Anisotropic thermal expansion and ionic conductivity of a crystal-oriented,Mg2+-conducting NASICON-type solid electrolyte

Multivalent ion-conducting ceramics are required for the manufacture of high-safety, high-capacity rechargeable batteries. However, the low ionic conductivity of solid electrolytes and discrepancies in the thermal expansion between the battery components limit their widespread application. Furthermore, anisotropic thermal expansion in crystals during battery manufacturing and the charge-discharge cycles causes the formation of microcracks, which degrade the battery performance. The physical properties of ceramic materials with anisotropic crystal structures can be modified by varying the crystallographic orientation of their grains. In this study, a co-precipitation approach was used to synthesize an Mg²⁺-conducting (Mg_0.1Hf_0.9)_4/3.8Nb(PO₄)₃ solid electrolyte, and the grain orientation in the bulk sample was controlled using strong magnetic fields during the slip casting process. The results showed that inducing an orientation along the c-axis enhanced the apparent ionic conductivity of the bulk sample. It was also observed that (Mg_0.1Hf_0.9)_4/3.8Nb(PO₄)₃ crystal has a negative volumetric thermal expansion despite a positive linear thermal expansion along its c-axis. By adjusting the c-axis orientation of the grains, (Mg_0.1Hf_0.9)_4/3.8Nb(PO₄)₃ electrolytes with negative or positive linear thermal expansion coefficient have been produced. The findings of this study suggest that solid-electrolytes with negative, positive, or zero linear thermal expansion can be produced to create more compatible and higher-performance solid-state devices.     

Structural,optical, and electrical properties of tin iodide-based vacancy-ordered-double perovskites synthesized via mechanochemical reaction

Over the recent past, lead-based halide perovskite materials have drawn significant attention due to their excellent optical and electrical properties for solar cells and optoelectronics applications. However, the toxicity of lead elements and instability under ambient conditions leads to develop alternative compositions. Herein, we report a novel mechanochemical synthesis of tin iodide-based double perovskites (A₂SnI₆; A = Rb⁺, Cs⁺, methylammonium, and formamidinium), and their structural, optical, and electrical properties are investigated. Importantly, we found that the hydrogen iodide (HI) addition during the ball-milling process minimizes secondary phase formation in the synthesized A₂SnI₆ powders. The effects of HI addition and the A-site substitution are investigated with respect to the lattice parameters, optical bandgaps, and electrical properties of the synthesized perovskite materials. Our results demonstrate essential information to improve the understanding of halide perovskite materials and develop efficient lead-free perovskite photoelectric devices.     

Enhanced mechanical properties of porous titanium implants via in-situ synthesized titanium carbide in lamellar pore walls

Directional lamellar porous titanium scaffolds are widely used as bone implant bearing materials because of their anisotropic pore structure. Their mechanical properties can be effectively improved by enhancing the strength of pore walls through the introduction of ceramics. In this work, porous titanium implants were prepared by freeze casting combined with TiH₂ decomposition. The graphene was introduced into the pore walls of porous titanium, which could transform into titanium carbide (TiC) in situ upon sintering. TiC was evenly distributed in the lamellar pore walls, and the interface was well bonded. The compression strength of the fabricated implants was up to 389.94 MPa when the graphene content was 3 wt%, which was 377.8% times as high as the porous titanium. The crack propagation was resisted by TiC because of the “pinning” effect on the pore wall. Some of TiC were pulled out from the matrix, and others were fractured. The strength of the fabricated implants was improved significantly by the large consumption of fracture energy. Also, fabricated porous titanium implants with TiC are suitable for bone implantation.     

Synergistically improved thermal stability and electromagnetic interference shielding effectiveness (EMI SE) of in-situ synthesized polyaniline/sulphur doped reduced graphene oxide (PANI/S-RGO) nanocomposites

Polyaniline (PANI) and its composite with sulphur doped reduced graphene oxide (S-RGO) have been successively synthesized via in-situ chemical oxidative polymerization of aniline in presence of 10 wt. % S-RGO nanosheets. Physico-chemical analyses of the synthesized nanomaterial was performed with various characterization techniques such as X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDS), Atomic Force Microscopy (AFM) and Thermogravimetric analysis/Differential Scanning Calorimetry (TGA/DSC). The results interpreted from the various characterizations confirm the doping of RGO with sulphur as well as strong interaction of PANI nanofibers and S-RGO nanosheets. TG/DSC curves confirm the enhanced thermal stability of polyaniline/sulphur doped reduced graphene oxide (PANI/S-RGO) nanocomposites with heat resistance index (T_HRI) of 155.2 °C in comparision to pure PANI (T_HRI = 145.3 °C) at a filler loading of 10 wt. %. TGA validates that thermal stability of PANI/S-RGO nanocomposite improves by 6–7 °C than pure PANI in terms of weight loss percentage at a temperature of 1117 °C. However DSC analysis confirms that PANI/S-RGO retains its structural integrity and conformity to temperatures as high as 900 °C beyond which the polymer composite starts to degrade. The electromagnetic interference shielding effectiveness (EMI SE) of PANI and PANI/S-RGO nanocomposites were measured via open-ended coaxial probe set-up connected to a Vector Network Analyser (VNA) at a broadband frequency range of 1–20 GHz (1000–20000 MHz). For EMI SE measurements the various nanomaterials were incorporated into paraffin wax and made into composite pellets of thickness 5 mm by solution casting technique. The dielectric properties, electrical conductivity and EMI SE were all greatly enhanced for the PANI/S-RGO/Paraffin composite pellets. The as synthesized PANI/S-RGO/Paraffin composite pellets exhibited highest EMI SE of ?22.5 dB (>99%) as compared to ?15.89 dB of PANI/Paraffin composite pellets. The prepared composite pellets revealed an absorption dominant mechanism of shielding with highest SE_A of ?14.6 dB for PANI/S-RGO/Paraffin composite pellets.     

Crystallization and relaxation dynamics of glass-forming liquids at the Kauzmann temperature

If the entropy extrapolation of supercooled liquids (SCL) suggested by Kauzmann was correct, then they would have the same entropy as their stable crystalline phase at a certain low temperature, below the laboratory glass transition (T_g), known as the Kauzmann temperature (T_K). Extrapolating even further, the liquid entropy would be null at a temperature above absolute zero, violating the Third Law of Thermodynamics and constituting a paradox. Several possibilities have been proposed over the past 70 years to solve this paradox with different degrees of success. Our objective here is to access liquid dynamics at deep supercoolings to test the so-called crystallization solution to the paradox. By comparing the relaxation and crystallization kinetics determined above T_g and extrapolated down to T_K, a possible solution would be that the crystallization time is shorter than the relaxation time, which would mean that a SCL cannot reach the T_K. In this case, the liquid stability limit or kinetic spinodal temperature (T_ks) should be higher than T_K. We tested two fragile glass-forming liquids (diopside and wollastonite) and two strong liquids (silica and germania). For the fragile substances, T_ks ? T_K, hence such a supercooled liquid cannot exist at T_K, and the entropy crisis is averted. On the other hand, the results for the strong liquids were inconclusive. We hope the findings of this work encourage researchers to further investigate the liquid dynamics of different strong glass-forming systems at deep supercoolings.     

Microstructure and mechanical properties of α/β-Si3N4 composite ceramics with novel ternary additives prepared via spark plasma sintering

In this study, α/β-Si₃N₄ composite ceramics with high hardness and toughness were fabricated by adopting two different novel ternary additives, ZrN–AlN–Al₂O₃/Y₂O₃, and spark plasma sintering at 1550 °C under 40 MPa. The phase composition, microstructure, grain distribution, crack propagation process and mechanical properties of sintered bulk were investigated. Results demonstrated that the sintered α/β-Si₃N₄ composite ceramics with ZrN–AlN–Al₂O₃ contained the most α phase, which resulted in a maximum Vickers hardness of 18.41 ± 0.31 GPa. In the α/β-Si₃N₄ composite ceramics with ZrN–AlN–Y₂O₃ additives, Zr₃AlN MAX-phase and ZrO phase were found and their formation mechanisms were explained. The fracture appearance presented coarser elongated β-Si₃N₄ grains and denser microstructure when 20 wt% TiC particles were mixed into Si₃N₄ matrix, meanwhile, exhibited maximum mean grain diameter of 0.98 ± 0.24 μm. As a result, the compact α/β-Si₃N₄ composite ceramics containing ZrN–AlN–Y₂O₃ additives and TiC particles displayed the optimal bending strength and fracture toughness of 822.63 ± 28.75 MPa and 8.53 ± 0.21 MPa?m^1/2, respectively. Moreover, the synergistic toughening of rod-like β-Si₃N₄ grains and TiC reinforced particles revealed the beneficial effect on the enhanced fracture toughness of Si₃N₄ ceramic matrix.     

Planar proton-conducting ceramic cells for hydrogen extraction: Mechanical properties,electrochemical performance and up-scaling

Proton-conducting ceramics, which selectively separate H₂ from any hydrogen-containing gas could play a role in the future of the growing hydrogen market. In recent years, membrane technologies related to H₂ extraction became attractive solutions to produce pressurized high-purity hydrogen. Yttrium-doped barium zirconate/cerate materials (BaCe_xZr_1-x-yY_yO_3-δ) are among the most studied and used materials. In this study, symmetrical cells consisting of a protonic electrolyte (BaCe_0·2Zr_0·7Y_0·1O_3-δ (BCZY27), 10–15 μm in thickness) surrounded by two cermet electrodes (BCZY27–Ni (50?50 vol%), 150 μm) were prepared for H₂ extraction applications. The cells were prepared via tape-casting and co-sintered at 1575 °C. The cells were up-scaled to an area of 135 cm². The fracture toughness of the cermet electrodes was determined to be 2.07 (±0.05) MPa · m^1/2 at room temperature using the double torsion technique. Impedance spectra were recorded on the symmetrical cells between 650 and 800 °C in 3% humidified 50% H₂/50% N₂ atmosphere and at 650 °C varying the hydrogen partial pressure (20% < pH₂<100%). In 50% H₂/50% N₂ with 3% H₂O the cells demonstrated an ohmic resistance of 0.59 and 0.44 Ω cm,² an average electrode polarization resistance of 0.10 and 0.09 Ω cm² (per one electrode) at 650 and 800 °C, respectively. Moreover, a stability test was performed over 400 h highlighting the stable electrochemical properties of the symmetrical membranes.     

Use of La2O3 with 8YSZ as thermal barrier coating and its effect on thermal cycle behavior,microstructure, mechanical properties and performance of diesel engine operated by hydrogen-algae biodiesel blend

In this present work, the effect of lanthanum oxides (La₂O₃) on the thermal cycle behavior of TBC coatings and mechanical properties such as adhesion strength and microhardness of 8% Yttria Stabilized Zirconia (8YSZ) TBCs were investigated. CoNiCrAlY and aluminium alloy (Al–13%Si) were used as bond coat and substrate materials. 8YSZ and different wt % of La₂O₃ (10, 20, and 30%) top coatings were applied using the atmospheric plasma spray (APS) method. The thermal cycling test for TBC coated samples were conducted at 800 °C in the electric furnace. The XRD pattern shows that the La₂O₃ doped 8YSZ material transformed to cubic pyrochloric structured La₂Zr₂O₇ during thermal cycling. Further, the Taguchi-based grey relation analysis (GRA) method was applied to optimize the TBC coating parameters to achieve better mechanical properties such as adhesion strength and microhardness. And the optimized La₂O₃/8YSZ TBC coating was coated on CRDI engine combustion chamber components. The engine was tested with microalgae biodiesel and hydrogen, and the results were promising for the TBC-coated engine. The engine performance increased while using La₂O₃/8YSZ coated components, and the emissions from engine exhaust gas such as CO, HC, and smoke reduced considerably. It was found that there was no separation crack and spallation of the coating layer in the microstructure. Ultimately, the microstructural analysis of the optimized TBC coated piston sample after 50 h of running in the diesel engine confirmed that the developed coating had a superior thermal insulation effect and longer life.     

The investigation of the physical properties and hydrogenated mechanism of TM5Si4 (TM=Ti,Zr, Hf)

The outstanding physical properties make TM₅Si₄ silicides become the potential silicon-based transition-metal ultrahigh-temperature materials. In present work, we adopt the first-principles scheme to explore the structural stability, mechanical properties and explain the hydrogenated mechanism of Ti₅Si₄, Zr₅Si₄ and Hf₅Si₄ using the electronic structures. And the investigation increases the theoretical support for the developments and applications of TM₅Si₄ silicides. Three hydrogenated models have shown that the hydrogen displays the stability for hydrogenated TM₅Si₄ compounds. Furthermore, the introduction of hydrogen occupation has weakened the elastic properties of TM₅Si₄. The metallic property of TM₅Si₄ and three hydrogenated models was confirmed by the electronic structures. The localized hybridization between hydrogen and TM₅Si₄ confirm the hydrogenated structural stability.     

Oxidative characteristics and gel properties of porcine myofibrillar proteins affected by l-lysine and l-histidine in a dose-dependent manner at a low and high salt concentration

This study investigated the effects of l -lysine (Lys) and l -histidine (His) on the oxidative characteristics and gel properties of porcine myofibrillar proteins (MP). Results showed that Lys and His had a strong ferrous ion-chelating ability and hydroxyl radical-scavenging activity. Moreover, Lys and His inhibited the protein carbonyl formation and MP aggregation at 0.2 M and 0.6 M NaCl, respectively, in a dose-dependent manner. Furthermore, 2 and 4 mg mL⁻¹ Lys and His decreased the oxidation-induced loss of the tertiary structure of MP accompanied by the lower surface hydrophobicity. The water-holding capacity and gel strength of MP gels increased with increasing Lys and His concentrations due to more regular and lamellar structures with smaller and homogeneous pores at 0.6 M NaCl and more orderly crosslinking via fibrous filament at 0.2 M NaCl. In summary, Lys and His chelated the ferrous ions and scavenged hydroxyl radicals, decreased the oxidation-induced physicochemical changes, thus preventing oxidative damage during the formation of a three-dimensional gel network, which resulted in better gel quality.