Citation
Tan, Kar Ban and Tan, P.Y. and Feng, Y. and Khaw, C.C. and Lim, T.Z. Alvin and Kechik, M.M.A. and Chen, S.K. and Chan, K.Y. and Lu, M. and Sun, J. and Zhou, D.
(2025)
Optimising bismuth magnesium niobate pyrochlores as potential ceramic dielectrics: Reaction progression, phase equilibria and impedance properties.
Ceramics International.
pp. 1-15.
ISSN 0272-8842;
Abstract
The phase-pure Bi2O3-MgO-M2O5 (BMN) cubic pyrochlores formed across a broad compositional range, with
bismuth content varying from 41.88 to 44.50 mol %. The quadrilateral subsolidus region is defined by two
substitution mechanisms: (i) Mg2+ substitution by Nb5+, balanced by oxygen stoichiometry variations and (ii)
one-to-one Bi3+ replacement by Nb5+, with charge compensation by O2− . This yields a general formula of
Bi3.36+xMg1.92-yNb2.72-x + yO13.76-x+(3/2)y, involving two variables with the corresponding subsolidus solution
limits of 0.10 ≤ x ≤ 0.20 and 0.00 ≤ y ≤ 0.16, respectively. Notably, these BMN pyrochlores exhibit high
dielectric constants, ε′ in the range of 167–204 at 30 ◦C, 1 MHz and low dielectric losses, tan δ in the order of
10− 4 - 10− 3
. The elevated dielectric constant is likely due to the enhanced polarisability of Nb2O5 within the
crucial BO6 octahedra of the pyrochlore structure. Furthermore, these pyrochlores display negative temperature
coefficients of permittivity, TCε’ ranging from − 528 to − 742 ppm/◦C at 30–300 ◦C and 1 MHz. These thermally
stable and highly insulating BMN pyrochlores with high activation energies, Ea >1.0 eV, are promising candidate
for potential application in ceramic capacitors.
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