XRF 1062

Quantitative Analysis of Soda-lime Glass with Supermini200 Introduction Glass is very common material used in various situa-tions with long historical roots. Soda-lime glass is con-sidered to be the first human made glass, and is still being used in many forms such as light bulbs for lamps, touch panels, LCD monitors, solar panels, insulators, tableware, containers, windows and mirrors. Although the basic component of glass is SiO2, elements such as Na2O and CaO are added to change the character-istics of the glass depending on the intended use. Ad-dition of different elements in certain quantities can change the physical and chemical properties such as melting point, moisture resistance and thermal expan-sion. Some trace elements can color glass. X-ray fluorescence (XRF) analysis quickly and easily offers precise elemental analysis results allowing con-trol of glass composition in the production process. This application note describes the excellent perfor-mance of Supermini200 for the analysis of soda-lime glass. Instrument The Supermini200 is a benchtop sequential wave-length dispersive XRF (WDXRF) spectrometer de-signed specifically to deliver excellent performance while eliminating conventional installation requirements such as cooling water, special power supply and large

floor space. By selecting the optional sealed propor-tional counter instead of the gas flow proportional counter, requirement of P10 gas can be eliminated as well, realizing a truly utility free WDXRF instrument. Featuring a unique air-cooled 200W X-ray tube, two detectors, up to three analyzing crystals with se-lectable vacuum or helium atmosphere, the Supermi-ni200 can analyze elements from oxygen to uranium. The Windows®-based software used to operate the Supermini200 shares the same platform running Rigaku’s popular high-power WDXRF ZSX family in-struments. This means that it has the same advanced algorithms, multiple language support and an intuitive user-friendly interface. Standards and Sample Preparation NIST glass disk standards were measured to set up calibrations. The glass samples were measured without sample preparation. Measurement and Calibration Measurements for nine elements SiO2, Na2O, CaO, MgO, SO3, Al2O3, Fe2O3, K2O and TiO2 were performed on the Supermini200. Measurement conditions are shown in Table 1.

Glass soda-lime glass matrix correction theoretical alpha

Benchtop wavelength dispersive X-ray fluorescence spectrometer Supermini200

Copyright Shandchem

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XRF 1062

Table 1 Measurement condition

Element Si Na Ca Mg S

Line Kα Kα Kα Kα Kα kV-mA 50-4.0 50-4.0 50-4.0 50-4.0 50-4.0

Primary Filter OUT OUT OUT OUT OUT Crystal PET RX25 PET RX25 PET

Detector F-PC F-PC SC F-PC F-PC Time (s) 40 40 40 40 40

Element Al Fe K Ti

Line Kα Kα Kα Kα kV-mA 50-4.0 50-4.0 50-4.0 50-4.0

Primary Filter OUT OUT OUT OUT Crystal PET LiF(200) PET LiF(200)

Detector F-PC SC F-PC SC Time (s) 40 40 40 40

The calibration curves were generated using the fol-lowing CRMs shown below: National Institute of Standards and Technology

(NIST) standards SRM 620, 621, 1830 and 1831 In order to extend the calibration range, NIST glass standards SRM 93a, 1411, and 1412 were added. Ma-trix (theoretical alpha) correction was applied to the components except for SiO2, Na2O, MgO and SO3. The correction coefficients were calculated by the funda-mental parameter (FP) method. The calibration curves are shown in Figure 1 and the calibration results are listed in Table 2. Table 2 Calibration results (unit : mass%)

Component Calibration range Accuracy

SiO2 58.04 - 80.8 0.68

Na2O 3.98 - 14.39 0.17

CaO 0.01 - 10.71 0.073

MgO 0.005 - 3.91 0.034

SO3 0.13 - 0.28 0.013

Al2O3 0.12 - 7.52 0.15

Fe2O3 0.031 - 0.121 0.0038

K2O 0.014 - 4.14 0.023

TiO2 0.011 - 0.02 0.00038

The accuracy of the calibration curves are calculated by the following equation:

Ci: calculated value of standard sample

iĈ : certified value of standard sample n: number of standard samples m: degree of freedom (linear : 2, quadratic : 3 )

Analysis Results Repeatability test for soda-lime glass was carried out and the result is shown in Table 3. The standard devia-tions for both major and minor components are very small. Conclusions The results show that high precision analysis of ele-ments in soda-lime glass can be performed using the benchtop WDXRF spectrometer Supermini200. The calibration curves obtained using the theoretical alpha corrections show good correlation for both major and trace components. Supermini200 is a benchtop spectrometer with a small footprint and is able to be operated with only a wall power outlet. Since Supermini200 is not site-specific, it has the great advantage that it can be installed any-where, and is therefore particularly matched for small laboratories and beside production area.

( )mn

CCAccuracy i

ii

−

−=∑

2ˆ

2

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Figure 1 Calibration curves of common components in soda-lime glass.

: before correction : corrected result : corrected result (uncertified) : certified

Accuracy = 0.68(mass%)

Accuracy = 0.17(mass%)

Accuracy = 0.073(mass%)

Accuracy = 0.034(mass%)

Accuracy = 0.013(mass%)

Accuracy = 0.15(mass%)

Accuracy = 0.0038(mass%

Accuracy = 0.023(mass%)

Accuracy = 0.00038(mass%

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Table 3 Repeatability test results for a soda-lime glass disk (unit : mass%) SiO2 Na2O CaO MgO SO3 Al2O3 Fe2O3 K2O TiO2 *

N=1 69.82 12.83 8.50 3.37 0.12 1.95 0.071 1.40 0.040

2 69.85 12.92 8.51 3.36 0.12 1.96 0.070 1.41 0.038

3 69.85 12.92 8.51 3.37 0.12 1.96 0.071 1.41 0.037

4 69.84 12.89 8.51 3.33 0.13 1.96 0.071 1.40 0.038

5 69.86 12.90 8.51 3.38 0.12 1.95 0.071 1.41 0.037

6 69.79 12.91 8.52 3.35 0.12 1.96 0.072 1.41 0.037

7 69.83 12.83 8.51 3.36 0.12 1.96 0.071 1.41 0.041

8 69.85 12.82 8.52 3.34 0.12 1.96 0.072 1.40 0.037

9 69.85 12.95 8.52 3.37 0.13 1.96 0.071 1.40 0.038

10 69.86 12.79 8.52 3.39 0.12 1.95 0.071 1.41 0.040

Average 69.84 12.87 8.51 3.36 0.12 1.96 0.071 1.41 0.038

Maximum 69.86 12.95 8.52 3.39 0.13 1.96 0.072 1.41 0.041

Minimum 69.79 12.79 8.50 3.33 0.12 1.95 0.070 1.40 0.037

Range 0.07 0.16 0.02 0.06 0.01 0.01 0.002 0.01 0.004

Standard deviation 0.021 0.054 0.007 0.018 0.002 0.004 0.001 0.004 0.001

RSD % 0.03 0.42 0.08 0.53 1.34 0.22 0.80 0.28 3.90

* : Quantitative results of TiO2 are out of calibration range.

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