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Phase Stability and Properties of Superionic PbSnF4 as a Function of the Method of Preparation

Published online by Cambridge University Press:  15 February 2011

Raimondo Calandrino ,
Anthony Collin ,
Georges Denes ,
M. Cecilia Madamba  and
Juanita M. Parris
Raimondo Calandrino
Affiliation:
Laboratory of Solid State Chemistry and Mössbauer spectroscopy, Laboratories for Inorganic Materials, Department of Chemistry and Biochemistry, Concordia University, Montreal, Quebec, H3G 1M8, Canada, gdenes@vax2.concordia.ca
Anthony Collin
Affiliation:
Laboratory of Solid State Chemistry and Mössbauer spectroscopy, Laboratories for Inorganic Materials, Department of Chemistry and Biochemistry, Concordia University, Montreal, Quebec, H3G 1M8, Canada, gdenes@vax2.concordia.ca
Georges Denes
Affiliation:
Laboratory of Solid State Chemistry and Mössbauer spectroscopy, Laboratories for Inorganic Materials, Department of Chemistry and Biochemistry, Concordia University, Montreal, Quebec, H3G 1M8, Canada, gdenes@vax2.concordia.ca
M. Cecilia Madamba
Affiliation:
Laboratory of Solid State Chemistry and Mössbauer spectroscopy, Laboratories for Inorganic Materials, Department of Chemistry and Biochemistry, Concordia University, Montreal, Quebec, H3G 1M8, Canada, gdenes@vax2.concordia.ca
Juanita M. Parris
Affiliation:
Laboratory of Solid State Chemistry and Mössbauer spectroscopy, Laboratories for Inorganic Materials, Department of Chemistry and Biochemistry, Concordia University, Montreal, Quebec, H3G 1M8, Canada, gdenes@vax2.concordia.ca
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Abstract

Superionic PbSnF4 can be prepared using a variety of different methods. It crystallizes in various different unit-cells. All structures are closely related to that of the fluorite type structure, with various degrees of order/disorder and different types of superstructures. Reaction of lead(ll) nitrate and stannous fluoride in water gives highly stressed and highly oriented tetragonal α-PbSnF4, however, in HF/H2O, it gives orthorhombic O-PbSnF4, which is also stressed but less. Reactions of solid α-PbF2 with an aqueous solution of SnF2, in excess SnF2, also gives stressed α-PbSnF4. Solid state reactions of SnF2 and PbF2 give unstressed and much less oriented α-PbSnF4 at 250°C, whereas tetragonal β-PbSnF4 is obtained above 270°C and is quenchable to ambient temperature. At 390°C, cubicy-PbSnF4 is obtained, however, this is not quenchable. Ball milling of o-PbSnF4 gives stressed α-PbSnF4, and ball milling of a- and β-PbSnF4 gives microcrystalline γ-PbSnF4. Annealing the latter gives unstressed and non oriented α-PbSnF4. Stirring a slurry of microcrystalline γ-PbSnF4 in water gives α-PbSnF4 except the one originating from o-PbSnF4, which gives back o-PbSnF4. The texture of these phases, and therefore the macroscopic properties related to it, can be drastically modified by modifying the method of preparation.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 453: Symposium R – Solid State Chemistry of Inorganic Materials , 1996 , 585
Copyright
Copyright © Materials Research Society 1997

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References

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