HR: 08:45h
AN: GP21C-04 [Abstracts]
TI: The Verwey Transition Under Nonhydrostatic Stress
AU: * Coe, R S
EM: rcoe@es.ucsc.edu
AF: University of California, Earth Sciences Department and Institute of Geophysics and Planetary Physics,
Santa Cruz, CA 95064
United States
AB:
Because the Verwey transition in magnetite is a coherent, reversible transformation that is characterized by a change in
shape as well as volume, its thermodynamic phase boundary will be sensitive to nonhydrostatic stress. Synchrotron X-ray
diffraction experiments by Wright [2002] imply that, as the low-temperature structure forms, the lattice extends 0.31 percent
along a direction that departs by 3.7 degrees from the [111] cube diagonal and lies in the plane containing the monoclinic
c-axis and bisecting the a- and b-axes. The lattice also contracts by about 0.15 percent perpendicular to that direction in
the same plane and by about 0.12 percent perpendicular to that plane. Because these principal transformation strains involve
both extension and contraction, the volumetric strain is considerably smaller than any of the principal strains in absolute
value. Thus nonhydrostatic stress can have a larger effect on the Verwey transition temperature per GPa than hydrostatic
pressure. Using Shepherd et al.'s [1991] entropy of transition of -5.91 J/mol K, thermodynamic theory predicts changes in
the Vervey temperature of -23.3, 9.1, and 11.1 K/GPa for compression along each of the principal directions, respectively.
This compares with -3.2 K/GPa for hydrostatic pressure. Internal nonhydrostatic stresses due to impurities and dislocations,
as well as those generated by differential thermal contraction in igneous rocks, can be large, so their effect could be
significant. Whether nonhydrostatic stress contributes significantly to the scatter in observed Verwey temperatures remains
to be seen. One would think that as a crystal of cubic magnetite cools under nonhydrostatic stress, it would be transform to
the most favorable twin orientation of the low-temperature monoclinic phase (the twin with the highest calculated Verwey
temperature), unless physical constraints prevent it from doing so. In such case nonhydrostatic stress could only raise the
Verwey temperature.
DE: 3939 Physical thermodynamics
DE: 1540 Rock and mineral magnetism
SC: Geomagnetism and Paleomagnetism [GP]
MN: 2004 AGU Fall Meeting