Phase Stability of Graphitelike BC4N up to 2100 K and 7 GPa

Thermal phase stability of graphitelike BC₄N (g-BC₄N) has been studied up to 7 GPa and 2100 K using in-situ powder diffraction of synchrotron radiation. It has been shown that the process of g-BC₄N decomposition at ambient pressure starts at 2050 K and occurs to form highly ordered hexagonal graphitelike boron nitride (hBN) and disordered graphite. As the pressure increases up to 6.6 GPa, the temperature of the decomposition onset decreases to 1070 K. At this pressure in the 1070-1400 K temperature range (decomposition degree of less than or equal to 0.1), the decomposition products remain the same, whereas at higher temperatures, the decomposition of g-BC₄N is accompanied by the formation of cubic boron nitride (cBN) and disordered graphite. Measurement of 298 K equation of state of g-BC₄N results in a zero-pressure bulk modulus of 18.1 ± 0.2 GPa and its pressure derivative of 6.6 ± 0.1. Thermodynamic analysis has shown that the g-BC₄N decomposition is a nonequilibrium process and the phase itself is metastable.     

The highly selective catalytic hydrogenation of CO2 to CO over transition metal nitrides

Three transition metal-like facet centered cubic structured transition metal nitrides, γ-Mo₂N, β-W₂N and δ-NbN, are synthesized and applied in the reaction of CO₂ hydrogenation to CO. Among the three nitride catalysts, the γ-Mo₂N exhibits superior activity to target product CO, which is 4.6 and 76 times higher than the other two counterparts of β-W₂N and δ-NbN at 600 ℃, respectively. Additionally, γ-Mo₂N exhibits excellent stability on both cyclic heating–cooling and high space velocity steady state operation. The deactivation degree of cyclic heating–cooling evaluation after 5 cycles and long-term stability performance at 773 and 873 K in 50 h are all less than 10%. In-situ XRD and kinetic studies suggest that the γ-Mo₂N itself is able to activate both of the reactants CO₂ and H₂. Below 400 ℃, the reaction mainly occurs at the surface of γ-Mo₂N catalyst. CO₂ and H₂ competitively adsorbe on the surface of catalyst and CO₂ is the relatively stronger surface adsorbate. At a higher temperature, the interstitial vacancies of the γ-Mo₂N can be reversibly filled with the oxygen from CO₂ dissociation. Both of the surface and bulk phase sites of γ-Mo₂N participate in the high temperature CO₂ hydrogenation pathway.     

Fabrication of CrN/Cr2N Bulk Composites and Their Mechanical Properties

Bulk CrN/Cr₂N billet with almost full density was successfully fabricated using spark-plasma sintering. Elastic moduli, hardness, and fracture toughness were evaluated to investigate the effect of sintering conditions on the mechanical properties. Ball-on-disk testing was performed to understand the wear and friction behavior of this bulk CrN/Cr₂N composite solid. The wear map was constructed as a function of the sliding velocity and the applied pressure, to categorize the wear mechanism of this nitride composite.     

Synthesis and properties of single phase diamond ceramics

We report on the synthesis of single phase diamond ceramics and its microstructural and physical characterization. The most relevant physical properties are listed and are compared to natural diamond. The ceramic solid has been fabricated from chemically treated micro crystalline diamond powder, where oxy-functional groups have been attached to the surface. The special surface treatment is considered essential to achieve direct atomic bonding between adjacent grains.The hot isostatic pressing method (HIP) has been applied for materials processing that pertains to the stability region of the related carbon phase diagram. No further additives have been used for preparation. Transmission and scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction and Raman spectroscopy have been used for the micro structural analysis. The achievable density is close to that of natural diamond, revealing porosity values of <3%. The micro structural analyses indicated the presence of small amounts of isolated diamond micro crystals, embedded into a matrix of polycrystalline diamond with a very small grain size. The grains are much smaller than the originally used micro crystalline source material, indicating crystal break-up and atomic rebonding during the sintering process. Also traces of sp²-hybridized carbon have been identified, located primarily at grain boundaries. Fracture of the material appears mostly transgranular. Relevant physical properties as thermal and electrical conductivity, hardness and Young's modulus approach those of natural diamond.     

Hot Isostatic Pressing of Chromium Nitrides (Cr2N and CrN) Prepared by Self-Propagating High-Temperature Synthesis

Cr₂N, CrN, and their mixtures (with desired fractions) have been prepared via self-propagating high-temperature synthesis (SHS) under a controlled nitrogen pressure, followed by hot isostatic pressing at 1300°C and 196 MPa under an atmosphere of argon gas. The combustion temperature increased as the nitrogen pressure increased. Single-phase Cr₂N was formed at 1040°C under a pressure of 0.18 MPa, and single-phase CrN was formed at 1730°C under a pressure of 2 MPa. The mechanical properties of the dense nitride ceramics (99.2% of the theoretical density) have been examined; the Vickers hardness (11.2 GPa for CrN and 14.5 GPa for Cr₂N) increased linearly as the fraction of Cr₂N increased, whereas the fracture toughness (∼4.7 MPa·m^1/2) and bending strength (∼355 MPa) are constant, regardless of the fraction of Cr₂N/CrN.     

水分含量对正己胺-Tf2N型质子化离子液体物理化学性质的影响

通过Br?nsted酸碱中和反应,合成了由碱正己胺（hexylamine, Hexam）与酸双三氟甲基磺酰亚胺[bis(trifluoromethylsulfonyl) imide,HTf₂N]形成的质子化离子液体（protic ionic liquids, PILs）,简称为HHexam(Tf₂N)型PILs,其疏水性较强,但仍溶解少量水,其中饱和水含量可达6.33% (w₀=[H₂O]/[PIL]=1.44 )。PILs中水分含量的多少对其物理化学性质影响较大,因此本研究在温度T=303.15~353.15K的范围内、不同含水量（w₀=0.12、0.23、0.47、0.74、1.0、1.28）条件下,测定了HHexam(Tf₂N)的密度、黏度及电导率。结果显示,在相同温度条件下,随着水分含量的增加,其密度和黏度值均降低,电导率升高。在相同含水量条件下,随着温度的升高,其密度值呈直线下降,黏度均呈指数下降趋势,电导率均呈指数上升趋势,并且lnη、lnσ与1000/T之间基本呈线性关系,基本符合Arrhenius方程。在w₀=0.12~1.28 范围内,HHexam(Tf₂N)的Walden线均在ΔW=0.5~1.0内,离子性较好,并且随着水分含量的增加,其Walden线靠近KCl理想线,即离子化程度增大。另外,当漏极电压为-0.6V时,由HHexam(Tf₂N)制备的聚(3,4-亚乙二氧基噻吩)有机电化学晶体管（PEDOT OECT）的最大跨导（2.79mS）为水溶液获得的PEDOT:PSS OECT最大跨导（0.832mS）的3.4倍。     

Synthesis of ordered small pore mesoporous silicates with tailorable pore structures and sizes by polyoxyethylene alkyl amine surfactant

Ordered mesoporous silicates with tailorable pore structures and small pore sizes have been synthesized by using polyoxyethylene alkyl amine surfactant PN-430 [CH₃(CH₂)₁₇N(EO)_x(EO)_y, x + y = 5] as a structure-directing agent under acidic condition. Two-dimensional (2-D) hexagonal (p6mm) mesoporous silicates have been prepared via an evaporation-induced self-assembly (EISA) process. The N₂ sorption isotherms show that the product has a small uniform pore size distribution of 1.8 nm by BJH model, a BET surface area of 730 m²/g and a pore volume of 0.36 cm³/g. 3-D cubic (Pm-3n) mesoporous silicate with small uniform pore size (1.76 nm) can also be prepared at high concentration of PN-430 by EISA method in tetrahydrofuran solvent. The solvothermal post-treatment by n-hexane at 70 °C for 3 d to the above material results in the phase transition of the mesostructure from Pm-3n to P6₃/mmc based on XRD and TEM analyses. In comparison, by using nonionic oligometric alkyl-ethylene oxide surfactant such as Brij 78 (C₁₈H₃₇EO₂₀) or Triton X-100 (CH₃C(CH₃)₂CH₂C(CH₃)₂C₆H₄ EO₁₀) as co-templates, high-quality hexagonal (p6mm) small pore mesoporous silicates have also been prepared in ethanol media. Our results show that the blend templates composed of PN-430 and a small amount of nonionic surfactant can increase the efficiency of organic and inorganic hybrid species assembly, improve the quality of the structural regularity, and decrease the pore size to about 1.65 nm.     

Zirconia stabilized with a mixture of the rare earth oxides

A hydrothermal technique was used to prepare micropowders of ZrO₂ solid solutions stabilized by the mixture of rare earth oxides and yttria (Ln₂O₃) recovered from phosphogypsum. Phase compositions and particle sizes of the powders were measured. Zirconia solid solutions of cubic and tetragonal symmetry are the major phases. A larger Ln₂O₃ concentration promotes a greater cubic phase content. Powders having low Ln₂O₃ concentrations have small amounts of monoclinic phase present.

The phase composition, fracture toughness (K_Ic) and Vickers hardness of samples sintered at temperatures ranging from 1250 to 1350°C were measured. Tetragonal and, in some cases, monoclinic zirconia solid solutions are found in the microstructure of the sintered bodies. Two ordered phases with the formulae Ln₂Zr₂O₇ and Ce₂Zr₃O₁₀ were also detected in the system. Tetragonal zirconia polycrystals (TZP) with high (10 MPaM^0·5) fracture toughness were found.     

Subsolidus Phase Equilibria and Ordering in the System ZrO2-Y2O3

The subsolidus phase relations in the entire system ZrO₂-Y₂O₃ were established using DTA, expansion measurements, and room- and high-temperature X-ray diffraction. Three eutectoid reactions were found in the system: ( a ) tetragonal zirconia solid solution→monoclinic zirconia solid solution+cubic zirconia solid solution at 4.5 mol% Y₂O₃ and ∼490°C, ( b ) cubic zirconia solid solutiow→δ-phase Y₄Zr₃O₁₂+hexagonalphase Y₆ZrO₁₁ at 45 mol% Y₂O₃ and ∼1325°±25°C, and ( c ) yttria C -type solid solution→wcubic zirconia solid solution+ hexagonal phase Y₆ZrO₁₁ at ∼72 mol% Y₂O₃ and 1650°±50°C. Two ordered phases were also found in the system, one at 40 mol% Y₂O₃ with ideal formula Y₄Zr₃O₁₂, and another, a new hexagonal phase, at 75 mol% Y₂O₃ with formula Y₆ZrO₁₁. They decompose at 1375° and >1750°C into cubic zirconia solid solution and yttria C -type solid solution, respectively. The extent of the cubic zirconia and yttria C -type solid solution fields was also redetermined. By incorporating the known tetragonal-cubic zirconia transition temperature and the liquidus temperatures in the system, a new tentative phase diagram is given for the system ZrO₂-Y₂O₃.     

碱金属氧化物Na2 O对陶瓷结合剂金刚石磨具性能的影响

通过调整陶瓷结合剂中碱金属氧化物Na₂O含量,来探究碱金属氧化物Na₂O对陶瓷结合剂金刚石磨具性能的影响。当n(Na₂O)/n(SiO₂)=0.1时,磨具试样的强度(57.7 MPa)和硬度(117 HRB)达到最大值。随着碱金属氧化物Na₂O添加量的增加,结合剂的耐火度随之显著降低,流动性显著增加。磨具试样断口SEM照片表明,适量的碱金属氧化物Na₂O能够使磨具断面空隙减少,孔隙度降低,结合剂与磨料分布更加均匀,结合剂与磨料结合界面更加紧密。XRD分析表明,磨具试样在720 ℃下烧结,结合剂中除了玻璃相还产生了一种晶相,结合剂中碱金属氧化物Na₂O的含量对烧结后产生的晶相种类无影响。     

Microstructure of a Molybdenum Nitride Layer Formed by Nitriding Molybdenum Metal

For pure molybdenum nitrided at 1373 K in NH₃ gas, microstructural observations of a molybdenum nitride layer were conducted through a transmission electron microscope. The molybdenum nitride layer consisted of two molybdenum nitrides: an outer one of γ-Mo₂N and an inner one of β-Mo₂N. A great number of (011)[0     1] type twins were observed in the β-Mo₂N phase, whereas the microstructure of the γ-Mo₂N phase was almost free from lattice defects except for slightly observed {111}〈112〉 type twin.     

Revised Phase Diagram of the System ZrO2-CeO2 Below 1400°C

The phase diagram of the system ZrO₂-CeO₂ was rein-vestigated using hydrothermal techniques. Cubic, tetragonal, and monoclinic solid solutions are present in this system. The tetragonal solid solution decomposes to monoclinic and cubic solid solutions by a eutectoid reaction at 1050°50°C. The solubility limits of the tetragonal and cubic solid solutions are about 18 and 70 mol% CeO₂, respectively, at 1400°C, and about 16 and 80 mol% CeO₂, respectively, at 1200°C. Solubility limits of the monoclinic and cubic solid solutions are about 1.5 and 88 mol% CeO₂ at 1000°C, and 1.5 and 98 mol% CeO₂ at 800°C, respectively. The compound Ce₂Zr₃O₁₀ is not found in this system.     

Raman scattering,AFM and nanoindentation characterisation of diamond films obtained by hot filament CVD

In this work, structure and mechanical properties of diamond films fabricated by HFCVD on silicon substrates with nanodiamond seeding were investigated. Raman spectroscopy was used to characterise the diamond phase content, crystalline quality and source of stresses in these films. Topography, hardness and Young's modulus were studied by scanning force microscopy (SFM) and nanoindentation methods. It has been ascertained that for the diamond films grown on silicon substrates with nanodiamond seeding hardness and crystalline quality is higher than for films on scratched silicon. The diamond films demonstrate Raman upshift with respect to natural diamond, indicating presence of internal compressive stress. It was shown that various types of impurities and defects induce compressive stresses in the diamond grains.     

Phase Relations in the System UO2-UO3– Y2O3

The phase relations in the system U02-U03-Yz03, particularly in the Y203-rich region, were examined by X-ray and chemical analyses of reacted powders heated at temperatures up to 1700°C in H₂, CO₂-CO₂ and air. Four phases were identified in the system at temperatures between 1000° and 1700°C: U308, face-centered cubic solid solution, body-centered cubic solid solution, and a rhombohedral phase of composition (U,Y)₇O₂ ranging from 52.5 to 75 mole % Y₂O₃. The rhombohedral phase oxidized to a second rhombohedral phase with a nominal composition (U,Y), at temperatures below 1000°C. This phase transformed to a face-centered cubic phase after heating in air above 1000° C. The solubility of UO, in the body-centered cubic phase is about 14 mole % between 1000° and 1700°C but decreases to zero as the uranium approaches the hexavalent oxidation state. The solubility of Yz03 in the face-centered cubic solid solution ranges from 0 to 50 mole % Y2O3 under reducing conditions and from 33 to 60 mole % Y2O3 under oxidizing conditions at 1000°C. At temperatures above 1000° C, the face-centered cubic solid solution is limited by a filled fluorite lattice of composition (U,Y)O₂. For low-yttria content, oxidation at low temperatures (<300°C) permits additional oxygen to be retained in the structure to a composition approaching (U,Y)O_2.25 A tentative ternary phase diagram for the system UO₂-UO₃-Y₂O₃ is presented and the change in lattice parameter and in cell volume for the solid-solution phases is correlated with the composition.     

Phase Relations in the System ZrO2-Y2O3 at Low Y2O3 Contents

Subsolidus phase relations in the low-Y₂O₃ portion of the system ZrO_2-Y₂O₃ were studied using DTA with fired samples and X-ray phase identification and lattice parameter techniques with quenched samples. Approximately 1.5% Y₂O₃ is soluble in monoclinic ZrO₂, a two-phase monoclinic solid solution plus cubic solid solution region exists to ∼7.5% Y₂O₃ below ∼500°C, and a two-phase tetragonal solid solution plus cubic solid solution exists from ∼1.5 to 7.5% Y₂O₃ from ∼500° to ∼1600°C. At higher Y₂O₃ compositions, cubic ZrO₂ solid solution occurs.     

三维菱形结构微通道内气液传质与强化

研究了具有三维交错菱形结构的微通道对离子液体1-丁基-3-甲基咪唑四氟硼酸盐([Bmim][BF₄])水溶液吸收CO₂过程的传质增强作用。实验主要聚焦于弹状流和破碎弹状流。考察了弹状流型下气液流量、离子液体浓度对体积传质系数k_La、增强因子E、CO₂吸收率X及压力降ΔP的影响。结果表明,较之于直通道,三维菱形通道可以显著提高体积传质系数和CO₂吸收率,其增强因子可达2.1,压力降仅增加 0.9 kPa。提出了一个新的体积传质系数k_La预测式,预测效果良好。采用VOF法模拟了微通道内气液两相流动过程,获得了连续相的速度矢量场。三维菱形通道能诱导涡流,强化传质过程。     

Reaction During Sintering of Barium Titanate with Lithium Fluoride

The reactions occurring during sintering of stoichiometric BaTiO₃ with small additions of LiF were studied at temperatures between 700° and 900°C. BaTiO₃ reacts with LiF to form a cubic solid solution and Li₂TiO₃ During sintering, the cubic solid solution coexists with Li₂Ti0₃ and forms a liquid phase at 740°± 5°C. The occurrence of a liquid phase at this temperature results in an enhancement of the sintering process and leads to the development of a highly dense microstructure.     

Thermodynamic Assessment of the ZrO2─YO1.5 System

An optimal set of thermodynamic functions for the ZrO₂─YO_1.5 system are obtained using phase diagram and thermodynamic data. The liquid is described by a subregular solution model. Both cubic ZrO₂ and YO_1.5 solid solutions are regarded as one cubic solution, which is also treated as a subregular solution. The ordered Zr₃Y₄O₁₂ phase is treated as a stoichiometric compound. A regular solution model is applied to the other solid solutions. Tentative equilibrium boundaries between monoclinic and tetragonal ZrO₂ solid solutions are evaluated from information about the T ₀ line. The calculated phase diagram and thermodynamic functions agree well with experimental data.     

High-Pressure Phase Transitions in Zirconia and Yttria-Doped Zirconia

Raman spectroscopy has been utilized to characterize the phase transformations and transition pressures in pure and doped zirconia containing 3, 4, and 5 wt% Y₂O₃. The pressure-induced transformations were investigated to over 6 GPa (at room temperature) using a diamond anvil pressure cell. Pure zirconia single-crystal samples transformed to a "new" tetragonal phase (different from the one obtained at high temperatures at atmospheric pressure) at about 4 GPa. The pressure transformation, like the temperature transition, was reversible and exhibited an approximately 0.45-GPa hysteresis at room temperature. The 3 and 4 wt% Y₂O₃ crystals underwent a monoclinic ( P 2_1/b) to tetragonal ( P 4_{2 nmc}) phase transition similar to that observed at high temperatures. This phase change was found to be irreversible on releasing the pressure. The 5 wt% Y₂O₃ at atmospheric pressure consists of a tetragonal modification in a disordered cubic matrix; a gradual, but reversible, disordering transformation of the tetragonal precipitate takes place with pressure.     

Pyrochlore Phase Formation in the System Bi2O3–ZnO–Ta2O5

The subsolidus phase diagram of the system Bi₂O₃–ZnO–Ta₂O₅ in the region of the cubic pyrochlore phase has been determined at 1050°C. This phase forms a solid solution area that includes the ideal composition P, Bi₃Zn₂Ta₃O₁₄; possible solid solution mechanisms are proposed, supported by density measurements of Zn-deficient solid solutions. The general formula of the solid solutions is Bi_{3+ y} Zn_{2− x} Ta_{3− y} O_{14− x − y} , based on the creation of Zn²⁺, O²⁻ vacancies in Zn-deficient compositions and a variable Bi/Ta ratio.