Bas XRD PDF

Introduction to
Powder X-Ray Diffraction

History
Basic Principles
Folie.1
2001 Bruker AXS All Rights Reserved
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.
Basics-in-XRD.2
The Principles of an X-ray Tube
X-Ray
Cathode
Fast electrons
Anode
focus
Basics-in-XRD.3
The Principle of Generation Bremsstrahlung
Ejected
electron
(slowed down
and changed
direction)
nucleus
Fast incident
electron
electrons
Atom of the anodematerial

X-ray
Basics-in-XRD.4
The Principle of Generation the Characteristic
Radiation
Photoelectron Emission
M K-Quant
Electron
L-Quant
K-Quant
Basics-in-XRD.5
The Generating of X-rays
Bohr`s model
Basics-in-XRD.6
energy levels (schematic) of the electrons
Intensity ratios
K1 : K2 : K = 10 : 5 : 2
L
K1 K2 K1 K2
K
Basics-in-XRD.7
Anode (kV) Wavelength, [Angstrm] K-Filter
K1 : 0,70926
Zr
Mo K2 : 0,71354
20,0 0,08mm
K1 : 0,63225
K1 : 1,5405
Cu 9,0 Ni
K2 : 1,54434 0,015mm
K1 : 1,39217
K1 : 1,78890
Co 7,7 Fe
K2 : 1,79279
0,012mm
K1 : 1,62073
K1 : 1,93597
Fe 7,1 Mn
K2 : 1,93991
0,011mm
K1 : 1,75654
Basics-in-XRD.8
Emission Spectrum of a
Molybdenum X-Ray Tube
Bremsstrahlung = continuous spectra
characteristic radiation = line spectra
Basics-in-XRD.9
History: Max Theodor Felix von Laue
Max von Laue put forward a(cos-cos0)=h

the conditions for scattering b(cos-cos0)=k
maxima, the Laue equations: c(cos-cos0)=l
Basics-in-XRD.10
Laues Experiment in 1912
Single Crystal X-ray Diffraction
Tube
Tube
Crystal
Collimator
Film
Basics-in-XRD.11
Powder X-ray Diffraction
Film
Tube
Powder
Basics-in-XRD.12
Powder Diffraction Diffractogram
Basics-in-XRD.13
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
Basics-in-XRD.14
Another View of Braggs Law
n = 2d sin
Basics-in-XRD.15
Crystal Systems
Crystal systems Axes system
cubic a = b = c , = = = 90
Tetragonal a = b c , = = = 90
Hexagonal a = b c , = = 90, = 120
Rhomboedric a = b = c , = = 90
Orthorhombic a b c , = = = 90
Monoclinic a b c , = = 90 , 90
Triclinic a b c ,
Basics-in-XRD.16
Reflection Planes in a Cubic Lattice
Basics-in-XRD.17
The Elementary Cell
a=b=c o
= = = 90
Basics-in-XRD.18
Relationship between d-value and the Lattice
Constants
= 2 d s in Braggs law
The wavelength is known
Theta is the half value of the peak position
d will be calculated
2 2 2 2 2 2 Equation for the determination of

1/d = (h + k )/a + l /c 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
Basics-in-XRD.19
Interaction between X-ray and Matter
d
incoherent scattering
Co (Compton-Scattering)
coherent scattering
wavelength Pr
Pr(Braggs-scattering)
absorption
Beers law I = I0*e-d
intensity Io
fluorescence
> Pr
photoelectrons
Basics-in-XRD.20
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
Basics-in-XRD.21
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).
n 1
d= sin = d sin =
2 sin 2 2 1

Basics-in-XRD.22
Introduction Part II
Contents: unit cell, simplified Braggs model,

Straumannis chamber, diffractometer, pattern
Usage: Basic, Cryst (before Cryst I), Rietveld I
Folie.23
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.
Basics-in-XRD.24
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.
Basics-in-XRD.25
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
n
d =
2 sin
Basics-in-XRD.26
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.
Basics-in-XRD.27
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.
n
This relation is quantified by Braggs law. d =
2 sin
A powder sample gives cones with high intensity of scattered beam.
Basics-in-XRD.28
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.
Basics-in-XRD.29
The Bragg-Brentano Geometry
Tube Detector
q
focusing- Sample 2q
circle
measurement circle
Basics-in-XRD.30
The Bragg-Brentano Geometry
Mono-
chromator
Divergence slit Antiscatter-
slit
Detector-
slit
Tube
Sample
Basics-in-XRD.31
Comparison Bragg-Brentano Geometry
versus Parallel Beam Geometry
Bragg-Brentano Parallel Beam Geometry

Geometry generated by Gbel Mirrors
Basics-in-XRD.32
Parallel-Beam Geometry with Gbel Mirror
Gbel Detector
mirror
Soller Slit
Tube
Sample
Basics-in-XRD.33
Grazing Incidence X-ray Diffraction
Detector
Soller slit
Tube
Sample
Measurement circle
Basics-in-XRD.34
Grazing Incidence Diffraction with
Gbel Mirror
Soller slit Detector
Gbel mirror
Tube
Sample
Measurement circle
Basics-in-XRD.35
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
Basics-in-XRD.36
Which Information does a Powder
Pattern offer?
peak position dimension of the

elementary cell
peak intensity content of the
elementary cell
peak broadening strain/crystallite size
scaling factor quantitative phase amount
diffuse background false order
modulated background close order
Basics-in-XRD.37
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.
Basics-in-XRD.38

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Introduction to

Powder X-Ray Diffraction

Wilhelm Conrad Rntgen discovered 1895 the X-rays. 1901 he was

Atom of the anodematerial

energy levels (schematic) of the electrons

Bremsstrahlung = continuous spectra

characteristic radiation = line spectra

Max von Laue put forward a(cos-cos0)=h

W.H. Bragg (father) and William

Hexagonal a = b c , = = 90, = 120

2 2 2 2 2 2 Equation for the determination of

P. P. Ewald 1916 published a simple and more elegant theory of X-ray

Contents: unit cell, simplified Braggs model,

Let us think of a very small crystal

The incident beam will be

A powder sample results in

The powder is fitted to a glass fibre or into a glass capillary.

A scintillation counter may be

Bragg-Brentano Parallel Beam Geometry

Soller slit Detector

a powder diffractogram is the result of a convolution of

The observed intensity yoi at the data point i is the result of

The calculated intensity yci at the data point i is the result of

peak position dimension of the

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