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Thermally induced phase transformations of 12-tungstophosphoric acid 29-hydrate: synthesis and characterization of PW8O26-type bronzes

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Abstract

The phase transformations of 12-tungstophosphoric H3PW12O40-29H2O (29-WPA) acid in the temperature range from ambient temperature to 1150°C were investigated and characterized by differential thermal analysis (DTA), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), infrared (i.r.) and Raman spectroscopies. From room temperature to 550°C, 29-WPA passes through a dehydration process, which characterizes the formation of different crystallohydrates, in anhydrous form as well as “denuded” Keggin's anions, the D-phase (PW12O38). During these processes, Keggin's anions are not disturbed too much and they are preserved up to about 550°C. The “D” phase is transformed by solid-solid recrystallization at about 600°C in a new monophosphate bronze type compound PW8O26. Unit cell dimensions were calculated from XRPD data (a o=0.7515 nm). With the temperature increasing up to 1150°C, novel synthesized cubic bronze passed through three polymorphous phase transitions. According to a general formula for monophosphate tungsten bronzes (WO3)2m (PO4)4 all four polymorphs have m=16.

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Authors and Affiliations

  1. Faculty of Physical Chemistry, University of Belgrade, P.O.Box 137, 11001, Belgrade, Macedonia

    U. B. Mioč

  2. Faculty of Mining and Geology, Department of Crystallography, University of Belgrade, Djusina 7, 11000, Belgrade, Macedonia

    R. Ž. Dimitrijević

  3. The Institute of Nuclear Sciences “Vinča”, P.O.Box. 522, 11001, Belgrade, Macedonia

    M. Davidović

  4. Faculty of Physical Chemistry, University of Belgrade, P.O.Box 137, 11001, Belgrade, Macedonia

    Z. P. Nedić

  5. Faculty of Physics, University of Belgrade, P.O.Box. 550, 11001, Belgrade, Macedonia

    M. M. Mitrović

  6. Laboratoire de Spectrochimie Infrarouge et Raman, CNRS, 2 rue Henri Dunant, 94320, Thiais, France

    Ph. Colomban

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  1. U. B. Mioč
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  2. R. Ž. Dimitrijević
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  6. Ph. Colomban
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Mioč, U.B., Dimitrijević, R.Ž., Davidović, M. et al. Thermally induced phase transformations of 12-tungstophosphoric acid 29-hydrate: synthesis and characterization of PW8O26-type bronzes. JOURNAL OF MATERIALS SCIENCE 29, 3705–3718 (1994). https://doi.org/10.1007/BF00357338

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