Powder X ray Diffraction

Why do we use x-rays?

The features were trying to see are on the order of the distance between atoms: 10-10 meters.

To see the atoms, we need to use light with a wavelength that is near to this distance.
X-Rays (x-ray wavelength. light) have a suitable

What is X-ray diffraction?

Non-destructive analytical technique for identification and

quantitative determination of the various crystalline forms,

known as phases. Is produced when X-rays are diffracted from a sample consisting of a very large number of randomly oriented crystalline particles.

The XRD pattern is often spoken as the FINGERPRINT of a

mineral or a crystalline substance, because it differs from pattern of every other mineral or crystalline substances.

Schematic diagram of X-Ray Diffractometer

Basic Component Of XRD Machine

Therefore any XRD machine will consist of three basic component. Monochromatic X-ray source () Sample-finely powdered or polished surface-may be rotated against the center (goniometer). Data collector- such as film, strip chart or magnetic medium/storage.

Monochromatic X-ray filters

 Every crystalline substance produce its own XRD pattern, which because it is dependent on the internal structure, is characteristic of that substance. The periodic lattice found in crystal structures may act as a diffraction grating for electromagnetic radiation with a wavelength of 1 . X rays which have the wavelength equivalent to interatomic distances and hence they will interact with a specimen as they pass through it. Braggs law determines the position of a reflected beam. Only d and I can be measured from a powder pattern. All the info from a 3-D reciprocal lattice has been compressed into one dimension! Identification is achieved by comparing the X-ray diffraction pattern

Diffraction

An ideal polycrystalline material or powder is an ensemble of a very large number of randomly oriented crystallites. The randomness of crystallites results in the formation of diffraction cones, each corresponding to a particular (hkl) plane.

Diffractograms and ICDD Card

Typical experimental XRD data

Angle (2) 27.47 27.82 28.45 44.87 46.68 47.11 55.88 68.89 76.12 83.19 87.74 92.49 94.68 94.99 106.44 106.78 113.81 114.26 127.24 127.82 d-value () 3.244 3.204 3.135 2.018 1.944 1.928 1.644 1.362 1.250 1.160 1.112 1.067 1.048 1.045 0.962 0.960 0.920 0.917 0.860 0.858 Rel. Int. (I) 26 49 100 2 30 64 41 6 10 1 10 1 13 6 2 1 5 2 4 2

Diffractograms

Diffractograms

Indexing
The alphabetical index
A given phase may be listed in several places in the inorganic alphabetical index

Hanawalt Index The Fink index

Based on three strongest Bragg peaks present in a powder diffraction pattern It covers inorganic compounds only, d spacing's and intensities are listed for the eight strongest lines of each substance.

Analysis of Crystallite size

SCHERRER FORMULA

Relates peak width to crystalline domain size

Crystallite thickness Wavelength Bragg Angle FWHM of sample and Standard in Radians

19 August 2012

USES OF POWDER DIFFRACTION

Identification of unknown compound

Qualitative and quantitative phase analysis

Multiphase analysis Crystalline to amorphous ratio determination Texture analysis Preferred orientation studies in thin films, fibers and sheets.

Strength and Limitations of X-Ray Powder Diffraction (XRD)

Strengths: Powerful and rapid (< 20 min) technique for identification of an

unknown material. In most cases, it provides an unambiguous mineral determination Minimal sample preparation is required. XRD units are widely available. Data interpretation is relatively straight forward.

Limitations: Homogenous and single phase material is best for identification of

an unknown For mixed materials, detection limits is ~2% of sample. For unit cell determinations, indexing of patterns for non-isometric crystal systems is complicated. Peak overlay may occur and worsens for high angle 'reflections'

DATABASES
Powder data file (PDF-2) CCDC ICSD PDB
Now ICDD (used to be JCPDS) www.icdd.com www.ccdc.cam.ac.uk
www.fiz-informationdienste.de/en/DB/icsd Web version at icsd.ill.fr/icsd

Free Software
Empirical Peak Fitting
XFit WinFit couples with Fourya for Line Profile Fourier Analysis Shadow couples with Breadth for Integral Breadth Analysis PowderX FIT succeeded by PROFILE

Whole Pattern Fitting

GSAS Fullprof Reitan

All of these are available to download from http://www.ccp14.ac.uk