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ChE 592

X-ray Diffraction

Merve Ayvaz
Chemical Engineering Department
Boazii University

Introduction
Atomic radii of atoms are smaller than 1/1000 of the wavelengths
present in the visible light.
A suitable wavelength to observe individual atoms is x-rays.
For Catalysis
It is used to identify crystalline phases inside catalysts by
means of lattice structural parameters, kinetics of bulk
transformation and to obtain an indication of particle size.

Niemantsverdriet J.W.

Introduction

The scattered monochromic X-rays that are in phase give


constructive interference.
Diffraction of x-rays by crystal planes allows one to drive lattice
spacing by using

Bragg relation: n =2d sin


d is charactesitic for a given compound
n: order of reflection; : wavelength of x-rays; d: distance between two lattice planes; :
angle between the incoming x-rays and the normal to the reflecting lattice plane

Jenkins R.,Snyder R.L.

Nature and Properties of X-rays


The x-rays have wavelength from 0.1 to 100 , which are located
between gamma radiation and ultraviolet rays.
The wavelengths most commonly used in crystallography, range
between 0.5 to 2.5 . If d < /2, then sin > 1, which is
impossible. n =2d sin
They are of the same order of magnitude as the shortest
interatomic distances observed both organic and
inorganic materials.

Jenkins R.,Snyder R.L.

Production of X-rays
X-ray tube
Sealed Tube
Rotating Anode Tube

Synchrotron

Percharsky V.K., Zavalij P.Y.

X-ray Tube
Known as a laboratory or conventional x-ray source,
Electromagnetic waves are generated from impacts of
high-energy electrons with a metal target.
Brightness is limited with the thermal properties of target
material,

Simple,
Most commonly used,
Must be continuously cooled,
Low efficiency,
Percharsky V.K., Zavalij P.Y.

Sealed Tube
Consist of a stationary anode coupled with
cathode, placed in a metal/glass or
metal/ceramic container sealed under
vacuum
Electrons are emitted by the cathode,
accelerate through the anode (30 to 60 kV),
Typical current is between 10 to 50 mA,
The x-rays are generated by the impacts of
high energy electrons,
The exit the tube from Be window,

Percharsky V.K., Zavalij P.Y.

Synchrotron
Advance source of x-ray radiation,
High energy electrons are confined in a storage
ring,
They move in a circular orbit, electrons accelerate
towards the center of the ring, thus emitting
electromagnetic radiation.
Extremely bright, (limited by the flux of electrons)
Thermal losses are minimized,
No target to cool,
Percharsky V.K., Zavalij P.Y.

Collimation and Monochromatization


The radiation comes out from the x-ray source is
polychromatic radiation. (K, K1, K2, K)

Jenkins R.,Snyder R.L.

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Monochromatization
Reducing the intensity of white radiation,
Eliminating the undesirable characteristic wavelengths
from x-ray spectrum to K1, K2,

Jenkins R.,Snyder R.L.

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Adsorption of x-rays and B-filter


Simplest method performed by means of filtering.
When x-ray penetrate into a matter, they are partially
transmitted and partially adsorbed.

It=I0 exp(-x)
:linear absorption coefficient of the material
Examples of filter elements: Sc,Ti,Cr,Mn,Fe,Co,Ni,Cu

Jenkins R.,Snyder R.L.

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Angular Divergence and Collimation


The simplest collimation can be achieved by placing a slit
between the x-ray source and the sample.
Angular divergence of thus collimated beam is
established by the dimensions of the source, the size and
the placement of the slit.

Jenkins R.,Snyder R.L.

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Detection of X-rays

Role is to measure intensity,


Sensitive to x-rays,
The oldest detector of x-ray is photographic film,
In modern detectors the signal, usually electric current,
easily digitized and transferred to a computer for further
processing and analysis,

Percharsky V.K., Zavalij P.Y.

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Gas Proportional Counter-Point Detector


The x-ray photons enter to the window and is absorbed
by the gas, it ionizes Xe atoms producing positively
charged ions and electrons.
The resulting electric current is measured
The number of current pulses is proportional to the
photons absorbed.
The second window is usually added to enable exit of
non-absorbed photons.

Percharsky V.K., Zavalij P.Y.

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Other types of detectors


Scintillation detector
Position sensitive detector
Area detectors

Percharsky V.K., Zavalij P.Y.

Theory of X-Ray Diffraction

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Diffraction
X-rays scattered from different parts of the atom
(nucleus and electrons) combine to give the effect of a
point source.
The radiation scattered by the atom depends on the
number of electrons associated to atom and their
distribution.

Nuffield E.W.

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Intensity of the Diffraction


The intensities of the diffracted waves;
Depend on the kind and arrangement of atoms in the
crystal structure
Proportional to the squares of amplitudes of the
composite reflected waves

Nuffield E.W.

Derivation of Braggs Law


AB = d sin
n = 2 d sin

Beams are parallel to each other


The second beam must travel the extra distance AB + BC
n = AB +BC
AB = BC
n = 2AB
Glenn A. Richard, Mineral Physics Institute, SUNY Stony Brook

Bragg
Relation

Diffraction Pattern
A diffraction pattern records the X-ray intensity as a function of 2theta angle.

Tube voltage
Current
--A starting 2-theta angle.
--A step-size (typically 0.005 degrees).
--A count time per step (typically 0.05-1 second).
--An ending 2-theta angle.

Purudue University, Geoscience Department

Lattice Structure
crystal can be arranged in
sheets in a number of ways

0A = 0B = 0C = a = the
length of the edge of the
unit cell
Bragg Equation Satisfied
for all planes

University of Saskatchewan, Physics Department

Miller Indices h,k,l plane


dhkl
h, k, l are required to describe the order of the
diffracted waves
Denote the orientation of the reflecting sheets
with respect to the unit cell
The path difference in units of wavelength
between identical reflecting sheets
dhkl= a/(h2 + k2 + l2)
University of Saskatchewan, Physics Department

Determination of the unit cell structure for


a cubic lattice
For a cubic lattice, primitive, fcc, bcc reflections are obsreved
See h,k,l in the increasing order of sum h2 + k2 + l2

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P 0 110 111 200 210 211 220 221 300 310 311
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F 1 200 220 311 222 400 331 420 422 333 511
11 sin2 1/ sin2 2 = (h12 + k12 + l12)/(h22 + k22 + l22)
B 0 200 211 220 310 222 321 400 411 330 420
P
1:2:3:4:5:6:8
1:1 1/3 : 2 2/3: 3 2/3: 4: 5
F
1/3: 6 1/3
B
1:2:3:4:5:6:7
Atkins,Physical Chemistry

All odd
or even
Sum is
even

Determination of the unit cell structure for


a cubic lattice
sin2 1/ sin2 2 = (h12 + k12 + l12)/(h22 + k22 + l22)
Powder diffraction angles () are red from the pattern are:
17.660, 25.400, 31.700, 37.350, 42.710, 47.980, 59.080
sin2 gives
0.0920, 0.1840, 0.2761, 0.3681, 0.4601, 0.5519, 0.7360
These number give the ratio 1:2:3:4:5:6:8
P

So the cell is primitive

F
B

1:2:3:4:5:6:8
1:1 1/3 : 2 2/3: 3 2/3: 4: 5
1/3: 6 1/3
1:2:3:4:5:6:7

Atkins,Physical Chemistry

Determination of unit cell edge length for a


cubic cell
dhkl= a/(h2 + k2 + l2)
= 2 d sin
(4 sin2 )/2 = (h2 + k2 + l2)/a2

(4 sin2 )/2 = (h2 + k2 + l2) *(1/a2)


Augustana Collage, Chemistry and Physics Department

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Principles of Determination of Crystallite Size


Rays A, D and M all make exact Bragg angle with
diffracting planes so A, D and M differ in phase
by an integer number of wavelengths (M-M
has a path length m greater than A-A)
Consider rays coming in at angle 1 (B and L). If
1 is selected so that the path length B-B differs
from that of L-L by (m+1), there will be a plane
in the middle of the crystal that scatters with path
length difference (m+1)/2 and destructively
interferes with x-rays on the B-B path. 1
represent the highest angle you can go to
before you get complete destructive
interference.
Consider rays coming in at angle 2 (C and N). If
2 is selected so that the path length C-C differs
from that of N-N by (m-1), then there will be a
plane in the middle of the crystal that scatters
with path length difference (m-1)/2 and
destructively interferes with Xrays on the C-C
path. 2 represent the lowest angle you can
Georgia Tech., Chemistry and Biochemisrty Department
go to before you get complete destructive

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Principles of Determination of Crystallite Size


Considering the path length differences between x-rays
scattered from the front and back planes of the crystal
2tsin1 = (m+1)
2tsin2 = (m-1)
If we subtract them
t(sin1 sin2)=
2tcos((1+2)/2)sin((1- 2)/2) =
Use small angle approximation and ( 1 + 2)/2 = B
2t[(1- 2)/2]cosB = ,
t = /(BcosB)
More rigorous treatment gives t = 0.9/(BcosB) for spherical
crystals of diameter t.
This is the Scherrer equation

Georgia Tech., Chemistry and Biochemisrty Department

Scherrer Equation

K
B 2
t cos

Peak width (B) is inversely proportional to crystallite thickness


(t)
As the crystallites in a powder get smaller the diffraction peaks in a
powder pattern get wider
B = (2 High) (2 Low)
B is the difference in angles
at half max
The constant of proportionality, K
(the Scherrer constant) depends on the
shape of the crystal, and the size distribution
the most common values for K are:
0.94 -0.89
K actually varies from 0.62 to 2.08

MIT, Center for Materials Science and Engineering

References

Glenn A. Richard, Mineral Physics Institute, SUNY Stony Brook


University of Saskatchewan, Physics Department
Atkins,Physical Chemistry
Augustana Collage, Chemistry and Physics Department
Purudue University, Geoscience Department
MIT, Center for Materials Science and Engineering
Jenkins R.,Snyder R.L., Introduction to X-ray Powder Diffractometry,
John Wiley & Sons, Inc. ,1996
Niemantsverdriet J.W., Spectroscopy in Catalysis, Wiley-VCH,2000
Nuffield E.W., X-ray Diffraction Methods, John Wiley & Sons, Inc.,
1966
Percharsky V.K., Zavalij P.Y., Fundamentals of Powder Diffraction
and Structural Characterization of Materials, Springer, 2005

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