MATERIALS CHARACTERIZATION TECHNIQUE

Course Objective:

• Help students obtain knowledge on the working principle and

applicability of methods used in materials characterisation.
• Selection of appropriate technique for a given application problem as
well as the appropriate measuring procedure.
• Process and interpret data generated with these techniques

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READING LIST

• L. Lin, A. Kumar, S. Zhang, Materials Characterization Techniques; CRC Press,

(2008).
• B. D. Cullity, R. S. Stock, Elements of X-Ray Diffraction, Prentice-Hall, (2001)
• M. B. Douglas, Fundamentals of Light Microscopy and Electronic Imaging,
Wiley-Liss, Inc. USA, (2001).
• A. K. Tyagi, M. Roy, S. K. Kulshreshtha, S. Banerjee, Advanced Techniques for
Materials Characterization, Materials Science Foundations (monograph
series), Volumes 49 – 51, (2009).
• S. K. Sharma, D. S. Verma, L. U. Khan, S. Kumar, S. B. Khan, Editors,
Handbook of Materials Characterization, Springer International Publishing,
2018 (ISBN: 9783319929545).
• Y. Leng, Materials Characterization: Introduction to Microscopic and
Spectroscopic Methods, John Wiley & Sons, 2nd Ed., 2013 (ISBN:
9783527334636).
• M. Sardela, Practical Materials Characterization, Springer, 2014 (ISBN: 978-
1-4614-9281-8).

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THERMAL ANALYSIS (TA)
Introduction:

• TA are analytical techniques that measures

materials properties as a function of
temperature.
• The properties that can change include
dimension, mass, phase and mechanical
behaviour.
• TA techniques are relatively simple compared
to probing a sample with ion beams or high
energy X-ray.
• Eg include thermogravimetry (TG) or
thermogravimetric analysis (TGA),
differential thermal analysis (DTA),
differential scanning calorimetry (DSC) and
dynamic mechanical analysis (DMA)
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TA

Instrumentation:

• TA techniques have 2 common

features: Furnace with a
controllable environment and a
transducer.
• Temperature profile or heating rate
can be constant, modulated or
isothermal.
• Peaks, discontinuities and slope
changes on TA curves relates to
thermal events.

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TA

Factors Affecting Experimental Results:

• Sample Mass and dimensions

• Heating or cooling rate
• Sample atmosphere
• Thermal and mechanical history of sample

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TA

Best Practices:

• Proper calibration of instrument

• Use of purge gas (N2 or He)
• Good. thermal contact between sample and temperature sensing
device
• Choose the right starting temperature (temperature below expected
transition temperature)
• Proper sample encapsulation (DSC)
• Slow scanning (heating) speeds
• Avoid decomposition in DSC analysis

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 Differential Scanning Calorimetry (DSC)

• Measures the heat-flow difference (heat

flux) between sample and reference.

DSC can be used to:

a) In isothermal mode to determine the
cure kinetics of thermosets.
b) Varying temperature mode to identify
the thermal events of thermoplastics.

2 Types
• Heat-flux (quantitative DTA)
• Power-compensation

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DSC

Heat-flux DSC:

• Sample and reference pans are placed on a metal block in the same
furnace.
• Heat capacity changes results in temperature differences relative to
the reference leading to a heat flow between the sample and reference.
• Use of gas flow through the cell is important to ensure volatiles are
swept away to provide the required atmosphere and to assist in heat
transfer.
• Majority of DSC are heat flux type.

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DSC

Power-compensation DSC:

• Individual microheaters and temperature sensors for the sample and

reference
• Separate heater/cooler provide background heating of the block.
• The average temperature of the sample and heater at a set temperature
Tp is maintained by the separate system (heater) by varying the power
• The enthalpy or heat capacity changes are measured by the energy
associated with the power changes.
• Exothermic events leads to a reduction in power to cool the sample
while endothermic events leads to a power increase to heat the
sample.

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DSC

Sample Requirement:

• Sample Form: powder, small disk, film and sheets

• Low-mass samples preferred (max 10mg) – large sample mass leads
to undesirable internal temperature gradient.
• Large shear forces should be avoided during sample cutting.

 DSC operates at low temperatures (<500 oC).

 Aluminium pans are usually used as sample and reference holders.
 Pans are often sealed to avoid sample mass change during test.

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DSC

Biggest Use:

Polymeric materials study

 Crystallinity
 Glass transition
 Melting
 Curing processes
 Polymer type
 Polymer stability

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DSC

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DSC

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DSC Examples

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DSC Examples

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DSC Examples

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DSC Examples

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DSC Examples

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Thermogravemetric Analysis

Introduction:

• Measuring mass change of a sample with temperature.

• A sample is placed in a furnace and mass change is monitored by a
thermobalance.
• Analyses decomposition and thermal stability through mass change
• Mass change as a function of temperature (in scanning mode) or time
(in isothermal mode).
• Decomposition is represented by two characteristics temperatures (Ti
and Tf).
• Ti lowest temp - onset of mass change while Tf lowest temp - mass
change is completed.

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TGA

Introduction:

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TGA

Instrumentation:
Thermobalance
• Microbalance, furnace, temperature programmer and computer.
• Microbalance measures mass change of ±1µg, Max mass 100 mg.
• Common microbalance is the null-point (maintains the sample in a
vertical position when its mass changes)
• The Cahn microbalance is the most common type.

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TGA

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TGA

Samples:

• Mass (small mass is preferred), Volume and

form (powder, flakes, etc) – IMPORTANT in
recording accurate and reproducible TG
curves.
• Reliability depends on minimal deviation
between sample temperature and programme
temperature.
• Deviation is usually caused either by
endothermic or exothermic reactions in the
sample.
• Block samples can be reduced into powder but
excessive force should be avoided during the
mechanical processing.
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 TGA

Atmosphere:

• Reactive (corrosive, oxidizing) or Nonreactive (Dry Ar, N2)

• Flow rate of 15-25ml/min is recommended for 2-10mg of
sample
• Gas flow carries volatile products out.
• Gas flow can cause thermal shielding and buoyancy effect
• Gas flow downwards to the sample holder will make the holder
shield the thermocouple junction from convective heat transfer
through the flowing gas.
• Gas flow upwards leads to a lifting force on the sample holder
(buoyancy effect) – difficult to eliminate but can be minimised
by careful calibration and good instrumental design.
• Thermocouple junction temperature will change depending on
whether a flow gas was used or not.
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 TGA
Heating Rate:

• For endothermic decomposition – high heat rate

increases the starting and finishing temperatures of
decomposition. The temperature range from start to
finish is wider when compared to a lower heating
rate.
• Low heat rate is more likely to generate thermal
equilibriuom and give a reproducible results (5-
10oC/min). 1oC/min for high resolution TGA
 Heat rate effects are caused by:
• Heat rate may cause the real sample temperature to
lag behind that of the thermocouple.
• Volatile products resulting from decomposition takes
time to diffuse out of the sample and be carried away
by the flowing gas.

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 TGA

Types of Curves:

I. No decomposition with mass loss

II. Rapid mass loss – due to drying or desorption
III. One-stage decomposition – defines stability limit
IV. Multistage decomposition with stable intermediates
V. Multistage decomposition with no stable intermediate.
May also be a high heating rate version of (IV)
VI. Chemical reaction with mass gain, eg oxidation of metals
VII. Mass gain followed by mass loss – very rare
 Decomposition temperature start and end points are defined
as the intersection of initial line tangent and tangent of the
line portion when the slope changed.
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 TGA

DTG:

 Derivative thermogravimetry (DTG) – used

when the slope change is uncertain
 DTG – plot of dm/dT versus temperature
 It clearly identifies the temperature at
maximum mass loss

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TGA

Application:

• Thermal stability
• Chemical reactions
• Quantify composite composition

OTHER CHARACTERISATION TECHNIQUES ARE OFTEN

REQUIRED TO HELP DETERMINE THE EXACT NATURE OF
REACTION/MATERIAL

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TGA

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TGA

HDPE

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TGA

Example:

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TGA

Empty Fruit Branch of Palm Nut

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TGA

Oriental Beech Wood Impregnated with Boric Acid (BA) as Fire Retardant

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TGA

Oriental Beech Wood Impregnated with Borax (BX) as Fire Retardant

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TGA

HDPE and HDPE/IFR Composites

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 Scanning Electron Microscopy (SEM)

Introduction:

• A source of electrons is focused into a

probe that is rastered over the sample
surface
• Electron interactions with the sample
leads to emission of electrons/photons.
• A fraction of the electrons are
collected by the detector and outputted
as an image by the cathode ray tube
(CRT) (i.e every point that the beam
strikes on the sample is mapped
directly onto a corresponding point on
the screen).
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 SEM
Electron Beam Interaction:
• Interactions yield photons and electrons via
elastic (atomic nucleus interaction) or inelastic (
atomic electrons interaction) scattering
processes.
 Elastic :
Incident electron’s path is changed by the columbic
field of the nucleus (Rutherford scattering). Path
can be changed by up to 180o but velocity remains
unchanged with 80-100% of beam energy
transferred. Eg. Backscattering of electrons
 Inelastic :
Incident electron transfers some energy to tightly
bound inner-shell electrons and loosely bound
outer-shell electrons. Eg. Secondary electron
excitation, Inner-shell ionization (Auger electrons,
X-Rays) and Plasmons

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 SEM

Interaction Volume (IV):

• 3D volume of space beneath the sample

surface over which the incident beam spreads
due to elastic collisions
• Size is 100X more than the probe size.

 Factors Affecting IV
• Accelerating Voltage (AV): Increase in
acceleration voltage increases IV
• Atomic number: Increase in atomic number
decreases IV.

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SEM

Effect of AV on SEM image:

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SEM

Image Formation in SEM:

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 SEM

Image:

 3 types of images are produced:

• Secondary electron image

• Backscattered electron image
• Elemental X-ray maps.

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SEM

Secondary Electron Image:

• Caused by inelastic collision. Loosely bound electrons near the

sample surface.
• The transferred energy should exceed the work function of the
material, electron emission is possible.
• When the energy of the emitted electron is below 50 eV, it is referred to
as Secondary Electron (SE) (Energy is 10 eV to 50 eV)
• Majority of emitted SE are produced within the first few nm
• SE produced from deep within the sample loses their energies and
remain within the solid due to additional inelastic collisions.
• SE yield increases with decreases energy of the incident electrons and
tilting of the sample with respect to the electron beam direction

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 SEM

Secondary Electron Image:

• 3 groups:
 SEI – produced from interactions of the
incident beam with the sample surface
 SEII – produced by BSE leaving the sample
after several inelastic scattering events.
 SEIII – produced by BSEs which have
exited the sample surface and further
interact with internal components on the
SEM (not related to the sample).
NB: SEII & SEIII originate from regions far
outside that defined by the incident probe
therefore can cause serious degradation of
image resolution. 43
SEM

Secondary Electron Image:

• Edges and ridges emit more SE’s

that flat surfaces.
• Tilting of the electron beam
means greater distance near
surface and increases SEII.

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 SEM

Back Scattered Electron (BSE) Image:

• BSE are electrons that exit the sample

with an energy > 50 eV.
• Incident electrons that reverse
direction with minimal energy loss
(caused by elastic scattering).
• Higher Z equals more chances of BSE
production (i.e. increase in image
brightness, therefore there is a built in
contrast caused by elemental
differences).

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 SEM

Electron Source:

2 Types:
• Traditional: Thermionic electron
gun – heating of W – wire or
LaB6 crystal
• Modern (cold guns): Field
emission gun (FEG) – A single W
crystal is etched to a thin tip with
electrons extraction achieved by
application of a strong electric
field.

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SEM

Thermionic Electron Gun (TEG):

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SEM

How TEG work:

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SEM

Field Emission Gun (FEG):

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SEM
How FEG works:

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SEM

FEG vs TEG:

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 SEM

Chemical Analysis:

Two ways to perform elemental analysis using

the SEM:

• Energy-Dispersive Spectroscopy (EDS)

• Wavelength-Dispersive Spectroscopy (WDS)

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SEM

Energy Dispersive Spectroscopy (EDS):

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SEM

Wavelength-Dispersive Spectroscopy (WDS):

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SEM

WDS vs EDS:

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Transmission Electron Microscopy (TEM)

TEM vs SEM:

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TEM

Sample Preparation:

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TEM

Sample Preparation:

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TEM

Sample Preparation:

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TEM

Sample Preparation:

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TEM

Sample Preparation:

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TEM

Sample Preparation:

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TEM

Sample Preparation:

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 ATOMIC ABSORPTION SPECTROSCOPY (AAS)

Determine the concentration of metal

atoms/ions in a sample.

Why ONLY metals?

HOW DOES IT WORK?

• Atoms absorb light at specific and

unique wavelength

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 AAS

Instrumentation

4 main parts:

 Light source (hollow cathode lamp)

 Atomization system (Flame or graphite
furnace)
 Monochromator (optical component)
 Detection system (photomultiplier
tube)
FAAS

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 AAS

Atomization (Flame):

• Sample is liquid
• Burner converts aerosol/gas mixture into
free ground state atoms
• Thin slit – 5 -10 cm long depending on
the type of burner
• Flame length defined by the slit and
determines how much light passes
through the atoms.
• Sensitivity is determined according to
Beer-Lambert Law

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 AAS

Atomisation (Flame):

4 Steps:
1. Desolvation (Drying) – nanoparticles
2. Vaporization
3. Atomization – formation of free
ground state atoms
4. Ionization – some free atoms are
converted to ions dependent on the
flame conditions and the ionization
potential of the analytes

Atomisation process in FAAS

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AAS

FAAS:

• Fuel gas must be burned in oxidant gas diluted with nitrogen or argon
FUEL OXIDANT TEMPERATURE
Acetylene Air 2400-2700
Acetylene Oxygen 3300-3400
Acetylene Nitrous oxide 2900-3100
Hydrogen Air 2300-2400

Disadvantages:
• 5-15% of sample reaches the flame
• Minimum sample volume of 0.5-1.0 ml is required for reliable reading
• Viscous samples require dilution with a solvent
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AAS

Graphite Furnace AAS (GFAAS):

• Electrothermal atomization
• Sample is placed in hollow graphite tube and vaporized.

Advantages

• More sensitivity than

• Detection

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