9/22/2015

X-Ray Diffraction

What is X-Ray Diffraction??

• Crystalline
substances (e.g.
minerals) consist of
parallel rows of atoms
separated by a
‘unique’ distance
• Simple Example:
– Halite (Na and Cl)

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Mo Target impacted by electrons accelerated by a 35 kV potential

K
Characteristic radiation →
White K
Intensity radiation
due to energy transitions
in the atom

0.2 0.6 1.0 1.4

Wavelength ()

Target Metal  Of K radiation (Å)

Mo 0.71

Cu 1.54

Co 1.79

Fe 1.94

Cr 2.29

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How Diffraction Works: Schematic

NaCl

 For electromagnetic radiation to be diffracted the

spacing in the grating should be of the same order as
the wavelength
 In crystals the typical interatomic spacing ~ 2-3 Å so
the
suitable radiation is X-rays
 Hence, X-rays can be used for the study of crystal
structures

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How Diffraction Works

• Wave Interacting with a Single Particle
– Incident beams scattered uniformly in all
directions
• Wave Interacting with a Solid
– Scattered beams interfere constructively in some NaCl
directions, producing diffracted beams
– Random arrangements cause beams to randomly
interfere and no distinctive pattern is produced
• Crystalline Material
– Regular pattern of crystalline atoms produces
regular diffraction pattern.
– Diffraction pattern gives information on crystal
structure

• Crystalline substances (e.g. minerals) consist of parallel rows

of atoms separated by a ‘unique’ distance
• Diffraction occurs when radiation enters a crystalline
substance and is scattered
• Direction and intensity of diffraction depends on orientation of
crystal lattice with radiation
• By varying wavelength and observing diffraction patterns,
information about lattice spacing is obtained

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The XRD Technique

• Takes a sample of the material and places a
powdered sample which is then illuminated with
x-rays of a fixed wave-length.
• The intensity of the reflected radiation is
recorded using a goniometer.
• The data is analyzed for the reflection angle to
calculate the inter-atomic spacing.
• The intensity is measured to discriminate the
various D spacing and the results are compared
to known data to identify possible matches.

Powdering Samples
• The samples are powdered to give a random
sampling of ALL atomic planes (crystal faces)
• Statistically accurate given samples are
powdered finely AND randomly oriented on
sample holder
– Intensities are a reflection of d-spacing abundance
• Problems arise with minerals that may
preferentially orient on sample holder
– Micas and clays have special preparation techniques

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Schematic X-Ray Diffractometer

Detector

X-Ray
Source

Powdered
sample

Sample XRD Pattern

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strong intensity = prominent crystal plane

weak intensity = subordinate crystal plane

background radiation

Determine D-Spacing from XRD patterns

Bragg’s Law
nλ = 2dsinθ
• n = reflection order (1,2,3,4,etc…)
• λ = radiation wavelength (1.54 angstroms)
• d = spacing between planes of atoms
(angstroms)
• θ = angle of incidence (degrees)

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strong intensity = prominent crystal plane

nλ = 2dsinθ
(1)(1.54) = 2dsin(15.5 degrees)
1.54 = 2d(0.267)
d = 2.88 angstroms

background radiation

d-spacing Intensity
2.88 100
2.18 46
1.81 31
1.94 25
2.10 20
1.75 15
2.33 10
2.01 10
1.66 5
1.71 5

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Factors that affect XRD data

• Sample not powdered fine enough
– May not give all d-spacing data (not random
enough)
• Analysis too fast (degrees/minute)
– May not give accurate peak data
• Mixture of minerals??
• Not crystalline – glass!!

Mixture of 2 Minerals

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Applications of XRD
• Unknown mineral ID
• Solid solution ID (e.g. feldspars, olivine)
• Mixtures of minerals
• Clay analyses
• Zeolites
• Crystallographic applications
• Phase purity
• Determination of crystallite size
• Structure determination
• …and much more!

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B is the halfwidth in radian

Equation y=y0 + (A/(w*sqrt(PI/2)))*exp(-2*((x-xc)/w)^2)

Adj. R-Square 0,7847

Value Standard Error
C y0 106,90196 1,65483
Intensity (a.u)

C xc 25,66698 0,02518
C w 2,04715 0,05158
C A 1096,71644 25,03718
C sigma 1,02358
C FWHM 2,41034
C Height 427,44841

20 30 40 50 60
2Cu()

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