Synthesis and performance of Li3V2(PO4)3/C composites as cathode materials

Carbon-coated Li₃V₂(PO₄)₃ cathode materials for lithium-ion batteries were prepared by a carbon-thermal reduction (CTR) method using sucrose as carbon source. The Li₃V₂(PO₄)₃/C composite cathode materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical measurement. The results show that the Li₃V₂(PO₄)₃ samples synthesized using sucrose as carbon source have the same monoclinic structure as the Li₃V₂(PO₄)₃ sample synthesized using acetylene black as carbon source. SEM image exhibits that the particle size is about 1 μm together with homogenous distribution. Electrochemical test shows that the initial discharge capacity of Li₃V₂(PO₄)₃ powders is 122 mAh·g⁻¹ at the rate of 0.2C, and the capacity retains 111 mAh−g⁻¹ after 50 cycles.     

Al—ZrOCl2反应体系制备ZrAl3（p）＋Al2O3（p）／Al复合材料

从Al-ZrOCl2体系利用熔体直接反应法制备了原位ZrAl3和Al2O3颗粒增强铝基复合材料。Al-Zr－O体系中原位形成的ZrAl3具有四方结构，其最大尺寸为4μm，纵横长度比小于2．0，此外，还有一定数量的亚微米级Al2O3颗粒生成，其晶体为六方结构，纵横长度比大于2．0.ZrAl3(p),Al2O3(p)/Al复合材料凝固组织，随ZrOCl2加入量的增加，生成的颗粒尺寸更小，分布更均匀，拉伸试验表明，Al-ZrOCl2体系的复合材料具有高度的强度和逆性，断口组织存在大量韧窝，韧窝中镶嵌嵌着细小颗粒，属韧性断裂。     

国外多孔基体氧化铝/氧化铝复合材料工程应用进展

氧化铝/氧化铝复合材料(Al2O3/Al2O3)是20世纪90年代兴起的一类连续陶瓷纤维增强陶瓷基复合材料,已经发展为与SiC/SiC、C/SiC等非氧化物陶瓷基复合材料并列的一类陶瓷基复合材料。与非氧化物陶瓷基复合材料相比,Al2O3/Al2O3具有长时抗氧化、高温耐腐蚀、低成本等独特优势,已经在航空发动机、地面燃气轮机等军民两用热结构材料领域展现出广阔的应用前景。本文从材料应用的角度出发,系统分析阐述了目前在Al2O3/Al2O3占主导地位的多孔基体Al2O3/Al2O3(P-Al2O3/Al2O3)的增韧机制、成型工艺和性能特点,重点归纳了国外近年来P-Al2O3/Al2O3的工程化应用进展及前景,最后指出了P-Al2O3/Al2O3存在的局限性并展望了未来发展方向,旨在为国内Al2O3/Al2O3体系发展提供借鉴和参考。     

Ultrasonic machining of Al2O3/LaPO4 composites

Al₂O₃/LaPO₄ composites of varying compositions were drilled on an ultrasonic machine with low carbon steel tools (solid and hollow), in order to evaluate the response to machining. Vickers hardness for different compositions indicate critical load dependency on LaPO₄ content. Significance of LaPO₄ content on material hardness highlights the critical content for good sinterability. X-ray diffraction was done to study the phase content. Acoustic emission (AE) signals emitted by the work piece during machining was also analyzed. Ultrascan inspection was carried out to check for any internal defects. The data presented in the paper illustrate the significance of LaPO₄ addition on machinability of Al₂O₃/LaPO₄ composites in terms of MRR, AE response and hole geometry and associated defects.     

Synthesis and characterization of 0.3 Vf TiC–Ti3SiC2 and 0.3 Vf SiC–Ti3SiC2 composites

In this work, two composite compositions—one with 30% (v/v) SiC, the other with 30% (v/v) TiC, balance Ti₃SiC₂—were synthesized and characterized. Fully dense samples were fabricated by hot isostatically pressing Ti, SiC and C powders for 8 h at 1500 or 1600 °C and a pressure of 200 MPa. Both TiC and SiC lower grain boundary mobility in Ti₃SiC₂. Coarsening of the SiC particles was also observed. At comparable grain sizes, all composites tested were weaker in flexure than the unreinforced Ti₃SiC₂ matrix, with the reduction in strength being the worst for the SiC composites. This reduction in strength is most probably due to thermal expansion mismatches between the matrix and reinforcement phases. The composite samples were exceptionally damage tolerant; in one case a 100 N Vickers indentation (in a 1.5-mm thick bar) did not reduce the flexural strength as compared to an unindented or as-fabricated samples. The same is true for thermal shock resistance; quenching samples from 1400 °C in room temperature water, resulted in strength reductions that were 12% at best and 50% at worst. In the 25–1000 °C temperature range, the thermal expansion coefficients of the two composites were indistinguishable at 8.2×10⁻⁶ K⁻¹. The Vickers hardness values depended on load; at 100 N, the hardnesses were ≈15 GPa; at 300 N, they asymptote to 7–8 GPa. For the most part, very few cracks emanate from the corners of the Vickers indents even at loads as high as 500 N. In the few cases where cracks did initiate, fracture toughness values were crudely estimated to lie in the 5–7.5 MPa √m range.     

Dielectric and microwave properties of ZrO2 doped CaO-SiO2-B2O3 ceramic matrix composites

The behavior of dielectric and microwave properties against sintering temperature has been carried out on CaO-SiO₂-B₂O₃ ceramic matrix composites with ZrO₂ addition. The results indicated that ZrO₂ addition was advantageous to improve the dielectric and microwave properties. X-ray diffraction (XRD) patterns show that the major crystalline β-CaSiO₃ and a little SiO₂ phase existed at the temperature ranging from 950 °C to 1050 °C. At 0.5 wt% ZrO₂, CaO-SiO₂-B₂O₃ ceramic matrix composites sintered at 1000 °C possess good dielectric properties: ?_r = 5.85, tan δ = 1.59 × 10⁻⁴ (1 MHz) and excellent microwave properties: ?_r = 5.52, Q · f = 28,487 GHz (11.11 GHz). The permittivity of Zr-doped CaO-SiO₂-B₂O₃ ceramic matrix composites exhibited very little temperature dependence, which was less than ±2% over the temperature range of −50 to 150 °C. Moreover, the ZrO₂-doped CaO-SiO₂-B₂O₃ ceramic matrix composites have low permittivity below 5.5 over a wide frequency range from 20 Hz to 1 MHz.     

In-situ high temperature X-ray diffraction study of Ni/Al2O3 interface reactions

In-situ experiments on the Ni/Al₂O₃ interface reaction were carried out with a high temperature X-ray diffractometer capable of measuring the X-ray diffraction pattern in 1–2 s using an imaging plate. The kinetic formation processes of the interface reaction layer were measured by short-period exposure experiments with a high temperature X-ray diffractometer. NiAl₂O₄ was formed at the Ni/Al₂O₃ interface from 1468 K to 1673 K in air. The formation of NiAl₂O₄ obeyed the parabolic rate law. The value of the activation energy suggests that the diffusion of Al through NiAl₂O₄ controls the rate of formation. The results of thermal expansion coefficient measurements suggest that when a sample is cooled to room temperature, the magnitude of the stress on the Al₂O₃ owing to NiAl₂O₄ is smaller than that caused by NiO.     

La2O3含量对Al2O3/Cu基复合材料组织与性能的影响

以La₂O₃粉、Al粉、CuO粉为反应物原料、纯铜为基体,采用原位合成技术和近熔点铸造法制备颗粒增强Cu基复合材料,研究La₂O₃对Al-CuO体系制备的Cu基复合材料组织及性能的影响。结果表明：添加La₂O₃可获得纳米Al₂O₃颗粒,且弥散分布于Cu基体中,制备的材料组织更加细小、均匀,其材料的电导率及摩擦磨损性能明显提高。当添加0.6%wtLa₂O₃,复合材料的电导率达到90.2%IACS,磨损量达到最小,相比未添加La₂O₃,其导电率提高10.1%,磨损量减小36.6%。     

Anion gap and stability of the metallic phase for (TMTSF)2ClO4

Starting with the prototype nesting spectrum of (TMTSF)₂PF₆, it is emphasized that the gap due to anion ordering (AO) would result in a somewhat different SDW state for ClO₄ if the 'antinesting' term, t_b^′ was omitted. The field then first diminishes that term, improving nesting. At the same time the field decreases pairing between subbands with nesting features because of the difference in the symmetry of their wavefunctions. This leads to the reentrance of the metallic state. The magnetic breakdown (MB) gradually decreases the effect of AO. Properties of the "prototype" PF₆-material are expected to be seen again at large magnetic fields. However, it occurs in a peculiar phase diagram with sharp spikes in T_SDW periodic in the inverse magnetic field, 1/H. Cyclotron resonance on open orbits is discussed to study whether the 'transverse' gap due to AO in (TMTSF)₂ ClO₄ manifests itself in other properties.     

Al2O3/TiB2/Al复合材料的微观结构和高温力学性能

以细雾化铝粉和TiB₂颗粒为原料,通过粉末冶金和热轧制制备微米TiB₂和纳米Al₂O₃颗粒增强铝基复合材料。室温时,由于TiB₂和Al₂O₃的综合强化作用,Al₂O₃/TiB₂/Al复合材料的屈服强度和抗拉强度分别为258.7 MPa和279.3 MPa,测试温度升至350℃时,TiB₂颗粒的增强效果显著减弱,原位纳米Al₂O₃颗粒与位错的交互作用使得复合材料的屈服强度和抗拉强度达到98.2MPa和122.5 MPa。经350℃退火1000 h后,由于纳米Al₂O₃对晶界的钉扎作用抑制晶粒长大,强度和硬度未发生显著的降低。     

Thermochemistry of GaBO3 and phase equilibria in the Ga2O3–B2O3 system

Employing a Tian-Calvet-type calorimeter operating in the scanning mode at temperatures from 1120 to 1220 K, the enthalpy change, Δ_dH, associated with the decomposition of GaBO₃ (=1/2β-Ga₂O₃+1/2B₂O₃(liq.)) and the corresponding decomposition temperature, T_d, were determined: Δ_dH=30.34±0.6 kJ/mol, T_d=1190±5 K. Using the transposed-temperature-drop method the thermal enthalpy, H(T)−H(295 K), of GaBO₃ was measured as a function of temperature, T, in the region from 760 to 1610 K; the results obtained are

[H(T)−H(295 K)]/(J/mol)=104.8·(T/K)−31 300 (760 K<T<1190 K),

[H(T)−H(295 K)]/(J/mol)=138.8·(T/K)−41 480 (1190 K<T<1590 K).

On the basis of the experimental results, the enthalpy and entropy of formation, Δ_fH and Δ_fS, respectively, of GaBO₃ from the component oxides were derived:

Δ_fH=−30.34 kJ/mol,Δ_fS=−25.50 J/(K·mol) at 1190 K,

Δ_fH=−10.55 kJ/mol,Δ_fS=−5.48 J/(K·mol) at 298 K.

The enthalpy versus temperature curve shows, apart from a step associated with the decomposition of GaBO₃, a further step at 1593 K which is attributed to a monotectic equilibrium.     

Elastic behavior of La0.67Ca0.33MnO3:ZrO2 composites

A series of Colossal Magneto Resistance materials, with compositional formula (1 − x) La_0.67Ca_0.33MnO₃ + xZrO₂ (where x = 0%, 10%, 20%, 40%, 60%, 80%) were prepared by sol–gel technique. When characterized structurally by X-ray diffraction they are found to have cubic structure. After measuring their bulk densities, the ultra sonic longitudinal (V_l) and shear velocities (V_s) were measured at room temperature using the pulse transmission technique. Using the ultrasonic data, the values of Young's and rigidity moduli along with Poisson's ratio and Debye temperatures have been calculated. As the materials are porous, zero porous elastic moduli have also been arrived at using a well-known model. The observed variation of elastic moduli with varying ZrO₂ concentration has been explained qualitatively.     

Thermodynamics and phase diagrams in the binary systems Na2O-SiO2, Na2O-GeO2, Na2O-B2O3, Li2O-B2O3, CaO-B2O3, SrO-B2O3, and BaO-B2O3

We applied our model to the enthalpy of mixing data of the binary systems Na₂O-SiO₂, Na₂O-GeO₂, Na₂O-B₂O₃, Li₂O-B₂O₃, CaO-B₂O₃, SrO-B₂O₃, and BaO-B₂O₃. The most stable composition in the liquid, that is where the enthalpy of mixing is most negative, is with a metal-oxygen ratio of 4 to 3, for monovalent metals (Na and Li) and 3 to 4 for divalent metals (Ba and Ca) in liquid silicates or borates. The same applies to the CaO-SiO₂, CaO-Al₂O₃, PbO-B₂O₃, PbO-SiO₂, ZnO-B₂O₃, and ZnO-SiO₂ systems. The oxygen to metal ratio, its constant value in various types of systems, reflects and describes the structure of the liquid. Using the analyzed enthalpies of mixing data and the available phase diagrams, we calculated the enthalpies of formation of the various binary compounds. The results are in excellent agreement with data in the literature that were obtained from direct solid-solid calorimetry.     

Micro-EDM process investigation and comparison performance of Al3O2 and ZrO2 based ceramic composites

This paper investigates the micro-EDM behaviour of an Al₃O₂ and ZrO₂ based electrically conductive ceramic composites. The influence of the generator parameters on material removal rate, relative tool wear, surface quality and material removal mechanism is investigated towards the definition of suitable micro-EDM technologies. The study is based on a design of experiments, supported by a fundamental investigation of the generator parameters. Similar variations trends to the machining of steel are observed within the investigated process window, for exception of the tool wear performance. The developed EDM technologies are finally validated through the fabrication of industrial demonstrators.     

Subsolidus phase relations in the ZnO-WO3-Bi2O3 system

The subsolidus phase relations of the ternary system ZnO-WO₃-Bi₂O₃ were investigated by means of X-ray diffraction (XRD). Six binary compounds and seven 3-phase regions were determined, and no ternary compounds were found in this ternary system. The phase diagram of pseudobinary system ZnO-Bi₂WO₆ was also constructed through XRD and differential thermal analysis (DTA) methods, which forms eutectic system with eutectic temperature about 945 °C, the corresponding eutectic component is 35 mol% ZnO and 65 mol% Bi₂WO₆.     

Synthesis, characterization and electrical properties of CdI2 doped Al2O3 and TiO2 superionic conductors

Superionic conductors were prepared by admixing metallic oxides (alumina and titania) with cadmium iodide in different proportions using direct mixing method. The synthesized materials were characterized by various qualitative techniques such as XRD (X-ray diffraction), DSC (differential scanning calorimetry) and SEM (scanning electron microscopy). Pure CdI₂ shows the standard pattern which corresponds to β-phase stable at room temperature, however, the diffractograms of the mixtures shows two phase nature of the materials with no effect of the second phase on the peak positions of the first, i.e. CdI₂. DSC curves also confirmed the formation of composite. SEM micrographs show the presence of great number of space charge regions which are very important in creating a great number of surfaces which in turn act as additional sources of point defects. It was also found that the conductivity of CdI₂ increases with mole fractions of dopants till x = 0.5 for alumina and x = 0.3 for titania. Arrhenius equation was used to study the temperature dependence of electrical conductivity and the activation energy of pure cadmium iodide was found to be 0.792 eV.     

Studies on La0.67Ca0.33MnO3-SrTiO3 composites using two-phase model

In this study we report the structural, electrical and magnetic properties of (1 − x)La_0.67Ca_0.33MnO₃ (LCMO)-(x)SrTiO₃(STO) composites. For this series we have observed a minute change in ferromagnetic (FM)-paramagnetic (PM) transition temperature with STO addition in LCMO matrix; however a reasonable change is observed in metal-insulator transition temperature, along with the occurrence of percolation threshold for x = 0.30 sample. Overall pattern for temperature dependence of resistivity for this series has been best-fitted using the formula 1/ρ = (1 − f)/ρ_PM + (f/ρ_FM), whereρ_PM and ρ_FM are the resistivities of the PM and FM contents in the sample and f is the volume fraction of FM phase in the sample. Investigations on magnetoresistance (MR) using magnetic field up to 3 T show enhancement of extrinsic MR in the composite samples which can be viewed in the light of spin polarized tunneling.     

Thermodynamic reassessment of the BaO-B2O3 system

The BaO-B₂O₃ pseudobinary system is assessed. A two-sublattice ionic solution model, (Ba²⁺) _P (O²⁻, BO ₃ ³⁻ , B₄O ₇ ²⁻ , B₃O_4.5) _Q , is adopted to describe the liquid phase. All the solid phases are treated as stoichiometric compounds. A set of parameters consistent with most of the available experimental data on both phase diagram and thermodynamic properties is obtained by using CALPHAD technique. A comparison between the calculated results and experimental data as well as a previous assessment is presented.     

Hydrogen in lanthanum-magnesium-nickel alloys with structures of the L 22, D 2 d , and L 60 types

A statistical theory of the solubility of hydrogen in alloys with structures of the L2₂, D2 _d , and L6₀ types and in phase mixtures of these alloys is developed. The isotherms of absorption and desorption have been studied; their dependence on the activity of hydrogen and concentration of magnesium has been established. It is shown that with an increase in the magnesium concentration and a decrease in the activity of hydrogen, a plateau (a horizontal segment) appears and is lengthened in the isotherms. Hysteresis effects have been investigated with allowance for volume effects; the hysteresis coefficients have been estimated. The decrease in the hysteresis coefficient with increasing magnesium concentration is substantiated. The results of the theoretical calculations are compared with experimental data. Original Russian Text ? S.Yu. Zaginaichenko, Z.A. Matysina, D.V. Shchur, 2007, published in Fizika Metallov i Metallovedenie, 2007, Vol. 104, No. 5, pp. 453–464.     

Phase equilibria in the system La2O3-BaO-P2O5: The partial system LaPO4-Ba2P2O7-Ba(PO3)2

The LaPO₄-Ba₂P₂O₇-Ba(PO₃)₂ portion of the oxide La₂O₃-BaO-P₂O₅ system has been investigated. Important parts of this investigation were the determination of equilibria in the LaPO₄-Ba(PO₃)₂ subsystem and the addition of liquidus data to the partially known LaPO₄-Ba(PO₃)₂-Ba₂P₂O₇ subsystem. These data were combined with known data from the LaPO₄-Ba₂P₂O₇ subsystem and with measurements of the equilibria within the LaPO₄-Ba₃P₄O₁₃ isopleth to determine the nature of the phase equilibria in the quasi-ternary LaPO₄-Ba₂P₂O₇-Ba(PO₃)₂ system.