The Gd2−xMgxZr2O7−x/2 Solid Solution: Ionic Conductivity and Chemical Stability in the Melt of LiCl-Li2O

Materials with pyrochlore structure A₂B₂O₇ have attracted considerable attention owing to their various applications as catalysts, sensors, electrolytes, electrodes, and magnets due to the unique crystal structure and thermal stability. At the same time, the possibility of using such materials for electrochemical applications in salt melts has not been studied. This paper presents the new results of obtaining high-density Mg²⁺-doped ceramics based on Gd₂Zr₂O₇ with pyrochlore structure and comprehensive investigation of the electrical properties and chemical stability in a lithium chloride melt with additives of various concentrations of lithium oxide, performed for the first time. The solid solution of Gd_2−xMg_xZr₂O_7−x/2 (0 ≤ x ≤ 0.10) with the pyrochlore structure was obtained by mechanically milling stoichiometric mixtures of the corresponding oxides, followed by annealing at 1500 °C. The lattice parameter changed non-linearly as a result of different mechanisms of Mg²⁺ incorporation into the Gd₂Zr₂O₇ structure. At low dopant concentrations (x ≤ 0.03) some interstitial positions can be substituted by Mg²⁺, with further increasing Mg²⁺-content, the decrease in the lattice parameter occurred due to the substitution of host-ion sites with smaller dopant-ion. High-density ceramics 99% was prepared at T = 1500 °C. According to the results of the measurements of electrical conductivity as a function of oxygen partial pressure, all investigated samples were characterized by the dominant ionic type of conductivity over a wide range of pO₂ (1 × 10^–18 ≤ pO₂ ≤ 0.21 atm) and T < 800 °C. The sample with the composition of x = 0.03 had the highest oxygen-ion conductivity (10⁻³ S·cm⁻¹ at 600 °C). The investigation of chemical stability of ceramics in the melt of LiCl with 2.5 mas.% Li₂O showed that the sample did not react with the melt during the exposed time of one week at the temperature of 650 °C. This result makes it possible to use these materials as oxygen activity sensors in halide melts.     

Low Temperature Synthesis and Characterization of AlScMo3O12

Recent interest in low and negative thermal expansion materials has led to significant research on compounds that exhibit this property, much of which has targeted the A₂M₃O₁₂ family (A = trivalent cation, M = Mo, W). The expansion and phase transition behavior in this family can be tuned through the choice of the metals incorporated into the structure. An undesired phase transition to a monoclinic structure with large positive expansion can be suppressed in some solid solutions by substituting the A-site by a mixture of two cations. One such material, AlScMo₃O₁₂, was successfully synthesized using non-hydrolytic sol-gel chemistry. Depending on the reaction conditions, phase separation into Al₂Mo₃O₁₂ and Sc₂Mo₃O₁₂ or single-phase AlScMo₃O₁₂ could be obtained. Optimized conditions for the reproducible synthesis of stoichiometric, homogeneous AlScMo₃O₁₂ were established. High resolution synchrotron diffraction experiments were carried out to confirm whether samples were homogeneous and to estimate the Al:Sc ratio through Rietveld refinement and Vegard’s law. Single-phase samples were found to adopt the orthorhombic Sc₂W₃O₁₂ structure at 100 to 460 K. In contrast to all previously-reported A₂M₃O₁₂ compositions, AlScMo₃O₁₂ exhibited positive thermal expansion along all unit cell axes instead of contraction along one or two axes, with expansion coefficients (200–460 K) of α_a = 1.7 × 10⁻⁶ K⁻¹, α_b = 6.2 × 10⁻⁶ K⁻¹, α_c = 2.9 × 10⁻⁶ K⁻¹ and α_V = 10.8 × 10⁻⁶ K⁻¹, respectively.     

Detailed Inspection of γ-ray,Fast and Thermal Neutrons Shielding Competence of Calcium Oxide or Strontium Oxide Comprising Bismuth Borate Glasses

For both the B₂O₃-Bi₂O₃-CaO and B₂O₃-Bi₂O₃-SrO glass systems, γ-ray and neutron attenuation qualities were evaluated. Utilizing the Phy-X/PSD program, within the 0.015–15 MeV energy range, linear attenuation coefficients (µ) and mass attenuation coefficients (μ/ρ) were calculated, and the attained μ/ρ quantities match well with respective simulation results computed by MCNPX, Geant4, and Penelope codes. Instead of B₂O₃/CaO or B₂O₃/SrO, the Bi₂O₃ addition causes improved γ-ray shielding competence, i.e., rise in effective atomic number (Z_eff) and a fall in half-value layer (HVL), tenth-value layer (TVL), and mean free path (MFP). Exposure buildup factors (EBFs) and energy absorption buildup factors (EABFs) were derived using a geometric progression (G–P) fitting approach at 1–40 mfp penetration depths (PDs), within the 0.015–15 MeV range. Computed radiation protection efficiency (RPE) values confirm their excellent capacity for lower energy photons shielding. Comparably greater density (7.59 g/cm³), larger μ, μ/ρ, Z_eff, equivalent atomic number (Z_eq), and RPE, with the lowest HVL, TVL, MFP, EBFs, and EABFs derived for 30B₂O₃-60Bi₂O₃-10SrO (mol%) glass suggest it as an excellent γ-ray attenuator. Additionally, 30B₂O₃-60Bi₂O₃-10SrO (mol%) glass holds a commensurably bigger macroscopic removal cross-section for fast neutrons (Σ_R) (=0.1199 cm⁻¹), obtained by applying Phy-X/PSD for fast neutrons shielding, owing to the presence of larger wt% of ‘Bi’ (80.6813 wt%) and moderate ‘B’ (2.0869 wt%) elements in it. 70B₂O₃-5Bi₂O₃-25CaO (mol%) sample (B: 17.5887 wt%, Bi: 24.2855 wt%, Ca: 11.6436 wt%, and O: 46.4821 wt%) shows high potentiality for thermal or slow neutrons and intermediate energy neutrons capture or absorption due to comprised high wt% of ‘B’ element in it.     

Impact of Annealing on Magnetic Properties and Structure of Co40Fe40W20 Thin Films on Si(100) Substrate

Co₄₀Fe₄₀W₂₀ monolayers of different thicknesses were deposited on Si(100) substrates by DC magnetron sputtering, with Co₄₀Fe₄₀W₂₀ thicknesses from 10 to 50 nm. Co₄₀Fe₄₀W₂₀ thin films were annealed at three conditions (as-deposited, 250 °C, and 350 °C) for 1 h. The structural and magnetic properties were then examined by X-ray diffraction (XRD), low-frequency alternative-current magnetic susceptibility (χ_ac), and an alternating-gradient magnetometer (AGM). The XRD results showed that the CoFe (110) peak was located at 2θ = 44.6°, but the metal oxide peaks appeared at 2θ = 38.3, 47.6, 54.5, and 56.3°, corresponding to Fe₂O₃ (320), WO₃ (002), Co₂O₃ (422), and Co₂O₃ (511), respectively. The saturation magnetization (Ms) was calculated from the slope of the magnetization (M) versus the CoFeW thickness. The Ms values calculated in this manner were 648, 876, 874, and 801 emu/cm³ at the as-deposited condition and post-annealing conditions at 250, 350, and 400 °C, respectively. The maximum M_S was about 874 emu/cm³ at a thickness of 50 nm following annealing at 350 °C. It indicated that the M_S and the χ_ac values rose as the CoFeW thin films’ thickness increased. Owing to the thermal disturbance, the M_S and χ_ac values of CoFeW thin films after annealing at 350 °C were comparatively higher than at other annealing temperatures. More importantly, the Co₄₀Fe₄₀W₂₀ films exhibited a good thermal stability. Therefore, replacing the magnetic layer with a CoFeW film improves thermal stability and is beneficial for electrode and strain gauge applications.     

Photocatalytic Water Splitting for Hydrogen Production with Gd2MSbO7 (M = Fe,In, Y) Photocatalysts under Visible Light Irradiation

Novel photocatalysts Gd₂FeSbO₇, Gd₂InSbO₇ and Gd₂YSbO₇ were synthesized by the solid state reaction method for the first time. A comparative study about the structural and photocatalytic properties of Gd₂MSbO₇ (M = Fe, In, Y) was reported. The results showed that Gd₂FeSbO₇, Gd₂InSbO₇ and Gd₂YSbO₇ crystallized with the pyrochlore-type structure, cubic crystal system and space group Fd3m. The lattice parameter a for Gd₂FeSbO₇, Gd₂InSbO₇ or Gd₂YSbO₇ was 10.276026 Å, 10.449546 Å or 10.653651 Å. The band gap of Gd₂FeSbO₇, Gd₂InSbO₇ or Gd₂YSbO₇ was estimated to be 2.151 eV, 2.897 eV or 2.396 eV. For the photocatalytic water-splitting reaction, H₂ or O₂ evolution was observed from pure water with Gd₂FeSbO₇, Gd₂InSbO₇ or Gd₂YSbO₇ as catalyst under visible light irradiation (wavelength > 420 nm). Moreover, H₂ or O₂ also spilt by using Gd₂FeSbO₇, Gd₂InSbO₇ or Gd₂YSbO₇ as catalyst from CH₃OH/H₂O or AgNO₃/H₂O solutions under visible light irradiation (λ > 420 nm). Gd₂FeSbO₇ showed the highest activity compared with Gd₂InSbO₇ or Gd₂YSbO₇. At the same time, Gd₂InSbO₇ showed higher activity compared with Gd₂YSbO₇. The photocatalytic activities were further improved under visible light irradiation with Gd₂FeSbO₇, Gd₂InSbO₇ or Gd₂YSbO₇ being loaded by Pt, NiO or RuO₂. The effect of Pt was better than that of NiO or RuO₂ for improving the photocatalytic activity of Gd₂FeSbO₇, Gd₂InSbO₇ or Gd₂YSbO₇.     

Solid-State-Activated Sintering of ZnAl2O4 Ceramics Containing Cu3Nb2O8 with Superior Dielectric and Thermal Properties

Low-temperature co-fired ceramics (LTCCs) are dielectric materials that can be co-fired with Ag or Cu; however, conventional LTCC materials are mostly poorly thermally conductive, which is problematic and requires improvement. We focused on ZnAl₂O₄ (gahnite) as a base material. With its high thermal conductivity (~59 W·m⁻¹·K⁻¹ reported for 0.83ZnAl₂O₄–0.17TiO₂), ZnAl₂O₄ is potentially more thermally conductive than Al₂O₃ (alumina); however, it sinters densely at a moderate temperature (~1500 °C). The addition of only 4 wt.% of Cu₃Nb₂O₈ significantly lowered the sintering temperature of ZnAl₂O₄ to 910 °C, which is lower than the melting point of silver (961 °C). The sample fired at 960 °C for 384 h exhibited a relative permittivity (ε_r) of 9.2, a quality factor by resonant frequency (Q × f) value of 105,000 GHz, and a temperature coefficient of the resonant frequency (τ_f) of −56 ppm·K⁻¹. The sample exhibited a thermal conductivity of 10.1 W·m⁻¹·K⁻¹, which exceeds that of conventional LTCCs (~2–7 W·m⁻¹·K⁻¹); hence, it is a superior LTCC candidate. In addition, a mixed powder of the Cu₃Nb₂O₈ additive and ZnAl₂O₄ has a melting temperature that is not significantly different from that (~970 °C) of the pristine Cu₃Nb₂O₈ additive. The sample appears to densify in the solid state through a solid-state-activated sintering mechanism.     

Effect of Gd2O3 Addition on the Microstructure and Properties of Gd2O3-Yb2O3-Y2O3-ZrO2 (GYYZO) Ceramics

Gd and Yb elements have high chemical stability, which can stabilize the solid solution in ZrO₂. Gd₂O₃ and Yb₂O₃ have high melting points, and good oxidation resistance in extreme environments, stable chemical properties. Therefore, Gd₂O₃ and Yb₂O₃ were added to ZrO₂ to stabilize oxides, improve the high temperature stability, and effectively decrease the thermal conductivity at high temperature. In this work, 5 wt% Yb₂O₃ and 5 wt%, 10 wt%, 15 wt% Gd₂O₃ were doped into 8 wt% Y₂O₃ stabilized ZrO₂ (8YSZ) powders as thermal barrier coating materials, and sintered at 1650 °C for 6 h, 12 h, 24 h. The effects of Gd₂O₃ addition on the microstructure, density, thermal conductivity, hardness, and fracture toughness of Gd₂O₃-Yb₂O₃-Y₂O₃-ZrO₂ (GYYZO) bulk composite ceramics were investigated. It was found that the densification of the 8YSZ bulk and GYYZO bulk with 15 wt% Gd₂O₃ reached 96.89% and 96.22% sintered at 1650 °C for 24 h. With the increase of Gd₂O₃ addition, the hardness, elastic modulus and fracture toughness of the GYYZO bulk increased and the thermal conductivity and thermal expansion coefficient of the GYYZO bulk decreased. GYYZO bulk with 15 wt% Gd₂O₃ sintered at 1650 °C for 24h had the highest hardness, elastic modulus and fracture toughness of 15.61 GPa, 306.88 GPa, 7.822 MPa·m^0.5, and the lowest thermal conductivity and thermal expansion coefficient of 1.04 W/(m·k) and 7.89 × 10⁻⁶/°C at 1100 °C, respectively. The addition of Gd₂O₃ into YSZ could not only effectively reduce the thermal conductivity but also improve the mechanical properties, which would improve the thermal barrier coatings’ performances further.     

Impact of Li3BO3 Addition on Solid Electrode-Solid Electrolyte Interface in All-Solid-State Batteries

All-solid-state lithium-ion batteries raise the issue of high resistance at the interface between solid electrolyte and electrode materials that needs to be addressed. The article investigates the effect of a low-melting Li₃BO₃ additive introduced into LiCoO₂- and Li₄Ti₅O₁₂-based composite electrodes on the interface resistance with a Li₇La₃Zr₂O₁₂ solid electrolyte. According to DSC analysis, interaction in the studied mixtures with Li₃BO₃ begins at 768 and 725 °C for LiCoO₂ and Li₄Ti₅O₁₂, respectively. The resistance of half-cells with different contents of Li₃BO₃ additive after heating at 700 and 720 °C was studied by impedance spectroscopy in the temperature range of 25–340 °C. It was established that the introduction of 5 wt% Li₃BO₃ into LiCoO₂ and heat treatment at 720 °C led to the greatest decrease in the interface resistance from 260 to 40 Ω cm² at 300 °C in comparison with pure LiCoO₂. An SEM study demonstrated that the addition of the low-melting component to electrode mass gave better contact with ceramics. It was shown that an increase in the annealing temperature of unmodified cells with Li₄Ti₅O₁₂ led to a decrease in the interface resistance. It was found that the interface resistance between composite anodes and solid electrolyte had lower values compared to Li₄Ti₅O₁₂|Li₇La₃Zr₂O₁₂ half-cells. It was established that the resistance of cells with the Li₄Ti₅O₁₂/Li₃BO₃ composite anode annealed at 720 °C decreased from 97.2 (x = 0) to 7.0 kΩ cm² (x = 5 wt% Li₃BO₃) at 150 °C.     

The Formation of Cr-Al Spinel under a Reductive Atmosphere

In the present work, for the first time, the possibility of formation of CrAl₂O₄ was shown from the equimolar mixture of co-precipitated Al₂O₃ and Cr₂O₃ oxides under a reductive environment. The crystallographic properties of the formed compound were calculated using the DICVOL procedure. It was determined that it has a cubic crystal structure with space group Fd-3m and a unit cell parameter equal to 8.22(3) Å. The formed CrAl₂O₄ is not stable under ambient conditions and easily undergoes oxidation to α-Al₂O₃ and α-Cr₂O₃. The overall sequence of the phase transformations of co-precipitated oxides leading to the formation of spinel structure is proposed.     

Effects of Annealing and Thickness of Co60Fe20Yb20 Nanofilms on Their Structure,Magnetic Properties,Electrical Efficiency,and Nanomechanical Characteristics

X-ray diffraction (XRD) analysis showed that metal oxide peaks appear at 2θ = 47.7°, 54.5°, and 56.3°, corresponding to Yb₂O₃ (440), Co₂O₃ (422), and Co₂O₃ (511). It was found that oxide formation plays an important role in magnetic, electrical, and surface energy. For magnetic and electrical measurements, the highest alternating current magnetic susceptibility (χ_ac) and the lowest resistivity (×10⁻² Ω·cm) were 0.213 and 0.42, respectively, and at 50 nm, it annealed at 300 °C due to weak oxide formation. For mechanical measurement, the highest value of hardness was 15.93 GPa at 200 °C in a 50 nm thick film. When the thickness increased from 10 to 50 nm, the hardness and Young’s modulus of the Co₆₀Fe₂₀Yb₂₀ film also showed a saturation trend. After annealing at 300 °C, Co₆₀Fe₂₀Yb₂₀ films of 40 nm thickness showed the highest surface energy. Higher surface energy indicated stronger adhesion, allowing for the formation of multilayer thin films. The optimal condition was found to be 50 nm with annealing at 300 °C due to high χ_ac, strong adhesion, high nano-mechanical properties, and low resistivity.     

Effect of Sintering Process on Ionic Conductivity of Li7-xLa3Zr2-xNbxO12 (x = 0, 0.2, 0.4, 0.6) Solid Electrolytes

Garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is considered as a promising solid electrolyte. Nb-doped LLZO ceramics exhibit significantly improved ion conductivity. However, how to prepare the Nb-doped LLZO ceramics in a simple and economical way, meanwhile to investigate the relationship between process conditions and properties in Li_7-xLa₃Zr_2-xNb_xO₁₂ ceramics, is particularly important. In this study, Li_7-xLa₃Zr_2-xNb_xO₁₂ (LLZN_xO, x = 0, 0.2, 0.4, 0.6) ceramics were prepared by conventional solid-state reaction. The effect of sintering process on the structure, microstructure, and ionic conductivity of LLZN_xO (x = 0, 0.2, 0.4, 0.6) ceramics was investigated. Due to the more contractive Nb-O bonds in LLZN_xO ceramics, the cubic structures are much easier to form and stabilize, which could induce the decreased preparation time. High-performance garnet LLZN_xO ceramics can be obtained by optimizing the sintering process with lower calcining temperature and shorter holding time. The garnet samples with x = 0.4 calcined at 850 °C for 10 h and sintered at 1250 °C for 4 h exhibit the highest ionic conductivity of 3.86 × 10⁻⁴ S·cm⁻¹ at room temperature and an activation energy of 0.32 eV, which can be correlated to the highest relative density of 96.1%, and good crystallinity of the grains.     

Nickel-Containing Perovskites,PrNi0.4Fe0.6O3–δ and PrNi0.4Co0.6O3–δ, as Potential Electrodes for Protonic Ceramic Electrochemical Cells

Protonic ceramic fuel cells (PCFCs) offer a convenient means of converting chemical energy into electricity with high performance and efficiency at low- and intermediate-temperature ranges. However, in order to ensure good life-time stability of PCFCs, it is necessary to ensure rational chemical design in functional materials. Within the present work, we propose new Ni-based perovskite phases of PrNi_0.4M_0.6O_3–δ (where M = Co, Fe) for potential utilization in protonic ceramic electrochemical cells. Along with their successful synthesis, functional properties of the PrNi_0.4M_0.6O_3–δ materials, such as chemical compatibility with a number of oxygen-ionic and proton-conducting electrolytes, thermal expansion behavior, electrical conductivity, and electrochemical behavior, were comprehensively studied. According to the obtained data, the Co-containing nickelate exhibits excellent conductivity and polarization behavior; on the other hand, it demonstrates a high reactivity with all studied electrolytes along with elevated thermal expansion coefficients. Conversely, while the iron-based nickelate had superior chemical and thermal compatibility, its transport characteristics were 2–5 times worse. Although, PrNi_0.4Co_0.6O_3–δ and PrNi_0.4Fe_0.6O_3–δ represent some disadvantages, this work provides a promising pathway for further improvement of Ni-based perovskite electrodes.     

Laminin-111 protein therapy prevents muscle disease in the mdx mouse model for Duchenne muscular dystrophy

Duchenne muscular dystrophy (DMD) is a devastating neuromuscular disease caused by mutations in the gene encoding dystrophin. Loss of dystrophin results in reduced sarcolemmal integrity and increased susceptibility to muscle damage. The α₇β₁-integrin is a laminin-binding protein up-regulated in the skeletal muscle of DMD patients and in the mdx mouse model. Transgenic overexpression of the α₇-integrin alleviates muscle disease in dystrophic mice, making this gene a target for pharmacological intervention. Studies suggest laminin may regulate α₇-integrin expression. To test this hypothesis, mouse and human myoblasts were treated with laminin and assayed for α₇-integrin expression. We show that laminin-111 (α₁, β₁, γ₁), which is expressed during embryonic development but absent in normal or dystrophic skeletal muscle, increased α₇-integrin expression in mouse and DMD patient myoblasts. Injection of laminin-111 protein into the mdx mouse model of DMD increased expression of α₇-integrin, stabilized the sarcolemma, restored serum creatine kinase to wild-type levels, and protected muscle from exercised-induced damage. These findings demonstrate that laminin-111 is a highly potent therapeutic agent for the mdx mouse model of DMD and represents a paradigm for the systemic delivery of extracellular matrix proteins as therapies for genetic diseases.     

Phase Transition and Coefficients of Thermal Expansion in Al2−xInxW3O12 (0.2 ≤ x ≤ 1)

Materials from theA₂M₃O₁₂ family are known for their extensive chemical versatility while preserving the polyhedral-corner-shared orthorhombic crystal system, as well as for their consequent unusual thermal expansion, varying from negative and near-zero to slightly positive. The rarest are near-zero thermal expansion materials, which are of paramount importance in thermal shock resistance applications. Ceramic materials with chemistry Al_2−xIn_xW₃O₁₂ (x = 0.2–1.0) were synthesized using a modified reverse-strike co-precipitation method and prepared into solid specimens using traditional ceramic sintering. The resulting materials were characterized by X-ray powder diffraction (ambient and in situ high temperatures), differential scanning calorimetry and dilatometry to delineate thermal expansion, phase transitions and crystal structures. It was found that the x = 0.2 composition had the lowest thermal expansion, 1.88 × 10⁻⁶ K⁻¹, which was still higher than the end member Al₂W₃O₁₂ for the chemical series. Furthermore, the AlInW₃O₁₂ was monoclinic phase at room temperature and transformed to the orthorhombic form at ca. 200 °C, in contrast with previous reports. Interestingly, the x = 0.2, x = 0.4 and x = 0.7 materials did not exhibit the expected orthorhombic-to-monoclinic phase transition as observed for the other compositions, and hence did not follow the expected Vegard-like relationship associated with the electronegativity rule. Overall, compositions within the Al_2−xIn_xW₃O₁₂ family should not be considered candidates for high thermal shock applications that would require near-zero thermal expansion properties.     

Linking the Electrical Conductivity and Non-Stoichiometry of Thin Film Ce1−xZrxO2−δ by a Resonant Nanobalance Approach

Bulk ceria-zirconia solid solutions (Ce_1−xZr_xO_2−δ, CZO) are highly suited for application as oxygen storage materials in automotive three-way catalytic converters (TWC) due to the high levels of achievable oxygen non-stoichiometry δ. In thin film CZO, the oxygen storage properties are expected to be further enhanced. The present study addresses this aspect. CZO thin films with 0 ≤ x ≤ 1 were investigated. A unique nano-thermogravimetric method for thin films that is based on the resonant nanobalance approach for high-temperature characterization of oxygen non-stoichiometry in CZO was implemented. The high-temperature electrical conductivity and the non-stoichiometry δ of CZO were measured under oxygen partial pressures pO₂ in the range of 10⁻²⁴–0.2 bar. Markedly enhanced reducibility and electronic conductivity of CeO₂-ZrO₂ as compared to CeO_2−δ and ZrO₂ were observed. A comparison of temperature- and pO₂-dependences of the non-stoichiometry of thin films with literature data for bulk Ce_1−xZr_xO_2−δ shows enhanced reducibility in the former. The maximum conductivity was found for Ce_0.8Zr_0.2O_2−δ, whereas Ce_0.5Zr_0.5O_2-δ showed the highest non-stoichiometry, yielding δ = 0.16 at 900 °C and pO₂ of 10⁻¹⁴ bar. The defect interactions in Ce_1−xZr_xO_2−δ are analyzed in the framework of defect models for ceria and zirconia.     

The Effect of Bi2O3 and Fe2O3 Impurity Phases in BiFeO3 Perovskite Materials on Some Electrical Properties in the Low-Frequency Field

Pure bismuth ferrite (BFO) and BFO with impurity phases (Bi₂O₃ or Fe₂O₃) were synthesized by the hydrothermal method. Complex dielectric permittivity (ε) and electrical conductivity (σ) were determined by complex impedance measurements at different frequencies (200 Hz–2 MHz) and temperatures (25–290) °C. The conductivity spectrum of samples, σ(f), complies with Jonscher’s universal law and the presence of impurity phases leads to a decrease in the static conductivity (σ_DC); this result is correlated with the increased thermal activation energy of the conduction in impure samples compared to the pure BFO sample. The conduction mechanism in BFO and the effect of impurity phases on σ and ε were analyzed considering the variable range hopping model (VRH). Based on the VRH model, the hopping length (R_h), hopping energy (W_h) and the density of states at the Fermi level (N(E_F)) were determined for the first time, for these samples. In addition, from ε(T) dependence, a transition in the electronic structure of samples from a semiconductor-like to a conductor-like behavior was highlighted around 465–490 K for all samples. The results obtained are useful to explain the conduction mechanisms from samples of BFO type, offering the possibility to develop a great variety of electrical devices with novel functions.     

A Simple and Efficient Method for Preparing High-Purity α-CaSO4·0.5H2O Whiskers with Phosphogypsum

A simple and efficient approach for the high-purity CaSO₄·2H₂O (DH) whiskers and α-CaSO₄·0.5H₂O (α-HH) whiskers derived from such phosphogypsum (PG) was proposed. The impact of different experimental parameters on supersaturated dissolution–recrystallization and preparation processes of α-CaSO₄·0.5H₂O was elaborated. At 3.5 mol/L HCl concentration, the dissolution temperature and time were 90 °C and 20 min, respectively. After eight cycles and 5–8 times cycles, total crystallization amount of CaSO₄·2H₂O was 21.75 and 9.97 g/100 mL, respectively, from supersaturated HCl solution. The number of cycles affected the shape and amount of the crystal. Higher HCl concentration facilitated CaSO₄·2H₂O dissolution and created a much higher supersaturation, which acted as a larger driving force for phase transformation of CaSO₄·2H₂O to α-CaSO₄·0.5H₂O. The HCl solution system’s optimum experimental conditions for HH whiskers preparation involved acid leaching of CaSO₄·2H₂O sample, with HCl concentration 6.0 mol/L, reaction temperature 80 °C, and reaction time 30 min–60 min. Under the third cycle conditions, α-CaSO₄·0.5H₂O whiskers were uniform in size, clear, and distinct in edges and angles. The length range of α-CaSO₄·0.5H₂O whiskers was from 106 μm to 231 μm and diameter range from 0.43 μm to 1.35 μm, while the longest diameter ratio was 231. Purity of α-CaSO₄·0.5H₂O whiskers was approximately 100%, where whiteness reached 98.6%. The reuse of the solution enables the process to discharge no waste liquid. It provides a new reference direction for green production technology of phosphogypsum.     

Role of Liquid-Phase Amount in Ceramization of Silicone Rubber Composites and Its Controlling

The reliable mechanical properties of ceramizable silicone rubber composites during pyrolysis are necessary for their application in the fire-resistant fields. The effects of liquid-phase amount on the mechanical properties of silicone rubber composites are investigated. The results show a positive correlation between the liquid-phase amount and the flexural strength of the residual products pyrolysis below 800 °C. The nano-γ-Al₂O₃ in the fillers reacts with liquid B₂O₃ to form aluminum borate above 800 °C, which consumes the liquid phase and strengthens the residual products to a certain extent. Increasing the B₂O₃ addition and introducing nano-γ-Al₂O₃ can control the liquid-phase amount in the range of 15% to 30%, which makes the composites have better residual strength and support performance. The residual strength of composites pyrolysis at 500 °C to 1000 °C is higher than 2.50 MPa, and the maximum is up to 18.7 MPa at 1000 °C.     

Microstructures and Electrical Conduction Behaviors of Gd/Cr Codoped Bi3TiNbO9 Aurivillius Phase Ceramic

In this work, a kind of Gd/Cr codoped Bi₃TiNbO₉ Aurivillius phase ceramic with the formula of Bi_2.8Gd_0.2TiNbO₉ + 0.2 wt% Cr₂O₃ (abbreviated as BGTN−0.2Cr) was prepared by a conventional solid-state reaction route. Microstructures and electrical conduction behaviors of the ceramic were investigated. XRD and SEM detection found that the BGTN−0.2Cr ceramic was crystallized in a pure Bi₃TiNbO₉ phase and composed of plate-like grains. A uniform element distribution involving Bi, Gd, Ti, Nb, Cr, and O was identified in the ceramic by EDS. Because of the frequency dependence of the conductivity between 300 and 650 °C, the electrical conduction mechanisms of the BGTN−0.2Cr ceramic were attributed to the jump of the charge carriers. Based on the correlated barrier hopping (CBH) model, the maximum barrier height W_M, dc conduction activation energy E_c, and hopping conduction activation energy E_p were calculated with values of 0.63 eV, 1.09 eV, and 0.73 eV, respectively. Impedance spectrum analysis revealed that the contribution of grains to the conductance increased with rise in temperature; at high temperatures, the conductance behavior of grains deviated from the Debye relaxation model more than that of grain boundaries. Calculation of electrical modulus further suggested that the degree of interaction between charge carriers β tended to grow larger with rising temperature. In view of the approximate relaxation activation energy (~1 eV) calculated from Z″ and M″ peaks, the dielectric relaxation process of the BGTN−0.2Cr ceramic was suggested to be dominated by the thermally activated motion of oxygen vacancies as defect charge carriers. Finally, a high piezoelectricity of d₃₃ = 18 pC/N as well as a high resistivity of ρ_dc = 1.52 × 10⁵ Ω cm at 600 °C provided the BGTN−0.2Cr ceramic with promising applications in the piezoelectric sensors with operating temperature above 600 °C.     

Vacancy Defects in Ga2O3: First-Principles Calculations of Electronic Structure

First-principles density functional theory (DFT) is employed to study the electronic structure of oxygen and gallium vacancies in monoclinic bulk β-Ga₂O₃ crystals. Hybrid exchange–correlation functional B3LYP within the density functional theory and supercell approach were successfully used to simulate isolated point defects in β-Ga₂O₃. Based on the results of our calculations, we predict that an oxygen vacancy in β-Ga₂O₃ is a deep donor defect which cannot be an effective source of electrons and, thus, is not responsible for n-type conductivity in β-Ga₂O₃. On the other hand, all types of charge states of gallium vacancies are sufficiently deep acceptors with transition levels more than 1.5 eV above the valence band of the crystal. Due to high formation energy of above 10 eV, they cannot be considered as a source of p-type conductivity in β-Ga₂O₃.