Thermal properties of hierarchical YSZ and LZO ceramic microspheres with multi-scaled voids investigated by using theoretical,experimental and simulation methods

Heat transfer within ceramic feedstock powders is still unclear, which impedes optimization of the thermal and mechanical properties of the thermal sprayed coatings. The microspheres (yttria-stabilized zirconia YSZ and lanthanum zirconate LZO) were prepared via the electro-spraying assisted phase inversion method (ESP). The thermal properties of the two ESP microspheres and a commercial hollow spherical powder (HOSP) were investigated by using theoretical, experimental, and simulation methods. Thermal conductivity of the single microsphere was estimated via a novel nest model that was derived from the Maxwell-Eucken 1 and the EMT model. Thermal conductivity of a single YSZ/LZO-ESP microsphere prepared at 1100–1200 °C was within 0.36–0.75 W/m K, which was ～ 20 % lower than that of a single YSZ-HOSP microsphere with a similar porosity. Heat flux simulation showed that high tortuosity around the multi-scaled voids of the ESP microsphere led to a more efficient decrease in thermal conductivity compared with total porosity.     

Can lanthanum doping enhance catalytic performance of silver in direct propylene epoxidation over NaMoAg/SiO_2?

In the attempt to reduce surface free energy of silica to improve interaction of silica with silver, silica was doped by different amounts of low surface energy lanthanum, La_2O_3, through impregnation. The doped and undoped silica were used as supports for preparation of Na/Ag/Mo/La_2O_3-SiO_2 catalysts. Catalytic performances of the catalysts were evaluated in direct epoxidation of propylene(DPO) using molecular oxygen under atmospheric pressure and without adding hydrogen. Adding 5 wt%La to the Na/Ag/Mo/SiO_2 catalyst improves both the catalysts electivity in DPO and its stability over 20h of time-on-stream.The characterization results show that La_2O_3 species interact strongly with silver particles on the silica surface which result in significant improvement in the dispersion profile of silver and marked decrease in the size of silver nanoparticles(AgNPs). The estimated mean diameter of AgNPs is ca. 4.0 nm in Na/Ag/Mo/5 wt%La_2O_3-SiO_2, which is smaller than that(53.9 nm) found in Na/Ag/SiO_2. The presence of subnanometer AgNPs on Ag/La_2O_3-SiO_2 prior addition of MoO_3 and NaCl to the sample can enhance the mutual electronic synergism between Ag, MoO_3 and Na for selective production of propylene oxide.     

Improving room-temperature electrochemical performance of solid-state lithium battery by using electrospun La2Zr2O7 fibers-filled composite solid electrolyte

Low ionic conductivity at room temperature and poor interfacial compatibility are the main obstacles to restrain the practical application of polymer solid electrolytes. In this work, lanthanum zirconate (LZO) fibers were prepared by electrospinning method and used for the first time as fillers in sandwich polypropylene carbonate (PPC)-based solid electrolyte. Meanwhile, a graphite coating was applied on one surface of the composite solid electrolyte (CSE) membrane. The results show that the LZO fibers significantly increases the room-temperature electrochemical performance of the CSE, and the graphite coating enhances the interfacial compatibility between electrolyte and lithium anode. Furthermore, an ultra-thin PPC-LZO CSE with a total thickness of 22 μm was prepared and used in NCM622/CSE/Li solid-state cell, which shows an initial discharge capacity of 165.6 mAh/g at the current density of 0.5C and a remaining capacity of 113.0 mAh/g after 250 cycles at room temperature. Rise to 1C, the cell shows an initial discharge capacity of 154.2 mAh/g with a remaining capacity of 95.6 mAh/g after 250 cycles. This ultra-thin CSE is expected to be widely applied in high energy-density solid-state battery with excellent room-temperature electrochemical performances.     

Influence of lanthanum on enhancement of mechanical and electrical properties of Cu-Al_2O_3 composites

Two kinds of Cu-Al_2O_3 composites(with and without La) were prepared via mechanical alloying-spark plasma sintering(MA-SPS) method. Microstructure, mechanical properties and electrical resistivity were investigated systematically using metallography, scanning electron microscopy, transmission electron microscopy, mechanical and electrical properties testing. The results indicate that an appropriate amount of La can homogenize the distribution of Al_2O_3. As such, yield strength, ultimate tensile strength and elongation of Cu-Al_2O_3-La are greatly increased. Some semi-coherent interface between Cu and Al_2O_3 is found, which means a low interface energy. The grain shape of Cu changes to irregular band with the addition of La. This change results in a density decrease of grain boundary and reduces electrical resistance. Lanthanum may exist in the form of La_2O_3.     

The effect of Na addition on the first hydrogen absorption kinetics of cast hypoeutectic Mg–La alloys

With superior properties of Mg such as high hydrogen storage capacity (7.6 wt% H/MgH₂), low price, and low density, Mg has been widely studied as a promising candidate for solid-state hydrogen storage systems. However, a harsh activation procedure, slow hydrogenation/dehydrogenation process, and a high temperature for dehydrogenation prevent the use of Mg-based metal hydrides for practical applications. For these reasons, Mg-based alloys for hydrogen storage systems are generally alloyed with other elements to improve hydrogen sorption properties. In this article, we have added Na to cast Mg–La alloys and achieved a significant improvement in hydrogen absorption kinetics during the first activation cycle. The role of Na in Mg–La has been discussed based on the findings from microstructural observations, crystallography, and first principles calculations based on density functional theory. From our results in this study, we have found that the Na doped surface of Mg–La alloy systems have a lower adsorption energy for H₂ compared to Na-free surfaces which facilitates adsorption and dissociation of hydrogen molecules leading to improvement of absorption kinetic. The effect of Na on the microstructure of these alloys, such as eutectic refinement and a density of twins is not highly correlated with absorption kinetics.     

Preparation and corrosion resistance of nonstoichiometric lanthanum zirconate coatings

Lanthanum zirconate is a promising thermal barrier coating material owing to its excellent thermophysical properties and La plays the key role in its corrosion resistance. Here, an amorphous precursor is used as raw feedstock material so as to synthesize lanthanum zirconate coatings with tailorable composition by atmospheric plasma spray (APS). Three lanthanum zirconate coatings of La_1.7Zr_2.3O_7.15, La_2.0Zr_2.0O_7.0 and La_2.3Zr_1.7O_6.85 are fabricated. Furthermore, the corrosion resistance of the as-sprayed coatings against CaO-MgO-Al₂O₃-SiO₂ at 1250℃ is investigated. The increased La content promotes the formation of a sealing layer of the crystalline Ca₂La₈(SiO₄)₆O₂ apatite, which slows down the penetration of molten CaO-MgO-Al₂O₃-SiO₂. Therefore, the infiltration rate of the La_2.3Zr_1.7O_6.85 coating decreased up to 42.6 % compared with the other two coatings. This work develops a feasible preparation strategy to control the La composition for the improved corrosion resistance, which is expected to guide the future coating design and synthesis for the materials with big composition changes during the APS process.     

Heterostructured thin LaFeO3/g-C3N4 films for efficient photoelectrochemical hydrogen evolution

The deposition of LaFeO₃ at the surface of a graphitic carbon nitride (g-C₃N₄) film via magnetron sputtering followed by oxidation for photoelectrochemical (PEC) water splitting is reported. The LaFeO₃/g-C₃N₄ film was investigated by various characterization techniques including SEM, XRD, Raman spectroscopy, XPS and photo-electrochemical measurements. Our results show that the hydrogen production rate of a g-C₃N₄ film covered by a LaFeO₃ film, exhibiting both a thickness of ca. 50 nm, is of 10.8 μmol h⁻¹ cm⁻² under visible light irradiation. This value is ca. 70% higher than that measured for pure LaFeO₃ and g-C₃N₄ films and confirms the effective separation of electron-hole pairs at the interface of LaFeO₃/g-C₃N₄ films. Moreover, the LaFeO₃/g-C₃N₄ films were demonstrated to be stable and retained a high activity (ca. 70%) after the third reuse.     

Phase relation studies in the CeO2–La2O3–Er2O3 system at 1500°C

Materials based on CeO₂–La₂O₃–Er₂O₃ system are promising candidates for a wide of applications, but the phase relationship has not been studied systematically previously. To address this challenge, the isothermal section of the phase diagram for 1500 °C was investigated. The phase relations in the CeO₂–La₂O₃–Er₂O₃ ternary system at 1500 °C were studied by X-ray diffraction and scanning electron microscopy in the overall concentration range. To study phase relationships at 1500 °C the as-repared samples were thermally treated in two stages: at 1100 °C (for 300 in air) and then at 1500 °C (for 70 h in air) in the furnaces with heating elements based on Fecral (H23U5T) and Superkanthal (MoSi2), respectively. The solid solutions based on various polymorphous forms of constituent phases and with perovskite-type structure of LaErO₃ (R) with orthorhombic distortions were revealed in the system. No new phases were found. The isothermal section of the phase diagram for the CeO₂–La₂O₃–Er₂O₃ system has been constructed. It was established that in the ternary CeO₂–La₂O₃–Er₂O₃ system there exist fields of solid solutions based on hexagonal (A) modification of La₂O₃, cubic modification of CeO₂ with fluorite-type structure (F), cubic modification Er₂O₃ and with perovskite-type structure of LaErO₃ (R) with orthorhombic distortions. The maximal solubility of ceria in LaErO₃ was found to be around ∼ 2 mol% CeO₂ along the section CeO₂–(50 mol % La₂O₃ –50 mol% Er₂O₃).     

Effect of lanthanum content on the conduction behaviors and relaxation processes of lead lanthanum zirconate titanate antiferroelectric ceramics

(Pb_1-xLa_x) (Zr_0.92Ti_0.08)_1-x/4O₃ (PLZT x/92/8, x = 3, 5 and 7 at%) ceramics with compositions near the antiferroelectric (AFE)-ferroelectric (FE) phase boundary were fabricated by a solid-state reaction method. The effect of lanthanum content on the conduction behaviors and relaxation processes has been investigated. It was verified that the main phase with orthorhombic structure was formed in all compositions. The increase of lanthanum substitution resulted in an enhancement of diffuse phase transition. Impedance analysis suggested that the ac conductivity decreased with increasing lanthanum content. Moreover, thermally stimulated depolarization current study was utilized to establish the correlation between defect structures and relaxation processes. It showed three peaks with distinct characteristics, which originated from dipole orientation, oxygen vacancy migration and phase transition respectively. The oxygen vacancy-related defects induced by lanthanum doping were mainly responsible for the variation of conduction behaviors and relaxation processes.     

Synergistic effect of La and Co co-doping on room-temperature ferromagnetism enhancement of TiO2 nanoparticles

The synergistic influence of lanthanum and cobalt co-doping on room temperature ferromagnetism (RTFM) of TiO₂ system is investigated. A series of Ti_0.97?xCo_0.03La_xO₂ nanoparticles were prepared and their structures and properties were systematically studied with X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy, UV–vis spectrophotometer, Raman spectra and magnetic measurement techniques, respectively. Detailed experimental characterizations indicate that the as-prepared La and Co co-doped samples exhibit single anatase phase, and all the samples exhibit strong visible photoluminescence associated with oxygen vacancies and a clear ferromagnetic hysteresis loop, both of which were dramatically enhanced with La and Co co-doping, and the maximum saturation magnetization (M_s) reaches 1.38 emu/g at the La content of 6 mol%. It is speculated that oxygen vacancies modulated by ionic La play an important role in the enhanced RTFM, which can be attributed to the bound magnetic polarons (BMPs) formed via ferromagnetic coupling between two neighboring Co²⁺ ions mediated by oxygen vacancy (F⁺ center). Our results present an alternative method to obtain high performance RTFM.