Rotating crystal method
Rotating crystal patten of quartz crystal
192025 37
Powder Method
> In the powder method, the crystal to be examined is reduced to a very fine powder
or already is In the form of loase or consolidated microscopic grains.
> The sample in a suitable holder is placed in a beam of monochromatic x-rays.
>Each particle of the powder is a tiny crystal, or assemblage of smaller crystals,
oriented at random with respect to the incident beam.
pet re
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(b)
Miller Indices
Miller indices are defined as the recijprocals of the fractional intercepts which the
plane makes with the crystallographic axes
> For example, if the Miller indices of a plane are (hk), written in parentheses, then
the plane makes fractional intercepts of Wh, k,M with the axes, and, if the axial
lengths are a, b. c, the plane makes actual intercepts of a/h, blk, cl, as shown in
Figure (a).
Parallel to any plane In, any lattice, there is a whole set of parallel equidistant
planes, one of which passes through the origin; the Miller indices (hk) usually refer
to that plane in the set which is nearest the origin, although they may be taken as
referring toany other plane in the set or to the whole set taken together.
Avial lengths 3A
Intercept lengths 4A
Fractional interccpts 14 12 1
Miller indices 4 2
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Planes of NaCI
(111)
(10)
(111)
(10) (10) (1)
(111)
o Na CI
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Indexing
Indexing is the process of determining the unit cell dimensions from the peak
positions.
To index a powder diffraction pattern it is necessary to assign Miller indices, hkl,
toeach peak.
> A
diffraction pattern cannot be analyzed until it has been indexed.
>Itis always the first step In analysis.
Unfortunately it is not just the simple reverse of calculating peak positions from
the unit celldimensions and wavelength.
We will show how one can manually index diffraction patterns of high symmetry
structures.
2 For lower symmetry struclures (orthorhomblc, monoclinic, triclinic) it is usually
necessary touse a computer algorithm.
This ls called Autoindexing. 12
Itcan be funl Like solving a puzzle
Indices needed to calculate lattice parameters
Need (hk) and d, for all reflections. Use all rellecions to get high precision
Cubicd =al/[+k)
Tetragonal: 1d,= (h² + kya +Rlo
Hexagonal: 1/d=(4/3)(h +k?+ hkya +B/c
Orthorhombic: 1/d.=h?la +k?b? +Plc
h²+ k²+ 12 P F
(100)
(110) (I10)
(111) (111)
(200) (200) (200)
(210)
(211) (211)
(220) (220) (220)
(300)
10 (310) (310)
11 (311) (311)
12 (222) (222) (222)
Slight complication: 3different Bravais lattices In cubic
Pcubic- Allplanes, reflections possible. Icubic- (hkl) present only if h+ k+|=even
Foubic -(hk) present only if h,kl all even or all odd
Miller indices calculation for cubic system of
copper (a=3.597A)
2-Theta hkl
22.21
31.61
38.97
45.31
51.01
56.29
66.00
70.58
75.03
79.39
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Powder diffraction is more aptly named
polycrystalline difraction
Samples can be powder, sintered pellets, coatings onsubstrates, engine blocks...
> The ideal "powder sample contains tens of thousands of randomly oriented
crystallites
- Every diffraction peak is the product of X-fays scattering from an equal
number of crystallites
-Onlya small fraction of the crystallitesin the specimen actually contribute to the
measured diffraction pattern
Inadiating a larger volume of material can help ensure that a statistically relevant
number of grains contribute to the diffraction pattem
Small sample quantities pose a problem because the sample size limits the
number of crystallites that can contribute to the measurement
http/prisumit edw'xrayloldsite Basic%20of%20X-Ray%20Powder%20Diliracion pdt
Asingle crystal specimen in a diffractometer would produce only one family of peaks in th
diffraction pattern.
(100)
-(110)
-(111) (210)
(200)
20 25 30 35 40 45
A A
[110), Two-Theta (deg) (200]1
20
At 20.6 20, Bragg's law The (110) planes would diffract at 29.3 The (200) planes are parallel to the (100)
futriled for the (100) planes, 20; however. they are not properiy planes. Therefore, they also diffract for this
producing a ditfraction peak algned to produce a ditfraction peak crystal. Since dag ls V2 des they appear at
(ne perpendicular to those planes does 42 20
not bisect the incident and dffracted
beams). Only backaround Is observed.
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