Determination of Silicon Dioxide (SiO2) in Silica Sand by X-Ray Fluorescence Spectrometry (XRFS)

1.0

Principle

The sample is fused using a mixture of lithium tetraborate and lithium metaborate flux. The fusion melt is cooled and undergo crystallization forming a clear fused bead. The fused bead is then irradiated by a high energy X-ray beam to produce a secondary X-ray. The characteristic beam is then dispersed by mean of crystal, and the produce intensities are measured by suitable detector at selected wavelength. Concentration of the elements are determined by relating the measured radiation of unknown sample to analytical curve prepared from reference materials of known concentration.

2.0

Scope

2.1.

This procedure covers the method for determination of silicon dioxide in silica sand.

3.0

Apparatus Analytical Balance with a readability of 0.1 mg. Plate Grinder or Pulverizer, with one static and one rotating disk for further grinding. Rotary Disk Mill or Shatter Box, with hardened grinding containers and timer control for final grinding. 3.4. 3.5. Fusion Equipment. Furnace or Gas burners, with a timer, capable of heating the sample and flux to at least 1000 C and homogenizing the melt. 3.6. 3.7. Platinum/Gold Crucible, 95 % platinum/5 % gold alloy, 30 to 35 ml capacity. Platinum/ Gold Casting Dish, 95 % platinum/5 % gold alloy, 30 to 35-ml capacity, with a flat bottom 30 to 35 mm in diameter. 3.8. 3.9. Glass rod. Wavelength Dispersive X-Ray Fluorescence Spectrometer (WDXRFS).
o

3.1. 3.2. 3.3.

Test Method Reference:

TMM/XRF/SILICA

Determination of Silicon Dioxide (SiO2) in Silica Sand by X-Ray Fluorescence Spectrometry (XRFS)

4.0

Reagents 4.1. Claisse Lithium Borate Pre-Fused Flux (49.75% Lithium Tetraborate : 49.75% Lithium Metaborate : 0.5% Lithium Bromite) 4.2. Detector Gas , consisting of a mixture of 90 % argon and 10 % methane for use with gas flow proportional counters only. 4.3. Reference Materials- Certified reference materials are available from the National

Institute for Standards and Technology (NIST) and other international certification agencies.

5.0

Preparation of Fusion Glass Bead

5.1

Weigh to the nearest 0.0001 g, 0.6000g of the finely ground sample into a crucible platinum containing 6.0000g of Claisse Lithium Borate pre-fused flux. (Note 9.1, Note 9.2)

5.2

Mix flux and sample properly using a glass rod, and wipe the glass rod to ensure most of the sample and fluxs is transfer back to the platinum crucible.

5.3

Place the crucible on the Claisse M4 fusion machine.

5.4

Choose the fusion silicate ingredient / method and set up the fusion parameter according to the sample decomposition requirement. (Appendix A)

5.5

Fuse the sample and flux mixture according to fusion ingredient until a complete decomposition of the sample.

5.6

After a complete dissolution transfer the hot melt to a platinum dish / mould and let the melt to cool and undergo crystallization.

5.7

Keeps the bead in air tight sample cup inside a desiccators ensuring that a minimal exposure with low relative humidity less than 15 for longer live spend of the bead.

Test Method Reference:

TMM/XRF/SILICA

Determination of Silicon Dioxide (SiO2) in Silica Sand by X-Ray Fluorescence Spectrometry (XRFS)

6.0

Calibration

6.1.

Fuse a series of calibration standard that comprise of Certified Reference Material (CRM) and In-House Reference Material (HRM) using above procedure (As in Para. 5.0) (Refer Appendix B). Set up the instrument according to the Manufacturers Instruction Manual.

6.2.

6.3.

Define the measurement parameters of the instrument to ensure repeatable analyses. (Refer Appendix C)

6.4.

Place the fuse glass bead onto an aluminium sample cup.

6.5.

Calibrate the instrument using the prepared fused glass bead of Certified Reference Material (CRM) and In-House Reference Material (HRM). Establish the calibration curve by a linear least square curve fit of the x-ray intensity measurement versus the corresponding weight percent concentration of element in the reference materials.

7.0

Calculation

)]

Ci Di Lij Cj Ei Ri
ij

= =

Concentration on element of interest / Mass Fraction (%) y-axis intercept Line Overlap Correction Corrected coefficient / factor of concentration on element of interest Inverse of sensitivity during calibration Nett Count Rate Matrix Influences Coefficient (Alpha Coefficient)

=
= = =

Test Method Reference:

TMM/XRF/SILICA

Determination of Silicon Dioxide (SiO2) in Silica Sand by X-Ray Fluorescence Spectrometry (XRFS)

8.0

Measurement

8.1.

Verification of Calibration (Drift Correction)

8.1.1.

Verify the calibration by measuring the verification glass (Herasil). The result of the verification glass should be in the range of 2. (Refer Table 1.1)

8.1.2.

If the result is not within the acceptable value (X - 2 / X + 2), measure drift monitor (Ausmon) to correct the calibration drift.

8.1.3.

After the drift monitor measurement is completed, re-measure the verification glass (Herasil) and compare the concentration obtained with the established concentration.

8.2.

Sample Measurement

Single Sample Measurement

8.2.1.

Sample is prepared in duplicate with the presence of In-House Reference Material (GS/SND 2009).

8.2.2.

The measurement of the sample duplicates are performed together with a InHouse Reference Material (GS/SND 2009) and Certified Reference Material (SGT8).

Sample Measurement in Batch

8.2.3.

Sample is prepared in duplicate with the presence of In-House Reference Material (GS/SND 2009).

8.2.4.

Each sample duplicates are measure in the presence of a In-House Reference Material (GS/SND 2009) Measurement of the Certified Reference Material (SGT8) is conducted at the end of the sample batch.

Test Method Reference:

TMM/XRF/SILICA

Determination of Silicon Dioxide (SiO2) in Silica Sand by X-Ray Fluorescence Spectrometry (XRFS)

9.0

Notes 9.1. The balance in use must be verified using internal calibration mode. Otherwise the calibration could be verified using an E2 type standard weight.

9.2.

Each batch of the fusion flux is checked for its spectrometric different. A conversion factor is determined by analyzing a series of In-House Reference Material (HRM-SND 2009) that is prepared using proposed procedure .

9.3.

Drift correction allows to apply a calibration perform on a given date to data measured subsequently. A drift check is conducted by measuring a verification glass called Herasil. If the intensity of the verification glass (Herasil) falls out of the proposed 2 value, a drift correction need to be performed by measuring a drift monitor (Ausmon).

Table 1.1 Verification Value of Herasil

SiO2 X + 2 Mean, X X - 2 709.70 709.60 709.50

Table 1.2 Verification Value of Ausmon

SiO2 X + 2 Mean, X X - 2 267.30 267.25 267.20

Test Method Reference:

TMM/XRF/SILICA

Determination of Silicon Dioxide (SiO2) in Silica Sand by X-Ray Fluorescence Spectrometry (XRFS)

9.4.

The Certified

Reference

Material

(SGT8)

and

In-House

Reference

Material

(GS/SND 2009) are to ensure that the sample preparation is conducted in a proper procedure. Any systematic error that is contributed during sample preparation is corrected by the In-House Reference Material (GS/SND 2009) (Refer Appendix D).

Table 1.3 Certified Value of the SGT8

SiO2 (%) X + 3 X + 2 Mean, X X - 2 X - 3 95.96 95.85 95.63 95.41 95.30

Table 1.4 Consensus Value of the SND 2009

SiO2 (%) X + 3 X + 2 Mean, X X - 2 X - 3 93.80 93.65 93.35 93.05 92.90

Test Method Reference:

TMM/XRF/SILICA

Determination of Silicon Dioxide (SiO2) in Silica Sand by X-Ray Fluorescence Spectrometry (XRFS)

Appendix A Fusion Parameter for the Preparation of Fused Glass Bead for the Determination of Silicon Dioxide (SiO2) in Silica Sand (Using Claisse M4 Fusion Machine)

Test Method Reference:

TMM/XRF/SILICA

Determination of Silicon Dioxide (SiO2) in Silica Sand by X-Ray Fluorescence Spectrometry (XRFS)

Appendix B List of Calibration Standard for the Determination of Silicon Dixoide (SiO 2) in Silica Sand

No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

Standards NIST SRM 165a GS/SND 99 SGT9 GS/SND 2002 NBS 267 SGT 8 NBS 102 GS/SND 2009 NIST SARM 1413 XRF- 4002 BCS 375/1 NIST SRM 70a GBW 03103 IPT 72 IPT 53 XRF-SOL 5a SY-3 NIST SRM 98b NIST SRM 97b JB-2 BCS CRM 348 NIST SRM 688 KK-1 JMG-Clay 2107 JMG-Clay 2207 NBS 697

Material Sand Silica Sand Glass Sand Silica Sand Glass Sand Glass Sand Glass Sand Silica Sand High Aluminium Sand Ryolite Feldspar Feldspar Kaolin Feldpar Feldpar Soil Syenite Plastic Clay Flint Clay Basalt Ball Clay Basalt Kaolin Clay Clay Bauxite

Test Method Reference:

TMM/XRF/SILICA

Determination of Silicon Dioxide (SiO2) in Silica Sand by X-Ray Fluorescence Spectrometry (XRFS)

Appendix C Measurement Parameter for the Determination of Silicon Dixoide(SiO 2) in Silica Sand Parameter Element Line Crystal Collimator Detector Voltage (kV) Ampere (mA) 2Th (Peak) Value Si K XS-55 0.23 Flow Counter 30 60 15.040

Test Method Reference:

TMM/XRF/SILICA

Determination of Silicon Dioxide (SiO2) in Silica Sand by X-Ray Fluorescence Spectrometry (XRFS)

Appendix D Consensus Value of In-House Reference Material (HRM) GS/SND 2009

Test Method Reference:

TMM/XRF/SILICA

10