Crystal Structure from
Powder Diffraction data
a feasible way
Prof. Dr. Alexandre Cuin
Chemistry Department – UFJF
Juiz de Fora – Minas Gerais -
Brazil
Antonella Guagliardi
Istituto di Cristallografia, CNR, Bari, Italia
Università dell’Insubria, Como, Italia
[Link]@[Link]
Quantitative Phase Analysis
The Rietveld Method for a Quantitative Phase Analysis (QPA)
Building and Optimization of a diffraction pattern model of a polyphasic
polycrystalline mixture
Building and Optimization of a diffraction pattern model of each single
crystal phase present in the mixture
The whole diffraction pattern of the mixture is the “weighted” sum of
the patterns of each single phase (and of a background)
Determination of the weight fractions of the crystalline phases within
the mixture using the refined scale factors
Quantitative Phase Analysis
Advantages of the Rietveld QPA
There is no need to build calibration curves
The entire diffraction pattern is used, not only single portions, more accurate results
Peak overlap is less problematic complex mixtures can be analyzed
Introduce analytical corrections for micro absorption, preferred orientation (PO),
anisotropic broadening of the peaks, etc.
(Microabsorption and PO are the principal sources of error in QPA)
Limitations of the Rietveld QPA
It is mandatory to have a sufficiently accurate model for the crystal structure of all phases
(form single-crystals or powders)
If a single phase structure is not known, the method cannot be used (not yet!)
Not particularly efficient for partially disordered systems (clays, polymers, etc)
1. Uses a data bank containing ascii files (.pha) with all structural information for
the crystal phases. This data bank can be increased and/or modified by the user at
his/her own will (and responsability!) (Quanto Data Bank);
2. Requires an input file (.qua) with a limited number of experimental information
and pointing to the phases data bank folder;
3. Make automatic runs;
4. The interaction with the user is limited and facilitated by a “user friendly”
graphical interface;
5. Contains a robust model (March-Dollase formulation) to correct for PO effects;
6. Contains Brindley model to correct for microabsorption effects;
7. Can estimate the amorphous material content by the addition of an internal
standard;
[Link] a “Help on line”, which describes the basics of the method, the used
equations and the program functionionality.
By Norberto Masciocchi
More accurate explanation
from [Link]’s course
By Norberto Masciocchi
By Norberto Masciocchi
Details on: Hill, R.J. and Fischer, R.X. (1987). [Link], 23, 462-468 and NM Brazil course
How to prepare the three basic “Quanto files”?
The main file for Quanto is the .QUA file;
The crystallographic phase information should be written as ‘.pha’ files;
The experimental data should be written as ascii (columns);
.QUA file Example:
%window
%job miscela 7 fasi
%mixture miscela There are 7 phases!
%init
%data
phase [Link]
phase [Link]
phase [Link]
File content
phase [Link]
experimental data
phase [Link]
phase [Link]
phase [Link]
pattern [Link]
record 8
Format (f7.0,7f8.0)
range 10.000 70.000 0.050
wavelength 1.54051 1.54433 0.50000
%prelim Some detail of how the experimental
%rietveld data were obtained and saved
%continue
.PHA file Example:
Cell parameters (a,b,c, α,β,γ)
Title Calcite and space group
cell 4.9895 4.9895 17.0757 90.0000 90.0000 120.0000
space R -3 C
Coord Ca 0.00000 0.00000 0.00000 1.00000
Coord C 0.00000 0.00000 0.25000 2.00000
Coord O 0.25042 0.00000 0.25000 2.00000
Atomic features
Quanto
<Command > <atom symbol (type)> <x y z coordinates> <B factor>
Experimental data file Example: .xy 5 361
5.02003 326
5.04005 337
1st column -> 2th values 5.06008 357
5.0801 327
5.10013 320
5.12015 316
5.14018 328
5.1602 383
5.18023 344
Step: 0.02003 (2th)
or more accurate: 0.020025 (th)
2nd column -> intensity
