elastically
scattered electrons TEM
Transmitted and inelastically
scattered electrons

Specimen
current

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 Specimen – Electron Beam Interaction

Electron beam

Cathodoluminescence Auger electrons

Bremsstrahlung Secondary electrons

Characteristic x-rays Backscattered electrons

SEM
Heat

Elastically
scattered electrons TEM
Transmitted and inelastically
scattered electrons

Specimen
current

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 Specimen – Electron Beam Interaction

Electron beam

Cathodoluminescence Auger electrons

Bremsstrahlung Secondary electrons

Characteristic x-rays Backscattered electrons

SEM
Heat

Elastically
scattered electrons TEM
Transmitted and inelastically
scattered electrons

Specimen
current

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74
❑ SEM is based on scattered electrons while TEM is based on
transmitted electrons.
❑ The sample in TEM has to be cut thinner whereas there is no such
need with SEM sample.
❑ SEM allows for large amount of sample to be analysed at a time
whereas with TEM only small amount of sample can be analysed at
a time.
❑ SEM is used for surfaces, powders, polished & etched
microstructures, IC chips, chemical segregation whereas TEM is
used for imaging of dislocations, tiny precipitates, grain boundaries
and other defect structures in solids
❑ TEM has much higher resolution than SEM.

75
A simplified ray diagram of a
TEM consists of an electron
source, condenser lens with
aperture, specimen, objective
lens with aperture, projector
lens and fluorescent screen.

76
 LIGHT MICROSCOPE

Optical glass lens, Small depth of

Field, lower magnification, do not
Require vacuum, Low price.

ELECTRON MICROSCOPE

Magnetic lens, Large depth of field,

Higher magnification and better
Resolution, Operates in HIGH
vacuum, Price tag.

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Sample Holder of TEM

78
Fluorescent Screen

❑ Fluorescence: Property of emitting radiation under the influence of

electromagnetic or electron beam bombardment.

❑ In the TEM, screen coated with a material in the visible range, eg

zinc sulphide, is installed beneath the projector lens in the path of
the electron beam.

❑ Screen emits visible light when bombarded with electrons.

❑ The resolution of the fluorescent screen is limited to 70-100µm by

the grain size of the fluorescent material and by light scattering
within this material.

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Bright field imaging allowing transmitted beam

80
Bright field imaging allowing diffracted beam

81
Specimens are usually in one or two forms:
– Powder
– Thin foil
– Replica

Types of Grid

Three types of grid for TEM specimens. (a) A plainmesh

Grid, (b) A ‘finder’ grid marked with identification
letters and (c) A slot grid for large specimens
144
 Powder Sample

Thin foil preparation

Initial size reduction involves mechanical method
1. Cut the specimen to < 1mm thin and 3mm dia ( soft
material- Mechanical Punch & Hard material use
Ultrasonic Drill)
✓ piezoelectric crystal that changes slightly in length when
a voltage is applied between electrodes on its surfaces

Upon applying a high-frequency ac voltage, the tube oscillates vertically thousands of

times per second, driving SiC particles against the sample and cutting an annular groove
in the slice
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2. Disk is then thinned further by polishing
with abrasive paper (coated with diamond
or silicon carbide particles) or by using a
dimple grinder

✓ Metal wheel rotates rapidly against the surface (covered with a SiC slurry or diamond
paste)
✓ Specimen disk is rotated slowly about a vertical axis.
✓ The result is a dimpled specimen of 10 µm to 50 µm thickness at the center but
greater (100 µm to 400 µm) at the outside, which provides the mechanical strength
needed for easy handling.

✓ In the case of biological tissue, a

common procedure is to use an
ultramicrotome to directly cut slices
of 100 nm or more in thickness. The
tissue block is lowered onto a glass
or diamond knife that cleaves the
material apart . The ultramicrotome
can also be used to cut thin slices of
the softer metals, such as aluminum.
84
3. Chemically thinning: A chemical solution
dissolves the original surface and reduces
the specimen thickness to a value suitable
for TEM imaging.

✓ In the simplest case, a thin piece of material is floated onto the surface of a chemical
solution that attacks its lower surface; the sample is retrieved (e.g, by picking up by a
TEM grid held in tweezers) before it dissolves completely.
✓ More commonly, a jet of chemical solution is directed at one or both surfaces of a
thin disk. As soon as a small hole forms in the center (detected by the transmission of
a light beam), the polishing solution is replaced by rinse water.

4. Electrochemical thinning : Carried out with

a direct current flowing between the
specimen (at a negative potential) and a
positive electrode, immersed in a chemical
solution.
✓ Only used for conducting samples

85
Window-frame method: Specimen is in the form of a thin sheet (1 cm or more in height
and width) whose four edges are previously painted with protective lacquer to prevent
erosion at the edge. When partially immersed in the electrolytic solution, thinning is most
rapid at the liquid/air interface, which perforates first

Jet Thinning: Apply a dc voltage between the specimen and jet electrodes.
When thinning metals, glycerin is sometimes added to the solution to make the liquid
more viscous, helping to give the thinned specimen a polished (microscopically smooth)
surface.

5. Ion Milling/Ion-beam Milling: Used for chemically inert material

Schematic diagram of typical ion-beam thinning equipment

86
6. Replication: These are prepared by different techniques
✓ Surface or Carbon replica
✓ “Extraction” replica

Surface Or Carbon Replica:

This is produced from a specimen.
✓ The specimen surface is coated with a cellulose acetate film (e.g., collodion) to
produce a negative impression of the surface features.
✓ The plastic film is stripped from the specimen surface and coated with a layer of
carbon (about 10 to 20 nm thick). The carbon-coating process takes place in a
vacuum evaporator unit.
✓ The plastic is then removed (dissolved) from the carbon replica by solvent.
✓ Before the replica is observed in the microscope, it is usually shadowed (sputtered)
with carbon or a heavy element to enhance the topographical features of the
surface.

149
“Extraction” replica:
✓ The metallographic specimen is etched
beforehand to put particles and
carbides in relief.
✓ Carbon film is deposited on the surface
of the etched specimen.
✓ The carbon film itself is not physically
stripped from the specimen surface, but
etched or “floated” away from the
surface so that those particles attached
to the deposited carbon film will be
extracted from the specimen.

159
Applications of TEM
A Transmission Electron Microscope is ideal for a number of different fields such
as:
life sciences
nanotechnology
medical
biological and material research
forensic analysis
gemology and metallurgy
industry and education
TEMs provide topographical, morphological, compositional and crystalline information.
The images allow researchers to view samples on a molecular level, making it possible to analyze structure
and texture.
This information is useful in the study of crystals and metals, but also has industrial applications.
TEMs can be used in semiconductor analysis and production and the manufacturing of computer and silicon
chips.
Technology companies use TEMs to identify flaws, fractures and damages to micro-sized objects; this data can
help fix problems and/or help to make a more durable, efficient product.
Colleges and universities can utilize TEMs for research and studies.
Although electron microscopes require specialized training, students can assist professors and learn TEM
techniques.
Students will have the opportunity to observe a nano-sized world in incredible depth and detail.
Advantages:
A Transmission Electron Microscope is an impressive instrument with a number of advantages such as:
TEMs offer the most powerful magnification, potentially over one million times or more
TEMs have a wide-range of applications and can be utilized in a variety of different scientific, educational and
industrial fields
TEMs provide information on element and compound structure
Images are high-quality and detailed
TEMs are able to yield information of surface features, shape, size and structure
They are easy to operate with proper training
Disadvantages:
Some cons of electron microscopes include:
TEMs are large and very expensive
Laborious sample preparation
Potential artifacts from sample preparation
Operation and analysis requires special training
Samples are limited to those that are electron transparent, able to tolerate the vacuum chamber and
small enough to fit in the chamber
TEMs require special housing and maintenance
Images are black and white
❑X-rays were discovered in 1895 by the German physicist
Wilhelm Conrad Röntgen and were so named because their
nature was unknown at the time.
❑ He was awarded the Nobel prize for physics in 1901.

❑X ray, invisible, highly penetrating electromagnetic

radiation of much shorter wavelength (higher frequency)
than visible light. The wavelength range for X rays is from
about 10-8 m to about 10-11 m, the corresponding frequency
range is from about 3 × 1016 Hz to about 3 × 1019 Hz.

W.C. Röntgen
(1845-1923)

Energy of Photons:
hc
E =

❑Visible light photons and X-ray
photons are both produced by the
movement of electrons in atoms.
Electrons occupy different energy
levels, or orbitals, around an atom's
nucleus.
❑When an electron drops to a lower
orbital, it needs to release some energy;
it releases the extra energy in the form
of a photon. The energy level of the
photon depends on how far the electron
dropped between orbitals.

❑X-rays are produced when any electrically charged

particle of sufficient kinetic energy is rapidly decelerated. Evacuated glass bulb
Electrons are usually used for this purpose. Cathode
Anode
❑When a high voltage is applied between the electrodes,
streams of electrons (cathode rays) are accelerated from
the cathode (W or any high melting point element) to the
anode and produce X rays as they strike the anode.
 Filament
X-ray tube
❑ Filament tube consists of an
evacuated glass envelope which
insulates the anode at one end
from the cathode at the other,
the cathode being a tungsten
filament and the anode a water-
cooled block of copper
containing the desired target
metal (mainly Mo, Cu, Co, Cr,
Fe) as a small insert at one end.

❑ One lead of the high-voltage transformer is connected to the filament and the other to
ground, the target being grounded by its own cooling water connection.
❑ The filament is heated by a filament current of about 3 amp and emits electrons which
are rapidly drawn to the target by the high voltage across the tube.
❑ A small metal cup maintained at the same high (negative) voltage as the filament is
present surrounding the filament. It repels the electrons and tends to focus them into a
narrow region of the target, called the focal spot.
❑ X-rays are emitted from the focal spot in all directions and escape from the tube
through two or more windows in the tube housing. Since these windows must be
vacuum tight and yet highly transparent to x-rays, they are usually made of beryllium,
aluminum, or mica.
❑Visible light photons and X-ray
photons are both produced by the
movement of electrons in atoms.
Electrons occupy different energy
levels, or orbitals, around an atom's
nucleus.
❑When an electron drops to a lower
orbital, it needs to release some energy;
it releases the extra energy in the form
of a photon. The energy level of the
photon depends on how far the electron
dropped between orbitals.

❑X-rays are produced when any electrically charged

particle of sufficient kinetic energy is rapidly decelerated. Evacuated glass bulb
Electrons are usually used for this purpose. Cathode
Anode
❑When a high voltage is applied between the electrodes,
streams of electrons (cathode rays) are accelerated from
the cathode (W or any high melting point element) to the
anode and produce X rays as they strike the anode.
 Filament
X-ray tube
❑ Filament tube consists of an
evacuated glass envelope which
insulates the anode at one end
from the cathode at the other,
the cathode being a tungsten
filament and the anode a water-
cooled block of copper
containing the desired target
metal (mainly Mo, Cu, Co, Cr,
Fe) as a small insert at one end.

❑ One lead of the high-voltage transformer is connected to the filament and the other to
ground, the target being grounded by its own cooling water connection.
❑ The filament is heated by a filament current of about 3 amp and emits electrons which
are rapidly drawn to the target by the high voltage across the tube.
❑ A small metal cup maintained at the same high (negative) voltage as the filament is
present surrounding the filament. It repels the electrons and tends to focus them into a
narrow region of the target, called the focal spot.
❑ X-rays are emitted from the focal spot in all directions and escape from the tube
through two or more windows in the tube housing. Since these windows must be
vacuum tight and yet highly transparent to x-rays, they are usually made of beryllium,
aluminum, or mica.
Bragg Law
Two geometrical facts are worth remembering:
(1)The incident beam, the normal to the reflecting plane, and the diffracted beam are
always coplanar.
(2)The angle between the diffracted beam and the transmitted beam is always 2θ. This
is known as the diffraction angle, and it is this angle, rather than θ, which is usually
measured experimentally.

▪ The path difference between ray 1 and ray 2 = 2d Sin

▪ For constructive interference: n = 2d Sin
Deviation = 2
Ray 1

Ray 2
 

 d

102
Bragg Law
Two geometrical facts are worth remembering:
(1)The incident beam, the normal to the reflecting plane, and the diffracted beam are
always coplanar.
(2)The angle between the diffracted beam and the transmitted beam is always 2θ. This
is known as the diffraction angle, and it is this angle, rather than θ, which is usually
measured experimentally.

▪ The path difference between ray 1 and ray 2 = 2d Sin

▪ For constructive interference: n = 2d Sin
Deviation = 2
Ray 1

Ray 2
 

 d

103
❑As diffraction occurs only at specific Bragg angles, the chance that a reflection is
observed when a crystal is irradiated with monochromatic X-rays at a particular angle is
small (added to this the diffracted intensity is a small fraction of the beam used for
irradiation).
❑The probability to get a diffracted beam (with sufficient intensity) is increased by either
varying the wavelength () or having many orientations (rotating the crystal or having
multiple crystallites in many orientations).
❑ The three methods used to achieve high probability of diffraction are shown below.

Many s (orientations) POWDER λ → fixed

Monochromatic X-rays Powder specimen METHOD θ → variable

LAUE λ → variable
Panchromatic X-rays Single 
TECHNIQUE θ → fixed

ROTATING λ → fixed
 Varied by rotation CRYSTAL
Monochromatic X-rays θ → rotated
METHOD
174
❑The Laue method is mainly used to determine the orientation of large single crystals
while radiation is reflected from, or transmitted through a fixed crystal.

❑The diffracted beams form arrays of spots, that lie

on curves on the film.
❑The Bragg angle is fixed for every set of planes in
the crystal. Each set of planes picks out and diffracts
the particular wavelength from the white radiation
that satisfies the Bragg law for the values of d and θ
involved.

Back-reflection Laue Method

❑ In the back-reflection method, the film is
placed between the x-ray source and the crystal.
❑The beams which are diffracted in a backward
direction are recorded.

❑One side of the cone of Laue reflections is

defined by the transmitted beam. The film
Single
intersects the cone, with the diffraction Crystal
spots generally lying on an hyperbola.
Film
X-Ray 175
Transmission Laue Method
❑In the transmission Laue method, the film is
placed behind the crystal to record beams which
are transmitted through the crystal.
❑One side of the cone of Laue reflections is
defined by the transmitted beam. The film
intersects the cone, with the diffraction spots
generally lying on an ellipse.
X-Ray
Laue Pattern
Single Film
❑The symmetry of the spot pattern reflects the Crystal
symmetry of the crystal when viewed along the
direction of the incident beam. Laue method is
often used to determine the orientation of single
crystals by means of illuminating the crystal with
a continuos spectrum of X-rays.
❑Although the Laue method can also be used to
determine the crystal structure, several
wavelengths can reflect in different orders from
the same set of planes, with the different order
reflections superimposed on the same spot in the
film. This makes crystal structure determination
by spot intensity diffucult. 176
❑In the rotating crystal method, a single crystal
is mounted with an axis normal to a
monochromatic x-ray beam. A cylindrical film
is placed around it and the crystal is rotated
about the chosen axis.
❑As the crystal rotates, sets of lattice planes will
at some point make the correct Bragg angle for
the monochromatic incident beam, and at that
point a diffracted beam will be formed.
❑The reflected beams are located on the surface
of imaginary cones. By recording the

diffraction patterns (both angles and intensities)

for various crystal orientations, one can
determine the shape and size of unit cell as well
as arrangement of atoms inside the cell. Film

❑Lattice constant of the crystal can be determined by means of this method; for a
given wavelength if the angle θ at which a reflection occurs is known, dhkl can be
determined. a
d =
h2 + k 2 + l2
❑If a powdered specimen is used, instead of a single crystal, then there is no need to
rotate the specimen, because there will always be some crystals at an orientation for
which diffraction is permitted. Here a monochromatic X-ray beam is incident on a
powdered or polycrystalline sample.
❑ This method is useful for samples that are difficult to obtain in single crystal form.
❑In the powder method the specimen has crystallites (or grains) in many orientations
(usually random).
❑Monochromatic X-rays are irradiated on the specimen and the intensity of the
diffracted beams is measured as a function of the diffracted angle.
❑The powder method is used to determine the value of the lattice parameters accurately.
Lattice parameters are the magnitudes of the unit vectors a, b and c which define the unit
cell for the crystal.
❑For every set of crystal planes, by chance, one or more crystals will be in the correct
orientation to give the correct Bragg angle to satisfy Bragg's equation. Every crystal
plane is thus capable of diffraction. Each diffraction line is made up of a large number of
small spots, each from a separate crystal. Each spot is so small as to give the appearance
of a continuous line.
❑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.
❑If a monochromatic x-ray beam is directed at a single crystal, then only one or two
diffracted beams may result.
❑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.
Bravais lattice determination

Lattice parameter determination

Determination of solvus line in phase diagrams

Long range order

Crystallite size and Strain

More

110
Introduction to Molecular Spectroscopy
• Introduction to spectroscopy

• Classification of spectroscopic techniques

• Common types and their introduction

• Infra-Red spectroscopy: Fundamental concepts

• Vibrations in IR- Region and calculations of different

vibrational energies in terms of frequencie.
 Spectroscopy
Definition:
The study of the interaction between radiations and matter as a function of
wavelength λ.
Interactions with particle radiation or a response of a material to an alternating
field or varying frequency ν.
Spectrum:
A plot of the response as a function of wavelength or more commonly
frequency is referred to as a spectrum.
Spectrometry:
It is the measurement of these responses and an instrument which performs
such measurements is a spectrometer or spectrograph, although these terms
are more limited in use to the original field of optics from which the concept
sprang.
Spectroscopy is often used in physical and analytical chemistry for the
identification of substances through the spectrum emitted from or absorbed by
them. Spectroscopy is also heavily used in astronomy and remote sensing. Most
large telescopes have spectrometers, which are used either to measure the
chemical composition and physical properties of astronomical objects or to
measure their velocities from the Doppler Shift of their spectral lines.
Classification of Methods
The type of spectroscopy depends on the physical quantity measured. Normally, the
quantity that is measured is an intensity, either of energy absorbed or produced.
Most spectroscopic methods are differentiated as either atomic or molecular based on
whether or not they apply to atoms or molecules. Along with that distinction, they can
be classified on the nature of their interaction:
Absorption spectroscopy
It uses the range of the electromagnetic spectra in which a substance absorbs. This
includes atomic absorption spectroscopy and various molecular techniques, such as
infra-red spectroscopy in that region and Nuclear Magnetic resonance spectroscopy in
the radio region.
Emission spectroscopy
It uses the range of electromagnetic spectra in which a substance radiates (emits). The
substance first must absorb energy. This energy can be from a variety of sources, which
determines the name of the subsequent emission, like luminescence. Molecular
luminescence techniques include spectroflourimetry.
Scattering spectroscopy
It measures the amount of light that a substance scatters at certain wavelengths,
incident angles, and polarization angles. The scattering process is much faster than the
absorption/emission process. One of the most useful applications of light scattering
spectroscopy is Raman Spectroscopy.
 Common types
• Fluorescence spectroscopy
• X.ray spectroscopy and crystallography
• Flame spectroscopy
1 Atomic emission spectroscopy
2 Atomic absorption spectroscopy
3 Atomic fluorescence spectroscopy
• Plasma emission spectroscopy
• Spark or arc emission spectroscopy
• UV/VIS spectroscopy
• IR spectroscopy
• Raman spectroscopy
• NMR spectroscopy
• Photo thermal spectroscopy
• Thermal infra-red spectroscopy
• Mass Spectroscopy
 Brief about
1- Fluorescence spectroscopy: spectroscopy
Fluorescence spectroscopy uses higher energy photons to excite a sample,
which will then emit lower energy photons. This technique has become
popular for its biochemical and medical applications.
 Cont’
2- X-ray spectroscopy: d
X-rays of sufficient frequencies interact with material and excite the atoms
contained. Due to this excitation Auger Effect is produced and some
excitation radiations are absorbed or evolved if vice versa occurs.
X-ray absorption and emission spectroscopy is used in chemistry and
material sciences to determine elemental composition and chemical
bonding.

Very good and versatile technique but a little complex. It needs some
scattering light detectors along with X-ray source. Overall X-ray
diffraction technique is one that is used most widely for bond length and
angle measurements.
 Cont’d
3 Flame Spectroscopy:
Liquid solution samples are aspirated into a burner or nebulizer/burner
combination, desolvated, atomized, and sometimes excited to a higher
energy electronic state. The use of a flame during analysis requires fuel
and oxidant, typically in the form of gases. Common fuel gases used are
acetylene (ethyne) or hydrogen. Common oxidant gases used are oxygen,
air, or nitrous oxide. These methods are often capable of analyzing
metallic element in the PPM, billion, or possibly lower concentration
ranges. Light detectors are needed to detect light with the analysis
information coming from the flame.
- Atomic absorption Spectroscopy
- Atomic emission spectroscopy
- Atomic fluorescence spectroscopy

How would you differentiate in them?

4- Spark or arc (emission) spectroscopy :
It is used for the analysis of metallic elements in solid samples.
For non-conductive materials, a sample is ground with graphite powder to
make it conductive.
In traditional arc spectroscopy methods, Since the conditions producing
the arc emission typically are not controlled quantitatively, the analysis
for the elements is qualitative. Nowadays, the spark sources with
controlled discharges under an argon atmosphere allow that this method
can be considered eminently quantitative, and its use is widely expanded
worldwide through production control laboratories of foundries and steel
mills.
5- UV/VIS spectroscopy: Cont’d
• It basically involves the spectroscopy of photons and spectrophotometery.
• It uses light in the visible and adjacent near ultraviolet (UV) and near
infrared (NIR) ranges.
• UV/Vis spectroscopy is routinely used in the quantitative determination of
solutions of transition metal ions and highly conjugated
organic compounds.
• For the quantitative measurements, Beer-Lambert law is followed.
• The Beer-Lambert Law is useful for characterizing many compounds but
does not hold as a universal relationship for the concentration and
absorption of all substances. A 2nd order polynomial relationship
between absorption and concentration is sometimes encountered for
very large, complex molecules such as organic dyes.
6- Infra-red Spectroscopy: Cont’d
• (IR spectroscopy) is the subset of spectroscopy that deals with the
infrared region of the electromagnetic spectrum. It covers a range of
techniques, the most common being a form of absorption spectroscopy.
As with all spectroscopic techniques, it can be used to identify compounds
or investigate sample composition.
• Infrared spectroscopy offers the possibility to measure different
types of inter atomic bond vibrations at different frequencies. Especially in
organic chemistry the analysis of IR absorption spectra shows what type of
bonds are present in the sample.
• Infrared spectroscopy exploits the fact that molecules have specific
frequencies at which they rotate or vibrate corresponding to discrete
energy levels.
 7- Raman Spectroscopy: Cont’d

• It relies on inelastic scattering, or Raman scattering of monochromatic light, usually from a

• the visible, near infrared, or near ultraviolet range. The laser light interacts with phonons or other
excitations in the system, resulting in the energy of the laser photons being shifted up or down. Th
energy gives information about the phonon modes in the system.
Spontaneous Raman scattering is typically very weak, and as a result the main difficulty of Raman spe
separating the weak inelastically scattered light from the intense Rayleigh scattered laser light. Raman spect
typically use holographic diffraction gratings and multiple dispersion stages to achieve a high degree of laser
8 Nuclear magnetic resonance: Cont’d
Nuclear magnetic resonance spectroscopy analyzes the magnetic
properties of certain atomic nuclei to determine different electronic local
environments of hydrogen, carbon, or other atoms in an
organic compound or other compound. This is used to help determine the
structure of the compound.

9 Photo thermal spectroscopy:

It is a group of high sensitivity spectroscopy techniques used to measure
optical absorption and thermal characteristics of a sample. The basis of
photo-thermal spectroscopy is the change in thermal state of the sample
resulting from the absorption of radiation. Light absorbed and not lost by
emission results in heating. The heat raises temperature thereby
influencing the sample thermodynamic properties. Measurement of the
temperature, pressure, and/or density changes that occur due to optical
absorption are ultimately the basis for the photo-thermal spectroscopic
measurements.
10- Thermal infrared spectroscopy : Cont’d
TIR spectroscopy is the subset of IR spectroscopy that deals with radiation
emitted in the infrared part of the e.m. spectrum. The emitted infrared
radiation, though similar to blackbody radiation, is different in that the
radiation is banded at characteristic vibrations in the material. The
method measures the thermal IR radiation emitted (as opposed to being
transmitted or reflected) from a volume or surface. This method is
commonly used to identify the composition of surface by analyzing its
spectrum and comparing it to previously measured materials. It is
particularly suited to airborne and space borne applications.
 Infra Red Spectroscopy
Introduction:
The absorption of infra-red radiations causes the various bands in a
molecule to stretch or bend w.r.t. one another.

Near IR-Region 0.8 – 2.5 micron Rotational Spec.

Mid infra red region 2.5 – 1.5 micron Vib-Roto Spec.
Far IR-Region 15 – 200 micron Overtone or harmonic

Band intensity is either expressed as absorbance or transmittance.

 Cont’d

• To establish the identity of two compounds (comparative study)

• To determine the structure of a new compound from its functional groups

• To determine the nature of contaminants in a sample

• For quantitative analysis of a component in the overall mixture

• For the quantitative analysis of contaminants in given sample

• Some advanced physical properties of the materials

 Basic Principles: Molecular Vibrations
• Absorption in the infra-red region is due to the changes in the vibrational
and Rotational levels.
• With low energy radiations, molecular rotations occur
• With high energy radiations, molecular vibrations occur

• Due to IR-radiation energy, a vib-rotational spectrum is obtained. The

vibrational energy depends upon the followings:
1- masses of atoms present in the molecule
2- Strength of bonds and bond distances
3- The arrangement of atoms within a molecule
 Types of vibrations in a molecule
Two fundaments types:
1 Stretching
2 Bending

Stretching:
The distance between the two atoms increases or decreases but the
atoms remain in the same bond axis.

Bending:
The position of the atoms changes with respect to the original bond axis.

Stretching occurs at high frequencies and bending at low ?

 Cont’d

Stretching Vibrations:
c) Symmetric stretch
d) Asymmetric stretch

Bending Vibrations:
g) Scissoring
h) Rocking
i) Wagging
j) Twisting

See the moving image