RAW MATERIALS XRF APPLICATION USING AUNIVERSAL BORATE FUSION METHODOLOGY

© Corporation Scientifique Claisse®, 2013. All Rights Reserved.

Anne-Catherine Breton, Mathieu Bouchard, John Anzelmo and Sébastien Rivard

Corporation Scientifique Claisse, Québec, Canada

21ST CENTURY INDUSTRY REALITY

• Raw Materials:– Natural ores and rocks– Use of industrial by-products– Not necessarily obtain from well

known sources

• Fuels: – Less expensive fuel and waste

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LAB MANAGERS REALITY

• Analyze a very wide range of sample types(raw materials, in process samples, final products)

• Meet requirements of standard test methods

• Laboratory operators and/or technicians with limited scientific background

• Limit cost of analysis– Need safe, simple and efficient analytical methods– Need to limit the sources of manipulation errors– Need to limit the use of reference materials and/or pure

oxides

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4PRESSED POWDERS FOR XRF

Pressed pellets can generate good accuracy only when:

• A distinct calibration curve is made for every type of matrix

• Standards that match exactly the unknown samples for particle size and mineralogy are available

• Grinding and pressing conditions are optimized and rigorously repeated

• The standards and the samples can be ground enough to reduce the particle size effect significantly

• The pellets are stable enough (use of binder) to avoid causing cross-contamination

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FUSION FOR XRF

• No particle effect

• All elements transformed into simple oxides

• No mineralogical effect

• All standard and unknown specimens have the same matrix which is a borate glass

• Calibration is much simplerand flexible

MATERIAL TYPES

• Cement• Blended cement• Cement with additions• Aluminate cement• Clinker• Kiln feed• Raw Mix• Limestone

• Gypsum• Sand• Clay• Bauxite• Silica Fume• Slag• Fly ash• Iron Ore

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DEVELOPMENT OF THE GLOBAL FUSION METHOD

• 200 different samples from 14 material types

• Both ignited and non ignited samples

• 3 different sample:flux ratios

• We tried different dry oxidation methods

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THE EQUIPMENT USED

Muffle Furnace:

- Fisher ScientificIsotemp® Programmable- Max. Temp.: 1125°C- Power: 50/60 Hz 208/240 VAC

Spectrometer:

- Bruker S4 Explorer- WDXRF- Tube: 1000 Watts

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Automatic Fluxer:

- Claisse M4 or TheOxFluxer

THE EQUIPMENT USED - FLUXER

Automatic Electric Fluxer:Automatic Gas Fluxer:

- Claisse® M4TM Fluxer- Propane/Air Heating- 3 Positions

- Claisse® TheOxTM Fluxer- Electrical Heating- 6 Positions

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CEMENT AND RAW MATERIALS FUSION METHOD

• Ignition: Necessary for All Cement related and Raw Materials

950oC for 1 hour

• Crucible: Claisse Optimix crucible, Pt-Au alloy (95%-5%)

• Mold: 32mm Pt-Au alloy (95%-5%)

• Flux: Li2B4O7 / LiBO2 49.75% / 49.75% flux with integrated

LiBr non-wetting agent 0.50%

• Ratio: 1:10 sample to flux

• Mixing: 15 seconds on a vortex mixer

• Fusion time: 18 min. (including cooling) for M4 Fluxer

22 min. (including cooling) for TheOx

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CALIBRATION STANDARDS

• The calibration of the WDXRF raw materials application was executed using a wide variety of RMs

• Bureau of Analysed Samples Ltd. (BAS): British Chemical Standard Certified Reference Materials

• Domtar® Inc. Research Center: Canadian Certified Reference Materials• China National Analysis Center for Iron and Steel: NCS DC Reference Material• European Committee for Iron and Steel Standardization • European Coal and Steel Community (ECSC): Euro-Standard• Geological Institute for Chemical Minerals: GBW Reference Material• Institut de Recherches de la Sidérurgie (IRSID) : Échantillon-Type• Instituto de Pesquisas Tecnológicas (IPT) : Reference Material• Japan Cement Association (JCA): Reference Materials for X-ray Fluorescence

Analysis • National Institute of Standards & Technology (NIST): Standard Reference

Material®• Slovak Institute of Metrology (SMU): Slovak Reference Material• South Africa Bureau of Standards: SARM Certified Reference Material

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CALIBRATION STANDARDS12

RM element concentration as an oxide equivalent

MATERIAL TYPES

• Not included in this analytical process1) Copper Slags2) Other samples with copper at higher level than traces3) Some Iron Ores

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• Easy to fuse

14CALIBRATION

Inter-element corrections and squarred correlation coefficients for raw materials application

SENSITIVITY, PRECISION AND ACCURACY RESULTS15

Raw Materials application results

CONCLUSION

• Borate fusion allows to developed a robust and universalsample preparation method which is able to fuse the largerange of raw materials and cements

• It is possible to obtain a precise and accurate universalcalibration, able to cover a wide range of raw materials

• Precise and accurate results can be obtained using bothtype of fluxers: TheOx or M4.

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QUESTIONS AND COMMENTS

If you have questions, please feel free to ask me now or later at HRT Labortechnik’s booth.

Thank you for your attention!

www.claisse.com

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