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1. Exploring the Pb _{1− x} Sr _x HfO ₃ System and Potential for High Capacitive Energy Storage Density and Efficiency

   https://doi.org/10.1002/adma.202105967  

   Acharya, Megha; Banyas, Ella; Ramesh, Maya; Jiang, Yizhe; Fernandez, Abel; Dasgupta, Arvind; Ling, Handong; Hanrahan, Brendan; Persson, Kristin; Neaton, Jeffrey_B; et al (October 2021, Advanced Materials)

   Abstract The hafnate perovskites PbHfO₃(antiferroelectric) and SrHfO₃(“potential” ferroelectric) are studied as epitaxial thin films on SrTiO₃(001) substrates with the added opportunity of observing a morphotropic phase boundary (MPB) in the Pb_1−xSr_xHfO₃system. The resulting (240)‐oriented PbHfO₃(Pba2) films exhibited antiferroelectric switching with a saturation polarization ≈53 µC cm⁻²at 1.6 MV cm⁻¹, weak‐field dielectric constant ≈186 at 298 K, and an antiferroelectric‐to‐paraelectric phase transition at ≈518 K. (002)‐oriented SrHfO₃films exhibited neither ferroelectric behavior nor evidence of a polarP4mmphase . Instead, the SrHfO₃films exhibited a weak‐field dielectric constant ≈25 at 298 K and no signs of a structural transition to a polar phase as a function of temperature (77–623 K) and electric field (–3 to 3 MV cm⁻¹). While the lack of ferroelectric order in SrHfO₃removes the potential for MPB, structural and property evolution of the Pb_1−xSr_xHfO₃(0 ≤x < 1) system is explored. Strontium alloying increased the electric‐breakdown strength (E_B) and decreased hysteresis loss, thus enhancing the capacitive energy storage density (U_r) and efficiency (η). The composition, Pb_0.5Sr_0.5HfO₃produced the best combination ofE_B = 5.12 ± 0.5 MV cm⁻¹,U_r = 77 ± 5 J cm⁻³, and η = 97 ± 2%, well out‐performing PbHfO₃and other antiferroelectric oxides. 

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2. Additive manufacturing of refractory metals and carbides for extreme environments: an overview

   https://doi.org/10.1177/13621718241235471  

   Mukherjee, Poulomi; Gabourel, Ashlee; Firdosy, Samad_A; Hofmann, Douglas_C; Moridi, Atieh (March 2024, Science and Technology of Welding and Joining)

   Refractory metals and their carbides possess extraordinary properties when subjected to high temperatures and extreme environments. Consequently, they can act as key material systems for advancing many sectors, including space, energy and defence. However, it has been difficult to process these materials using the conventional routes of manufacturing. Additive manufacturing (AM) has shown a lot of potential to overcome the challenges and develop new material systems with tailored properties. This review provides a fundamental understanding of the challenges in the processing of refractory metals and their carbides, including microcracking, formation of brittle oxide phases and high ductile to brittle transition temperature (DBTT). We also highlight some of the novel approaches that have been taken to improve the processability of these challenging material systems using AM. These include in-situ reactive printing, ultrasonic vibration, laser beam shaping, multi-laser deposition and substrate pre-heating with a focus on microstructural changes to improve the properties of printed parts. 

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3. Spontaneous formation of multilayer refractory carbide coatings in a molten salt media

   Constantin, Loic; Fan, Lisha; Pouey, Mathilde; Roger, Jérôme; Cui, Bai; Silvain, Jean-François; Lu, Yongfeng (April 2021, Proc Natl Acad Sci)

   Refractory materials hold great promise to develop functional multilayer coating for extreme environments and temperature applications but require high temperature and complex synthesis to overcome their strong atomic bonding and form a multilayer structure. Here, a spontaneous reaction producing sophisticated multilayer refractory carbide coatings on carbon fiber (CF) is reported. This approach utilizes a relatively low-temperature (950 °C) moltensalt process for forming refractory carbides. The reaction of titanium (Ti), chromium (Cr), and CF yields a complex, high-quality multilayer carbide coating composed of 1) Cr carbide (Cr3C2), 2) Ti carbide, and 3) Cr3C2 layers. The layered sequence arises from a difference in metal dissolutions, reactions, and diffusion rates in the salt media. The multilayer-coated CFs act as a permeable oxidation barrier with no crystalline degradation of the CFs after extreme temperature (1,200 °C) and environment (oxyacetylene flame) exposure. The synthesis of high-quality multilayer refractory coating in a fast, efficient, easy, and clean manner may answer the need for industrial applications that develop cheap and reliable extreme environment protection barriers. 

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4. Epitaxial stabilization versus interdiffusion: synthetic routes to metastable cubic HfO ₂ and HfV ₂ O ₇ from the core–shell arrangement of precursors

   https://doi.org/10.1039/c9nr07316g  

   Fleer, Nathan A.; Thomas, Melonie P.; Andrews, Justin L.; Waetzig, Gregory R.; Gonzalez, Oscar; Liu, Guan-Wen; Guiton, Beth S.; Banerjee, Sarbajit (November 2019, Nanoscale)

   Metastable materials that represent excursions from thermodynamic minima are characterized by distinctive structural motifs and electronic structure, which frequently underpins new function. The binary oxides of hafnium present a rich diversity of crystal structures and are of considerable technological importance given their high dielectric constants, refractory characteristics, radiation hardness, and anion conductivity; however, high-symmetry tetragonal and cubic polymorphs of HfO 2 are accessible only at substantially elevated temperatures (1720 and 2600 °C, respectively). Here, we demonstrate that the core–shell arrangement of VO 2 and amorphous HfO 2 promotes outwards oxygen diffusion along an electropositivity gradient and yields an epitaxially matched V 2 O 3 /HfO 2 interface that allows for the unprecedented stabilization of the metastable cubic polymorph of HfO 2 under ambient conditions. Free-standing cubic HfO 2 , otherwise accessible only above 2600 °C, is stabilized by acid etching of the vanadium oxide core. In contrast, interdiffusion under oxidative conditions yields the negative thermal expansion material HfV 2 O 7 . Variable temperature powder X-ray diffraction demonstrate that the prepared HfV 2 O 7 exhibits pronounced negative thermal expansion in the temperature range between 150 and 700 °C. The results demonstrate the potential of using epitaxial crystallographic relationships to facilitate preferential nucleation of otherwise inaccessible metastable compounds. 

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5. Self-assembled HfO ₂ -Au nanocomposites with ultra-fine vertically aligned Au nanopillars

   https://doi.org/10.1039/D2NR03104C  

   Zhang, Yizhi; Zhang, Di; Liu, Juncheng; Lu, Ping; Deitz, Julia; Shen, Jianan; He, Zihao; Zhang, Xinghang; Wang, Haiyan (August 2022, Nanoscale)

   Oxide-metal-based hybrid materials have gained great research interest in recent years owing to their potential for multifunctionality, property coupling, and tunability. Specifically, oxide-metal hybrid materials in a vertically aligned nanocomposite (VAN) form could produce pronounced anisotropic physical properties, e.g. , hyperbolic optical properties. Herein, self-assembled HfO 2 -Au nanocomposites with ultra-fine vertically aligned Au nanopillars (as fine as 3 nm in diameter) embedded in a HfO 2 matrix were fabricated using a one-step self-assembly process. The film crystallinity and pillar uniformity can be obviously improved by adding an ultra-thin TiN-Au buffer layer during the growth. The HfO 2 -Au hybrid VAN films show an obvious plasmonic resonance at 480 nm, which is much lower than the typical plasmonic resonance wavelength of Au nanostructures, and is attributed to the well-aligned ultra-fine Au nanopillars. Coupled with the broad hyperbolic dispersion ranging from 1050 nm to 1800 nm in wavelength, and unique dielectric HfO 2 , this nanoscale hybrid plasmonic metamaterial presents strong potential for the design of future integrated optical and electronic switching devices. 

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