Beruflich Dokumente
Kultur Dokumente
Milestones
1966 7th Congress of the IUCr in Moscow 1969 publication in J.Appl.Crystallogr. 1977 acceptance for X-ray diffraction 1983 Quantitative Phase Analysis Dr. Hugo M. Rietveld
pictures by courtesy of Hugo Rietveld (http://home.wxs.nl/~rietv025/)
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Rietveld Method
Full profile fitting Using crystallographic constraints Lattice parameters and space group to constrain peak positions Crystal structure to constrain peak intensities
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Profile Fitting
An accurate description of the line profile shapes in a powder pattern is critical to the success of any profile fitting application!
Todays profile fitting techniques: Analytical profile fitting Direct convolution approach
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Fitting
Single peak fitting Full pattern fitting Le Bail / Pawley methods Rietveld method
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Calculate:
yio observed step intensity yco calculated step intensity Needs profile function
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Use lattice parameters and spacegroup info to constrain peak positions calculate
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WPPF
structure solution
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Rietveld
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Step Intensity
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synchrotron radiation: LP = 90 (totally polarized) filters, energy dispersive detector: LP = 0 (not polarized) monochromator cystals: LP = Bragg angle
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sin Kr f = 4 (r ) dr r
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2 B sin f j = 0f j exp 2
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Structure Model
Cell parameters (edge lengths, angles) a,b,c, alpha, beta, gamma Symmetry group, space group Asymmetric unit i.e. atom coordinates, TDPs, occupancy:
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Rietveld Refinement
Preferred Orientation
March Dollase function
Pk = G cos k + 1
2 2
( G )sin ]
2 k
Spherical harmonics only even orders (Friedels Law) start always with lowest order increase order until no improvement of Rwp is obtained !!! Check plot of phase intensity for negative values !!!
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Sample
The grains in the powder should be randomly oriented!
Typical sample-related problems: Not enough scattering particles (spotiness) Sample not representative for the bulk Bad sampling / particle heterogeneity / phase separation Preferred orientation Extinction Microabsortion (multiphase samples)
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For quantitative Rietveld (mixture): As a general rule, do not refine positional (x, y, z) and displacement vectors (B)
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More can be found in: Rietveld refinement guidelines Mc. Cusker et al. Journal of Applied Crystallography 32 (1999) 36-50
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