Dharmapadmi P. K.

195160100111028

X-ray Diffraction

History of X-ray
 In 1895 Anna Bertha Röntgen and Wilhelm Conrad Röntgen discovers x-
rays. In 1901 they received the first Nobel Prize in physics.
 In 1914 Max Von Laue received the Nobel prize for physics, discovery of
the diffraction of x-ray by crystals "Diffraction pattern"
 In 1915 W.H. Bragg and his son W.L. Braggand the diffraction of x-ray by
crystals received the Nobel prize for physics, analysis of crystal structure
using x-rays

Applications of x-ray in general

The famous section of X-rays is electromagnetic waves or EM. X-rays use
for material analysis, security, medical diagnostics, pharma quality, electronics
inspection, heavy industries, food security, and medical treatment. All parts
are interconnected.

X-ray diffraction and basic principle

X-rays are divided into two, hard x-ray (used for x-ray crystallography,
mammography, medical CT, and airport security) and soft x-ray. X-ray
diffraction includes power x-ray diffraction (PXRD), small angel x-ray, single
crystal x-ray, and x-ray imaging.
Powder x-ray diffraction (PXRD) is primarily used for phase identification
of crystalline material (phase composition). Provide information on unit cell
dimensions. The X-ray diffractometer has an x-ray tube, sample stage, and
detector. X-rays are produced whenever high-speed electrons collude with a
metal target. All metals are crystalline solids. Solid can be divided into
amorphous (atoms in an amorphous solid are arranged randomly-no order)
and crystalline (atoms in a crystalline solid are arranged in a repetitive three-
dimensional pattern Long Range order).
Diffraction is a wave that interacts with a single practice and a
crystalline material. A single particle is a particle that scatters the incident
beam uniformly in all directions. The crystalline material is the scattered beam
that may add together in a few directions and reinforce each other to give
diffracted beams.

Bragg’s and Scherrer’s equation

Constructive interference of waves occurs only when the path difference of
the scattered waveform consecutive layers of atoms is a multiple of the
wavelength of the x-ray. Diffraction occurs only when Bragg's Law is satisfied.
Constructive interference occurs only when nλ = AB + BC, then λ = 2dhklsinθhkl.
Basic crystallography and miller indices
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.
Crystals consist of a plane of atoms that are spaced a distance d apart but can
resolve into many atomic planes, each with a different d-spacing. a, b, and c
(length) and alpha, beta, and gamma (angles between a, b, and c) are lattice
constants or parameters that can be determined by XRD.
Crystal systems include cubic, tetragonal, orthorhombic, rhombohedral,
hexagonal, monoclinic, and triclinic. Miller indices form a notation system in
crystallography for planes in crystal lattices. Miller indices the reciprocals of
the fractional intercepts that the planes make with crystallographic axes.

XRD pattern and FWHM

The significance of peak shape in XRD is divided into, peak position,
peak width, and peak intensity. Peak width (full width at half
maximum/FWHM) determines, particle or grain size and residual strain.
XRD patterns from other states of matter are divided into a crystal, liquid
or amorphous solid, and monoatomic gas. In powder x-ray diffraction, a
powder sample is an assemblage of small crystallites, oriented at random in
space.

Phase identification
Phase identification of the sample includes obtaining XRD patterns,
measuring d-spacings and integrated intensities (dI list), and comparing data
with known standards in JCPDS/ICCDD files (> 200,000 files). JCPDS (Joint
Committee on Power Diffraction Standards, 1969) was replaced by ICDD
(International Center for Diffraction Data) in 1978.
ICCD database contains dI list for thousands of crystalline phases. The
PDF contains more than 200,000 diffraction patterns, a modern computer
program can help you determine what phases are present in your sample by
quickly comparing your diffraction data to all of the patterns in the database,
and the PDF card for an entry contains a lot of useful information (including
literature references).

Sample preparation
Powder in size 0.1µm less than particle size (<40 µm). Peak broadening
less diffraction occurs. Smooth the surface after polishing, specimens should
be thermally annealed to eliminate any surface deformation induce during
polishing. An x-ray diffractometer has an x-ray tube, Gobel mirror, goniometer,
Soller slit, and detector.
Advantages
 Powerful and rapid (<20 min) technique for identification of unknown
inorganic materials
 In most cases, it provides an unambiguous mineral determination
 Minimal sample preparation is required
 XRD units are widely available
 Data interpretation is relatively straightforward

Disadvantages
 Homogeneous and single-phase material is the best for identification of
an unknown
 Must have access to a standard reference file of inorganic compounds (d-
spacings, hkls)
 Requires tenths of a gram of material which must be ground into a power
 For mixed materials, the detection limit is (3% of the sample)
 For unit cell determinations, indexing of patterns for non-isometric
crystal systems is complicated
 Peak overlay may occur and worsens for high angel reflections

PXRD caharacterisation for nanomaterial

 Pure phase determination
 Confirmation of the presence of the host-guest phase
 Host-guest interaction; intercalation, exfoliations, etc
 Nanostructure formation: eg. 2D layered structure, nanoparticles, etc.

Applications of XRD (a nondestructive technique)

 To identify the crystalline phase
 To determine structural properties à Lattice parameter, stain, grain size,
phase composition, preferred orientation, order-disorder transformation,
thermal expansion, etc.
 To measure the thickness of thin film and multilayers
 To determine atomic arrangement
 To image and characterize defects
1. 0D nanomaterial
Chitosan nanoparticles divided into chitosan-hexaconzole NP, chitosan-
dazomet NP, and chitosan-hexaconzole/dazomet NP. Allotropy or
allotropism is material of the same chemical element but exists in two or
more different atomic arrangements. The atoms of the element are
bonded together differently.
2. XRD pattern of graphite (3D), GO (2D), rGO (2D), and MWCNTs (1D)
3. 2D nanolayered structure
 The type of materials is amorphous and crystalline. The spatial
orientation of the drug molecules in the layered inorganic interlamellar
depends on the size of the quest (ChemOffice) and spatial orientation of
the quest (XRD data and (a))
4. 3D nanomaterial (amourphous)
5. Physicochemical properties of hydroxyapatite or montmorillonite
nanocomposite prepared by powder sintering
 Quantitative phase analysis
To determine how much of each phase is present
 Unit cell lattice parameter refinement
Determination of the unit cell lattice parameters of the phases (by
accurately measuring peak positions over a long range of 2θ)
 Crystallite size
Crystallites smaller than 120nm create a broadening of diffraction
peaks. The peak broadening can be used to quantify the average
crystallite size of nanoparticles.

Application of PXRD in dentistry

 To determine phase/s exist in teeth/different parts of the teeth
Use hydroxyapatite/hydroxylapatite (HA/HAP), the main mineral for
dental enamel and dentin is carbonated calcium-deficient HA.
 Bone grafting of teeth/mechanism
 RDI in dentistry – nano dentistry (drug delivery, diagnostic, nano
theranostics, etc)