Introduction to Powder X-Ray Diffraction

History Basic Principles

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History: Wilhelm Conrad Rntgen

Wilhelm Conrad Rntgen discovered 1895 the X-rays. 1901 he was honoured by the Noble prize for physics. In 1995 the German Post edited a stamp, dedicated to W.C. Rntgen.

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The Principles of an X-ray Tube

X-Ray
Cathode

Fast electrons

Anode focus

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The Principle of Generation Bremsstrahlung

Ejected electron (slowed down and changed direction) nucleus

Fast incident electron

electrons

Atom of the anodematerial X-ray

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The Principle of Generation the Characteristic Radiation

Photoelectron

Emission
K-Quant

M L K
Electron

L-Quant

K-Quant

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The Generating of X-rays

Bohr`s model
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The Generating of X-rays

energy levels (schematic) of the electrons

M Intensity ratios L K
K1 K2 K1 K2

K1 : K2 : K = 10 : 5 : 2

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The Generating of X-rays

Anode
Mo Cu

(kV)
20,0 9,0

Wavelength, [Angstrm]
K1 : 0,70926 K2 : 0,71354 K1 : 0,63225

K-Filter
Zr 0,08mm Ni 0,015mm

K1 : 1,5405 K2 : 1,54434 K1 : 1,39217

Co

K1 : 1,78890

7,7

K2 : 1,79279 K1 : 1,62073

Fe 0,012mm

Fe

K1 : 1,93597

7,1

K2 : 1,93991 K1 : 1,75654

Mn 0,011mm
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The Generating of X-rays

Emission Spectrum of a Molybdenum X-Ray Tube

Bremsstrahlung = continuous spectra characteristic radiation = line spectra

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History: Max Theodor Felix von Laue

Max von Laue put forward the conditions for scattering maxima, the Laue equations:

a(cos-cos0)=h b(cos-cos0)=k c(cos-cos0)=l

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Laues Experiment in 1912 Single Crystal X-ray Diffraction

Tube

Tube

Crystal

Collimator Film

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Powder X-ray Diffraction

Film Tube

Powder

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Powder Diffraction Diffractogram

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History: W. H. Bragg and W. Lawrence Bragg

W.H. Bragg (father) and William Lawrence.Bragg (son) developed a simple relation for scattering angles, now call Braggs law.

n d= 2 sin
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Another View of Braggs Law

n = 2d sin
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Crystal Systems
Crystal systems
cubic Tetragonal Hexagonal Rhomboedric Orthorhombic Monoclinic Triclinic

Axes system
a = b = c , = = = 90 a = b c , = = = 90 a = b c , = = 90, = 120 a = b = c , = = 90 a b c , = = = 90 a b c , = = 90 , 90 a b c ,

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Reflection Planes in a Cubic Lattice

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The Elementary Cell

a=b=c o = = = 90

c a

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Relationship between d-value and the Lattice Constants

= 2 d s in
The wavelength is known Theta is the half value of the peak position d will be calculated

Braggs law

1/d = (h + k )/a + l /c

Equation for the determination of the d-value of a tetragonal elementary cell

h,k and l are the Miller indices of the peaks a and c are lattice parameter of the elementary cell if a and c are known it is possible to calculate the peak position if the peak position is known it is possible to calculate the lattice parameter

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Interaction between X-ray and Matter

d Co (Compton-Scattering) wavelength Pr intensity Io Pr(Braggs-scattering)
absorption Beers law I = I0*e-d fluorescence coherent scattering incoherent scattering

> Pr

photoelectrons

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History (4): C. Gordon Darwin

C. Gordon Darwin, grandson of C. Robert Darwin (picture) developed 1912 dynamic theory of scattering of X-rays at crystal lattice

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History (5): P. P. Ewald

P. P. Ewald 1916 published a simple and more elegant theory of X-ray diffraction by introducing the reciprocal lattice concept. Compare Braggs law (left), modified Braggs law (middle) and Ewalds law (right).
d= n 2 sin

sin = d 2

sin =

2 1

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Introduction Part II
Contents: unit cell, simplified Braggs model, Straumannis chamber, diffractometer, pattern Usage: Basic, Cryst (before Cryst I), Rietveld I

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Crystal Lattice and Unit Cell

Let us think of a very small crystal (top) of rocksalt (NaCl), which consists of 10x10x10 unit cells. Every unit cell (bottom) has identical size and is formed in the same manner by atoms. It contains Na+-cations (o) and Cl-anions (O). Each edge is of the length a.

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Braggs Description
The incident beam will be scattered at all scattering centres, which lay on lattice planes. The beam scattered at different lattice planes must be scattered coherent, to give an maximum in intensity. The angle between incident beam and the lattice planes is called . The angle between incident and scattered beam is 2 . The angle 2 of maximum intensity is called the Bragg angle.
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Braggs Law
A powder sample results in cones with high intensity of scattered beam. Above conditions result in the Bragg equation

s = n = 2 d sin
or

d =

n 2 sin
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Film Chamber after Straumannis

The powder is fitted to a glass fibre or into a glass capillary. X-Ray film, mounted like a ring around the sample, is used as detector. Collimators shield the film from radiation scattered by air.
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Film Negative and Straumannis Chamber

Remember The beam scattered at different lattice planes must be scattered coherent, to give an maximum of intensity. Maximum intensity for a specific (hkl)-plane with the spacing d between neighbouring planes at the Bragg angle 2 between primary beam and scattered radiation. This relation is quantified by Braggs law.

d =

n 2 sin

A powder sample gives cones with high intensity of scattered beam.

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D8 ADVANCE Bragg-Brentano Diffractometer

A scintillation counter may be used as detector instead of film to yield exact intensity data. Using automated goniometers step by step scattered intensity may be measured and stored digitally. The digitised intensity may be very detailed discussed by programs. More powerful methods may be used to determine lots of information about the specimen.

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The Bragg-Brentano Geometry

Tube

Detector

q
focusingcircle

Sample

2q

measurement circle

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The Bragg-Brentano Geometry

Divergence slit

Antiscatterslit

Monochromator

Tube Sample

Detectorslit

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Comparison Bragg-Brentano Geometry versus Parallel Beam Geometry

Bragg-Brentano Geometry

Parallel Beam Geometry generated by Gbel Mirrors

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Parallel-Beam Geometry with Gbel Mirror

Gbel mirror Detector

Soller Slit Tube

Sample

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Grazing Incidence X-ray Diffraction

Soller slit

Detector

Tube
Sample

Measurement circle

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Grazing Incidence Diffraction with Gbel Mirror

Soller slit
Gbel mirror

Detector

Tube
Sample

Measurement circle

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What is a Powder Diffraction Pattern?

a powder diffractogram is the result of a convolution of a) the diffraction capability of the sample (Fhkl) and b) a complex system function.
The observed intensity yoi at the data point i is the result of yoi = of intensity of "neighbouring" Bragg peaks + background The calculated intensity yci at the data point i is the result of yci = structure model + sample model + diffractometer model + background model

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Which Information does a Powder Pattern offer?

peak position peak intensity peak broadening scaling factor diffuse background modulated background

dimension of the elementary cell content of the elementary cell strain/crystallite size quantitative phase amount false order close order

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Powder Pattern and Structure

The d-spacings of lattice planes depend on the size of the elementary cell and determine the position of the peaks. The intensity of each peak is caused by the crystallographic structure, the position of the atoms within the elementary cell and their thermal vibration. The line width and shape of the peaks may be derived from conditions of measuring and properties - like particle size - of the sample material.
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