Bismuth-containing glassy reference materials for establishing the content of transition elements using luminescent-based methods

Modern express methods of analytical control are widely used for monitoring the quality of oxide materials. However, the possibilities of these methods are currently limited by the lack of versatile homogeneous reference materials (RMs). Such RMs can be produced most effectively by vitrification methods. In this connection, glassy RMs based on bismuthborate systems are of great interest. In the earlier research, bismuth-borate RMs were used for comparison purposes in determining the composition of complex oxide systems using the X-ray fluorescence method. This work considers issues associated with the synthesis and application of bismuth-borate glassy RMs for determining the content of transition elements in oxide compounds and mixtures using luminescence analysis. Luminescence analysis was used as a research method due to its high selectivity and low detection limits with respect to elemental impurities in controlled objects (usually constituting 1 · 10^–6–1 · 10^–4 wt %). Bismuth-borate glassy RMs are shown to be capable of luminescence under UV radiation in the visible range at the temperature of 77 K. It is established that the introduction of the oxides of transition and rare earth elements (REE) into the RM composition leads to the quenching of the exciton emission band in the glasses studied at 77 K, as well as to the appearance of bands typical of REE ion radiation both at 77 K and at 298 K. Glassy RMs doped with transitionelement oxides are found to quench the luminescence of both bismuth and REE ions at the temperature of 77 K. On the basis of the results obtained, procedures for determining the content of quenching elements in oxide materials have been developed. The metrological characteristics of these procedures have been evaluated.

1. Kutivitskij V. A., Borisova V. V., Mironova E. V., Maruf M. Development of the method of synthesis for polyfunctional vitreous samples on the basis of glassy flux in Bi2O3-B 2O3 system. Reference materials. 2015;4:34–45 (In Russ.).

2. GOST 8.531-2002. State system for ensuring the uniformity of measurements. Reference materials of composition of solid and disperse materials. Ways of homogeneity assessment. IPK Izdatelstvo standartov, Moscow, 2002, 12 p. (In Russ.).

3. R 50.2.031-2003. State system for ensuring the uniformity of measurements. Reference materials for the composition and properties of substances and materials. Procedure for assessing stability characteristics. IPK Izdatelstvo standartov, Moscow, 2003, 7 p. (In Russ.).

4. Pustovarov V. A. Rare-earth ion spectroscopy. Electronic publication. UrFU, Ekaterinburg. 2016. 69 p. https://www.stady.urfu.ru

5. Shulgin B. V., Polupanova T. I., Kruzhalov A. V. et al. Bismuth Orthogermanate. Sverdlovsk, Vneshtorgizdat, 1992, 170 p. (In Russ.).

6. Marfunin A. S. Spectroscopy, luminescence and radiation centers in minerals. Moscow, Nedra, 1985, 320 p. (In Russ.).

7. Kravchenko V. S. Chemical and materials science aspects of the studies of polycrystalline bismuth-based high-temperature superconductors. Russian Chemical Reviews, 2008;77(6): 585–614 (In Russ.).

8. Poluektov N. S. Spectroscopy in coordination and analytical chemistry. Kiev, Naukova Dumka, 1990, 119 p (In Russ.).

9. RMG 61–2010 Accuracy, trueness and precision measures of the procedures for quantitative chemical analysis. Methods of evaluation. Standartinform, Moscow, 2012, 58 p (In Russ.).