Advanced

Bulk moduli and high-pressure crystal structures of minium, Pb3O4, determined by X-ray powder diffraction

Dinnebier, RE; Carlson, Stefan LU ; Hanfland, M and Jansen, M (2003) In American Mineralogist 88(7). p.996-1002
Abstract
We report the pressure dependence of the crystal structure of lead tetroxide (P less than or equal to 41.05 GPa, T 298 K) using high-resolution angle-dispersive X-ray powder diffraction. Pb3O4 shows two reversible phase transitions in the measured pressure range. The crystal structures of the modifications identified have in common frameworks of Pb+4O6 octahedra and irregular Pb+2O4+1 respectively Pb2+O6+1 polyhedra. At ambient conditions, Pb3O4 crystallizes in space group P4(2)/mbc (phase 1). Between 0.11 and 0.3 GPa it exhibits a displacive second order phase transition to a structure with space group Pbam (phase II). A second displacive phase transition occurs between 5.54 and 6.6 GPa to another structure with space group Pbam (phase... (More)
We report the pressure dependence of the crystal structure of lead tetroxide (P less than or equal to 41.05 GPa, T 298 K) using high-resolution angle-dispersive X-ray powder diffraction. Pb3O4 shows two reversible phase transitions in the measured pressure range. The crystal structures of the modifications identified have in common frameworks of Pb+4O6 octahedra and irregular Pb+2O4+1 respectively Pb2+O6+1 polyhedra. At ambient conditions, Pb3O4 crystallizes in space group P4(2)/mbc (phase 1). Between 0.11 and 0.3 GPa it exhibits a displacive second order phase transition to a structure with space group Pbam (phase II). A second displacive phase transition occurs between 5.54 and 6.6 GPa to another structure with space group Pbam (phase 111) but halved c dimension. A non-linear compression behavior over the entire pressure range is observed, which can be described by two Vinet relations in the ranges from 0.28 to 5.54 GPa and from 6.6 to 41.05 GPa. The extrapolated bulk moduli of the high-pressure phases were determined to be K-0 = 21(2) GPa for phase 11 and K-0 = 91(3) GPa for phase III. The crystal structures of all phases were refined from X-ray diffraction powder data collected at several pressures between 0.06 and 41.05 GPa. Except for their cell dimensions, phases I and 11 were found to be isostructural to the corresponding phases at low temperatures, whereas phase III can be derived from the Sr2PbO4 aristotype. With increasing pressure, the lone pair which is localized at Pb2+ adopts increasingly pure s-character, which is reflected by the similar coordination polyhedra of Ph2+ in Pb3O4 (phase 111) and of Sr2+ in Sr2PbO4. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
American Mineralogist
volume
88
issue
7
pages
996 - 1002
publisher
Mineralogical Society of America
external identifiers
  • wos:000184045300007
  • scopus:0041627448
ISSN
0003-004X
language
English
LU publication?
yes
id
42840e07-20ec-49ee-963a-576ac9691765 (old id 306904)
alternative location
http://www.minsocam.org/msa/AmMin/TOC/Articles_Free/2003/Dinnebier_p996-1002_03.pdf
date added to LUP
2007-08-29 12:12:31
date last changed
2018-01-07 09:14:30
@article{42840e07-20ec-49ee-963a-576ac9691765,
  abstract     = {We report the pressure dependence of the crystal structure of lead tetroxide (P less than or equal to 41.05 GPa, T 298 K) using high-resolution angle-dispersive X-ray powder diffraction. Pb3O4 shows two reversible phase transitions in the measured pressure range. The crystal structures of the modifications identified have in common frameworks of Pb+4O6 octahedra and irregular Pb+2O4+1 respectively Pb2+O6+1 polyhedra. At ambient conditions, Pb3O4 crystallizes in space group P4(2)/mbc (phase 1). Between 0.11 and 0.3 GPa it exhibits a displacive second order phase transition to a structure with space group Pbam (phase II). A second displacive phase transition occurs between 5.54 and 6.6 GPa to another structure with space group Pbam (phase 111) but halved c dimension. A non-linear compression behavior over the entire pressure range is observed, which can be described by two Vinet relations in the ranges from 0.28 to 5.54 GPa and from 6.6 to 41.05 GPa. The extrapolated bulk moduli of the high-pressure phases were determined to be K-0 = 21(2) GPa for phase 11 and K-0 = 91(3) GPa for phase III. The crystal structures of all phases were refined from X-ray diffraction powder data collected at several pressures between 0.06 and 41.05 GPa. Except for their cell dimensions, phases I and 11 were found to be isostructural to the corresponding phases at low temperatures, whereas phase III can be derived from the Sr2PbO4 aristotype. With increasing pressure, the lone pair which is localized at Pb2+ adopts increasingly pure s-character, which is reflected by the similar coordination polyhedra of Ph2+ in Pb3O4 (phase 111) and of Sr2+ in Sr2PbO4.},
  author       = {Dinnebier, RE and Carlson, Stefan and Hanfland, M and Jansen, M},
  issn         = {0003-004X},
  language     = {eng},
  number       = {7},
  pages        = {996--1002},
  publisher    = {Mineralogical Society of America},
  series       = {American Mineralogist},
  title        = {Bulk moduli and high-pressure crystal structures of minium, Pb3O4, determined by X-ray powder diffraction},
  volume       = {88},
  year         = {2003},
}