X-RAY DIFFRACTION (XRD) IN

ENVIRONMENTAL FIELD
 X-ray

• Wilhelm Roentgen was awarded the very first Nobel Prize in

Physics after become first person that describe X-rays in 1895

• X-rays are a form of electromagnetic radiation just like other

radiation but X-rays are more energetic compared to others

• The wavelength is usually between 0.01 Å-10 Å, but not all X-

rays can be used for diffraction experiment

• Electrons ejected by thermal agitation from a hot

filament in a vacuum tube are accelerated through a
high voltage

• The high velocity electrons collide with a metal target,

the anode thus creating the X-rays
Level of atom
• In Bohr model, the nucleus of the atom containing the
protons and neutrons is surrounded by shells of
electrons.
• The innermost shell, called the K- shell, is surrounded
by the L- and M - shells.
• When the energy of the electrons accelerated toward
the target becomes high enough to dislodge K- shell
electrons, electrons from the L - and M - shells move
in to take the place of those dislodged.

L-shell to K-shell jump produces a K x-ray

M-shell to K-shell jump produces a K x-ray
 Bragg Law

Bragg’s Law was introduced by Sir W.H. Bragg and his son Sir W.L. Bragg

nλ = 2d sinθ
Where :
λ = the wavelength of the x-ray
d = the spacing of the crystal layers (path
difference)
θ = the incident angle (the angle between
incident ray and the scatter plane)
n = an integer
• When the x-ray is incident onto a crystal surface, its angle of incidence, θ, will reflect back
with a same angle of scattering, θ.
• And, when the path difference, d is equal to a whole number, n, of wavelength, a
constructive interference will occur.
• Consider a single crystal with aligned planes of lattice points separated by a distance d.
Monochromatic X-rays A and A’ are incident upon the crystal at an angle θ. They reflect off
atoms B and B’

The space between diffracting planes of atoms determines peak positions.

The peak intensity is determined by what atoms are in the diffracting plane.
 What is XRD

These method based on the

scattering of X-rays by the
atoms of a crystal that produces
an interference effect so that
the diffraction pattern gives
information on the structure of
the crystal or the identity of a
crystalline substance

Crystal
 A crystal consists of a periodic arrangement of
the unit cell into a lattice.
 The unit cell can contain a single atom or atoms
in a fixed arrangement. d
 Crystals consist of planes of atoms that are
spaced a distance d apart, but can be resolved
into many atomic planes, each with a different
d-spacing.
 INSTRUMENTATION

X-ray diffractometers consist of

 X-ray tube- Generated x-rays by bombarded of high velocity electron on metal target

 Collimators- close metal plates that separates by small gap that narrows a beam of
particles or waves

 Monochromator- allow requires wavelength to pass and absorbs the undesirable

radiation.

 Detector- records and processes this X-ray signal and converts the signal to a count
rate which is then output to a device such as a printer or computer monitor.
Monochromator : 1) Filter 2) Crystal
Diffraction X-ray requires an X-ray source that is essentially monochromatic but
the spectrum that produced composed of several X-ray lines. So the Kβ line in
the X-ray spectrum needs to be removed by using metal foil filters.

1. Filter
• reduce the intensity of the Kβ line in the X-ray
spectrum compared to Kα
• Ex. Ni, Fe, Mn, V, or Zr
• The choice of filter material depends upon the
choice of anode material in the X-ray tube as
shown :

Anode Cu Co Fe Cr Mo
Filter Ni Fe Mn V Zr

• The filter also removes much of the high energy background radiation as shown in graph
• But the background radiation is still high and that the transmitted radiation is still not very
monochromatic.
2. Monochromator - single-crystal monochromators is an alternative and more
selective way to produce a narrow wavelength distribution radiation beam.

• Commonly used materials are pyrolytic graphite and silicon that may be
distinguished based on the difference being in the mosaic spread of the crystals

• For pyrolytic graphite, the mosaic spread is relatively broad which can be used to
make broad band

• While silicon, germanium, or quartz in which the alignment of the mosaic blocks is
near perfect and can make narrow band (Δλ / λ) monochromators
The following properties are desirable for any material used as a laboratory X-ray
monochromator:

• The crystals chosen must be mechanically strong and stable in the beam.
• In order to obtained the desirable wavelength λ, interplanar distances d of the crystals
should suitable
• The structure factor corresponding to the d spacing must be as large as possible, i.e. the
Bragg reflection should be very intense.
• The mosaicity of the crystal must be of suitable magnitude and the distribution of crystal
block orientations should preferably be gaussian.
• Low absorption of the material
• Intensity loss should be minimize if 2θ is small. this can be done by adjusting the
combination of d and λ.
• The crystals should be reasonably easy to cut.
• The crystals should have a small coefficient of
thermal expansion so that the wavelength is
essentially unaffected by any fluctations in
ambient temperature that are likely
to be encountered.

single crystal x-ray diffraction

Detector
Both these type of methods depends
1. Photographic methods upon ability of x-rays to ionize matter and
differ only in the subsequent fate of
2. Counter method electron produced by the ionizing process
-Geiger-muller counter
-Proportional counter
-Scintillation counter
-Solid state semiconductor counter
-Semiconductor

Geiger–Müller counter
 Sampel preparation

• Powders
0.1 um <particle size < 40um
peak broadening less diffraction occurring

• Bulks : smooth surface after polishing, specimens should be thermal

annealed to eliminate any surface deformation induced during
polishing

Significance of peak shape in XRD

1. Peak position
2. Peak width
3. Peak intensity
 APPLICATIONS

1. Phase determination
2. Quantitative phase analysis
3. Calculation of lattice parameters
4. Analysis of crystalline size and strain
5. Structure solution
6. Structure of crystals
7. Polymer characterization
8. State of anneal in metals
9. Particle size determination
10.Spot counting method
11.Broadening of diffraction lines
12.Low-angle scattering
13.Applications of diffraction methods to complexes
14.Determination of cis- trans isomerism
15.Determination of linkage isomerism
16.Miscellaneous applications
Applications of XRD in environmental analysis include:
•Soil and sludge elemental analysis (heavy metals)
•Air filter elemental quantification
•Respirable silica quantification
•Asbestos mineral identification and quantification
•Rapid mineral identification
•Waste material analysis
•Biomass elemental analysis

Plate-like deposits found close to the surface of

environmentally exposed
Stabilisation/solidification (S/S ) waste

Diffraction Patterns of Types of Asbestos

XRD analysis of Waste Water Precipitate.
Wastewater is water containing wastes from residential, commercial, and industrial
processes.
This precipitation can be obtained using simple sedimentation techniques with the
solids recovered as slurry or sludge and then XRD analysis is carried out.

Typical Results of XRD Analysis (Wt%)

Waste Water Precipitate
Hematite 2.1
Quartz 4.8
Magnetite 2.7
Akermanite 16.7
Fluorite 15.7
Calcite 52.3
Monticellite 5.6
Fly ash is a by-product of thermal power plants partly used in concrete and cement
manufacturing. It is composed of minerals such as quartz, mullite, subordinately
hematite and magnetite, carbon, and a prevalent phase of amorphous alumino
silicate
The main crystalline phases are mullite and quartz. The broad hump in the region
between 10 and 25 °2θ indicates the abundant presence of glassy phase due to the
rapid cooling of fly ash at high temperatures
The high percentage of amorphous material and the presence of hematite/goethite
on trace give evidence of the application of these fly ashes in cement products and
zeolite synthesis.

SEM images of typical fly

ash shape X-ray diffraction patterns of each samples of fly ash and
relative weight fractions of minerals and amorphous
phases. Mul = mullite; Qtz = quartz.
Red mud is classified as hazardous due to its high pH. It is a solid waste produced
formed during the production of alumina when the bauxite ore is subject to caustic
leaching. The red mud was received in the form of a paste containing about 40%
free water and 60% of solids, collected
immediately after alumina recovery from the
digestion process.

The material was dried and crushed and XRD analysis is carried out on the red
mud collected. Figure above shows the corresponding XRD pattern.

The predominant components detected is aluminium hydroxide (Al(OH)3), calcium

carbonate (CaCO3), and iron oxide (Fe2O3),but the relative amounts of SiO2,
muscovite, FeO(OH) and Na2O (or NaOH) are also relevant. Some of these oxides
were also detected by XRD, in addition to aluminum hydroxide and a complex
Na5Al3CSi3O15 phase.
 Conclusion

 X-ray diffraction (XRD Analysis) is a rapid and nondestructive analytical

technique that can be used for phase identification of a crystalline material
which can provide information on unit cell dimensions.

 It is widely used for the identification of unknown crystalline materials and

also for characterizing crystalline materials

 The advantage for environmental sample analysis is non-destructive nature,

larger sample size capacity and definitive results provided

SEKIAN TERIMA KASIH 