TESTING OF MATERIALS

UNIT I INTRODUCTION TO MATERIALS TESTING 9

Overview of materials, Classification of material testing, Purpose of testing, Selection of material,
Development of testing, Testing organizations and its committee, Testing standards, Result Analysis,
Advantages of testing.
UNIT II MECHANICAL TESTING 9
Introduction to mechanical testing, Hardness test (Vickers, Brinell, Rockwell), Tensile test, Impact test
(Izod, Charpy) - Principles, Techniques, Methods, Advantages and Limitations, Applications. Bend test,
Shear test, Creep and Fatigue test - Principles, Techniques, Methods, Advantages and Limitations,
Applications.
UNIT III NON DESTRUCTIVE TESTING 9
Visual inspection, Liquid penetrant test, Magnetic particle test, Thermography test – Principles,
Techniques, Advantages and Limitations, Applications. Radiographic test, Eddy current test, Ultrasonic
test, Acoustic emission- Principles, Techniques, Methods, Advantages and Limitations, Applications.
UNIT IV MATERIAL CHARACTERIZATION TESTING 9
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.
UNIT V OTHER TESTING 9
Thermal Testing: Differential scanning calorimetry, Differential thermal analysis. Thermo-mechanical and
Dynamic mechanical analysis: Principles, Advantages, Applications. Chemical Testing: X-Ray
Fluorescence, Elemental Analysis by Inductively Coupled Plasma-Optical Emission Spectroscopy and
Plasma-Mass Spectrometry.
TOTAL: 45 PERIODS

TEXT BOOKS:
1. Baldev Raj, T.Jayakumar, M.Thavasimuthu “Practical Non-Destructive Testing”, Narosa Publishing
House, 2009.
2. Cullity, B. D., “Elements of X-ray diffraction”, 3rd Edition, Addison-Wesley Company Inc., New York,
2000. 3. P. Field Foster, “The Mechanical Testing of Metals and Alloys” 7th Edition, Cousens Press, 2007.
REFERENCES:
1. Metals Handbook: Mechanical testing, (Volume 8) ASM Handbook Committee, 9th Edition, American
Society for Metals, 1978.
2. ASM Metals Handbook, “Non-Destructive Evaluation and Quality Control”, American Society of
Metals, Metals Park, Ohio, USA.
3. Brandon D.G., “Modern Techniques in Metallography”, Von Nostrand Inc. NJ, USA, 1986.
 UNIT I INTRODUCTION TO MATERIALS TESTING

Overview of materials
Materials science, also commonly known as materials science and engineering, is an interdisciplinary field which
deals with the discovery and design of new materials. This relatively new scientific field involves studying materials
through the materials paradigm (synthesis, structure, properties and performance). It incorporates elements of
physics and chemistry, and is at the forefront of Nano science and nanotechnology research. In recent years,
materials science has become more widely known as a specific field of science and engineering
Like many other things, materials are classified in groups, so that our brain can handle the complexity. One could
classify them according to structure, or properties, or use. The one that we will use is according to the way the
atoms are bound together:
Metals:
The valence electrons are detached from atoms, and spread in an 'electron sea' that "glues" the ions
together. Metals are usually strong, conduct electricity and heat well and are opaque to light (shiny if
polished). Examples: aluminum, steel, brass, gold.
Semiconductors:
The bonding is covalent (electrons are shared between atoms). Their electrical properties depend
extremely strongly on minute proportions of contaminants. They are opaque to visible light but
transparent to the infrared. Examples: Si, Ge, GaAs.
Ceramics:
Atoms behave mostly like either positive or negative ions, and are bound by Coulomb forces between
them. They are usually combinations of metals or semiconductors with oxygen, nitrogen or carbon
(oxides, nitrides, and carbides).Examples: glass, porcelain, many minerals.
Polymers:
are bound by covalent forces and also by weak van der Waals forces, and usually based on H, C and
other non-metallic elements. They decompose at moderate temperatures
(100 – 400 C), and are lightweight. Other properties vary greatly. Examples: plastics (nylon, teflon, polye
ster) and rubber. Other categories are not based on bonding. A particular microstructureidentifies
Composites:
Composites made of different materials in intimate contact (example: fiberglass, concrete, wood) to
achieve specific properties.
Biomaterials can be any type of material that is biocompatible and used, for instance, to replace human
body parts.
 
Advanced Materials
Materials used in "High-Tec" applications, usually designed for maximum performance, and normally
expensive. Examples are titanium alloys for supersonic airplanes, magnetic alloys for computer disks,
special ceramics for the heat shield of the space shuttle, etc.
Modern Material's Needs
• Engine efficiency increases at high temperatures: requires high temperature with standing materials
• Use of nuclear energy requires solving problem with residues, or advances in nuclear
waste processing.
• Hypersonic flight requires materials that are light, strong and resist high temperatures.
• Optical communications require optical fibers that absorb light negligibly.
• Civil construction – materials for unbreakable windows.
• Structures: materials that are strong like metals and resist corrosion like plastics

Ionic Bonding
This is the bond when one of the atoms is negative (has an extra electron) and another is positive (has
lost an electron). Then there is a strong, direct Coulomb attraction. An example is NaCl. In the molecule,
there are more electrons around Cl, forming Cl- and less around Na, forming Na+. Ionic bonds are the
strongest bonds. In real solids, ionic bonding is usually combined with covalent bonding.
Covalent Bonding
In covalent bonding, electrons are shared between the molecules, to saturate the valence. The simplest
example is the H2 molecule, where the electrons spend more time in between the nuclei than outside,
thus producing bonding.
Metallic Bonding
In metals, the atoms are ionized, losing some electrons from the valence band. Those electrons form an
electron sea, which binds the charged nuclei in place, in a similar way that the electrons in between the
H atoms in the H2 molecule bind the protons.

Metallic Crystal Structures

Important properties of the unit cells are
 The type of atoms and their radii R
 Cell dimensions (side a in cubic cells, side of base a and height c in HCP) in terms of R.
 n, number of atoms per unit cell. For an atom that is shared with m adjacent unit cells, we only
count a fraction of the atom, 1/m
 CN, the coordination number, which is the number of closest neighbors to which an atom
is bonded.
 APF, the atomic packing factor, which is the fraction of the volume of the cell actually occupied
by the hard spheres.
 APF = Sum of atomic volumes/Volume of cell.

Classification of material testing

Why are metals tested?

 Ensure quality
 Test properties
 Prevent failure in use
 Make informed choices in using materials

Two forms of testing

Mechanical tests – the material may be physically tested to destruction. Will normally specify a
value for properties such as strength, hardness, toughness, etc.
Non-destructive tests (NDT) – samples or finished articles are tested before being used.

Classification of Destructive Testing or Mechanical tests

 Static Testing
 Impact Testing
 Cyclic Testing

What is Static Testing?

Where the load is applied gradually in static testing. different material testing methods available under
static testing. they are listed below.
 Tension Test - to measure tensile properties like Ultimate Tensile Strength, stress –strain curve,
modulus of elasticity,
  Compression Test
 Shear Test
 Hardness Test
 Creep Test

What is Impact (Dynamic) Testing?

When the given specimen is subjected to shock loads then it is known as the impact load testing or the
dynamic load testing.
 Charpy Test
 Izoid Test

What is Cyclic Testing?

When the load is repeatedly varied in magnitude and the direction then this test is called cyclic testing

Classification of Non-Destructive Testing

 Visual inspection
 Penetrant test
 Magnetic detection
 Ultrasonic test
 Radiography test
 Spark test

Purpose of testing

Why are materials tested?

 To determine and evaluate various properties of materials both quantitatively and qualitatively.
 To detect and evaluate the surface or sub- surface defects in raw materials or processed parts.
 To check chemical composition.
 To determine suitability of a materials for a particular application
 To predict the strength and serviceability of the materials.

Selection of material
What are the factors to be considered for the selection of materials for design of machine elements?
Following factors should be considered:
1. Availability : 2. Cost : 3. Mechanical Properties : 4. Manufacturing consideration :

1. Availability : The Material should be readily available in market in large enough quantities to
meet the requirement.
2. Cost :
 For every application, there is limiting cost beyond which the designer cannot go.
 When the limit exceeded the designer has to consider an alternative material.
 In cost analysis, there are two factors namely cost of material and the cost of processing
the material into finished goods.
 It is likely that the cost of material might be low but the processing may involve costly
machining operations.
3. Mechanical Properties : The important mechanical properties of material from the
consideration design are strength, rigidity, toughness, resilience, shock resistance, wear
resistance, creep characteristic, corrosion resistance, frictional properties and hardness.
Strength : The ability of material to withstand stress without fracture is called its strength.
Ductility : The property of a material to undergo deformation under tension without fracture is
called Ductility.
Hardness: The ability of a material to withstand scratching, wear and abrasion or indentation
(penetration) by harder bodies is known as hardness.
Toughness : Toughness is the amount of energy that a material can absorb before it fractures.
Resilience : It is the capacity of a material to absorb or store energy up to elastic limit, and to
resist shock and impact.
Creep : The slow and progressive deformation of a material with time at constant stress is called
Creep.
Corrosion resistance : It is the deterioration of a material by chemical reaction with its
environment.
Brittleness : The property of a material by virtue of which it will be fractured without
appreciable deformation is called brittleness.
Weldability : It is defined as the ease with which a material can be welded under a given set of
conditions.

4. Manufacturing consideration : It is important consideration in selection of materials. 

Sometimes, expensive materials are more economical than low cost material, which difficult to
machine.

Cast Iron
Properties:
• Lower melting point
• Low shrinkage and good fluidity and casting ability.
Application:
• Car parts – cylinder heads, blocks and gearbox cases.
• Foundation for big machines
• Cook wares – Excellent heat retention

Alloy steel
• Low Alloy ( 11 wt% Cr)
• Low Carbon (Medium Carbon (0.25 to 0.60wt%)
• High Carbon (0.6 to 1.4 wt%)
• High Alloy
• Stainless Steel (> 11 wt% Cr)

Low carbon steel

Properties:
• least expensive.
• Good Weldability and machinability.
Application:
• Automobile panels, nails, and wire.
• Low temperature pressure vessels.
Medium carbon steel
Properties:
• Addition of Cr, Ni, Mo improves the heat treating capacity.
• Heat treated alloys are stronger but have lower ductility.
Application:
• Railway wheels and tracks, gears, crankshafts.

High carbon steel

Properties:
• High C content provides high hardness and strength. Hardest and least ductile.
• Used in hardened and tempered condition.
Application:
• Used as tool and die steels owing to the high hardness and wear resistance property.

Aluminum alloys
Properties:
• Low specific gravity.
• Corrosion resistance.
• Easy to fabrication.
• High thermal conductivity.
Application:
• Engine cylinder blocks, casting for valve body, connecting rod, fly wheel housing.
• Piston and cylinder head.
Development of testing

 Harmonious, development of standardization and quality control in national and international arena
 Certification schemes for products and systems
 Growth and development of Indian industry, commerce and exports
 Consumer protection
 Standards formulated by BIS are primarily, voluntary in nature
 Through various Acts/ Regulations, out of the more than 18 000 standards formulated so far, only 68
standards are subject to Mandatory Certification
 All standards are widely circulated at draft stage
 Period of comments is generally not less than 3 months,
 For urgent reasons pertaining to safety, health or environment, period can be reduced
 Drafts documents are hosted on BIS website for public comments
 All comments are duly considered by the appropriate authorities
 Programme of Work is published and also hosted on BIS website and is periodically updated

OVERVIEW
 INDIAN STANDARDS PUBLISHED - 18315
 CORRESPONDING ISO/IEC STANDARDS - 5821
 STANDARDS HARMONIZED WITH ISO/IEC STANDARDS
(About 76%) - 4449
 DIVISIONAL COUNCILS 14
 TECHNICAL COMMITTEES - 301
  TECHNICAL EXPERTS 11750
(Sec. Com+ Sub Com+ Panel)

Criteria for notification includes assessment of:

• whether international standard exists or technical content differs from international
standards
• impact of regulation on trade
• whether regulation deals with technical requirements or SPS measures for a
product/group of products (relevance under the TBT and SPS Agreements)
Various sources that are consulted:
• TBT Agreement, and relevant Committee recommendations and decisions
• regulatory agency responsible for the regulation
PREPARATION
• Initiated by regulator of proposed legislations
• Complete notification format by the Regulatory Body in consultation with Ministry of
Commerce
• Clear and descriptive outline of the regulatory proposal
• Give adequate time to comment on the proposal
• Reasonable time for adoption of measure
SUBMISSION
• Prepared notifications are sent to WTO Central Registry of Notifications (CRN) by
National Notification Authority

TESTING ORGANIZATIONS AND ITS COMMITTEE

ASTM International
• Organized in 1898
• The largest U.S.-based standards developer
• Non-governmental, not-for-profit organization
• Provides a management system for the development of voluntary, consensus standards
• Does not provide certification, testing or accreditation services
• 140 technical committees
Consumer Products
Steel
Petroleum
Construction/Building Plastics
Paint
Textiles
Environmental
Medical Devices
• Over 75 nations utilize ASTM standards in their regulations or as the basis of their national
standards, China – 454, Colombia – 806, Egypt – 217, South Africa - 348
• No single organization, public or private, controls the U.S. standards development system
• In the U.S. there are multiple methods of standards development (600 developers)
• The system is coordinated - publicly and privately
• ASTM standards are international standards that are used globally
American Society of Mechanical Engineers (ASME)
ASME was founded in 1880 to provide a setting for engineers to discuss concerns brought by the rise
of the industrial revolution. The Society’s founders were some of the more prominent machine builders
and technical innovators of the late nineteenth century; led by prominent steel engineer Alexander
Lyman Holley, Henry Rossiter Worthington, John Edison Sweet and Henry Ford
• Organization started in 1880 by a small group of leading industrialists
• Has over 140,000 members in the society
• One of the worlds largest technical publishing operations
• ASME Standards are developed by volunteers from industry and government and considered
voluntary consensus standards. This means that the standards developed by ASME are
approved using a consensus process, which will be described on the following slides, and that
their use is optional until it has been incorporated into law or its use has been mandated in a
contract.
• ASME has established, and continues to establish various committees which each take part in
the development of one or more standards. These committees are comprised of members who
are volunteer experts from around the global from various industries. These experts are the
ones who help to keep ASME standards updated to meet the needs of the industry as it evolves.
• ASME recruits its committee members from all across the globe to be sure that ASME standards
are relevant and to understand the local needs of all potential users.
• ASME standards actions are approved by consensus. Consensus means that there is substantial
agreement by the affected interest categories on the proposed action. During the approval
process, all views are considered and attempts are made to resolve any objections from the
consensus body or any other source. In some instances it is not possible to satisfy all objections.
For consensus to be reached, unanimity is not required; this means that after attempts to
resolve the remaining objections are made and the objection still stands, the item can move
forward. ANSI Procedures require more than a simple majority approval, but not necessarily
unanimity. For example, ASME’s accredited procedures require a 2/3 affirmative vote of the full
consensus committee membership in order for a standards action to be considered approved.
• ASME has product certification programs for Boiler and Pressure Vessel Manufacturers, Nuclear
Component Manufacturers and quality programs, Bioprocessing equipment, pressure relief
devices, and reinforced thermoset plastics.

AASHTO (American Association of State Highway & Transportation Officials)

The American Association of State Highway & Transportation Officials (AASHTO) is a nonprofit,
nonpartisan association representing highway and transportation departments in the 50 states, the
District of Columbia and Puerto Rico. It is the only national public sector association that represents all
five transportation modes: air, highways, public transportation, rail and water. Its primary goal is to
foster the development, operation and maintenance of an integrated national transportation system.

ACI (American Concrete Institute)

The American Concrete Institute (ACI) serves the various components of the concrete industry. It has
about one hundred technical committees, and the documents produced by these committees are
arranged into five groups in the six-part Manual of Concrete Practice (MCP) (Engineering Library
Reference, TA681.A64)  which includes almost all of the Institute's codes, standards, and committee
reports including 318-08: Building Code Requirements for Structural Concrete and Commentary. They
include research and administration, materials and properties of concrete, design and construction
practices, structural analysis, and special products and processes.
ANSI (American National Standards Institute)  is the national coordinator of voluntary standards
activities in the U.S. ANSI approves and publishes standards after they are developed by various
engineering, industry and professional groups. ANSI is the U.S. representative to the International
Organization for Standardization (ISO) and the International Electrotechnical Commission (IEC).
ANSI does not produce standards.

AWS (American Welding Society)

The American Welding Society (AWS) works to advance the science, technology, and application of
welding and related joining disciplines. AWS has published more than 140 standards under the
guidelines of the American National Standards Institute. Search AWS in the UW Engineering Library
Standards Database to see what welding standards the Library holds.

IEEE Standards are developed by the IEEE Standards Association. The UW Libraries provides access to
these standards in full-text online at the IEEE Xplore Digital Library (UW Restricted). 
Included also are the Interpretations of IEEE Standards, which provide answers to questions that may
arise related to the meaning of portions of an IEEE standard concerning specific applications.
Interpretations explain and clarify the intent of the standard; they do not constitute an alteration to the
original standard or supply consulting information.

NEMA (National Electrical Manufacturers Association)

The National Electrical Manufacturers Association is the trade association through which the electrical
industry develops and promotes positions on standards and government regulations.

SAE International (Society of Automotive Engineers) publishes new, revised, and reaffirmed standards
each year in three categories: Ground Vehicle Standards (J-Reports); Aerospace Standards; and
Aerospace Material Specifications (AMS). 
The UW Engineering Library has the SAE Ground Vehicle standards (J-Reports) which are included in
the SAE Handbook on CD-ROM located at call number TL151 .S62. For other SAE Standards search
the Engineering Library Standards Database. For SAE Standards information, search the SAE
Standards database but online access to standards is not available at the UW Libraries.

IEC (International Electro technical Commission)

The IEC prepares and publishes international standards for all electrical, electronic and related
technologies. Explore the IEC technical publications on their site. Search our database to see the IEC
standards in our collection.

Testing standards
What is a standard?
A simplistic but idealized working definition…
Standard - a document, developed and used by consensus of the stakeholders, which describes how a
product is to be obtained or used.
 document - can be electronic or paper
 stakeholders – includes anyone with an interest without restriction
 product - can include hardware, software, analysis result, test result, protocol, definition, etc.
 obtained or used - can mean designed, built, procured, calculated,
tested, etc.
Benefits of standards
Good standards – those with credibility, integrity, and marketplace acceptance – reduce procurement
costs, improve products, expand markets, and/or lower risk
Standards do this by…
 Reducing duplication of effort or overlap and combining resources
 Bridging of technology gaps and transferring technology
 Reducing conflict in regulations
 Facilitating commerce
 Stabilizing existing markets and allowing development of new markets
 Protecting from litigation

“The good thing about standards is that there are many of them.”
A product should be designed to comply with industry standards (such as the requirements of
dimensional, physical, mechanical, electrical properties). While designing to standards does not ensure a
safe product, standards do tend to create safer products. Advertise and market wisely. Occasionally, a
company creates potential product misuse situations though its advertisements, marketing materials,
and sales personnel. Product liability loss prevention is not the sole responsibility of the product
designer or manufacturer; misrepresentation and exaggeration in advertisements and marketing
materials may also be involved. The infomercial has underscored the importance of testing.

Product testing
• According to a product’s nature, specifications and international regulations, various types of
tests such as
 Safety tests
 Life tests (reliability)
 Functional tests, and
 Packaging tests
must be performed to assure conformance and quality.
There are many different types of products and their associated tests.
• Chemical Testing
• Construction Materials
• Electrical and Electronic Products
• Food
• Textiles and Garments
• Toys and Children's Products, etc.

General product testing procedures:

 Raise problems: Emulation of practical using situation (proper and improper uses)
 Confirm test criteria: Directives and Standards
 Plan for the test: Facilities setup and test sequence
 Test implementation: Record and Analysis

Example: Product Testing for Safety of Toys

 Step 1:
 Emulate the users of the toy under various situations (normal and abnormal)
 Analyze and study the features/functions of the toy
 Identify the potential hazards of playing the toy (include packing)
 Step 2: Look up the standards and confirm the test criteria. For example, EN-71 or ASTM F963BS
  EN71-1: Mechanical & Physical Properties
 BS EN71-2: Flammability
 BS EN71-3: Specification for migration of certain elements
 BS EN71-4: Experimental sets for chemistry and related activities
 BS EN71-5: Chemical toys (sets) other than experimental sets
 BS EN71-6: Graphical symbols for age warning labelling

Result Analysis

Result analysis services evaluate material quality and provide the necessary insight to improve
performance and resolve failure or contamination issues. Materials such as polymers, plastics,
composites, metals, alloys, ceramics, paper and board have diverse properties that impact
performance.  An understanding of material’s properties, therefore, is essential to determine if your
material or product is suitable for its intended use or to understand and rectify a failure Materials
analysis services can ensure the quality of your materials, solve performance issues, support product
development and investigate failure issues by providing the information you need to understand your
material’s composition, structure, chemical properties, mechanical properties or physical properties.
Advantages of testing

Materials Testing is performed for a variety of reasons and can provide a wealth of information about the tested
materials, prototypes or product samples. The data collected during testing and the final test results can be very
useful to engineers, designers, production managers and others.
Here are some of the reasons material testing is important:
 Meeting requirements of regulatory agencies
 Selecting appropriate materials and treatments for an application
 Evaluating product design or improvement specifications
 Verifying a production process
 Testing is an essential part of both design and manufacturing processes, not only when safety is a concern, but
also for any company committed to selling reliable products and minimizing damage and costs if problems do
surface. Testing is often performed early on during product development to evaluate a planned production
process. It can also be just as relevant to provide validation for final products on an ongoing basis. Various types
of non-destructive testing services are used to evaluate finished products without causing damage to the items.
 Materials testing also plays a large role in failure analysis investigations to help identify defective products,
inadequate materials and, ultimately, the cause of a failure.
 When materials testing services are purchased from an independent laboratory like Laboratory Testing Inc., a
certified test report is provided that documents applicable accreditations, specifications/standards, other test
criteria and complete test results.
 It’s typical for a business to purchase mechanical testing services when specifying material for a new product
design. Testing may be performed to evaluate mechanical properties such as strength, hardness, elasticity and
fracture toughness. Corrosion testing can determine if the material will hold up under given conditions such as
humidity or a salt water environment.
 UNIT IV MATERIAL CHARACTERIZATION TESTING

Macroscopic and Microscopic observations

Macroscopic and microscopic testing belongs to the group of metallographic testing, and is
conducted in order to determine basic structure of the tested material. As it is the case of the welded
joint testing, this testing enables the determination of the derived welded joint quality from the
viewpoint of the defined acceptability criteria contained in the Standard EN 288-3 [3]. Besides the
evaluation of the applied welding technology, the testing should also determine the boundaries of the
individual welded joint structures. By visual and radiographic testing welded samples were characterized
as acceptable.

Optical and Electron microscopy (SEM and TEM)

Optical Microscopy
Microstructural features
• Grain size: from <m to the cm regime
• Grain shapes
• Precipitate size: mostly in the m regime
• Volume fractions and distributions of various phases
• Defects such as cracks and voids: <m to the cm regime
A microscope is an instrument designed to make fine details visible. The microscope must accomplish
three tasks:
1.To produce a magnified image of the specimen (magnification).
2. To separate the details in the image (resolution).
3. To render the details visible to the eye, camera, or other imaging device (contrast).

Use visible light as illumination source

 Has a resolution of ~o.2m
 Range of samples characterized - almost unlimited for solids and liquid crystals
 Usually nondestructive; sample preparation may involve material removal
 Main use – direct visual observation; preliminary observation for final characterization with
applications in geology, medicine, materials research and engineering, industries, and etc.
 Cost - $15,000-$390,000 or more

Refraction of Light
Light path bends at interface between two transparent media of different indices of refraction
(densities)
N - Refractive index of material

c- Speed of light in vacuum

v- Speed of light in material
Focusing Property of A Curved Surface
In entering an optically more dense medium (N 2>N1), rays are bent toward the normal to the interface at
the point of incidence

Curved (converging) glass surface

Focal plane

F - focal point f – focal length

Converging (Bi-Convex) Lens

The simplest magnifying lens f  curvature angle and lens materials (N) the larger N, the shorter f
lucite glass diamond
N: 1.47 1.51 2.42

Image Formation by a Converging Lens

Two fundamental properties of lenses:
1. Deviating a light beam parallel to its own axis, then making it to pass through the focus;
2. Leaving unaltered the path of the rays which pass through the lens center.
The A ray (principal ray) passes through the lens center and is not deflected.
The B ray comes to the lens moving parallel to the axis and passes through F1.
The C ray which in a similar way passes through F2 and leaves the lens parallel to the optical axis.
Any two of these three characteristic rays can be utilized to determine the size and placement of the
image formed by the lens.

Lens formula and magnification

Lens Formula f-focal length (distance)

O-distance of object from lens
i-distance of image from lens

Magnification
by objective

How Fine can You See with an Optical Microscope?

  Magnification M = 25L/fofe
If we can make lenses with extremely short focal length, can we design an optical microscope
for seeing atoms?
 Can you tell the difference between magnification and resolution?
 Imagine printing a JPEG file of resolution 320240 to a A4 size print!!

Resolution of an Optical Microscope – Physical Limit

 Owing to diffraction, the image of a point is no longer a point but an airy disc after passing
through a lens with finite aperture!
 The disc images (diffraction patterns) of two adjacent points may overlap if the two points are
close together.
 The two points can no longer be distinguished if the discs overlap too much
 To express the resolution in terms of a linear separation r, have to consider the Abbe’s theory
 Path difference between the two beams passing the two slits is
 Assuming that the two beams are just collected by the objective, then i =  and
dmin = /2sin
 If the space between the specimen and the objective is filled with a medium of refractive index
n, then wavelength in medium n = /n
The dmin = /2n sin = /2(N.A.)
For circular aperture
dmin= 1.22/2(N.A.)=0.61/(N.A.)
where N.A. = n sin is called numerical aperture

Optical Aberrations
Aberration in optical systems (lenses intended to produce a sharp image) generally leads to blurring of
the image. It occurs when light from one point of an object after transmission through the system does
not converge into a single point.
Two primary causes of non-ideal lens action:
• Spherical (geometrical) aberration – related to the spherical nature of the lens
• Chromatic aberration – arise from variations in the refractive indices of the wide range of
frequencies in visible light
Astigmatism, field curvature and chromatic aberrations are easily corrected with proper lens fabrication.

Spherical Aberration – Peripheral rays and axial rays have different focal points (caused by spherical
shape of the lens surfaces). causes the image to appear hazy or blurred and slightly out of focus. very
important in terms of the resolution of the lens because it affects the coincident imaging of points along
the optical axis and degrade the performance of the lens.

Chromatic Aberration
 Axial - Blue light is refracted to the greatest extent followed by green and red light, a
phenomenon commonly referred to as dispersion
 Lateral - chromatic difference of magnification: the blue image of a detail was slightly
larger than the green image or the red image in white light, thus causing color ringing of
specimen details at the outer regions of the field of view
 A converging lens can be combined with a weaker diverging lens, so that the chromatic
aberrations cancel for certain wavelengths: The combination – achromatic doublet
Astigmatism - The off-axis image of a specimen point appears as a disc or blurred lines instead of a
point. Depending on the angle of the off-axis rays entering the lens, the line image may be oriented
either tangentially

Types of Microscope Resolution Power

Compound Microscope 200 nanometers
Scanning Electron Microscope 10 nanometers
Transmission Electron Microscope 0.2 nanometers

Electron microscopy
Electron and ion microscopes, use a beam of charged particles, and electromagnetic or electrostatic
lenses. They can see features as small a tenth of a nanometer, such as individual atoms. Electron
Microscopes uses a beam of highly energetic electrons to examine objects on a very fine scale. This
examination brings the details about the observant.
 Topography
 Morphology
 Composition
 Crystallographic Structure

Types of Electron Microscope

Scanning Electron Microscope (SEM)

Transmission Electron Microscope (TEM)

SCANNING ELECTRO MICROSCOPE

 SEM focuses on the sample’s surface and its composition
 Scan a gold-plated specimen to give a 3-D view of the surface of an object which is black and
white.
 Used to study surface features of materials, cells and viruses.
 Scanning Electron microscope has resolution 1000 times better than Light microscope.
 This is a platinum wire that has been milled to 50nm in diameter. It is to be used a gas sensor


To directly visualize the surface topography of solid unsectioned specimens.
• Probe scans the specimen in square raster pattern.
• The first scanning electron microscope (SEM) debuted in 1938 ( Von Ardenne) with the first
commercial instruments around 1965.
• Differs from TEM in construction & operational modes
• TEM – information is obtained from transmitted electrons
• SEM – majority is obtained from secondary, backscattered electrons & from X-rays.
After the impingement of the primary electrons on the specimens, secondary electrons as well as
other forms of radiation are emitted.
• But only the secondary electrons will be collected by the signal detector.
• In the detector these electrons strike a scintillator and the light produced is converted to electric
signals by a photomultiplier.
• The electric signal is then amplified and displayed on the cathode ray tube (CRT).
• In the SEM the electron beam is rapidly scanned back and forth in an orderly pattern across the
specimen surface.
• It is a composite of many individual image spots similar to the image formed on the TV screen.
• The SEM has a specimen stage that allows the specimen to move freely so that the surface of the
specimen can be viewed from all angles.

Transmission Electron Microscope Principle

• TEM is the direct counterpart of Light microscope
• Involves passage of high velocity electron beam through specimen, thin enough to transmit 50%
of the electrons
• Transmitted electrons – focused by lens systems to form a 2 dimensional magnified image
• Stream of electrons is formed.
• Accelerated using a positive electrical potential
• Focused by metallic aperture and Electro magnets
• Interactions occur inside the irradiated sample which are detected and transformed into an
image .
• Scanning electron microscopy allows for higher magnification and better resolution than
standard light microscopy.
• Since the sample is bombarded with electrons rather than light, the level of detail in a smaller
area is much greater than a light microscope
 Analogy between LM & TEM
Arrangement & function of their components
1. Illuminating system – source & condensor
2. Imaging system – lenses to produce magnified image – objective & projector
3. Image translating system – Final image is viewed

Electron source
The electron source consists of a cathode and an anode.
• The cathode is a tungsten filament which emits electrons when being heated.
• A negative cap confines the electrons into a loosely focused beam.
• The beam is then accelerated towards the specimen by the positive anode.

Electromagnetic lens system

The system allows electrons within a small energy range to pass through, so the electrons in the
electron beam will have a well-defined energy.
1. Magnetic Lens: Circular electromagnets capable of generating a precise circular magnetic field.
The field acts like an optical lens to focus the electrons.
2. Aperture: A thin disk with a small (2-100 micrometers) circular through-hole. It is used to restrict
the electron beam and filter out unwanted electrons before hitting the specimen.

The Vacuum System

• The electron beam must be generated in and traverse through the microscope column under a high
vacuum condition.
• The presence of air molecules will result in the collision and scattering of the electrons from their path.
• In the electron microscope the vacuum is maintained by a series of highly efficient vacuum pumps.
• THE VACUUM FACTOR: Biological material must be properly fixed and preserved

Sample holder
• The sample holder is a platform equipped with a mechanical arm for holding the specimen and
controlling its position.

Imaging system
• The imaging system consists of another electromagnetic lens system and a screen.
• The electromagnetic lens - two lens, one for refocusing the electrons after they pass through the
specimen, and the other for enlarging the image and projecting it onto the screen.
• The screen has a phosphorescent plate which glows when being hit by electrons.

Image Formation in the TEM

• The basis of image formation in the TEM is the scattering of electrons.
• The scattering results in a shadow on the viewing screen or photographic film.
• Material with high atomic numbers will cause more scattering and produce a deep shadow. Such
material is termed "electron dense" and has high image contrast

TEM vs SEM
TEM SEM
6 lenses – C1, C2, objective, 3 projector 3 lenses – 2 condensor, 1 objective
High accelerating voltage - penetration low accelerating voltage
Not complicated Specimen Stage – complicated
X & y axis X,Y,Z-axis, tilting, rotating

• SEM is based on scattered electrons while TEM is based on transmitted electrons.

• SEM focuses on the sample’s surface and its composition whereas TEM provides the details
about internal composition. Therefore, TEM can show many characteristics of the sample, such
as morphology, crystallization, stress or even magnetic domains. On the other hand, SEM shows
only the morphology of samples.
• The sample in TEM has to be cut thinner whereas there is no such need with SEM sample.
• TEM has much higher resolution than SEM.
• SEM allows for large amount of sample to be analyzed at a time whereas with TEM only small
amount of sample can be analyzed 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
• In TEM, pictures are shown on fluorescent screens whereas in SEM, picture is shown on
monitor.
• SEM also provides a 3-dimensional image while TEM provides a 2-dimensional picture.
• TEM requires extensive sample preparation. The thickness of the specimens to be examined
under TEM should be less than 100nm.

Diffraction Method
X-rays were discovered by Wilhelm Roentgen who called them x-rays because the nature at first
was unknown so, x-rays are also called Roentgen rays. X-ray diffraction in crystals was discovered by
Max von Laue. The wavelength range is 10-7 to about 10-15 m. The penetrating power of x-rays
depends on energy also, there are two types of x-rays.
i) Hard x-rays: which have high frequency and have more energy.
ii) soft x-rays: which have less penetrating and have low energy
X-rays are short wave length electromagnetic radiations produced by the deceleration of high energy
electrons or by electronic transitions of electrons in the inner orbital of atoms
X-ray region 0.1to100 A˚, Analytical purpose 0.7 to 2 A˚

PRINCIPLE
X-ray diffraction is based on constructive interference of monochromatic x-rays and a crystalline sample.
These x-rays are generated by a cathode ray tube, filtered to produce monochromatic radiation,
collimated to concentrate and directed towards the sample. The interaction of incident rays with the
sample produces constructive interference when conditions satisfy Bragg’s law.

Braggs Equation

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

For constructive interference: n = 2d Sin

Constructive interference of the reflected beams emerging from two different planes will take place if
the path lengths of two rays is equal to whole number of wavelengths”.

for constructive interference,

nλ=2dsin this is called as BRAGG’S LAW

Instrumentation
 Production of x-rays
 Collimator
 Monochromator a.Filter b.Crystal monochromator
 Detectors a.Photographic methods b.Counter methods

PRODUCTION OF X-RAYS:
 X-rays are generated when high velocity electrons impinge on a metal target.
 Approximately 1% of the total energy of the electron beam is converted into x-radiation.
 The remainder being dissipated as heat.
  Many types of x-ray tubes are available which are used for producing x-rays.
 A Positive voltage in the form of anode having a target a
• b . Battery to emit thermoionic electrons
• C. Cathode –filament of tungsten metal
• The electrons are accelerated towards the target a
• On striking the target the electrons transfer their energy to its metallic surface which gives off x-
ray radiation

In order to get a narrow beam of x-rays, the x-rays generated by the target material are allowed to pass
through a collimator which consists of two sets of closely packed metal plates separated by a small gap.
The collimator absorbs all the x-rays except the narrow beam that passes between the gap.
TYPES OF MONOCHROMATORS
In order to do monochromatization,2 methods are available
1.Filter
2.Crystal monochromator
a)Flat crystal monochromator
b)Curved crystal monochromator
Materials used-Nacl,quartz etc,.
1.FILTER: X-ray beam may be partly monochromatized by insertion of a suitable filter. A filter is a
window of material that absorbs undesirable radiation but allows the radiation of required wavelength
to pass
2.CRYSTAL MONOCHROMATOR : Crystal monochromators is made up of suitable crystalline material
positioned in the x-ray beam so that the angle of reflecting planes satisfied the Bragg’s equation for the
required wavelength the beam is split up into component wavelengths crystals used in monochromators
are made up of materials like Nacl, lithium fluoride , quartz etc

DETECTORS
The x-ray intensities can be measured and recorded either by
 1)Photographic methods
 2)Counter methods
  a) Geiger - Muller tube counter
 b) Proportional counter
 c) Scintillation detector
 d) Solid state semi conductor detector
 e) Semi conductor detectors

Both these types of methods depends upon ability of x-rays to ionize matter and differ only in the
subsequent fate of electrons produced by the ionizing process.

Photographic method:
To record the position and intensity of x-ray beam a plane or cylindrical film is used
The film after exposing to x-ray is developed. The blackening of the developed film is expressed in terms
of density units D given by
D=log I₀/I
I₀- incident intensities
I- transmitted intensities
D-Total energy that causes blackening of the film D is measured by densitometer

The photographic method is mainly used in diffraction studies since it reveals the entire diffraction
pattern on a single film .
Dis advg: time consuming and uses exposure of several hours

COUNTER METHODS:
Geiger - Muller tube counter Geiger tube is filled with inert gas like argon. Central wire anode is
maintained at a positive potential of 800 to 2500V . The electron is accelerated by the potential gradient
and causes the ionization of large number of argon atoms, resulting in the production of avalanche of
electrons that are travelling towards central anode.

PROPORTIONAL COUNTER:
 Construction is similar to Geiger tube counter
 Proportional counter is filled with heavier gas like xenon and krypton
 Heavier gas is preferred because it is easily ionized
 Operated at a voltage below the geiger plateau
 The dead time is very short (~0.2μs), it can be used to count high high rates without significant error.

SCINTILLATION DETECTOR:
 In a scintillation detector there is large sodium iodide crystal activated with a small amount of
thallium  When x-ray is incident upon crystal , the pulses of visible light are emitted which can be
detected by a photo multiplier tube
  Useful for measuring x-ray of short wavelength
 Crystals used in scintillation detectors include sodium iodide , anthracene ,napthalene and p-
terphenol

Solid state semi-conductor detector

In this type of detector, the electrons produced by x-ray beam are promoted into conduction bands and
the current which flows is directly proportional to incident x-ray energy
Dis advantage: Semi – conductor device should be maintained at low temperatures to minimize noise
and prevent deterioration

 When x-ray falls on silicon lithium drifted detector an electron (-e) and a hole (+e)
 Pure silicon made up with thin film of lithium metal plated onto one end
 Under the influence of voltage electrons moves towards +ve charge and holes towards –ve
 Voltage generated is measure of the x-ray intensity falling on crystal
 Upon arriving at lithium pulse is generated
 Voltage of pulse=q/c; q-tot charge collected on electrode, c-detector capacity.

X-RAY DIFFRACTION METHODS

These are generally used for investigating the internal structures and crystal structures of various solid
compounds.
They are
1.Laue’s photographic method
a)Transmission method
b)Back reflection method
2.Bragg’s X-ray spectrometer method
3.Rotating crystal method
4.Powder method

Laue’s Method
In this method a single crystal is held stationary in the path of radiation of continuous wavelength. While
 is kept constant, the wavelength ,  is varied. A plane film receives the diffracted beams. A developed
film after its exposure shows a diffraction pattern that consists of series of spots.
Laue’s method is divided Into two types
a) Transmission Method
b) Back Reflection Method

Transmission 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. Can be used
to orient crystals for solid state experiments. Most suitable for the investigation of preferred orientation
sheet particularly confined to lower diffraction angles. Also used in determination of symmetry of single
crystals.

Back reflection 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 intersects the cone, with the diffraction spots generally lying
on an hyperbola. This method is similar to Transmission method however, black-reflection is the only
method for the study of large and thick specimens.
Disadvantage: Big crystals are required
Crystal orientation is determined from the position of the spots. Each spot can be indexed, i.e. attributed
to a particular plane, using special charts. The Greninger chart is used for back-reflection patterns and
the Leonhardt chart for transmission patterns. The Laue technique can also be used to assess crystal
perfection from the size and shape.

The Bragg’s x-ray spectrometer method:

Laue-beam of x-ray-crystal-emitted x-ray obtained on photographic plate-using photograph-brag
analysed structures of crystals of Nacl,Kcl,and Zns-brags equation. Single plane generates several
diffraction lines-sum tot of diffraction lines gives diffraction patterns-from the pattern we can deduce
different distances between planes-angle between planes in each of three dimensions.

A-anti cathode
B-B’ – Adjustable slits
C-crystal
E-ionization chamber
One plate of ionization chamber is connected to the positive terminal of a H.T Battery , while negative
terminal is connected to quadrant electrometer(measures the strength of ionization current)

Working:
 Crystal is mounted such that ѳ=0° and ionization chamber is adjusted to receive x-rays
 Crystal and ionization chamber are allowed to move in small steps
 The angle through which the chamber is moved is twice the angle through which the crystal is
rotated
 X-ray spectrum is obtained by plotting a graph between ionization current and the glancing angle
 Peaks are obtained. peaks correspond to Bragg’s reflection
 Different order glancing angles are obtained with known values of d and n and from the observed
value of ѳ , λ can be measured.

ROTATING CRYSTAL METHOD:

Photographs can be taken by:
1.Complete rotation method:in this method series of complete revolutions occur. Each set of a plane in
a crystal diffracts four times during rotation. Four diffracted beams are distributed into a rectangular
pattern in the central point of photograph
2.Oscillation method:the crystal is oscillated at an angle of 15° or 20°. The photographic plate is also
moved vack and forth with the crystal. The position of the spot on the plate indicates the orientation of
the crystal at which the spot wasformed

POWDER CRYSTAL METHOD:

X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase identification
of a crystalline material and can provide information on unit cell dimensions. The analyzed material is
finely ground, homogenized, and average bulk composition is determined.
Fine powder is struck on a hair with a gum, it is suspended vertically in the axis of a cylindrical
camera. When monochromatic beam is allowed to pass different possibilities may happen
1. There will be some particles out of random orientation of small crystals in the fine powder
2. Another fraction of grains will have another set of planes in the correct positions for the reflections to
occur
3. Reflections are possible in different orders for each set
If the angle of incidence is ѳ then the angle of reflection will be 2ѳ. If the radius is r the circumference
2πr corresponds to a scattering angle of 360°. From the above equation the value of ѳ can be calculated
and substituted in bragg’s equation to get the value of d

Applications
 o Useful for determining the complex structures of metals and alloys
o characterization of crystalline materials
o identification of fine-grained minerals such as clays and mixed layer clays that are difficult to
determine optically
o determination of unit cell dimensions
o measurement of sample purity

Application of XRD
1.Structure of crystals
2. Polymer characterization
3. State of anneal in metals
4. Particle size determination a) Spot counting method b) Broadening of diffraction lines c) Low-angle
scattering
5.Applications of diffraction methods to complexes a) Determination of cistrans isomerism b)
Determination of linkage isomerism
6.Miscellaneous applications like Soil classification based on crystallinity, Analysis of industrial dusts, and
Assessment of weathering & degradation of minerals & polymers.

For materials including metals, minerals, plastics, pharmaceuticals and semiconductors XRD apparatus
provide highly accurate tools for nondestructive analysis. The diffraction systems are also supported by
an extensive range of application software

Spectroscopic Techniques:

Spectroscopy was originally the study of the interaction between radiation and matter as a function of
wavelength (λ). In fact, historically, spectroscopy referred to the use of visible light dispersed according
to its wavelength, e.g. by a prism. Later the concept was expanded greatly to comprise any
measurement of a quantity as function of either wavelength or frequency. Thus it also can refer to a
response to an alternating field or varying frequency (ν). A further extension of the scope of the
definition added energy (E) as a variable, once the very close relationship E = hν for photons was realized
(h is the Planck constant). A plot of the response as a function of wavelength—or more commonly
frequency—is referred to as a spectrum; see also spectral linewidth. Spectrometry is the spectroscopic
technique used to assess the concentration or amount of a given species. In those cases, the instrument
that performs such measurements is a spectrometer or spectrograph.
Spectroscopy/spectrometry is often used in physical and analytical chemistry for the identification of
substances through the spectrum emitted from or absorbed by them.
Spectroscopy/spectrometry 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.
Types
Absorption
Absorption spectroscopy is a technique in which the power of a beam of light measured before and after
interaction with a sample is compared. When performed with tunable diode laser, it is often referred to
as Tunable diode laser absorption spectroscopy (TDLAS). It is also often combined with a modulation
technique, most often wavelength modulation spectrometry (WMS) and occasionally frequency
modulation spectrometry (FMS) in order to reduce the noise in the system.
Fluorescence
Fluorescence Spectrum of light from a fluorescent lamp showing prominent mercury peaks 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, and can be used for
confocal microscopy, fluorescence resonance energy transfer, and fluorescence lifetime imaging.
Flame
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 analytes in the part per million, billion, or possibly lower
concentration ranges. Light detectors are needed to detect light with the analysis information coming
from the flame.
• Atomic Emission Spectroscopy - This method uses flame excitation; atoms are excited from the heat of
the flame to emit light. This method commonly uses a total consumption burner with a round burning
outlet. A higher temperature flame than atomic absorption spectroscopy (AA) is typically used to
produce excitation of analyte atoms. Since analyte atoms are excited by the heat of the flame, no special
elemental lamps to shine into the flame are needed. A high resolution polychromator can be used to
produce an emission intensity vs. wavelength spectrum over a range of wavelengths showing multiple
element excitation lines, meaning multiple elements can be detected in one run. Alternatively, a
monochromator can be set at one wavelength to concentrate on analysis of a single element at a certain
emission line. Plasma emission spectroscopy is a more modern version of this method. See Flame
emission spectroscopy for more details.
• Atomic absorption spectroscopy (often called AA) - This method commonly uses a pre-burner
nebulizer (or nebulizing chamber) to create a sample mist and a slot-shaped burner which gives a longer
pathlength flame. The temperature of the flame is low enough that the flame itself does not excite
sample atoms from their ground state. The nebulizer and flame are used to desolvate and atomize the
sample, but the excitation of the analyte atoms is done by the use of lamps shining through the flame at
various wavelengths for each type of analyte. In AA, the amount of light absorbed after going through
the flame determines the amount of analyte in the sample. A graphite furnace for heating the sample to
desolvate and atomize is commonly used for greater sensitivity. The graphite furnace method can also
analyze some solid or slurry samples. Because of its good sensitivity and selectivity, it is still a commonly
used method of analysis for certain trace elements in aqueous (and other liquid) samples.
• Atomic Fluorescence Spectroscopy - This method commonly uses a burner with a round burning
outlet. The flame is used to solvate and atomize the sample, but a lamp shines light at a specific
wavelength into the flame to excite the analyte atoms in the flame. The atoms of certain elements can
then fluoresce emitting light in a different direction. The intensity of this fluorescing light is used for
quantifying the amount of analyte element in the sample. A graphite furnace can also be used for
atomic fluorescence spectroscopy. This method is not as commonly used as atomic absorption or
plasma emission spectroscopy.
Plasma Emission Spectroscopy
In some ways similar to flame atomic emission spectroscopy, it has largely replaced it. • Direct-current
plasma (DCP) A direct-current plasma (DCP) is created by an electrical discharge between two
electrodes. A plasma support gas is necessary, and Ar is common. Samples can be deposited on one of
the electrodes, or if conducting can make up one electrode.
• Glow discharge-optical emission spectrometry (GD-OES)
• Inductively coupled plasma-atomic emission spectrometry (ICP-AES)
• Laser Induced Breakdown Spectroscopy (LIBS) (LIBS), also called Laser-induced plasma spectrometry
(LIPS)
• Microwave-induced plasma (MIP)
Spark or arc (emission) spectroscopy - 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, a sample of the solid was commonly ground up and destroyed during
analysis. An electric arc or spark is passed through the sample, heating the sample to a high temperature
to excite the atoms in it. The excited analyte atoms glow emitting light at various wavelengths which
could be detected by common spectroscopic 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.
Visible
Many atoms emit or absorb visible light. In order to obtain a fine line spectrum, the atoms must be in a
gas phase. This means that the substance has to be vaporised. The spectrum is studied in absorption or
emission. Visible absorption spectroscopy is often combined with UV absorption spectroscopy in UV/Vis
spectroscopy. Although this form may be uncommon as the human eye is a similar indicator, it still
proves useful when distinguishing colours.
Ultraviolet
All atoms absorb in the Ultraviolet (UV) region because these photons are energetic enough to excite
outer electrons. If the frequency is high enough, photoionization takes place. UV spectroscopy is also
used in quantifying protein and DNA concentration as well as the ratio of protein to DNA concentration
in a solution. Several amino acids usually found in protein, such as tryptophan, absorb light in the
280 nm range and DNA absorbs light in the 260 nm range. For this reason, the ratio of 260/280 nm
absorbance is a good general indicator of the relative purity of a solution in terms of these two
macromolecules. Reasonable estimates of protein or DNA concentration can also be made this way
using Beer's law. Infrared
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. It is also an important method for analysing polymers and
constituents like fillers, pigments and plasticizers.
Near Infrared (NIR)
The near infrared NIR range, immediately beyond the visible wavelength range, is especially important
for practical applications because of the much greater penetration depth of NIR radiation into the
sample than in the case of mid IR spectroscopy range. This allows also large samples to be measured in
each scan by → NIR spectroscopy, and is currently employed for many practical applications such as:
rapid grain analysis, medical diagnosis pharmaceuticals/medicines , biotechnology, genomics analysis,
proteomic analysis, interactomics research, inline textile monitoring, food analysis and chemical
imaging/hyperspectral imaging of intact organisms, plastics, textiles, insect detection, forensic lab
application, crime detection, various military applications, and so on.
Raman
Raman spectroscopy uses the inelastic scattering of light to analyse vibrational and rotational modes of
molecules. The resulting 'fingerprints' are an aid to analysis.
Coherent anti-Stokes Raman spectroscopy (CARS)
CARS is a recent technique that has high sensitivity and powerful applications for in vivo spectroscopy
and imaging.
Nuclear magnetic resonance
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.
Photoemission
Mössbauer
Transmission or conversion-electron (CEMS) modes of Mössbauer spectroscopy probe the properties of
specific isotope nuclei in different atomic environments by analyzing the resonant absorption of
characteristic energy gamma-rays known as the Mössbauer effect.
Other types
• Acoustic spectroscopy
• Auger Spectroscopy A method used to study surfaces of materials on a micro-scale. It is often used in
connection with electron microscopy.
• Cavity ring down spectroscopy
• Circular Dichroism spectroscopy
• Dielectric spectroscopy
• Force spectroscopy
Applications
1. Identification of substance
2. Studying progress of reactions
3. Detection of impurities
4. Types of atoms and relative amount of atoms
5. Structural information about molecule
6. Detect isotopes
7. Carbon dating
8. Satellites and space craft

Electrical and magnetic Technique

Cyclic Voltammetry
Cyclic Voltammetry (CV) is one of the most extensively used electro-analytical technique for
characterizing the electrochemical behavior of electrochemically active species. It is often the primary
experiment done in any electrochemical study. In the year 1958, Kemulla et.al first practiced this
technique at a hanging mercury drop electrode for detection of concentrations of Cu, Tl, Pb, Cd and Zn
ions. CV is a multifaceted technology giving information about thermodynamic parameters like redox
potentials and equilibrium constants as well as kinetic parameters such as rate constants for reactions
involving electro active species. The electrochemical behavior of any system is studied by scanning the
potential at a working electrode relative to a reference electrode and monitoring the subsequent
current flowing through a counter electrode in a quiescent solution. The repeating triangular potential
excitation signal shown, facilitates the potential of working electrode to sweep back and forth between
two selected potential values known as switching potentials. The scan rate is reflected by the slope of
the plot. The potentiostat monitors the current corresponding to changing applied voltage. The plot
between recorded current and potential is known as cyclic voltammogram represents a typical cyclic
voltammogram of an electron transfer reaction in which the rate is governed by diffusion of the
electroactive species to electrode surface. As observed from the plot, no flow of electrons or current is
witnessed in the beginning of the scan. During the potential scan, when the applied potential achieves a
positive potential value which is more than that of redox couple present in the solution, the anodic
current starts flowing in the circuit due to oxidation of redox species at the electrode surface. The
anodic current increases rapidly until the concentration of redox species getting oxidized near the
surface of electrode becomes zero, as indicated by peak marked as Ipa. After the complete oxidation of
redox species near the electrode surface, resulting anodic current starts decreasing. Similarly, after
switching the direction of potential, the high negative potential at working electrode as compared to
reduction potential of redox species, results in reduction of redox species accumulated near the
electrode surface during the positive potential scan. The reduction of redox species is marked by
appearance of cathodic current. Again, the current increases with increasing scan further towards high
negative potential. The potential value at which the species getting reduced is almost depleted in the
vicinity of electrode is marked by Ipc in Figure 3.11. The critical parameters obtained from cyclic
voltammogram, i.e., the magnitude of anodic peak current (Ipa), magnitude of cathodic peak current
(Ipc) and their corresponding potentials at which peaks occur, Epa and Epc can be exploited further to
know the reaction kinetics occurring at the working electrode.
The rate of reaction could be determined by
 Mass transfer rate of the electro-active species.
 Rate of electron transfer between electrode and electro active species.
 Rate of adsorption or de-sorption at the surface of electrode.

Nernst Equation
For a redox reaction,
𝑅𝑒𝑑 ⇆ 𝑂𝑥 + 𝑛𝑒 –
the electrode potential at equilibrium is given by Nernst equation in terms of the concentration of
electroactive species involved in redox reaction as
𝐸 = 𝐸 0 + (0.059/ 𝑛) (𝑙𝑜𝑔10 [𝑂𝑠]/ [𝑅𝑠])
Where, E° is the formal potential;
E is the applied potential;
Os and Rs represent the concentration of the redox species at the interface, respectively.
In CV measurements, since the solution is static (no stirring) hence electron transfer from electroactive
species to electrode surface takes place via diffusion only. The concentration gradient created as a result
of conversion of redox species from one form to other is the driving force behind electron transfer via
diffusion. The concentration-distance profile is shown. Hence the current response of the electrode
would depend on 52 concentration of the electroactive species, the surface area of the electrode and
the voltage scan rate, in addition to the diffusivity of the electroactive species.

Magnetization studies using Vibrating Sample Magnetometer (VSM)

A Vibrating Sample Magnetometer (VSM) is used to measure the magnetic behavior of magnetic
materials. VSM operates on Faraday's law of induction; a changing magnetic field will produce an
electric field. This electric field can be measured and can give us information about the changing
magnetic field. When a sample is placed within a uniform magnetic field and made to undergo sinusoidal
motion (i.e. mechanically vibrated), there is some magnetic flux change. This induces a voltage in the
pick-up coils, which is proportional to the magnetic moment of the sample. Figure shows the block
diagram of a typical VSM setup. A VSM operates by first placing the sample to be studied in a constant
magnetic field. If the sample is magnetic, this constant magnetic field will magnetize the sample by
aligning the magnetic domains, or the individual magnetic spins, with the field. If the value of the
applied constant magnetic field is higher, then, magnetization will be higher. The magnetic dipole
moment of the sample will create a magnetic field around the sample, sometimes called the magnetic
stray field. As the sample is moved up and down, this magnetic stray field changes as a function of time
and can be sensed by a set of pickup coils. The alternating magnetic field will cause an electric field in
the pick-up coils according to Faraday's law of induction. This current will be proportional to the
magnetization of the sample. If the sample possesses higher magnetization, induced current will be
higher.

The induction current is amplified by a lock-in amplifier. The various components are hooked up to a
computer interface. Using controlling and monitoring software, the system can give information about
the magnetization value of sample and how its magnetization depends on the strength of the constant
magnetic field. A typical measurement on a sample is taken in the following manner:
The strength of the constant magnetic field is set
 The sample begins to vibrate
 The signal received from the probe is translated into a value for the magnetic moment of the
sample
 The strength of the constant magnetic field changes to a new value. no data is taken during this
transition
 The strength of the constant magnetic field reaches its new value
 The signal from the probe again gets translated into a value for the magnetization of the sample
 The constant magnetic field varies over a given range, and a plot of magnetization (M) versus
magnetic field strength (H) is generated
AC Resistance/Inductance Bridge:
The low temperature AC bridge measures resistance of materials as a function of temperature (10-400
K) and external magnetic field (500 Oe). The magnetic field is provided by Helmholtz coils. The resistance
is measured using four-probe method using Linear Research bridge. The bridge is sensitive up to 1 micro
Ohm reading. The sample stage is designed to study giant-magneto resistance materials in the presence
of in-plane magnetic field. The entire setup is controlled by LabView. The bridge is also used to study
susceptibility and magnetization of magnetic materials using inductance method.
Temperature Dependent High Resistance
Resistivity in the range of giga Ohms of materials is measured using SVS Lab resistivity bridge (TPR-EXP)
in the temperature range of 295-500 K.
Magneto-resistance Measurement:
Magneto-resistance measurement device is a home build device. The device is capable of measuring
magneto-resistance as a function of magnetic field (maximum 2000 Oe) and rotational angle of the
sample. The resistance is measured using Keithly 330 source meter in 4-point probe geometry and van
der paw geometry. The system automated using Labview program.
Electrometer for Current –Voltage (IV) characteristics An electrometer is an electrical device to measure
electrical potential difference. Different types of electrometer ranges from historical handmade
mechanical instruments to high-precision electronic devices. Modern electrometers can be used to
measure voltage and charge with very small leakage currents, down to 1 femtoampere.
 UNIT V OTHER TESTING
,.. Chemical Testing: X-Ray Fluorescence, Elemental Analysis by Inductively Coupled Plasma-
Optical Emission Spectroscopy and Plasma-Mass Spectrometry

Thermal Testing: Differential scanning calorimetry

Thermal analysis is a series of techniques that provide physical property measurement as a function of
temperature, time, and other variables.
Differential scanning calorimetry (DSC) is a technique used to investigate the response of polymers to
heating. DSC can be used to study the melting of a crystalline polymer or the glass transition. The DSC
set-up is composed of a measurement chamber and a computer. Two pans are heated in the
measurement chamber. The sample pan contains the material being investigated. A second pan, which
is typically empty, is used as a reference. The computer is used to monitor the temperature and regulate
the rate at which the temperature of the pans changes. A typical heating rate is around 10 ◦C/min. The
rate of temperature change for a given amount of heat will differ between the two pans. This difference
depends on the composition of the pan contents as well as physical changes such as phase changes. For
the heat flux DSC used in this lab course, the system varies the heat provided to one of the pans in order
to keep the temperature of both pans the same. The difference in heat output of the two heaters is
recorded. The result is a plot of the difference in heat (q) versus temperature (T).

Two types of DSC instruments are widely used: the heat flux DSC (eg. TA DSC and Mettler DSC) and the
power compensated DSC (Perkin-Elmer system).

Heat Flux DSC

In a heat flux DSC system the sample and reference are heated at the same rate from a single heating
source as shown in Figure. The temperature difference between the pans is recorded and converted to a
power difference. This power difference gives the difference in heat flow.
Power Compensated DSC
The sample and reference are heated separately in power compensated DSC, as shown in Figure. The
pan temperatures are monitored using thermocouples attached to the disk platforms. The
thermocouples are connected in series and measure the differential heat flow using the thermal
equivalent of Ohm’s Law
dq/dt = ∆T/ RD
where (dq/dt) is the heat flow, ∆T is the temperature difference between the reference and sample, and
RD is the thermal resistance of the disk platform. The heat flow to each pan is adjusted to keep their
temperature difference close to zero while the furnance temperature is increased linearly. The DSC 2920
Differential Scanning Calorimeter (TA Instruments) used in the PMM laboratory is a typical heat flux DSC
(Figure 8). It is used to obtain qualitative and quantitative information about the physical and chemical
changes that materials undergo during heating. It is also capable of modulated heating, the advantages
of which will be explained in the section on modulated differential scanning calorimetry.

Modulated DSC
 Modulated temperature DSC (MDSC) is an extension of DSC. The same heat ux DSC cell is used
for MDSC, but a sinusoidal temperature oscillation (modulation) is overlaid on the conventional linear
temperature ramp. This results in the heating rate at times being faster or slower than the underlying
linear heating rate. This variation in instantaneous heating is illustrated in Figure. The actual heating rate
depends on three experimental variables: the underlying heating rate, the amplitude of modulation and
the period (frequency) of modulation. Typical values for these parameters are a heating rate of +-1 to+-5
‫ﹾ‬C/min, an amplitude of +-0.5‫ ﹾ‬to +-1‫ﹾ‬C, and an oscillation period of 40 to 60 s. Higher resolution can be
achieved by decreasing the heating rate, increasing the amplitude, and decreasing the oscillation period.

Typical modulated temperature versus time plot for MDSC. A sinusoidal temperature variation is
overlaid on a linear heating.
Both conventional DSC and MDSC can be used to _nd transition temperatures, latent heats of phase
transitions and heat capacity. However, MDSC can be used to obtain more information than a single DSC
run and overcomes several limitations of conventional DSC. For instance, the heat capacity and heat
flow can be measured in a single experiment using MDSC. Temperature modulation also makes it
possible to separate complex transitions into more easily interpreted components. MDSC has a higher
sensitivity than DSC, which improves the detection of weak transitions. The resolution of these
transitions can also be increased without loss of sensitivity. Finally, MDSC provides more accurate
measurements of the degree of crystallinity in polymers and allows for direct determination of thermal
conductivity.

Advantages and disadvantages

One advantage of MDSC is the improved analysis of complex transitions. Many transitions are
complex, meaning that they actually involve multiple processes. An example is an endothermic process
known as enthalpy relaxation that can occur during the glass transition. The magnitude of enthalpy
relaxations depends on the thermal history of the material. In some cases, it can cause a glass transition
to look like a melting peak. Another example is the melting and crystallization of a polymer. These
processes can occur simultaneously, making it almost impossible to determine the true crystallinity of
the sample. Conventional DSC does not help in these cases since it only measures the total heat ow from
all thermal events in the sample at a given temperature. If multiple transitions occur in the same
temperature range, then the results are confusing and often misinterpreted. MDSC ameliorates this
problem by separating the total heat ow signal into its reversing and non-reversing components.
Conventional DSC is not well suited for the detection and accurate measurement of weak transitions.
This is due to noise in the baseline. Baseline noise that is short-term, occurring on the order of seconds,
can be effectively eliminated by signal averaging. Long-term variations in the baseline are more
problematic. This variation occurs on the order of minutes and is due to changes in the properties of the
DSC cell materials and purge gas with temperature. The degree of baseline drift varies across
commercial DSC instruments and cannot easily be corrected for. MDSC eliminates this problem by using
the ratio of two signals to calculate the real changes in the sample heat capacity rather than just the
absolute value of the heat ow signal. Conventional DSC is also limited by restrictions on the possible
resolution.

Differential thermal analysis

Thermal Analysis (TA) is a group of techniques that study the properties of materials as they
change with temperature. In practice thermal analysis gives properties like; enthalpy, thermal capacity,
mass changes and the coefficient of heat expansion. Solid state chemistry uses thermal analysis for
studying reactions in the solid state, thermal degradation reactions, phase transitions and phase
diagrams. Thermal analysis is the analysis of a change in a property of a sample, which is related to an
imposed change in the temperature. The sample is usually in the solid state and the changes that occur
on heating include melting, phase transition, sublimation, and decomposition. The analysis of the
change in the mass of a sample on heating is known as Thermogravimetric analysis (TG). TG measures
mass changes in a material as a function of temperature (or time) under a controlled atmosphere. Its
principal uses include measurement of a material's thermal stability and composition. TG is most useful
for dehydration, decomposition, desorption, and oxidation processes. The most widely used thermal
method of analysis is Differential thermal analysis (DTA). In DTA, the temperature of a sample is
compared with that of an inert reference material during a programmed change of temperature. The
temperature should be the same until thermal event occurs, such as melting, decomposition or change
in the crystal structure. In an endothermic event takes place within the sample, the temperature of the
sample will lag behind that of the reference and a minimum will be observed on the curve. On the
contrary, if an exothermal event takes place, then the temperature of the sample will exceed that of the
reference and a maximum will be observed on the curve. The area under the endotherm or oxotherm is
related to the enthalpy of the thermal event, ΔH. For many problems, it is advantageous to use both
DTA and TG, because the DTA events can then be classified into those which do or do not involve mass
change. A good example is shown as following: Fig.1 TG & DTA curves for Al4(Si4O10)(OH)8 At the
temperature range 500 to 700°C there is a change in mass occurred on the TG curve, which corresponds
to dehydration of Al4(Si4O10)(OH)8, and this dehydration shows up on DTA curve as an endotherm. At
950 to 980°C, a second DTA effects occurs but this effect not occurs on the TG curve, because this event
corresponds to recrystallization of the dehydrated kaolin. This recrystallization process is oxothermic.
TG-DTA modes can be used to determine the following:-
• Melting points
• Glass transition temperatures
• Cristallinity
• Moisture/ volatile content
• Thermal and oxidative stability
• Purity
• Transformation temperatures

The difference between DTA and DSC is that, in DTA the temperature of the sample is monitored with
respect to a reference sample; in DSC the sample and the reference are maintained at the same
temperature throughout the procedure.

The ideal reference material is a substance with the same thermal mass as the sample, but with no
thermal events over the temperature range of interest. In DTA is usually used alumina (Al2O3),
carborundum(SiC) or magnesium oxide(MgO) powder as the reference material for the analysis of
inorganic compounds.
 Modern DTA

The material under study and an inert reference are made to undergo identical thermal cycles. Any
temperature difference between sample and reference is recorded. In this technique the heat flow to
the sample and reference remain the same rather than the temperature. The differential temperature is
then plotted against time, or against temperature (DTA curve or thermogram).

Phenomena causing changes in heat / temperature

Physical
Adsorption (exothermic) Desorption (endothermic) A change in crystal structure (endo – or exothermic)
Crystallization (exothermic) Melting (endothermic) Vaporization (endothermic) Sublimation
(endothermic)
Chemical
Oxidation (exothermic) Reduction (endothermic) Break down reactions (endo – or exothermic)
Chemisorption (exothermic) Solid state reactions (endo – or exothermic)

Thermo-mechanical and Dynamic mechanical analysis: Principles, Advantages, Applications

Thermo-Mechanical Analysis
Thermomechanical analysis (TMA) measures linear or volumetric changes in the dimensions of a
sample as a function of time, temperature and force in a controlled atmosphere.

TMA Finds
1.Compatibity of materials that must function together: e.g., coatings and their substrates, adjacent
layers of laminates, resins or elastomers and their reinforcements or fillers, seals or encapsulants and
the mechanical systems they protect
2.Suitability of materials for use in harsh environments and temperature extremes: e.g., brake linings,
automotive gaskets, window seals, solder joints, adhesives, and protective coatings

Measured signals
 Length (strain) relative to zero position
 Rate of length change
 dL/dt = Creep (flow)
 dL/dT = Coefficient of Thermal Expansion (CTE)
 Stress (expansion and/or contraction forces)
 Temperature
 Time

Modes of operation
Compression Mode
1.Expansion
Measures:
Coefficient of Thermal Expansion (CTE), Glass Transition Temperature, Compression Modulus of
Polymeric Materials
2. Penetration
Measures: Softening and Melting Points, Coating and Film Evaluation
3.Dilatometry
Calculates: Volume Coefficient of Expansion of Bulk or Irregular-shaped Materials
4.Parallel Plate Rheometry
Analyzes low shear viscosity of materials
5.Flexure
Measures the deflection (bending) properties of stiff materials such as laminates and composites
Tension Mode
1.Films and Fibers

Probes Schematic diagram

Principle
A schematic diagram of the typical instrument is shown in Figure 2. The sample is placed in the chamber
where the temperature is controlled by the thermocouple placed close to the sample. The
measurements are performed in the protective atmosphere of inert gases like: nitrogen, helium or
argon but also the other gases could be used i.e. air, carbon monoxide, hydrogen. Because of the
relatively large mass of the sample the applied heating and cooling rates are usually slow. The rate of
5°C/ min is usually the maximum recommended value for good temperature equilibration across the
specimen. The dimensional changes of the sample relative to the holder appearing during heating or
cooling are transmitted via pushrod to the highly precise inductive transducer (LVDT) sensor. The
construction of the pushrod and sample holder depends on the mod of the measurements. The most
commercial instruments are supplied with a variety of probes for different applications. Figure presents
the examples of the holding devices taken from the TMA 402 F1 Hyperion, NETZSCH. Every displacement
of the pushrod is transformed into analog signal by the LVDT and in the next converted to digital form
then recorded in the PC system and finally presented by the software as a dimensional change versus
time or temperature.
Application
These techniques have been developed more recently than the others described so far, but applications
have grown rapidly. TMA and TD measurements are often carried out on the same sample with the
same apparatus. Examples of both expansion and penetration measurements on neoprene rubber. The
coefficient of linear thermal expansion, ct, can be determined from the slope of the expansion curve.
Both the glass-transition (Tg) and melting (T.) show up clearly. Another example [2J is the use of
penetration measurements for testing.
Dynamic Mechanical analysis
Dynamic Mechanical Analysis, otherwise known as DMA, is a technique where a small
deformation is applied to a sample in a cyclic manner. This allows the materials response to stress,
temperature, frequency and other values to be studied. The term is also used to refer to the analyzer
that performs the test. DMA is also called DMTA for Dynamic Mechanical Thermal Analysis.

Principle
DMA works by applying a sinusoidal deformation to a sample of known geometry. The sample
can be subjected by a controlled stress or a controlled strain. For a known stress, the sample will then
deform a certain amount. In DMA this is done sinusoidally. How much it deforms is related to its
stiffness. A force motor is used to generate the sinusoidal wave and this is transmitted to the sample via
a drive shaft. One concern has always been the compliance of this drive shaft and the effect of any
stabilizing bearing to hold it in position. A schematic of the analytic train of the DMA 8000, Figure ,
shows its innovative design that requires neither springs nor air-bearings to support the drive shaft.

DMA measures stiffness and damping, these are reported as modulus and tan delta. Because we are
applying a sinusoidal force, we can express the modulus as an in-phase component, the storage
modulus, and an out of phase component, the loss modulus, see Figure 2. The storage modulus, either
E’ or G’, is the measure of the sample’s elastic behavior. The ratio of the loss to the storage is the tan
delta and is often called damping. It is a measure of the energy dissipation of a material.

DMA Testing modes

Advantages
Thermomechanical Analysis, or TMA, applies a constant static force to a material and watches
the material change as temperature or time varies. It reports dimensional changes. On the other hand,
DMA applies an oscillatory force at a set frequency to the sample and reports changes in stiffness and
damping. DMA data is used to obtain modulus information while TMA gives coefficient of thermal
expansion, or CTE. Both detect transitions, but DMA is much more sensitive. Some TMAs can do limited
DMA and the PerkinElmer® DMA 8000 is the only DMA that can do TMA
Application
A photo-calorimeter only looks at the energy of photo-curing. Photo-curing in the DMA lets you see how
the physical properties change and when the modulus of the curing material has reached acceptable
limits in terms of strength and stiffness. This information is important for cost effective design of your
cure cycle. Using a DMA with UV also allows you to investigate the degradation of materials and so
evaluate additive packages, formulations, etc.

The DMA Results Can Correlate to

Molecular structures
MW and MWD, Branching, Crystallinity, Crosslinking, Phase, Relaxation
Processing
Heat history, Residual stress, Shear or orientation, Temperature, Fillers
Product properties
Transition temperatures (Tg, T β, T γ), Environmental resistance, Impact strength, Long term behavior,
aging, Adhesion
Provide information to polymer’s structure-property relationship.