Quantitative Powder XRD Phase Analysis Software for Windows Page updated: October 31st 2006

Contents of this page

• Rietveld Made Easy
• Version 3 Key Features
• General Description of the Siroquant software
• Unique Features of Siroquant
• The Method
• Measured Patterns as Standards
• Siroquant Program Dimensions and Recommended PC Specifications
• Test Applications and Results
• Literature References

We have released an update to Siroquant version 2.5 to fix reports of problems with Windows XP and Windows 2000.  To download the update go to the updates page

Siroquant Version 3.0

The new version of Siroquant, Version 3.0 is currently in the final stages of testing prior to release.  Special upgrade pricing is available to users of earlier versions.  For further details please see the updated features list below

Rietveld Made Easy

The book has finally been published!  This book is designed as a practical guide to the fundamentals of crystallography as applied to Rietveld analysis and is a essential companion to the User Guide supplied with the software.  The introduction to the book is available here as a PDF document.  Copies of the book can be ordered directly from Sietronics.

Siroquant Version 3.0

The key features of this release are:

1.  Expanded Crystal Structure Database: The database will consist of approx 1700 entries covering a much wider range of minerals than any of the earlier versions.  Expanded Clay Database

2. Full 32-bit version: This new version is a full 32-bit program and has been completely rewritten for the new platform.  Long file names are fully supported and used in V3.

3. Multiple Document Interface: More than one task may be open at any time and more than one task may be refined at any time.

4. Many user options can now be set and forget for the application: new features include a most recently used task list for easy access to tasks, use of refined backgrounds, automatically show the results, chi squared dialogs at the end of task refinement.

5. Tools available for task and cpi editing: Add-on tools for easy repathing of task files and editing of cpi files.

6. Indefinite limits: There is no longer a prescribed limit on the number of phases in a task; number of hkl lines in a hkl file; or the number of data points in a pattern. The pattern readings may be any real value, not just integers.

7. Flexible tasks:  The task may contain phases that can be excluded from refinement. This allows some experimentation without losing previously refined values.

8. Direct phase selection for tasks: Phases in the database can be selected for a task without the need to generate a hkl file first.

9. Overlaying Scans:  You can now overlay other pattern files in the current task.

10. “Modelling” of patterns: Patterns can be modeled and displayed

Key Features of Siroquant

• User-friendly: Windows operation ensures user-friendliness.
• Accurate: Corrects for preferred orientation and absorption contrast to give high absolute accuracy.
• Sensitive: Due to full-profile fitting, concentrations less than 1% can be determined.
• Conventional Standards not required: No requirements for artificial mixtures except to check amorphous contents.
• Simple to use: No special sample preparation other than standard XRD powder preparation techniques.
• PC-Based: Due to size and speed a Pentium 100MHz PC with 8Mbyte of RAM is recommended.
• Fast: Fully optimised code for rapid operation.

General Description

Siroquant is currently being used by many industrial, scientific and academic organisations around the world. It has a logical user friendly Windows interface including extensive on-line help. It requires a Windows PC (minimum 386DX processor) running Windows 3.x, Windows 9x or Windows NT.  The Windows version of the program has been available since 1993 and has been extensively debugged during this time. The system is equally useful for industrial and research applications.

Profile Functions:  Siroquant supports Gaussian and Lorentzian (and any mixture of the two) peak shapes using the Pearson VII and Pseudo-Voigt profile functions.  The March preferred orientation parameter is also refinable.

Refinable Profile Parameters:

• Phase Rietveld scales.
• Line asymmetry.
• Preferred orientation.
• Line-width parameters, U1, V1, W1 & U2, V2, W2. (Note: Two line-width functions are allowed for each phase)
• Instrument zero.
• Pearson M or Pseudo Voigt shape functions.
• Unit cell dimensions (a, b, c, alpha, beta, gamma).

Refinements can be performed in several stages with different combinations of varied parameters.

An automatic refinement procedure (Auto-prescale) is also available and produces good ball park estimates for most samples as well as a providing a basis for further refinements.

Siroquant contains an absorption/contrast correction which is essential for quantitative phase analysis. Major analytical error can occur without this correction.

The software uses Bragg-Brentano geometry calibration curves, this is essential where strong low-angle XRD peaks are present. Corrections of 2 x peak height are common at low angles.  Siroquant allows Rietveld analysis on minerals without a published crystal structure using a unique program structure featuring observed HKL files.  This allows the analysis of poorly crystalline clays.

The program can be used to analyse mixtures of up to 25 minerals. (Cement analysis requires >15 phases).  The program has includes "Anomalous Dispersion" corrections for the correction of resonance effects in the absorption of x-rays.

Siroquant has a robust least squares refinement scheme. Automatic staged refinement was recommended by industrial users to allow automatic plant analysis using a sequence of various refinements from a poorly defined starting point. Up to 100 variables can be refined in each cycle. (Note: refinement of an excessive number of variables in one stage increases the probability of an incorrect fit).

There are around 1700 industrially important minerals in the Siroquant data base. Additional phases can be added by users with a background in Crystallography by following a set of instructions in the manual or by Sietronics.

The manual has been assembled by users and technical experts to provide an easy to follow reference and a strong technical reference guide including a comprehensive list of references.

Diffractometer calibration curves can be supplied to correct for intensity aberrations in Bragg-Brentano diffractometers. As the upwards revision of diffractometer intensity at low angles can be as high as a factor of about 5, calibration is important for clay and zeolite work (see Taylor & Matulis, Powder Diffraction, Vol 7, pages 89 - 94 (1992) ).

The package allows up to 25 phases to be quantified at any one time with refinement of up to 100 variables in each stage.

Crystallite size can be calculated by the Scherrer equation and amorphicity can be determined with the addition of a spike phase.

Dual halfwidths are allowed for each phase allowing for sharp and diffuse reflections caused by disorder. This feature is essential when quantifying clay minerals as well as other classes of minerals.

Siroquant has wide acceptance in industry.  Siroquant is relatively easy to use and has a large enthusiastic user base.  The package is being used by major companies in the cement and aluminium industries including:

• Blue Circle Southern Cement (Australia)
• Pretoria Portland Cement (Republic of South Africa)
• F L Smidth (Denmark)
• Alcan
• Comalco
• ALCOA

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Unique Features of the Siroquant software

Siroquant has some unique features not found in other Rietveld programs, because it has been designed for quantitative analysis whereas the other packages have been developed primarily for structure analysis.

Among these unique features:

• Use of observed as well as calculated Rietveld Standard Profiles:  In the past, it was not possible to quantify important classes of compounds such as disordered clays in Rietveld refinements because their crystal structures are not defined.  Using Siroquant, these minerals can be quantified by using observed HKL files.   The software includes observed HKL files for minerals such as montmorillonite, illite, halloysite and various forms of kaolin.

In principle, any mineral can be included into the Siroquant data base whether its crystal structure is known or not.

• Brindley absorption contrast corrections: Absorption Contrast corrections are very important when the phases have different x-ray absorptive power.  The corrections are calculated according to Brindley.
  
• Amorphous content: Phases such as silica fume, meta-kaolin can be included as input phases in a Siroquant quantitative task.

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The Method:

Siroquant calculates a theoretical XRD profile and fits it to the measured pattern by full-matrix least-squares refinement of the following Rietveld parameters: phase scales, line asymmetry, phase preferred orientation, phase linewidths (U,V,W), instrument zero, the lineshape parameter for each phase, and the phase unit cell dimensions.

The program also corrects for the effects of particle size and absorption contrast (Brindley corrections) and an optional internal standard addition (spike) allows the calculation of overall amorphous content. Individual phase amorphicities can also be included.

A readily expandable file, the Crystal Structure Databank, contains the information necessary to quantify 304 common minerals and 17 observed hkl files, mostly for clays.

Operation:

• Siroquant is mouse-controlled through Windows screens.
• Press-button automatic prescaling gives a good ballpark first profile fit in a matter of minutes - this is the starting point for further refinement if needed.
• Pre-programming of up to 10 refinement stages with different variables is available.
• Automatic parameter writeback after a refinement if needed.
• Graphics system with zoom, overlay, (hkl) bars, and automatic or manual background selection. Linear or cubic spline background functions.
• Output of quantification results on pie chart or numerical listing.
• Colour printer publication mode graphics output.
• Graphical display of residuals chi-squared and mean parameter shift per phase over the refinement stages.
• Compatible with Bruker-AXS (Siemens), Philips, Rigaku, Scintag and other data files.
• Crystallite size and amorphous content calculations.
• Routine error messages installed for improved error detection and prevention.

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Measured Patterns as Standards

Normally, crystal structure data is needed to quantify a mineral with the Rietveld method.  However, minerals with unknown or imperfectly known crystal structures (eg. clays), can still be quantified with Siroquant Version 2. To do this an "observed (hkl) file" is used, instead of the normal calculated file, to give a standard Rietveld profile for the mineral. The results in Table 4 on the test applications were obtained with a measured (hkl) file for montmorillonite. 

Observed (hkl) files for use with Siroquant Version 2 have been prepared for clays (montmorillonite, kaolin, illite, halloysite, palygorskite, etc), cement phases and pseudorutile. This completely new Rietveld approach is described in Taylor and Zhu Rui (1992) and Taylor and Aldridge (1993) (see references).

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Siroquant Program Dimensions and Recommended PC Specifications

Up to 25 minerals are allowed in a sample. This complexity can occur in some materials such as bauxite, or coal ashes. The pattern can have up to 10,000 steps and 650 reflections are allowed for each mineral phase.

The system runs on an IBM-compatible PC 386 or 486 computer with at least 4Mb of RAM, WINDOWS 3.1, and DOS 5.0. It also runs on Windows 3.x, Win 9x and NT. A minimum PC configuration of a 100MHz Pentium Processor with 8Mbyte of RAM is recommended.

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Test Applications and Results:

Siroquant has been tested with many standard mixtures and used to quantify phases in beach sands, Portland cement, flyash, coal ash, opal C-T, clays. sandstones, slags, bauxites, china clays, zeolites, zirconia ceramics etc. Detailed applications notes have been prepared for Cement Fly ash, Opalised quartz-tridymite-cristobalite Clays, Sandstones and Boiler Slag - these are available from Sietronics.

Table 1: Portland Cement Results:

Results for Two Standard Portland Cements El and E2. Siroquant Version 2 results are compared with microscope grain counts. The cement minerals are given their usual shortened trade names.

Table 2: Results for some standard mixtures:

Siroquant errors are on the last significant digit. Mu/sigma is the mass absorption coefficient for CoKa.

Table 3: Albite/Tourmaline Mixtures:

5% amorphicity is assumed in the Tourmaline

Table 4: Quartz-Montmorillonite Standard Mixtures (Algerian Bentonite):

Corrected for Kaolin and Phlogopite impurities in the Quartz.

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Literature References:

Siroquant System

1. Taylor, J.C. (1991). Computer Programs for Standardless Quantitative Analysis of Minerals Using the Full Powder Diffraction Profile, Powder Diffraction, 6, pp 2-9.

Contrast Corrections:

1. Taylor J.C.. and Matulis. C.E. (1991) Absorption Contrast Effects in the Quantitative XRD Analysis of Powders by Full Multiphase Profile Refinement. J. Appl Cryst., 24, pp 14-17.

Rietveld Analysis:

1. Rietveld. H.M. (1969). A Profile Refinement Method for Nuclear and Magnetic Structures. J. Appl Cryst. 2,pp  65-71.

Portland Cement Analysis:

1. Taylor, J.C., Hinczak I, and Matulis, C.E., Rietveld full-profile quantification of Portland cement clinker: The importance of including a full crystallography of the major phase polymorphs.  Powder Diffraction 15, pp 7-18, March 2000
2. Taylor J.C.. and Aldridge. L.P (1993a) Full-Profile Quantitative XRD Analysis of Portland Cement Powder Diffraction: Testing of possible standard XRD profiles for the major phase, Tricalcium Silicate. Powder Diffraction 8 pp 138-144.
3. Taylor, J.C and Aldridge, L.P (1993b). Phase Analysis of Portland Cement by Full Profile Standardless Quantitative XRD-Accuracy and Precision. Advances in X-Ray Analysis, 36 pp 309-314.
4. Taylor, J.C. and Aldridge, L.P. (1994). International Ceramic Monographs, Proceedings of the International Ceramics Conference Austceram 94.  Vol 1, Num 1 1994 pp 141-146
5. Pipat Termkhajornkit ,Toyoharu Nawa and Kiyofumi Kurumisawa, Effect of water curing conditions on the hydration degree and compressive strengths of fly ash-cement paste, Cement and Concrete Composites, Vol. 28, Issue 9, Pages 781-789, October, 2006. (available online via ScienceDirect)
6. Pipat Termkhajornkit, Toyoharu Nawa and Kiyofumi Kurumisawa, Quantitative Study on Hydration of Fly ash and Portland Cement, CONMAT 2005.
7. Pipat Termkhajornkit, Toyoharu Nawa and Kiyofumi Kurumisawa, A Study of Fly ashcement Hydration by Rietveld analysis and Selective Dissolution, JCI annual meeting 2005, pp. 169-174
8. Pipat Termkhajornkit, Toyoharu Nawa, Jyunnosuke Fujisawa and Daisuke Minato, Influence of fly ash replacement ratio on compositions of C-S-H gel, JCI annual meeting 2006, pp. 281- 286.

Clay Analysis:

1. Taylor, J.C. and Matulis C.E. (1994). A new method for Rietveld clay analysis Part 1.  Use of a universal measured standard profile for Rietveld quantification of Montmorillonites. Powder Diffraction 9, pp 119-123.

Observed Patterns as Rietveld Standards:

1. Taylor, J.C. and Zhu Rui (1992). Simultaneous Use of Observed and Calculated Standard Profiles in Quantitative XRD Analysis of Minerals by the Multiphase Rietveld Method: The Determination of Pseudorutile in Mineral Sands Products. Powder Diffraction 7, pp 152-161.
2. Taylor, J.C., Zhu Rui and Aldridge, L.P. (1993). Simultaneous Use of Observed and Calculated Standard Profiles in Quantitative XRD Analysis of Minerals by the Multiphase Rietveld Method: Application to Phase Quantitation of Mineral Sands and Portland Cement EPDIC  Conference 1992, Materials Science Forum Vols 133-136 pp 329-334

Bragg-Brentano Intensity Calibration Curves:

1. Matulis. CE, and Taylor. J.C. (1992) Intensity Calibration Curves for Bragg-Brentano diffractometers Powder Diffraction, 7, 89-95.
2. Matulis. C.E. and Taylor. J.C. (1992). A Theoretical Model For the Correction of Intensity Aberrations in Bragg-Brentano X-Ray Diffractometers. J. Appl. Cryst., 26(3) pp 351-356

Structure Refinement:

1. Taylor. J.C. (1986). Study of Decomposition Methods for Refinement of H+-2SM5 Zeolite with Powder Diffraction Data, Z. Krist., 176, pp 183-192.
2. Taylor, J.C (1987). Comparison of Profile Decomposition and Rietveld Methods for Structural Refinement with Powder Diffraction Data. Z. Krist., 181. pp 151-160.

General Quantitative Analysis:

1. Liz Goodall & Natasha Wright: Rietveld Methods of Refinement for Zinc Oxide, Poster paper presented at Broome Crystallography Conference 2003, Broome, Australia, August 2003.

2. Timothy E Payne, Willem K. Bertram, Takashi Itakura and Mark D. Raven (2002): Relationship of quantitative X-ray diffraction measurements of geologic materials to cesium sorption, Radiochim. Acta 90, 705-711.

3. Chuan-De Ruan, Colin R. Ward (2001): Quantitative X-ray powder diffraction analysis of clay minerals in Australian coals using Rietveld methods, Applied Clay Science 776.

4. Ward C.R., Taylor J.C., Matulis C.E., Dale, L.S. (2001:) Quantitation of mineral matter in the Argonne Premium Coals using interactive Rietveld-based X-ray diffraction, International Journal of Coal Geology, 46, p 67-82.

5. Ward C.R. et al (1999) Mineral Matter and trace elements in coals of the Gunnedah Basin, New South Wales, Australia, International Journal of Coal Geology, 40, p 281-308.

6. Ward C.R., Taylor J.C., Cohen D.R. (1999) Quantitative Mineralogy Of Sandstones By X-Ray Diffractometry And Normative Analysis, Journal of Sedimentary Research, 69(5), p 1050.

7. Jackman J.M., Jones, R.C, Yost, R.S and Babcock, C.J (1997): Rietveld Estimates of Mineral Percentages to Predict Phosphate Sorption by Selected Hawaiian Soils.  Soil Sci Soc Am J 61 pp 618-625

8. Tilley, D.B, Barrows, T.T, Zimmerman, E.C (1997): Bauxitic Insect Pupal cases from Northern Australia, Alcheringa, 21 pp 157-160
   Dunbar, G, Ness, S, Freeman, R (1997): Quantitative Mineralogy of Marine Sediments, Private Communication James Cook University

9. Bierlein, F.P.et al (2000): Wall Rock Petrology and Geochemistry in Alteration Halos Associated with Mesothermal Gold Mineralization, Centreal Victoria, Australia, Economic Geology 95 pp 283-312

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Siroquant Agents

Siroquant can be purchased from Sietronics or from our agents as listed below in the designated countries

• North America: Contact Analytical X-ray Instrument Sales, Jerry Krause at jkxray@aol.com
• Europe: Contact Roentgenlabor, Dr Martin Ermrich at roentgenlabor-dr.ermrich@t-online.de

Please feel free to contact us at: spl@sietronics.com.au