DETERMINATION OF SILICON DIOXIDE (SIO2), FERRIC OXIDE (Fe2O3), TITANIUM

DIOXIDE (TiO2), CALCIUM OXIDE (CaO) AND MAGNESIUM OXIDE (MgO) IN SILICA
SAND BY X-RAY FLUORESCENCE SPECTROMETRY (XRFS)
In-house method by X-Ray Fluorescence Spectroscopy

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. Concentrations 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, ferric oxide,
calcium oxide, titanium dioxide, magnesium oxide in silica sand.

3.0 Apparatus

Nos. Apparatus Specification

3.1 Analytical Balance readability of 0.1 mg
3.2 Fusion Equipment
with a timer, capable of heating the sample and flux
or Furnace or Gas burners
to at least 1000oC and homogenizing the melt
3.3 Fusion Crucible Pt/Au, 95:5 % alloy, 30 to 35 ml capacity
Pt/Au, 95:5 % alloy, 30 to 35 ml capacity with a flat
3.4 Casting Dish
bottom 30 to 35 mm in diameter
3.5 Glass rod
3.6 WD-XRF Spectrometer

4.0 Reagents

Nos. Reagents Specification

Claisse Lithium Borate Pre- (49.75% Lithium Tetraborate : 49.75% Lithium
4.1
Fused Flux Metaborate : 0.5% Lithium Bromite)
Certified reference materials are available from the
4.2 Reference Materials National Institute for Standards and Technology
(NIST) and other international certification agencies
mixture of 90 % argon and 10 % methane for use with
4.3 Detector Gas
gas flow proportional counters

5.0 Procedure

5.1 Preparation of Fusion Glass Bead

Step Procedures
Weigh 0.6000g of the finely ground sample (to the nearest 0.0001g) into a crucible
5.1.1 platinum containing 6.0000g of Claisse Lithium Borate pre-fused flux. (Refer to WP-02
for sample preparation procedure) (Note 8.1 and 8.2)
Mix flux and sample properly using a glass rod, and wipe the glass rod to ensure
5.1.2
most of the sample and fluxs is transfer back to the platinum crucible
5.1.3 Place the crucible on the Claisse M4 fusion machine
Choose the fusion silicate ingredient / method and set up the fusion parameter
5.1.4
according to the sample decomposition requirement. (Appendix A)
 Fuse the sample and flux mixture according to fusion ingredient until a complete
5.1.5
decomposition of the sample
After a complete dissolution transfer the hot melt to a platinum dish / mould and let
5.1.6
the melt to cool and undergo crystallization
Keeps the bead in air tight sample cup inside a desiccators ensuring that a minimal
5.1.7
exposure with low relative humidity less than 15 for longer live spend of the bead

5.2 Measurement

5.2.1 Verification of Calibration (Drift Correction)

Step Procedures
Verify the calibration by measuring the verification glass (Herasil). The result of the
5.2.1.1
verification glass should be in the range of 2. (Refer Table 1.1)
If the result is not within the acceptable value (X - 2 / X + 2), measure drift monitor
5.2.1.2
(Ausmon) to correct the calibration drift
After the drift monitor measurement is completed, re-measure the verification glass
5.2.1.3
(Herasil) and compare the concentration obtained with the established concentration

5.2.2 Sample Measurement

Single Sample Measurement

Step Procedures
Sample is prepared in duplicate with the presence of In-House Reference Material
5.2.2.1
(GS/SND 2009)
The measurement of the sample duplicates are performed together with a In-House
5.2.2.2
Reference Material (GS/SND 2009) and Certified Reference Material (SGT8)

Sample Measurement in Batch

Step Procedures
Sample is prepared in duplicate with the presence of In-House Reference Material
5.2.2.3
(GS/SND 2009)
Each sample duplicates are measure in the presence of a In-House Reference
5.2.2.4 Material (GS/SND 2009) Measurement of the Certified Reference Material (SGT8)
is conducted at the end of the sample batch

6.0 Calibration

Step Calibration Protocol

Fuse a series of calibration standard that comprise of Certified Reference Material
6.1 (CRM) and In-House Reference Material (HRM) using above procedure (As in 5.0)
(Refer Appendix B)
6.2 Set up the instrument according to the Manufacturers Instruction Manual
Define the measurement parameters of the instrument to ensure repeatable
6.3
analyses. (Refer Appendix C and Appendix C)
6.4 Place the fuse glass bead onto an aluminium sample cup
Calibrate the instrument using the prepared fused glass bead of Certified Reference
Material (CRM) and In-House Reference Material (HRM). Establish the calibration
6.5
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

= ( ) + [1 + (ij Cj )] X 100 (Equation 1)

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

8.0 Notes

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

8.2 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 .

8.3 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 Fe2O3 K2O CaO MgO

X + 2 709.70 0.315 0.005 0.015 1.145
Mean, X 709.60 0.320 0.010 0.020 1.150
X - 2 709.50 0.325 0.015 0.025 1.155

Table 1.2 Verification Value of Ausmon

SiO2 Al2O3 Fe2O3 TiO2 K2O CaO MgO

X + 2 267.30 42.66 68.43 21.80 37.55 31.34 121.53
Mean, X 267.25 42.61 68.38 21.75 37.50 31.29 121.48
X - 2 267.20 42.56 68.33 21.70 37.45 31.24 121.43

8.4 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 Al2O3 Fe2O3 TiO2 K2O CaO MgO
(%) (%) (%) (%) (%) (%) (%)
X + 3 95.96 2.19 0.29 0.088 1.21 0.09 0.18
X + 2 95.85 2.15 0.28 0.083 1.16 0.08 0.16
Mean, X 95.63 2.07 0.26 0.073 1.06 0.06 0.12
X - 2 95.41 1.99 0.24 0.063 0.96 0.04 0.08
X - 3 95.30 1.95 0.23 0.058 0.91 0.03 0.06
Table 1.4 Consensus Value of SND 2009
SiO2 Fe2O3 TiO2 CaO MgO
(%) (%) (%) (%) (%)
X + 3 94.322 0.575 0.688 0.245 0.142
X + 2 93.998 0.563 0.644 0.222 0.136
Mean, X 93.348 0.537 0.557 0.178 0.124
X - 2 92.698 0.512 0.469 0.134 0.112
X - 3 92.374 0.499 0.425 0.112 0.106

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)
Appendix B List of Calibration Standard for the Determination of Silicon Dioxide (SiO2),
Ferric Oxide (Fe2O3),Titanium Dioxide (TiO2), Calcium Oxide (CaO) and Magnesium Oxide
(MgO) in Silica Sand

No Standards Material
1 NIST SRM 165a Sand
2 GS/SND 99 Silica Sand
3 SGT9 Glass Sand
4 GS/SND 2002 Silica Sand
5 NBS 267 Glass Sand
6 SGT 8 Glass Sand
7 NBS 102 Glass Sand
8 GS/SND 2009 Silica Sand
9 NIST SARM 1413 High Aluminium Sand
10 XRF- 4002 Ryolite
11 BCS 375/1 Feldspar
12 NIST SRM 70a Feldspar
13 GBW 03103 Kaolin
14 IPT 72 Feldpar
15 IPT 53 Feldpar
16 XRF-SOL 5a Soil
17 SY-3 Syenite
18 NIST SRM 98b Plastic Clay
19 NIST SRM 97b Flint Clay
20 JB-2 Basalt
21 BCS CRM 348 Ball Clay
22 NIST SRM 688 Basalt
23 KK-1 Kaolin
24 JMG-Clay 2107 Clay
25 JMG-Clay 2207 Clay
26 NBS 697 Bauxite
 Appendix C Measurement Parameter

Determination of Silicon Dioxide (SiO2)

Determination of Silicon Dioxide(SiO2)

Parameter Value
Element Si
Line Si KA1 HR - Min Si KA1 Maj
Crystal XS-55 XS-CEM
Collimator 0.23 0.23
Mask (mm) 28 28
Diffraction Crystal XS-55 XS-CEM
Gas Filled Flow
Detector Gas Filled Flow Counter
Counter
Tube Power (KVA/KW) 1.8 1.8
Estimated Current (mA) 60 60
Estimated Voltage (kV) 30 30
Analyze Layer / Penetration (m) 21.80.15 21.80.15
Calibration Information
Peak Position (2Th) 15.040 29.934
Peak Time (Sec) 260.0 22.0
Lower Background Position (2Th) None 27.625
Upper Background Position (2Th) None 32.213
Background Time (Sec) 246.0 22.0
Number of Standards 23 36
Squared Correlation Coefficient
0.999970 0.999991
(R2)
Slope (%/Kcps) 0.7356 2.77
Sensitivity (%/Kcps) 1.350 0.361
Absorption Correction Variable Alpha Variable Alpha
Drift Correction
Drift Monitor Ausmon Ausmon
Nett Peak Intensity
240.00.35 60.90.8
(kcp/sec)
Estimated Peak Intensity
240.7
(kcp/sec)
Nett Background (kcp/sec) 3.680
Raw Background Intensity
3.6600.10 0.3250.15
(kcp/sec)
Calculated Lower Limit of
35 281.7
Detection (ppm)
 Determination of Ferric Oxide (Fe2O3)

Determination of Ferric Oxide(Fe2O3)

Parameter Value
Element Fe
Line Fe KA1 ALT - Min Fe KA1 HR - Min
Crystal LiF220 LiF200
Collimator 0.23 0.23
Mask (mm) 28 28
Detector Scintillation Counter Scintillation Counter
Diffraction Crystal LiF220 LiF200
Tube Power (KVA/KW) 3.6 3.6
Estimated Current (mA) 60 60
Estimated Voltage (kV) 60 60
Analyze Layer / Penetration (mm) 0.7770.1 0.7770.1
Calibration Information
Peak Position (2Th) 85.736 57.552
Peak Time (Sec) 46.0 95.0
Lower Background Position (2Th) 83.371 55.218
Upper Background Position (2Th) 87.769 58.968
Background Time (Sec) 5.0 8.0
Number of Standards 36 37
Squared Correlation Coefficient
0.999998 0.999997
(R2)
Slope (%/Kcps) 0.6001 0.2004
Sensitivity (%/Kcps) 1.666 4.989
Absorption Correction Variable Alpha Variable Alpha
Drift Correction
Drift Monitor Ausmon Ausmon
Nett Peak Intensity
240.00.35 60.90.8
(kcp/sec)
Raw Background Intensity
3.6600.10 0.3250.15
(kcp/sec)
Calculated Lower Limit of
35 281.7
Detection (ppm)
 Determination of Calcium Oxide (CaO)

Determination of Calcium Oxide (CaO)

Parameter Value
Element Ca
Line Ca KA1 HR - Min
Crystal LiF200
Collimator 0.23
Mask (mm) 28
Detector Gas Filled Flow Counter
Diffraction Crystal LiF200
Tube Power (KVA) 1.253
Estimated Current (mA) 36
Estimated Voltage (kV) 5.0
Analyze Layer / Penetration (m) 82 0.5
Calibration Information
Peak Position (2Th) 113.14
Peak Time (Sec) 36.0
Lower Background Position (2Th) 110.642
Upper Background Position (2Th) 115.678
Background Time (Sec) 5.0
Number of Standards 38
Squared Correlation Coefficient (R2) 0.999996
Slope (%/Kcps) 0.6886
Sensitivity (%/Kcps) 1.452
Absorption Correction Variable Alpha
Drift Correction
Drift Monitor Ausmon
Nett Peak Intensity
31.2 0.2
(kcp/sec)
Estimated Peak Intensity (kcp/sec) 26.20 0.2
Calculated Lower Limit of Detection
3.29
(ppm)
 Determination of Magnesium Oxide (MgO)

Determination of Magnesium Oxide (MgO)

Parameter Value
Element Mg
Line Mg KA1 HR - Min
Crystal XS 55
Collimator 0.23
Mask (mm) 28
Detector Gas Filled Flow Counter
Tube Power (KVA) 3.78
Estimated Current (mA) 140
Estimated Voltage (kV) 27
Analyze Layer / Penetration (m) 9.1 0.5
Calibration Information
Peak Position (2Th) 20.804
Peak Time (Sec) 173
Lower Background Position (2Th) 27.210
Upper Background Position (2Th) None
Background Time (Sec) 30.0
Number of Standards 38
Squared Correlation Coefficient (R2) 0.999997
Slope (%/Kcps) 0.3561
Sensitivity (%/Kcps) 2.808
Absorption Correction Variable Alpha
Drift Correction
Drift Monitor Ausmon
Nett Peak Intensity
31.2 0.2
(kcp/sec)
Estimated Peak Intensity (kcp/sec) 26.20 0.2
Calculated Lower Limit of Detection
3.29
(ppm)
 Determination of Titanium Oxide (TiO2) in Silica Sand

Determination of Titanium Oxide (TiO2)

Parameter Value
Element Ti
Line Ti KA1 HR - Min
Crystal LiF200
Collimator 0.23
Mask (mm) 28
Detector Gas Filled Flow Counter
Tube Power (KVA) 3
Estimated Current (mA) 60
Estimated Voltage (kV) 50
Analyze Layer / Penetration (m) 9.1 0.5
Calibration Information
Peak Position (2Th) 86.19
Peak Time (Sec) 118.0
Lower Background Position (2Th) 84.747
Upper Background Position (2Th) 88.391
Background Time (Sec) 30.0
Number of Standards 30
Squared Correlation Coefficient (R2) 0.999996
Slope (%/Kcps) 0.7301
Sensitivity (%/Kcps) 1.37
Absorption Correction Variable Alpha
Drift Correction
Drift Monitor Ausmon
Nett Peak Intensity
31.2 0.2
(kcp/sec)
Estimated Peak Intensity (kcp/sec) 26.20 0.2
Calculated Lower Limit of Detection
3.29
(ppm)
Appendix D Consensus Value of In-House Reference Material (HRM) GS/SND 2009

LOI SiO2 Fe2O3 TiO2 CaO MgO

(%) (%) (%) (%) (%) (%)
1 0.860 93.170 0.523 0.595 0.156 0.119
2 0.850 93.660 0.538 0.541 0.162 0.130
3 0.880 93.220 0.542 0.525 0.161 0.131
4 0.880 93.250 0.525 0.544 0.152 0.123
5 0.950 93.290 0.529 0.548 0.161 0.128
6 0.870 92.990 0.539 0.557 0.172 0.126
7 0.890 92.880 0.556 0.549 0.163 0.120
8 0.870 92.910 0.559 0.573 0.163 0.123
9 0.870 93.320 0.535 0.563 0.160 0.126
10 0.890 93.220 0.553 0.548 0.169 0.123
11 0.870 93.840 0.523 0.614 0.186 0.126
12 0.880 93.830 0.510 0.528 0.186 0.129
13 0.910 93.680 0.524 0.554 0.194 0.131
14 0.890 93.890 0.539 0.611 0.169 0.123
15 0.910 93.740 0.537 0.601 0.170 0.121
16 0.900 93.360 0.536 0.577 0.176 0.104
17 0.910 93.370 0.545 0.513 0.220 0.125
18 0.900 93.180 0.542 0.417 0.219 0.125
19 0.890 93.000 0.556 0.585 0.214 0.125
20 0.900 93.160 0.535 0.588 0.212 0.122

MEAN, 0.889 93.348 0.537 0.557 0.178 0.124

n-1 0.022 0.325 0.013 0.044 0.022 0.006
2n-1 0.044 0.650 0.025 0.088 0.044 0.012
3n-1 0.066 0.974 0.038 0.131 0.066 0.018

+2n-1 0.932 93.998 0.563 0.644 0.222 0.136

-2n-1 0.845 92.698 0.512 0.469 0.134 0.112

+3n-1 0.954 94.322 0.575 0.688 0.245 0.142

-3n-1 0.823 92.374 0.499 0.425 0.112 0.106