Term 2 – 2018/2019

X-Ray Diffraction,
Transmission Electron
Microscope
ENMT 604009 & ENMT 614018

Wahyuaji NP
Departemen Teknik Metalurgi dan Material FTUI

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 What is X-Ray Diffraction??
❑ Crystalline substances (e.g.
minerals) consist of parallel
rows of atoms separated by
a ‘unique’ distance
❑ Simple Example:
▪ Halite (Na and Cl)
 Crystalline materials are
characterized by the orderly periodic
arrangements of atoms.
The (200) planes The (220) planes
of atoms in NaCl of atoms in NaCl

❑ The unit cell is the basic repeating unit that defines a crystal.
❑ Parallel planes of atoms intersecting the unit cell are used to define
directions and distances in the crystal.
▪ These crystallographic planes are identified by Miller indices.
❑ Crystalline substances (e.g. minerals) consist of parallel rows of atoms
separated by a ‘unique’ distance
❑ Diffraction occurs when radiation enters a crystalline substance and is
scattered
❑ Direction and intensity of diffraction depends on orientation of crystal
lattice with radiation
X-Rays
Wavelengths used for
XRD
 The XRD Technique
❑ Takes a sample of the material and places a powdered
sample which is then illuminated with x-rays of a fixed
wave-length.
❑ The intensity of the reflected radiation is recorded using
a goniometer.
❑ The data is analyzed for the reflection angle to calculate
the inter-atomic spacing.
❑ The intensity is measured to discriminate the various D
spacing and the results are compared to known data to
identify possible matches.
 Schematic X-Ray
Diffractometer

Detector

X-Ray
Source

Powdered
sample
X-Ray Diffraction
 Determine D-Spacing from XRD patterns
Bragg’s Law
nλ = 2dsinθ
• n = reflection order (1,2,3,4,etc…)
• λ = radiation wavelength (1.54 angstroms)
• d = spacing between planes of atoms (angstroms)
• θ = angle of incidence (degrees)
 DIFFRACTION AND THE BRAGG EQUATION
Max von Laue was the first to
incident reflected
suggest that crystals might beam o o beam
A x B
diffract X-rays and he also oo
UNIT
d a
provided the first explanation (1,0,0) CELL
m n
o o
for the diffraction observed. C y D
However, it is the explanation
provided by Bragg that is simpler (a)

and more popular.

In the Bragg view crystal incident reflected

beam o o beam
planes act a mirrors. A x B
oo
Constructive interference d
m n UNIT
is observed when the path o o
a
(2,0,0) y CELL
E F
difference between the two
O P d
reflected beams in (a) = nl.
The path difference in (a) is C Z D

2my. Since my/d = sin

2my = 2dsin = nl (b)
where d is the interplanar spacing.
Fig. 11
 Bragg’s Law
In (a) above it is clear that the planes are the (1,0,0) set of planes.
If the path difference is simply one wavelength the Bragg condition
can be stated as

2d (1,0,0) sin  = l
This is a first order reflection.

If the path difference is two wave lengths the Bragg condition becomes

2d (1,0,0) sin  = 2l
and the reflection is a second order reflection.
 Powdering Samples
❑ The samples are powdered to give a random sampling of
ALL atomic planes (crystal faces)
❑ Statistically accurate given samples are powdered finely
AND randomly oriented on sample holder
▪ Intensities are a reflection of d-spacing abundance

❑ Problems arise with minerals that may preferentially

orient on sample holder
▪ Micas and clays have special preparation techniques
 A polycrystalline sample should contain thousands of crystallites. Therefore, all
possible diffraction peaks should be observed.

2 2 2

▪ For every set of planes, there will be a small percentage of crystallites that are properly oriented to
diffract (the plane perpendicular bisects the incident and diffracted beams).

▪ Basic assumptions of powder diffraction are that for every set of planes there is an equal number of
crystallites that will diffract and that there is a statistically relevant number of crystallites, not just one
or two.
Sample XRD Pattern
Calculations using X-ray powder diffraction patterns.
For an orthogonal system (a = b =  = 90°) the relationship between
interplanar spacing (d) and the unit cell parameters is given by the
expression:

1 h2 k2 l2
2
= 2
+ 2
+
d ( h, k , l ) a b c2

This is the expression for an orthorhombic crystal.

For the tetragonal system it reduces to
1 (h 2 + k 2 ) l2
2
= 2
+
d ( h,k ,l ) a c2
and, for the cubic system, it further reduces to

1 (h 2 + k 2 + l 2 )
2
=
d ( h,k ,l ) a2
Mineral Identification
• For most materials the peaks and their intensity are
documented
• JCPDS (Joint Committee on Powder Diffraction
Standards )
• ICDD (International Centre for Diffraction Data)
Mineral Identification
Pattern from JCPDS

http://ww1.iucr.org/cww-top/crystal.index.html
Mineral Identification
Name and formula
Reference code: 00-001-1260
PDF index name: Nickel
Empirical formula: Ni
Chemical formula: Ni
Crystallographic parameters
Crystal system: Cubic
Space group: Fm-3m
Space group number: 225
a (Å): 3.5175
b (Å): 3.5175
c (Å): 3.5175
Alpha (°): 90.0000
Beta (°): 90.0000
Gamma (°): 90.0000
Measured density (g/cm^3): 8.90
Volume of cell (10^6 pm^3): 43.52
Z: 4.00
RIR: -
Status, subfiles and quality
Status: Marked as deleted by ICDD
Subfiles: Inorganic
Quality: Blank (B)
References
Primary reference: Hanawalt et al., Anal. Chem., 10, 475, (1938)
Optical data: Data on Chem. for Cer. Use, Natl. Res. Council Bull. 107
Unit cell: The Structure of Crystals, 1st Ed.
Mineral Identification
Mineral Identification
 Applications of XRD
❑ Unknown mineral ID
❑ Solid solution ID (e.g. feldspars, olivine)
❑ Mixtures of minerals
❑ Clay analyses
❑ Zeolites
❑ Crystallographic applications
❑ Material Science
Factors that affect XRD data
❑ Sample not powdered fine enough
▪ May not give all d-spacing data (not random enough)

❑ Analysis too fast (degrees/minute)

▪ May not give accurate peak data

❑ Mixture of minerals??
❑ Not crystalline – glass!!
Mixture of Minerals
Diffraction from a Variety of Materials

(From “Elements of X-ray

Diffraction”, B.D. Cullity,
Addison Wesley)
 Thin Film Specimen

B B
Grazing angle (very small, ~1-5)
Film or Coating

Substrate

❑ Smaller volume i.e. less intensity of the scattered beam from the film
❑ Grazing angle
▪ Useful only for polycrystalline specimens
Transmission Electron
Microscope
(TEM)
 Historical Background
▪ Developed in 1931 by Dr. Ernst, scientist from University of Berlin
▪ Transmission Electron Microscope (TEM) is a microscope able to perform
magnification up to 2 million times, using electro static and magnetics to
control the illumination and image formation. It also has better resolution
compared with SEM.
▪ TEM design is similar with optical microscope. High energy electron
(>100 kV) is used as light source. Electron is transmitted through the
sample, and the image is formed by set of lenses. This image is projected
to fluorescence screen or CCD camera,
 TEM Classification

❑ Depends on the purpose of analysis and microscope configuration,

TEM is classified into:

1. Conventional transmission electron microscopy

2. High resolution electron microscopy
3. Analytical electron microscopy
4. Energy-filtering electron microscopy
5. High voltage electron microscopy
6. Dedicated scanning transmission electron microscopy
TEM INSTRUMENT
TEM INSTRUMENT
 TEM INSTRUMENT

SEM TEM
 TEM INSTRUMENT

➢ Condenser Systems

➢ Objective Lenses System

➢ Projector Lenses System

➢ Intermediate Lenses System

 TEM Principals
1. Diffraction (Selected Area Electron Diffraction)
Accelerated electron from electron gun in vacuum is focused by
condenser system into specimen

2. Image Formation
Electron loss and scattering by the specimen is focused by objective
lenses, therefore forming an image on fluorescence screen.
TEM Principals
 TEM Principals

Elastically Scattered Electron

(by specimen’s nucleus)
for “image contrast”

Unscattered Electron
Passed through the specimen and creating
electron-lucent of the image

Inelastically Scattered Electron

Smaller scattering angle
 TEM Data
Data produced by TEM:

1. Image

2. Diffraction (SAED)

Templated Synthesis of Magnetic Nanoparticles through the Self-Assembly of Polymers and Surfactants., Vo Thu An Nguyen 1,2,3,

Mario Gauthier 3 and Olivier Sandre 1,2,*., Nanomaterials 2014, 4(3), 628-685
 TEM Data
The structure of regularly twisted poly(m-phenylene isophthalamide) (MPDI)
strands formed by slow crystallization from solution

Source: C. Kübel, D. P. Lawrence, D. C. Martin, "Super-Helically Twisted MPDI Fibers", Macromolecules,

2001, 34(26), 9053-9058.
 Data Interpretation
❑ Observation from the TEM data includes
1. Structure of materials
• Crystalline or amorphous materials
• Materials with nanometres dimension
2. Composition of materials
3. Morphology of materials
• Shape, dimension, particle distribution in specimen
 TEM Specimen
• Medical and biological field

Specimen is placed on carbon or formvar film. Virus specimen must

be frozen in thin ice

• Metallography
Conventional metallography preparation must be done until the
sample is electron-transparent
TEM Specimen
 TEM Application
• Life Sciences
• Mainly for screening diagnostic and some biological cell and
pharmaceutical research.
• Material Sciences
• For research and quality control in manufacturing process of
any materials i.e.: metals and their alloys, semiconductors,
ceramics, composites, polymers and magnetic materials.
 TEM Advantages

• Higher magnification and resolution

• Higher image details
• Provides elements information and composition
• Widely used in many applications and science field
• Provides crystallography information in materials
 TEM Disadvantages
• TEM instrument is quite large and costly
• Special skills needed to operate, interpret, and analyse data
• Specimen must be electron-transparent
• TEM instrument need special maintenance and specific room conditions
• Sample preparation is very challenging to obtain good image
Group Work for Next Lecture
• Group work will be held on 14 and 17 May 2019
• Make a group of 6 students (5 students for international class)
• Bring 1 laptop for each group
• Download ImageJ software at:
https://imagej.nih.gov/ij/download.html
• Install the software on the laptop
• Try to calculate the area percentage of black phase on the
following microstructure image
• Screenshot your calculation using the software, and submit
the screenshot to scele