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Thermal Behavior of M +B5O6(OH)4 · 2H2O (M + = K, Rb, Cs) and Polymorphic Transformations of CsB5O8

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Abstract

Phase transformations (dehydration, amorphization, crystallization, polymorphic transitions) and thermal expansion of M +B5O6(OH)4 · 2H2O (M + = K, Rb, Cs) compounds and the polymorphic transformations of the CsB5O8 compound are investigated using the methods of glass crystallization, thermal X-ray diffraction, and differential thermal analysis (DTA). It is shown that the dehydration of RbB5O6(OH)4 · 2H2O and CsB5O6(OH)4 · 2H2O, like KB5O6(OH)4 · 2H2O, proceeds in two stages. After the first stage of the dehydration (with a loss of three water molecules), all three compounds transform into the amorphous state. At the second stage, the fourth water molecule leaves the amorphous phase. At temperatures above the glass transition point, anhydrous pentaborates MB5O8 (M = K, Rb, Cs) crystallize and subsequently undergo polymorphic transformations.

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REFERENCES

  1. Wu, Y., Sasaki, T., Nakai, S., Yokotani, A., Tang, H., and Chen, C., CsB 3 O 5: A New Nonlinear Optical Crystal, Appl. Phys. Lett., 1993, vol. 62, pp. 2614-2615.

    Google Scholar 

  2. Lin, S., Sun, Z., Wu, B., and Chen, C., The Nonlinear Optical Characteristics of a LiB 3 O 5 Crystal, J. Appl. Phys., 1990, vol. 67, no. 2, pp. 634-638.

    Google Scholar 

  3. Chen, C., Wu, B., Jiang, A., and You, G., A New-Type Ultraviolet SHG Crystal-??-BaB 2 O 4, Sci. China, 1985, vol. 28, pp. 235-243.

    Google Scholar 

  4. Ramachandra Raja, C., Gobinathan, R., and Gna-nam, F.D., Growth and Characterization of Potassium Pentaborate Single Crystals, Cryst. Res. Technol., 1993, vol. 28, no. 4, pp. 453-456.

    Google Scholar 

  5. Becker, P., Held, P., and Bohaty, L., Crystal Growth and Optical Properties of the Polar Hydrated Pentaborates RbB 5 O 6 (OH)4 · 2H 2 O and NH 4 B 5 O 6 (OH)4 · 2H 2 O and Structure Redetermination of the Ammonium Com-pound, Cryst. Res. Technol., 2000, vol. 35, nos. 11-12, pp. 1251-1262.

    Google Scholar 

  6. Rajasekar, S.A., Thamizharasan, K., Joseph Arul Pra-gasam, A., Packiam Julius, J., and Sagayaraj, P., Growth and Characterization of Pure and Doped Potassium Pen-taborate (KB5) Single Crystals, J. Cryst. Growth, 2003, vol. 247, pp. 199-206.

    Google Scholar 

  7. Ramachandra Raja, C., Gobinathan, R., and Gna-nam, F.D., Dielectric Properties of Beta Barium Borate and Potassium Pentaborate Single Crystals, Cryst. Res. Technol., 1993, vol. 28, pp. 737-743.

    Google Scholar 

  8. Krogh-Moe, J., The Crystal Structure of the High-Tem-perature Modification of Potassium Pentaborate, Acta Crystallogr., Sect. B.: Struct. Crystallogr. Cryst. Chem., 1972, vol. 28, no. 1, pp. 168-172.

    Google Scholar 

  9. Krogh-Moe, J., Least-Squares Refinement of the Crystal Structure of Potassium Pentaborate, Acta Crystallogr., 1965, vol. 18, pp. 1088-1089.

    Google Scholar 

  10. Krzhizhanovskaya, M.G., Bubnova R.S., Filatov S.K., Belger, A., and Paufler, P., Crystal Structure and Thermal Expansion of ??-RbB 5 O 8 from Powder Diffraction Data, Z. Kristallogr., 2000, vol. 215, pp. 740-743.

    Google Scholar 

  11. Penin, N., Seguin, L., Touboul, M., and Novogrocki, G., Crystal Structures of Three MB 5 O 8 (M = Cs, Rb) Borates ?-CsB 5 O 8, ??-CsB 5 O 8, and ??-CsB 5 O 8 ), J. Solid State Chem., 2001, vol. 161, pp. 205-213.

    Google Scholar 

  12. Bubnova, R.S., Fundamensky, V.S., Anderson, Yu.E., and Filatov, S.K., Determination of the Crystal Structure and Thermal Expansion of the High-Temperature Modi-fication á?-CsB 5 O 8, in Tezisy dokladov II Natsional'noi konferentsii po primeneniyu rentgenovskogo, sinkhron-nogo izluchenii neitronov i elektronov dlya issledovaniya materialov (RSNE-99) (Abstracts of Papers of II Natio-nal Conference on Applications of X-ray Synchronous Radiation of Neutrons and Electrons to Investigations of Materials), Moscow: Institute of Crystallography, Rus-sian Academy of Sciences, 1999, p. 62.

  13. Bubnova, R.S., Fundamensky, V.S., Anderson, J.E., and Filatov, S.K., New Layered Polyanion in-CsB 5 O 8 High-Temperature Modification, Solid State Sci., 2002, vol. 4, pp. 87-91.

    Google Scholar 

  14. Touboul, M. and Nowogrocki, G.J., Dehydration Process of TlB 5 O 6 (OH)4 2H 2 O and Crystal Structure of TlB 5 O 8, J. Solid State Chem., 1998, vol. 136, pp. 216-220.

    Google Scholar 

  15. Wiesch, A. and Bluhm, K., Ag 2 Cs[B 15 O 24 ]: Ein wasserfreies quaternäres Silber(I)-Borat mit einem neu-artigen Boratanion mit helixartigem Aufbau, Z. Natur-forsch., B: Chem. Sci., 1998, vol. 53, pp. 157-160.

    Google Scholar 

  16. Touboul, M., Bertourne, E., and Seguin, L., Crystal Structure of LiB 5 O 8 · 5H 2 O, Mater. Sci. Forum, 1996, vol. 228, pp. 741-746.

    Google Scholar 

  17. Timper, K., Heller, G., and Shakibaie-Moghadam, M., Sborgit und ??-Sborgit-Eine zweite synthetishe Modifi-cation von Na[B 5 O 6 (OH)4 ] · 3H 2 O, Z. Naturforsch., B: Chem. Sci., 1990, vol. 45, pp. 1155-1166.

    Google Scholar 

  18. Zachariasen, W.H. and Plettinger, H.A., Refinement of the Structure of Potassium Pentaborate Tetrahydrate, Acta Crystallogr., 1963, vol. 16, pp. 376-379.

    Google Scholar 

  19. Behm, H., Rubidium Pentaborate Tetrahydrate, Rb[B 5 O 6 (OH)4 ] · 2H 2 O, Acta Crystallogr., Sect. C: Cryst. Struct. Commun., 1984, vol. 40, pp. 217-220.

    Google Scholar 

  20. Woller, K.-H. and Heller, G., Die Struktur von Tl[B 5 O 6 (OH)4 ] · 2H 2 O, Z. Kristallogr., 1981, vol. 156, pp. 159-166.

    Google Scholar 

  21. Behm, H., Structure Determination on a Twinned Crystal of Cesium Pentaborate Tetrahydrate, Cs[B 5 O 6 (OH)4 ] · 2H 2 O, Acta Crystallogr., Sect. C: Cryst. Struct. Com-mun., 1984, vol. 40, pp. 1114-1116.

    Google Scholar 

  22. Penin, N., Seguin, L., Gerand, B., Touboul, M., and Novogrocki, G., Crystal Structure of a New Form of Cs[B 5 O 6 (OH)4 ] · 2H 2 O and Thermal Behavior of M[B 5 O 6 (OH)4 ] · 2H 2 O (M = K, Rb, Cs), J. Alloys Compd., 2002, vol. 334, pp. 97-109.

    Google Scholar 

  23. Bubnova, R.S., Polyakova, I.G., Anderson, Yu.E., and Filatov, S.K., Polymorphism and Thermal Expansion of the MB 5 O 8 Crystalline Modifications (M = K, Rb) in Relation to Glass Transition of Their Melts, Fiz. Khim. Stekla, 1999, vol. 25, no. 2, pp. 242-255 [Glass Phys. Chem. (Engl. transl.), 1999, vol. 25, no. 2, pp. 183-194].

    Google Scholar 

  24. Anderson, Yu.E., Bubnova, R.S., Polyakova, I.G., and Filatov, S.K., Polymorphic Transformations of CsB 5 O 8, in Materialy mezhdunarodnoi konferentsii "Kristallo-genezis i Mineralogiya" (Proceedings of the Interna-tional Conference "Crystallogenesis and Mineralogy"), St. Petersburg, 2001, p. 17.

  25. Rollet, A.-P., Sur les borates de potassium: Etude du sys-teme K 2 O-B 2 O 3, C. R. Acad. Sci., 1935, vol. 200, no. 21, pp. 1763-1765.

    Google Scholar 

  26. Rollet, A.-P. and Kocher, J., Le systeme binaire oxyde de rubidium-anhydride borique, C. R. Acad. Sci., 1964, vol.259, no. 25, pp. 4692-4695.

    Google Scholar 

  27. Toledano, P., Contribution a l'etude radiocristal-lographique de quelques de potassium et de rubidium, Bull. Soc. Chim. France, 1966, no. 7, pp. 2302-2309.

  28. Dimitriev, J.V., Marinov, M.R., and Stevrakeva, D.A., Phasengleiichgewicht und glasbilding im system Rb 2 O-B 2 O 3, C. R. Acad. Bulg. Sci., 1966, vol. 11, no. 11, pp.1055-1058.

  29. Kocher, J., Etude des borates de rubdium et de cesium, Rev. Chim. Miner., 1966, vol. 3, pp. 209-257.

    Google Scholar 

  30. Kocher, J., Contribution a l'etude radiocristallographique de quelques de rubidium et de cesium, Bull. Soc. Chim. France, 1968, no. 3, pp. 919-924.

  31. Polyakova, I.G. and Tokareva, E.V., A Study of Phase Equilibria in the Potassium Borate System: Glass Crys-tallization and Solid State Reaction, Fiz. Khim. Stekla, 1997, vol. 23, no. 5, pp. 506-523 [Glass Phys. Chem. (Engl. transl.), 1997, vol. 23, no. 5, pp. 354-367].

    Google Scholar 

  32. Bubnova, R.S., Polyakova, I.G., Filatov, S.K., and Krzhizhanovskaya, M.G., Crystal Structure and Thermal Behavior of Rubidium Borates, in Proceedings of II International Conference on Borate Glasses, Crystals, and Melts, Wright, A.C., Feller, S.A., and Hannon, A.C., Eds., Sheffield: The Society of Glass Technology, 1997, pp. 120-127.

  33. Filatov, S.K., Vysokotemperaturnaya kristallokhimiya (High-Temperature Crystal Chemistry), Leningrad: Nedra, 1990.

    Google Scholar 

  34. Inorganic Crystal Structure Database (ICSD), Gaithers-burg: National Institute of Standards and Technology, 2001.

  35. Touboul, M. and Betourne, E., Dehydration Process of Lithium Borates, Solid State Ionics, 1996, vol. 84, pp.189-197.

    Google Scholar 

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Anderson, Y.E., Filatov, S.K., Polyakova, I.G. et al. Thermal Behavior of M +B5O6(OH)4 · 2H2O (M + = K, Rb, Cs) and Polymorphic Transformations of CsB5O8 . Glass Physics and Chemistry 30, 450–460 (2004). https://doi.org/10.1023/B:GPAC.0000045927.07697.c6

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