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Phase Transitions in Lead(II) Fluoride Upon Milling

Published online by Cambridge University Press:  10 February 2011

Georges DÉnÉ
Affiliation:
Department of Chemistry and Biochemistry, Laboratory of Solid State Chemistry and Mössbauer Spectroscopy, Laboratories for Inorganic Materials, Concordia University, Montreal, Qudbec, H3G 1M8, Canada, gdenes@vax2.concordia.ca
M. Cecilia Madamba
Affiliation:
Department of Chemistry and Biochemistry, Laboratory of Solid State Chemistry and Mössbauer Spectroscopy, Laboratories for Inorganic Materials, Concordia University, Montreal, Qudbec, H3G 1M8, Canada, gdenes@vax2.concordia.ca
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Abstract

PbF2 is known to exist under two different polymorphic structures. Orthorhombic α-PbF 2 is stable at ambient temperature. It has the PbC12 structure. Cubic β-PbF2 is obtained by heating α-PbF2. It does not transform back to α-PbF2 on cooling, and it seems to be infinitely stable in the metastable state under ambient conditions. β-PbF2 crystallizes in the fluorite (CaF2) type. Owing to the large number of potential interstitial sites, many F- Frenkel defects can be formed, which make β-PbF2 the highest performance fluoride ion conductor among binary fluorides. In this work, both phases of PbF2 have been ball milled. Milling α-PbF2 results in a partial transformation to microcrystalline β-PbF2. The energy required for obtaining the high temperature phase is probably provided in the mechanical form. Milling β-PbF2 leads to partial amorphization and formation of α-PbF2. In this case, milling transforms the high temperature polymorph to the low temperature form, by providing the energy required to overcome the activation energy that keeps PbF2 trapped in the high temperature β-form after cooling.

Type
Research Article
Copyright
Copyright © Materials Research Society 1998

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References

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