Material Characterizations

SEM & TEM

DSC, DTA, & TGA

XRD

FTIR
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
1
Bangladesh; [email protected].
 SEM & TEM
➢ The upper limit of magnification for optical microscopes is about 2000 times.

➢ Thus, additional forms of microscopy have been developed that allow near to actual atomic
observation of material surfaces.

➢ Electron microscopy utilizes an electron beam to act as the sensing radiation in place of light. High-
energy electrons take on wave character as they approach the speed of light.

➢ The wavelength is inversely proportional to the electron speed or velocity. When accelerated over
large voltages (10-20 KV), electrons can be made to travel at speeds to permit wavelengths on the
order of 0.003 nm.

➢ The electron beam is focused and the image is formed using magnetic lenses.

➢ The two most common forms of electron microscopy are scanning electron microscopy (SEM) and
transmission electron microscopy (TEM).
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
2
Bangladesh; [email protected].
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
3
Bangladesh; [email protected].
Scanning Electron Microscopy (SEM)

➢ In scanning electron microscopy (SEM), the material surface is scanned

using an electron beam with the reflected or backscattered beam of
electrons collected and displayed on a cathode ray tube screen.

➢ The image represents the surface contour of the scanned material.

➢ Since the surface must be conductive, most polymer surfaces must be

overlaid with a conductive coating.

➢ Magnifications up to about 50,000 are carried out using SEM.

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

4
Bangladesh; [email protected].
Transmission Electron Microscopy (TEM)

➢ Transmission electron microscopy (TEM) utilizes an image formed by an electron

beam that passes through the sample.

➢ This allows internal microstructures to be determined.

➢ Structural details of materials can be observed on an atomic level by looking at

contrasts in the image caused by various concentrations of different elements.

➢ Very thin films are employed.

➢ Under good conditions, magnifications up to one million are possible employing

the TEM.

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

5
Bangladesh; [email protected].
Comparison between SEM and TEM

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

6
Bangladesh; [email protected].
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
7
Bangladesh; [email protected].
Sample Preparation for SEM

Cleaning

Fixation
➢ SEM cannot be used for living
cells imaging

➢ It produces images of a sample

Dehydration
by scanning the surface

Dry

Coating
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
8
Bangladesh; [email protected].
Basic tools

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

9
Bangladesh; [email protected].
Operation Principle of SEM

20 KV Primary Electron

Raster scan generator

More SE = Bright
Less SE = Grey
No SE = Black

Dr. Mohammad Zakaria, Professor, TE, DUET,

Gazipur-1707, Bangladesh; 10
[email protected].
Image Analysis

10 μm

ImageJ photo editing software: https://imagej.nih.gov/ij/download.html

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

11
Bangladesh; [email protected].
 Image Analysis
Figure 3 shows the optical and SEM images of both
commercial and developed PP nanofibrous membrane
surfaces. The optical images of the surface of both
commercial and prepared PP membranes were identical but
their SEM images were significantly dissimilar. A densely
placed and compact surface covering was visualized for
MPP-70 and MPP-80 for their very low ranges of fiber
diameter. Their very fine fibers construct a densely arranged
fibrous mesh even inside the tiny den or pit of the membrane
surface, as shown clearly in the inset of Figure 3e. These
compact mesh structures of the nanofibers resulted in a
smooth surface covering of the membranes and form a large
number of smaller pores in a unit area. That makes it more
advantageous for the separation of micro to nano-sized
targeted particles with high efficiency. On the other hand,
too larger opening was observed on the commercial
membrane surface compared to the developed PP
nanofibrous membranes. In case of MPP-50, some localized
portion of the membrane having a very low diameter fiber
and more dense surface covering were observed (inset of
Figure 3d shows the clearer view), however, in the other
portion, the fiber dimension, arrangement, and surface
opening were almost identical to the commercial membrane 12
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707, Bangladesh; [email protected].
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
13
Bangladesh; [email protected].
The quality and usefulness of the data obtained using a TEM is much more dependent
on the quality of sample inserted than the microscope itself!!!

❖ Representative
❖ Thin (< 100 nm)
❖ Stable
The ideal TEM specimen is: ❖ Clean
❖ Flat
❖ Parallel-sided
❖ Conductive
❖ Free from segregation
❖ Self-supportive

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

14
Bangladesh; [email protected].
 Sample Preparation for TEM

▪ Nanoparticles are so easy

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

15
Bangladesh; [email protected].
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
16
Bangladesh; [email protected].
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
17
Bangladesh; [email protected].
Summary

➢ TEM has one of the highest spatial resolutions of any imaging

technique
➢ The spatial resolution allows imaging of atomic structure
➢ TEM are somewhat complicated to operate
➢ TEM is 95% sample preparation and 5% microscopy
➢ TEM is a powerful tool in our materials characterization toolbox

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

18
Bangladesh; [email protected].
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.

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

19
Bangladesh; [email protected].
Types of thermal analysis
I. Differential scanning calorimetry (DSC): heat difference/enthalpy (W=J/sec)
II. Differential thermal analysis (DTA): temperature difference (℃)
III. Thermogravimetric analysis (TGA): mass change as a function of temp (gram)
IV. Pressurized TGA (PTGA): mass changes as function of pressure (gram)
V. Thermo mechanical analysis (TMA): deformations and dimension (meter)
VI. Dynamic mechanical analysis (DMA): Elasticity (Pa= N/𝑚2 )
VII.Evolved gas analysis (EGA): gaseous decomposition products

Often different properties may be measured at the same time:

TGA-DTA, TGA-EGA

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

20
Bangladesh; [email protected].
Material Transition

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

21
Bangladesh; [email protected].
Phenomenon/Property Technique
DSC TGA TMA DMA
1. Melting (Tm) O -- ∆ ∆
2. Glass transition (Tg) O -- O O
3. Crystallization O -- ∆ O
4. Reaction (Curing/ Polymerization) O ∆ O O
5. Sublimation/ Evaporation/ Dehydration ∆ O -- --
6. Thermal decomposition ∆ O -- --
7. Thermal expansion/ Thermal shrinkage -- -- O --

8. Thermal history O -- O O
9. Specific heat capacity (Cp = J⋅K−1⋅kg−1) O -- -- --
0: Measurement Object, ∆: Some Compatible, --: Not Measured
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
22
Bangladesh; [email protected].
Differential Scanning Calorimetry (DSC)
DSC is fundamental tool in thermal analysis and widely used in many industries like,
Pharmaceuticals, Polymers, Agriculture, Nanomaterials, etc.

DSC is a thermo analytical technique, in which the heat or energy necessary to

establish a zero temperature difference between sample and reference is measured as
a function of temperature, when both are heated or cooled at predetermined rate.

It cover the temperature ranges: From - 40 to 750 ℃

It was developed by E. S. Watson and M. J. O’Neill (1962)

It has two basic types

a. Power Compensated DSC
b. Heat Flux DSC Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
23
Bangladesh; [email protected].
Same heat flows into both samples; When a
change occurs (endo or Exo) a ∆T signal is
generated which is proportional to the heat
flow difference.
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
24
Bangladesh; [email protected].
 Power Compensated DSC

➢ Two identical and separate heaters are used

➢ Zero temperature difference is maintained
➢ Temperature difference during phase transition or
reaction in the sample are compensated by varying
electrical current supplied to heaters.
➢ The supplied electrical current is directly
proportional to heat absorbed during the process
➢ Gives better regulation
➢ Rapid cooling and heating
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
25
Bangladesh; [email protected].
Heat Flux DSC

➢ Single heater is used to heat sample and reference

➢ Allow temperature between sample and reference
to vary
➢ This temperature difference is used to get required
heat flow
➢ Less sensitive
➢ Slower heating and cooling
Chromel alloy = 90% Nickel & 10% Chromium
➢ Less accurately measures heat capacity and Alumel alloy = 95% Nickel, 2 % Aluminum, 2 %
Magnesium & 1 % Silicon
enthalpy
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
26
Bangladesh; [email protected].
 Working Principle of HFDSC
➢ Sample & Ref. sealed in Al or Cu pan
➢ Placed adjacent to each other
➢ Common heating applied to both
➢ Heater heats S & R at constant rate and sensor senses temp.
➢ Now sample tends to absorb or release heat due to transitions &
tempt varies
➢ To maintain constant tempt more or less heat supplied to sample
➢ The amount of heat transferred to sample is monitored by PC and
output received in the form of thermogram.

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

27
Bangladesh; [email protected].
Difference between PCDSC and HFDSC

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

28
Bangladesh; [email protected].
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
29
Bangladesh; [email protected].
DSC Curve

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

30
Bangladesh; [email protected].
 DSC Curve
• The measurement is typically expressed in units of heat flow per unit
mass, such as milliwatts per milligram (mW/mg). This unit
represents the rate at which heat energy is absorbed or released by the
sample relative to its mass, usually during processes like melting,
crystallization, or glass transition.
• In DSC curves:
• Endothermic peaks indicate that heat flows into the sample, often
associated with melting or other endothermic transitions.
• Exothermic peaks show that heat is released from the sample,
typically seen in crystallization or exothermic reactions.
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
31
Bangladesh; [email protected].
Factors affecting the DSC curve

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

32
Bangladesh; [email protected].
Applications

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

33
Bangladesh; [email protected].
Thermo Analytical Analysis (DTA)
DTA is a thermo-analytical technique for qualitative and quantitative assessment of the analyte “by simply detecting the
difference of temperature between 2 pans” without any compensation.

This technique is almost similar to the HFDSC

It has the better accuracy and longer temperature ranges
Types of Transition
up to -150 to 1600 ℃

Physical Chemical

Melting, Freezing,
Crystallization, Oxidation,
Evaporation, Reduction,
Vaporization & Degradation
Sublimation
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
34
Bangladesh; [email protected].
DTA responses to melting and freezing of a pure material under ideal conditions. a-onset
temperatures (taken here as starting of melting), b-peak signals, c-peak temperatures (Tm).
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
35
Bangladesh; [email protected].
Thermogravimetric Analysis (TGA)
Change in mass (∆m) of the analyte is studied due to the different
physical and chemical transitions when the analyte are heated at a
predetermined rate. Here change of mass is analyzed with the change
of temperature.

Range: 0 to 2000 ℃
Types of Analysis:
a. Dynamic TGA: We constantly change the temperature and see, at
which point change in mass (∆m) occurs.
b. Static or Isothermal TGA: Temp. remains the same, and we see,
after how much time, there is a change in mass of analyte is
occurred.
c. Quasistatic TGA: We provide temp & go to a limit, where
sample gets stable & further increase in temp will not change the
mass of the analyte.

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

Bangladesh; [email protected]. 36
 Types of Transition

Physical Chemical

Adsorption, Desorption, Oxidation, Reduction,

Sublimation, Evaporation, Chemosorption, Loss on
Vaporization drying, Degradation

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

37
Bangladesh; [email protected].
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
38
Bangladesh; [email protected].
Difference Between TGA and HFDSC/DTA Curves

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

39
Bangladesh; [email protected].
Applications

❖ Physical transition
❖ Chemical transition
❖ Loss of drying
❖ Purity
❖ Stability

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

40
Bangladesh; [email protected].
X-ray Diffraction (XRD)

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

41
Bangladesh; [email protected].
What is X-ray?
➢ X-ray is electromagnetic radiation
➢ X-rays are produced by bombarding high energy electrons on
any heavy metal
➢ According to Mosley’s law every element has its unique
signature in the form of Kα emission
➢ X-rays diffract treating inter atomic distances as slits

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

42
Bangladesh; [email protected].
Why X-ray??

❖ An Electromagnetic radiation can be diffracted by atomic

planes only when the half of its wavelength is less than the
inter atomic distance (D).

λ/2 ≤ D

❖ X-Rays are used over visible light for crystal diffraction

because of its shorter wavelength.

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

43
Bangladesh; [email protected].
Diffraction
Diffraction of light wave
Thomas Young (1803)
demonstrating interference from two closely
spaced slits.

Diffraction of sound wave in water

A: constructive interference
B: destructive interference

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

44
Bangladesh; [email protected].
What is X-ray diffraction??
The atomic planes of a crystal cause an incident beam of X-rays to
interfere with one another as they leave the crystal. The
phenomenon is called X-ray diffraction.

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

45
Bangladesh; [email protected].
How X-ray??
Diffraction is the main technique used to identify crystal structure.

•When a parallel beam diffracted from a single slit causes a path difference of
d.Sinө and when incident beam is also at an angle ө then the path difference is
2.d.Sinө

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

46
Bangladesh; [email protected].
 X-ray Diffraction
1895: Wilhelm Röntgen discovered X-rays
1912: Max von Laue suggested that they might be diffracted when passed through a crystal, for
by then he had realized that their wavelengths are comparable to the separation of lattice planes.
This suggestion was confirmed almost immediately by Walter Friedrich and Paul Knipping

Sin⍬ = (λ/2)/d
λ/2 = dSin⍬
λ = 2dSin⍬

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

47
Bangladesh; [email protected].
X-ray Diffractometer

X-ray Detector

Sample Holder

X-ray Source

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

48
Bangladesh; [email protected].
Pick Position
Therefore, the position of a peak determines the inter-planar spacing for a family of planes.
d = Inter-plannar spacing
n = 1 for the first diffraction maxima
If ‘d’ decreases then sinө should increase
2d.sinө = nλ

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

49
Bangladesh; [email protected].
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
50
Bangladesh; [email protected].
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
51
Bangladesh; [email protected].
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
52
Bangladesh; [email protected].
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
53
Bangladesh; [email protected].
Application of X-ray diffraction

1. Structure of Crystals

The analytical applications of X-ray diffraction are numerous. The method is non-
destructive and gives information on the molecular structure of the sample. Perhaps
its most important use has been to measure the size of crystal planes. The patterns
obtained are characteristic of the particulars compounds from which the crystal was
formed.

2. Polymer Characterisation

This method can be used to determine the degree of crystalline of the polymer. The
non-crystalline portion simply scatters the X-ray beam to give a continuous
background, while the crystalline portion causes diffraction lines that are not
continuous.
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
54
Bangladesh; [email protected].
3. State in metals

A property of metals that can be determined by X-ray diffraction is the state of

anneal. Well-annealed metals are in well-ordered crystal form and give sharp
diffraction lines. If the metal is subjected to drilling, hammering, or bending, it
becomes fatigued," that is, its crystals become broken and the X-ray pattern
more diffuse.

4. Particle size Determination

A variety of X-ray may be used to determine the size of particles or crystallites.

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

55
Bangladesh; [email protected].
 What is Infrared
➢ Infrared radiation lies between the visible and
microwave portions of the electromagnetic spectrum.
➢ Infrared waves have wavelengths longer than visible
and shorter than microwaves, and have frequencies
which are higher than visible and shorter than
microwaves.
➢ The Infrared region is divided into near, mid and far-
infrared. Near-infrared refers to the part of the
infrared spectrum that is closest to visible light and
far-infrared refers to the part that is closer to the
microwave region.
➢ Mid-infrared is the region between these two.
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
56
Bangladesh; [email protected].
 Fourier Transform Infrared (FTIR) Spectroscopy
FTIR Spectroscopy is a molecular spectroscopy by which a molecule can be
characterized (identified) by its molecular vibrations, based on the
absorption and intensity of specific infrared wavelengths.
➢ The sample bombarded with infrared radiation.
➢ When frequency of the infrared radiation matches natural frequency of
the bond, the amplitude of the vibration increases, and the infrared is
absorbed.
➢ The bonds between atoms in the molecule stretch and bend, absorbing
infrared energy and creating the infrared spectrum.
➢ output of an infrared spectrophotometer is a chart.
➢ For isopropyl alcohol, CH(CH3)2OH, the infrared absorption bands identify
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
the various functional groups of the molecule. Bangladesh; [email protected].
57
Basic Principle of IR Spectroscopy
Source Sample Detector
Liquid, Solid, Gas

IR radiation Formaldehyde

Interatomic bond
Diff. wavelength
100, 200, 300, 400 Vibrate
Light
Stretching Bending
Symmetric, Asymmetric Twisting, Wagging,
Scissoring, Rocking
Energy
Wavenumber
The bonds between atoms in the molecule stretch and bend, absorbing infrared energy and creating the
infrared spectrum. A molecule such as CH2O will absorb infrared light when the vibration (stretch or bend)
results in a molecular dipole moment change
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
58
Bangladesh; [email protected].
Types of atomic vibration

Question: How many normal modes of vibration does the C02 molecule possess?

Answer: CO2 is Linear molecule. For linear molecules formula is 3N -5 In Case of CO2, N is 3
where N = No. of atoms, so = (9-5) = 4 Vibrations
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
59
Bangladesh; [email protected].
Spectroscopic Process of FTIR
Stationary mirror

IR Source

Moveable mirror
Beam splitter

Sample

Detector

Constructive interference: OPD=O, λ, 2λ, 3λ, etc. (integral number of wavelengths)

Destructive interference: OPD=λ/2, 3 λ/2, 5 λ/2, etc. (half-integral number of wavelengths)
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
60
Bangladesh; [email protected].
 Wavenumber
In Fourier Transform Infrared (FTIR) spectroscopy, the wavenumber is used
instead of wavelength as the units of energy. The wavenumber is equal to the
reciprocal of the wavelength and is typically expressed in units of cm−1.
This is because wavenumber is a more convenient unit for representing the
energy difference between states in the context of spectroscopy.
To convert wavenumber to wavelength, you can use the following equation:
λ= 1/nν
where
λ is the wavelength of light,
n is the refractive index of the medium, and ν is the wavenumber.
FTIR spectroscopy is mainly used to measure light absorption of mid-infrared
light, with wavenumbers typically ranging from 4,000 to 400 cm^{-1}
(wavelengths between 2.5 to 25 µm).
By analyzing the absorption of infrared radiation at different wavenumbers, it is
possible to identify and quantify various materials.Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707, 61
Bangladesh; [email protected].
Fourier Transform from Interferogram

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

62
Bangladesh; [email protected].
Typical FTIR Library

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

63
Bangladesh; [email protected].
 Finger print region

• The region to the right-hand of the

diagram (from about 1600 to 500 cm-1)
• Usually contain a very complicated
series of absorptions
• Contains peaks due to bending
vibrations
• It is rarely possible to assign a specific
peak to a specific group Absorption Region - Wavenumber Range is
from 4000 to 1600 cm-1

Fingerprint Region - Wavenumber Range is

from 1600 to 400 cm-1

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

64
Bangladesh; [email protected].
Pick properties

1. Intensity (weak, medium or strong)

2. Shape (broad or sharp)
3. Position (cm-1) in the spectrum.

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

65
Bangladesh; [email protected].
Applications of Infrared Analysis
➢ Pharmaceutical research
➢ Forensic investigations
➢ Polymer analysis
➢ Lubricant formulation and fuel additives
➢ Foods research
➢ Quality assurance and control
➢ Environmental and water quality analysis methods
➢ Biochemical and biomedical research
➢ Coatings and surfactants
Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,
66
Bangladesh; [email protected].
THANKS

Dr. Mohammad Zakaria, Professor, TE, DUET, Gazipur-1707,

67
Bangladesh; [email protected].