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1. Phase equilibria and metastability in the high-entropy A6B2O17 oxide family with A = Zr, Hf and B = Nb, Ta

   https://doi.org/10.1007/s10853-023-08396-5  

   Jackson Spurling, R. ; Skidmore, Chloe ; McIlwaine, Nathaniel S. ; Maria, Jon-Paul ( April 2023 , Journal of Materials Science)

   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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2. Enhanced Piezoelectric, Ferroelectric, and Electrostrictive Properties of Lead‐Free (1‐ x )BCZT‐( x )BCST Electroceramics with Energy Harvesting Capability

   https://doi.org/10.1002/smll.202300549  

   Baraskar, Bharat G. ; Kolekar, Yesappa D. ; Thombare, Balu. R. ; James, Ajit. R. ; Kambale, Rahul C. ; Ramana, C. V. ( May 2023 , Small)

   Next‐generation electronics and energy technologies can now be developed as a result of the design, discovery, and development of novel, environmental friendly lead (Pb)‐free ferroelectric materials with improved characteristics and performance. However, there have only been a few reports of such complex materials’ design with multi‐phase interfacial chemistry, which can facilitate enhanced properties and performance. In this context, herein, novel lead‐free piezoelectric materials (1‐x)Ba_0.95Ca_0.05Ti_0.95Zr_0.05O₃‐(x)Ba_0.95Ca_0.05Ti_0.95Sn_0.05O₃, are reported, which are represented as (1‐x)BCZT‐(x)BCST, with demonstrated excellent properties and energy harvesting performance. The (1‐x)BCZT‐(x)BCST materials are synthesized by high‐temperature solid‐state ceramic reaction method by varyingxin the full range (x= 0.00–1.00). In‐depth exploration research is performed on the structural, dielectric, ferroelectric, and electro‐mechanical properties of (1‐x)BCZT‐(x)BCST ceramics. The formation of perovskite structure for all ceramics without the presence of any impurity phases is confirmed by X‐ray diffraction (XRD) analyses, which also reveals that the Ca²⁺, Zr⁴⁺, and Sn⁴⁺are well dispersed within the BaTiO₃lattice. For all (1‐x)BCZT‐(x)BCST ceramics, thorough investigation of phase formation and phase‐stability using XRD, Rietveld refinement, Raman spectroscopy, high‐resolution transmission electron microscopy (HRTEM), and temperature‐dependent dielectric measurements provide conclusive evidence for the coexistence of orthorhombic + tetragonal (Amm2+P4mm) phases at room temperature. The steady transition ofAmm2crystal symmetry toP4mmcrystal symmetry with increasingxcontent is also demonstrated by Rietveld refinement data and related analyses. The phase transition temperatures, rhombohedral‐orthorhombic (T_R‐O), orthorhombic‐ tetragonal (T_O‐T), and tetragonal‐cubic (T_C), gradually shift toward lower temperature with increasingxcontent. For (1‐x)BCZT‐(x)BCST ceramics, significantly improved dielectric and ferroelectric properties are observed, including relatively high dielectric constantε_r≈ 1900–3300 (near room temperature),ε_r≈ 8800–12 900 (near Curie temperature), dielectric loss, tanδ≈ 0.01–0.02, remanent polarizationP_r≈ 9.4–14 µC cm⁻², coercive electric fieldE_c≈ 2.5–3.6 kV cm⁻¹. Further, high electric field‐induced strainS≈ 0.12–0.175%, piezoelectric charge coefficientd₃₃≈ 296–360 pC N⁻¹, converse piezoelectric coefficient ≈ 240–340 pm V⁻¹, planar electromechanical coupling coefficientk_p≈ 0.34–0.45, and electrostrictive coefficient (Q₃₃)_avg≈ 0.026–0.038 m⁴C⁻²are attained. Output performance with respect to mechanical energy demonstrates that the (0.6)BCZT‐(0.4)BCST composition (x= 0.4) displays better efficiency for generating electrical energy and, thus, the synthesized lead‐free piezoelectric (1‐x)BCZT‐(x)BCST samples are suitable for energy harvesting applications. The results and analyses point to the outcome that the (1‐x)BCZT‐(x)BCST ceramics as a potentially strong contender within the family of Pb‐free piezoelectric materials for future electronics and energy harvesting device technologies.

    

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3. High‐entropy transparent ceramics: Review of potential candidates and recently studied cases

   https://doi.org/10.1111/ijac.13856  

   Zhang, Guangran ; Wu, Yiquan ( August 2021 , International Journal of Applied Ceramic Technology)

   High‐entropy ceramics have been widely explored and extensively studied since the first demonstration of the configuration entropy stabilized reversible transitions between multiple and single phases by Rost et al. in 2015. Most of the current research on high‐entropy ceramics has focused on properties like thermal conductivity, thermoelectricity, structures, and others. Some recent studies have extended the high‐entropy concept to the field of transparent ceramics. We reviewed these papers and proposed four potential ceramics groups for high‐entropy transparent ceramics including fluoride ceramics, fluorite‐deficient and/or ordered pyrochlore A₂B₂O₇ceramics, garnet ceramics, and sesquioxide ceramics. In this article, we review ceramic powder synthesis, the fabrication of transparent ceramics, high‐entropy ceramics, and limited cases of high‐entropy transparent ceramics for each category. High‐entropy transparent ceramics with diverse compositions and structures will provide more possibilities for functional transparent ceramics in the future.

    

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4. Perovskite Na-ion conductors developed from analogous Li 3x La 2/3−x TiO 3 (LLTO): chemo-mechanical and defect engineering

   https://doi.org/10.1039/d1ta04252a  

   Lin, Yu-Ying ; Gustafson, William J. ; Murray, Shannon E. ; Shoemaker, Daniel P. ; Ertekin, Elif ; Krogstad, Jessica A. ; Perry, Nicola H. ( September 2021 , Journal of Materials Chemistry A)

   Na-ion conducting solid electrolytes can enable both the enhanced safety profile of all-solid-state-batteries and the transition to an earth-abundant charge-carrier for large-scale stationary storage. In this work, we developed new perovskite-structured Na-ion conductors from the analogous fast Li-ion conducting Li 3 x La 2/3− x TiO 3 (LLTO), testing strategies of chemo-mechanical and defect engineering. Na x La 2/3−1/3 x ZrO 3 (NLZ) and Na x La 1/3−1/3 x Ba 0.5 ZrO 3 (NLBZ) were prepared using a modified Pechini method with varying initial stoichiometries and sintering temperatures. With the substitution of larger framework cations Zr 4+ and Ba 2+ on B- and A-sites respectively, NLZ and NLBZ both had larger lattice parameters compared to LLTO, in order to accommodate and potentially enhance the transport of larger Na ions. Additionally, we sought to introduce Na vacancies through (a) sub-stoichiometric Na : La ratios, (b) Na loss during sintering, and (c) donor doping with Nb. AC impedance spectroscopy and DC polarization experiments were performed on both Na 0.5 La 0.5 ZrO 3 and Na 0.25 La 0.25 Ba 0.5 ZrO 3 in controlled gas environments (variable oxygen partial pressure, humidity) at elevated temperatures to quantify the contributions of various possible charge carriers (sodium ions, holes, electrons, oxygen ions, protons). Our results showed that the lattice-enlarged NLZ and NLBZ exhibited ∼19× (conventional sintering)/49× (spark plasma sintering) and ∼7× higher Na-ion conductivities, respectively, compared to unexpanded Na 0.42 La 0.525 TiO 3 . Moreover, the Na-ion conductivity of Na 0.5 La 0.5 ZrO 3 is comparable with that of NaNbO 3 , despite having half the carrier concentration. Additionally, more than 96% of the total conductivity in dry conditions was contributed by sodium ions for both compositions, with negligible electronic conductivity and little oxygen ion conductivity. We also identified factors that limited Na-ion transport: NLZ and NLBZ were both challenging to densify using conventional sintering without the loss of Na because of its volatility. With spark plasma sintering, higher density can be achieved. In addition, the NLZ perovskite phase appeared unable to accommodate significant Na deficiency, whereas NLBZ allowed some. Density functional theory calculations supported a thermodynamic limitation to creation of Na-deficient NLZ in favor of a pyrochlore-type phase. Humid environments generated different behavior: in Na 0.25 La 0.25 Ba 0.5 ZrO 3 , incorporated protons raised total conductivity, whereas in Na 0.5 La 0.5 ZrO 3 , they lowered total conductivity. Ultimately, this systematic approach revealed both effective approaches and limitations to achieving super-ionic Na-ion conductivity, which may eventually be overcome through alternative processing routes. 

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5. Pyrochlore nanocrystals as versatile quasi-single-source precursors to lithium conducting garnets

   https://doi.org/10.1039/d0ta05842d  

   Weller, J. Mark ; Chan, Candace K. ( September 2020 , Journal of Materials Chemistry A)

   null (Ed.)

   Lithium conducting garnets are attractive solid electrolytes for solid-state lithium batteries but are difficult to process, generally requiring high reaction and sintering temperatures with long durations. In this work, we demonstrate a synthetic route to obtain Ta-doped garnet (Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 ) utilizing La- and Ta-doped lanthanum zirconate (La 2.4 Zr 1.12 Ta 0.48 O 7.04 ) pyrochlore nanocrystals as quasi-single-source precursors. Via molten salt synthesis (MSS) in a highly basic flux, the pyrochlore nanocrystals transform to Li-garnet at reaction temperatures as low as 400 °C. We also show that the pyrochlore-to-garnet conversion can take place in one step using reactive sintering, resulting in densified garnet ceramics with high ionic conductivity (0.53 mS cm −1 at 21 °C) and relative density (up to 94.7%). This approach opens new avenues for lower temperature synthesis of lithium garnets using a quasi-single-source precursor and provides an alternative route to highly dense garnet solid electrolytes without requiring advanced sintering processes. 

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