We have learnt

How do crystallites arrange in a polycrystalline material How to represent polycrystal information in stereographic projection

Todays objective
To get an overview of diffraction phenomenon, in general, and X-ray diffraction, in particular

X-Ray Diffraction (XRD): Suitable for the study of the structure of crystalline materials

Why

The typical interatomic spacing in a crystal is of the order of , the wavelength of X-ray is of the same order This makes crystals to act as diffraction grating for Xradiation

X-rays can be conveniently produced in Laboratory

Based on the diffraction principles, the following can be measured in a crystalline materials:
Interplanar spacing, hence lattice parameter

Orientation of a single crystal or grain

Measure the size, shape and internal strain of small crystalline regions Crystal structure of an unknown material

Diffraction
Diffraction is essentially a scattering phenomena where at some particular angle the scattered radiation forms constructive interface (arises when an electromagnetic waves interact with the periodic structure )

Diffraction is basically Reinforced Coherent Scattering

Understanding constructive interference

A C =+ B

If two waves A and B are propagating in same phase, the resulting wave C will have magnitude of addition of both A and B

Bragg law is satisfied when the wavelength satisfies; n 2d

If 2: Bragg angle, and : X-ray wavelength

90 z A 90-

Constructive interference will occur when: = AB + BC AB=BC n = 2AB sin =AB/d AB=d sin n =2d sin = 2dhklsin hkl

= 2dhklsinhkl

Essentially, it gives relationship between the angle of incidence ,wavelength of the incident radiation and the spacing between parallel lattice plane of a crystal.

When the diffraction condition is met there will be a diffracted X-ray beam

2dSin
d

a h2 k 2 l 2 2 2 4 a sin 2 2 2 2 h k l 2 4a 2 2 2 (h k l ) 2 sin 2

There are three variables: , , and d

is known (X-ray Source)

is measured in the experiment (2) d can be calculated using the Braggs relation

(h k l ) sin
2 2 2 2

For the planes (hkl), the cell parameter a can be calculated

 - 2 Scan
The - 2 scan maintains these angles with the sample, detector and X-ray source
Normal to surface

surface

Only (hkl) planes of atoms that share the surface normal will be seen in the - 2 Scan

Diffraction from a crystal

The structure of a crystal can be defined as: Crystal = Lattice + Motif A beam of X-rays directed at a crystal interacts with the electrons of the atoms in the crystal , undergoes diffraction and gives rise to intensity distribution in the diffracted output, which is characteristic of the crystal structure. The output is known as diffraction pattern.
Diffraction pattern consists of a set of peaks with certain height (intensity) and spaced at certain intervals (not the same interval between each of the peaks)

 Lattice decides the position of the peaks (spacing between the peaks), while the motif decides the height of the peaks. Therefore, based on arrangement of atoms in a crystal, intensities of particular diffraction peak is modified sometimes the pattern go missing

Examples of diffraction from crystals

Extinction Rules
Structure Factor (F): The resultant wave scattered by all atoms of the unit cell The Structure Factor is Lattice = SC Lattice = BCC independent of the No missing reflections 100 missing reflection (F = 0) shape and size of the unit cell; but is dependent on the Lattice = FCC position of the atoms 100 missing reflection (F = 0) within the cell
110 missing reflection (F = 0)

Diffraction Extinction Criteria for different materials with different crystals structures
Bravais Lattice Simple Diffraction Condition all Reflections necessarily absent None

Body centred
Face centred
h2 + k2 + l2
1 2 3 100 110 111

(h + k + l) even
h, k and l unmixed
Face Centred Cubic

(h + k + l) odd
h, k and l mixed
Body Centred Cubic
110

Simple Cubic

111

4
5 6 7 8 9

200
210 211 220 300, 221

200

200
211

220

220

Typical X-ray diffraction pattern of a BCC material (IF steel)

Radiation: Cu K, = 1.54

Why are the peaks broad??

If uniform crystallites (no misorientation within them, imaginary) But there is always some misorientation within the grains (each crystallites always misorientated with each other , reality)

Uniform Crystallites

Misorientatio n of Crystallites

B: Bragg Angle

Full width at half maximum (FWHM)

2B

2 1

2 B

2 2

Crystallites Size: Essentially uniform agglomeration of crystals posses same reflection patterns Scherrer Formula: Relation between the crystallites size and the FWHM

K t B cos B

t = thickness of crystallite K = constant dependent on crystallite shape (~ 0.89) l = x-ray wavelength B = FWHM (full width at half maximum) B = Bragg Angle

Limitations of Scherrer equation

Crystallite size <1000 Error >20% Peak broadening can be contributed by other factors, like, size, strain and instrument

Questions
1. Out of the following, which can be measured using X-ray diffraction: (a) Interplanar spacing, hence lattice parameter (b) Orientation of a single crystal or grain (c) Grain boundary character (d) Size, shape and internal strain of small crystalline regions Which of the following grain sizes can not be measured using X-ray diffraction: (a) 10 m (b) 0.1 m (c) 0.01 m (d) 0.001 m

2.

4. Determine the values of 2 and (hkl) for the first three lines on the powder patterns of substances with the following structures (Cu K=3.14) in FCC unit cell (a = 3.00). 5. Calculate the crystallite size for FWHM B for = 10, 45, and 80.