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We report on temperature-dependent dielectric behavior of disordered ternary A6B2O17 (A = Zr, Hf; B = Nb, Ta)-form oxides in the GHz frequency range. The microwave dielectric properties including relative permittivity, dielectric loss, and temperature-dependent relative permittivity were characterized using cylindrical dielectric resonators using a resonant post measurement technique. Dielectric measurements through the resonant post method approach generally agree with dielectric measurements of A6B2O17 bulk ceramics measured through standard resonant post techniques. Coefficients describing the temperature-dependent relative permittivity for ternary A6B2O17 phases are strongly positive, suggesting contributions to polarizability arising from long-range mechanisms potentially associated with structural disorder. These observations support the working hypothesis that material functionality can be engineered by the chemical diversity and structural disorder possible in high configurational entropy A6B2O17 phases.
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Phase equilibria and metastability in the high-entropy A6B2O17 oxide family with A = Zr, Hf and B = Nb, Ta
The present work details experimental phase stabilization studies for the disordered, multi-cation A6B2O17 (A = Zr, Hf; B = Nb, Ta) system. We leverage both high-temperature in situ and ex situ X-ray diffraction to assess phase equilibrium and metastability in A6B2O17 ceramics produced via reactive sintering of stoichiometric as-received powders. We observe that the A6B2O17 phase can be stabilized for any stoichiometric combination of Group 4B and 5B transition metal cations (Zr, Nb, Hf, Ta), including ternary and quinary systems. The observed minimum stabilization temperatures for these phases are generally in agreement with prior calculations for each disordered A6B2O17 ternary permutation, offering further support for the inferred cation-disordered structure and suggesting that chemical disorder in this system is thermodynamically preferable. We also note that the quinary (Zr3Hf3)(NbTa)O17 phase exhibits enhanced solubility of refractory cations which is characteristic of other high-entropy oxides. Furthermore, A6B2O17 phases experience kinetic metastability, with the orthorhombic structure remaining stable following anneals at intermediate temperatures.
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- PAR ID:
- 10478826
- Publisher / Repository:
- Spring Link
- Date Published:
- Journal Name:
- Journal of Materials Science
- Volume:
- 58
- Issue:
- 14
- ISSN:
- 0022-2461
- Page Range / eLocation ID:
- 6164 to 6173
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract We report on the structure and dielectric properties of ternary A6B2O17(A = Zr; B = Nb, Ta) thin films and ceramics. Thin films are produced via sputter deposition from dense, phase‐homogenous bulk ceramic targets, which are synthesized through a reactive sintering process at 1500°C. Crystal structure, microstructure, chemistry, and dielectric properties are characterized by X‐ray diffraction and reflectivity, atomic force microscopy, X‐ray photoelectron spectroscopy, and capacitance analysis, respectively. We observe relative permittivities approaching 60 and loss tangents <1 × 10−2across the 103–105 Hz frequency range in the Zr6Nb2O17and Zr6Ta2O17phases. These observations create an opportunity space for this novel class of disordered oxide electroceramics.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1007/s10853-023-08396-5
