Jm. Amarilla et al., POLYMORPHISM, PHASE-TRANSFORMATIONS, AND OXIDE-ION CONDUCTIVITY IN BI1.56U0.22LA0.22O3.33, Chemistry of materials, 10(2), 1998, pp. 574-580
This paper deals with the polymorphism, phase transitions, and the oxi
de ion conduction of Bi1.56U0.22La0.22O3.33. Thermal treatment at 950
degrees C of a mixture of alpha-Bi2O3 and LaUO4+x, followed by slow co
oling to room-temperature, yields a hexagonal phase of that compositio
n with cell parameters a(H) = 4.0066(7) and c(H) = 9.543(2) Angstrom.
Quenching of the reaction mixture from 950 degrees C leads to the form
ation of a cubic fluorite-type phase with a(c) = 5.6273(8) Angstrom. A
nnealing of both cubic and hexagonal phases at 600 degrees C for 500 h
yields a new polymorph that is indexed with a monoclinic lattice, the
cell parameters being a(M) = 7.778(3), b(M) = 7.834(4), c(M) = 5.763(
3) Angstrom, and beta = 89.71(2)Angstrom. Phase transitions experience
d by each polymorph with temperature are followed by high-temperature
X-ray powder diffraction. The three phases are transformed into a new
C cubic phase at temperatures above 820 degrees C. The oxide ion cond
uction exhibited by each Bi1.56U0.22La0.22O3.33 polymorph is rather di
fferent. At 300 degrees C the cubic phase, which is the best conductin
g one, shows a value of sigma = 7.2 x 10(-5) S cm(-1), the conductivit
y of the hexagonal phase is 2.5 x 10(-5) S cm(-1), and the monoclinic
phase shows the lowest conductivity, 6.6 x 10(-7) S cm(-1). The plot o
f conductivity vs inverse temperature shows a linear dependence for ea
ch phase. The nonlinear dependencies also observed in the conductivity
plots are related to structural transformations taking place during t
hermal treatments.