Chemical vapour deposition of molybdenum carbides: aspects of phase stability

Thin films of different molybdenum carbides (δ-MoC_1−x, γ′-MoC_1−x and Mo₂C) have been deposited from a gas mixture of MoCl₅/H₂/C₂H₄ at 800°C by CVD. The H₂ content in the vapour has a strong influence on the phase composition and microstructure. Typically, high H₂ contents lead to the formation of nanocrystalline δ-MoC_1−x films while coarse-grained γ′-MoC_1−x is formed with an H₂-free gas mixture. This phase has previously only been synthesized by carburization of Mo in a CO atmosphere and it has therefore been considered as an oxycarbide phase stabilized by the presence of oxygen in the lattice. Our results, however, show that γ′-MoC_1−x films containing only trace amounts of oxygen can be deposited by CVD. Stability calculations using a FP-LMTO method confirmed that the γ′-MoC_1−x phase is stabilized by oxygen but that the difference in energy between e.g. δ-MoC_0.75 and oxygen-free γ′-MoC_0.75 is small enough to allow the synthesis of the latter phase in the absence of kinetic constraints. Annealing experiments of metastable δ-MoC_1−x and γ′-MoC_1−x films showed two different reaction products suggesting that kinetic effects play an important role in the decomposition of these phases.     

Determination of matrix and precipitate elastic constants in (γ–γ′) Ni-base model alloys, and their relevance to rafting

A complete set of high-temperature data relevant to rafting, i.e. the elastic constants of the individual γ and γ′ phases and the elevated temperature lattice mismatch between the phases, was generated for two model ternary Ni–Al–Mo single crystal alloys. The directionality of rafting was examined experimentally in the same alloys upon uniaxial loading in compression and tension along a 100 cube axis. The key material properties and corresponding directional coarsening observations are discussed in view of the various models for rafting published in the literature.     

Gamma double prime precipitation kinetic in Alloy 718

Gamma double prime (γ′′), precipitation was studied in Alloy 718 using isothermal and isochronal aging heat treatments applied between 943 and 1003 K. It is shown, that the coarsening behavior of γ′′ precipitates follows the coarsening kinetic predictions of the Lifshitz–Slyozov–Wagner (LSW) theory. The activation energy for γ′′ growth has been determined as equal to 272 kJ mol⁻¹ and seems to be controlled by volume diffusion of niobium in the matrix. The energy of the γ′′/matrix interface, Γ, has been found to be 95 ± 17 mJ m⁻² by assuming that the γ′′ precipitates adopt a disk shape which minimizes the total energy. This energy includes a volume distortion term calculated from the Eshelby inclusion theory and a surface component which is assumed to be isotropic. This interfacial energy is discussed and compared with the energy of γ′/matrix and γ′′/matrix interfaces in other superalloys. The constant K′′ of the LSW law time dependence has been calculated using the value of interfacial energy and the activation energy of γ′′ precipitates coarsening and is found to be in good agreement with our experimental values.     

Pre-ageing of AlSiCuMg alloys in relation to structure and mechanical properties

The effect of magnesium addition to the AlSi9Cu3.5 alloy on the hardening and precipitates morphology during ageing at RT, 160°C or two stage ageing (TSA) was studied using TEM and XSAS methods. It was found that only alloys with Mg addition harden during RT ageing and they also attain the highest hardness maximum at 160°C or during TSA. Two types of precipitates (starting from 0.4 and 1.2 nm) were identified during ageing at RT using XSAS method. They cause streaks in the electron diffraction patterns. In alloys aged at 160°C with Mg addition the S′ phase was identified using lattice imaging technique in addition to the θ′ plates formed during ageing of the ternary AlSiCu alloy.     

Effect of an aluminide coating on precipitate rafting in superalloys

The microstructure of single crystal superalloy SRR99 is shown to be significantly affected by the combined effect of the application of an aluminide diffusion coating and the mechanical deformation caused by thermomechanical fatigue. In the case of an R = −∞ cycle (compressive strains), plates parallel to the coating surface develop in a layer underneath the subcoating zone, markedly differing from the precipitate coalescence observed, in the bulk. This effect is absent in the R = 0 cycles (tensile strains). This phenomenon is successfully explained in the light of a criterion for the prediction of γ′ rafting, by considering the superposition of the strains produced both by the TMF cycling and by a layer of γ′ which is observed to develop during the tests with R = −∞.     

多级结构α-MoO3空心微球的构筑及其对有机染料的吸附性能

具有多级结构的半导体金属氧化物, 其特有的立体空间结构使材料具有超高活性, 在吸附领域具有应用潜力。研究采用简单的一步溶剂热法制备了空心球状的MoO₂前驱体, 400 ℃热处理后得到多级结构α-MoO₃空心微球。空心球的直径为600~800 nm, 由宽度约70 nm的纳米棒构筑而成。该球状α-MoO₃纳米材料对亚甲基蓝(MB)染料具有优良的吸附性能。当α-MoO₃吸附剂用量为0.5 g/L、MB染料浓度为20 mg/L、吸附时间为5 min时, 移除率可达到73.40%。吸附60 min时, 吸附达到平衡, 此后移除率为97.53%~99.65%。该吸附动力学过程符合拟二级动力学模型, 吸附等温线符合 Langmuir 模型拟合, 最大吸附量为 1543.2 mg/g。α-MoO₃微球由于多级且中空的纳米结构, 对MB染料具有用量少、吸附速率快和吸附完全等特点。该材料可以用于吸附废水中其他有机染料。     

Research and Improvement on structure stability and corrosion resistance of nickel-base superalloy INCONEL alloy 740

INCONEL alloy 740 is a newly developed Ni–Cr–Co–Mo–Nb–Ti–Al superalloy in the application to ultra-supercritical boilers with steam temperatures up to 700 °C. By means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), micro-chemical phase analyses, and corrosion-resisting test, this paper investigates the structure stability of the alloy at elevated temperature and concentrates on coal ash corrosion performance of the alloy under the simulated coal ash/flue gas condition. Experimental results show that the most important structure instabilities of the alloy during prolonged aging are γ′ coarsening, γ′ to η transformation and G phase formation at grain boundary. The performance of corrosion resistance of the alloy would meet the requirement of ultra-supercritical boiler tubes. The phase computation by means of Thermo-Calc has been adopted in chemical composition modification for structure stability improvement. Two suggested new modified alloys in adjustment of the Al and Ti contents and in control of Si level, and also in maintenance of Cr content of the alloy were designed and melted for experimental investigation. These two modified alloys exhibit more stable microstructure during 760 °C long time aging.     

Analysis of interface states and series resistance at MIS structure irradiated under Co γ-rays

In this research, we investigated the effect of ⁶⁰Co γ-ray exposure on the electrical properties of Au/SnO₂/n-Si (MIS) structures using current–voltage (I–V) measurements. The fabricated devices were exposed to γ-ray doses ranging from 0 to 300 kGy at a dose rate of 2.12 kGy h⁻¹ in water at room temperature. The density of interface states N_ss as a function of E_c–E_ss is deduced from the forward bias I–V data for each dose by taking into account the bias dependence effective barrier height and series resistance of device at room temperature. Experimental results show that the γ-irradiation gives rise to an increase in the zero bias barrier height Φ_BO, as the ideality factor n and N_ss decrease with increasing radiation dose. In addition, the values of series resistance were determined using Cheung's method. The R_s increases with increasing radiation dose. The results show that the main effect of the radiation is the generation of interface states with energy level within the forbidden band gap at the insulator/semiconductor interface.     

合成具有高效光催化活性的片状β-Bi2O3的一种新方法

采用萃取-反萃-热分解法以辉铋矿的盐酸浸出液为原料制备了层片状的β-Bi₂O₃。所制备的样品分别用X衍射仪及透射电镜对其物相及形貌进行表征, 以罗丹明B为污染物研究了其光催化活性。结果表明: 所制备的β-Bi₂O₃是一种层状的纳米片, 具有较低的禁带宽度。在实验条件下, 对罗丹明B进行4 h的降解, 降解率达到99.23%, 样品的重复降解实验还表现出良好的循环稳定性。     

高Q值(1-x)(Sr0.2Nd0.208Ca0.488)TiO3-xNd(Ti0.5Mg0.5)O3微波陶瓷的微结构及介电性能研究

采用固相法制备了(1-x)(Sr_0.2Nd_0.208Ca_0.488)TiO₃-xNd(Ti_0.5Mg_0.5)O₃(0.3≤x≤0.4, SNCT-NTMx)系微波介质陶瓷材料, 并研究了该体系的相组成、显微结构、烧结性能和微波介电性能之间的关系。结果表明: 在x = 0.3~0.35范围内, SNCT-NTMx陶瓷形成了正交钙钛矿固溶体, 并伴随有少量未知第二相; 当x增至0.4时, 第二相含量有所增加。介电性能研究结果显示: 随着x的增加, 体系介电常数(ε_r)减小, 但品质因子(Q×f)得到改善; 此外, 体系谐振频率温度系数(τ_f)随NTM含量的增加逐渐向负值方向移动。当x = 0.35, 陶瓷样品在1520℃烧结4 h 得到的微波介电性能较优: ε_r=50.1, Q×f =44910 GHz, τ_f= -1.7×10^-6/℃。     

Dielectric properties, ac conductivity and thermal behaviour of flux grown cadmium titanate crystals

The dependence of loss tangent (tan δ) and both real and imaginary parts of the dielectric constant (′ and ″) on temperature in the range 298–923 K and frequency in the range 10³–10⁶ Hz for flux grown CdTiO₃ single crystals is reported. The ln σ_ac versus T plots suggest the conduction mechanism to be ionic hopping conduction. From ln σ_ac versus frequency curves, it can be seen that the slope decreases with the rise in temperature, suggesting that the ionic hopping conduction diminishes with the rise in temperature. The activation energy at various fixed frequencies is calculated from the slope of the graph between ln σ_ac versus 1/T (×10³ K⁻¹). Thermal behaviour of flux grown CdTiO₃ crystals using thermoanalytical techniques including TG, DTA and DTG is discussed. Thermal analysis suggests decomposition of CdTiO₃ in the temperature interval of 1386–1693 K leading to the formation of TiO₂ as the final product. Results obtained on application of TG based models viz. Horowitz–Metzger, Coats–Redfern and Piloyan–Novikova are reported. The results of kinetics of thermal decomposition suggest contracting cylinder model as the one that is relevant to the decomposition of CdTiO₃. The kinetic parameters viz. the order of reaction, activation energy, frequency factor, and entropy of activation using the above mentioned models are computed.     

Magnetoimpedance effect at various temperatures for manganite La0.7Ca0.3MnO3−δ

In the present work, the AC magnetoimpedance effect in La_0.7Ca_0.3MnO_3−δ at various temperatures are investigated. The peak of the metal–insulator transition occurs in the temperature dependence of impedance. Negative magnetoimpedance effect in the La_0.7Ca_0.3MnO_3−δ is obtained at frequencies f≤10 MHz. In the magnetoimpedance effect of manganites, the magnetic field not only decreases the permeability μ_t, but also reduces the resistivity ρ by aligning the local spins and varying the transfer integral t_ij. The AC magnetoimpedance participated by the DC colossal magnetoresistance (CMR) in manganites, should be connected with the combined effects of double exchange interaction, electron–phonon coupling and skin effect.     

Mechanical behaviour of a two-phase material from the behaviour of its components: Interface modelling by finite element method

In this paper, the principle of a solution for “thermal” connection between two solids is analyzed. We shows results given by the solution applied to the mechanical behaviour of a γ/γ′ two-phase material and to “artificial” structures obtained from modern techniques for epitaxial deposit. It appears that the use of a true or fictitious thermal loading constitutes a simple “connection” procedure, but is particularly coherent with the mechanics of two-phase crystalline materials with different lattice parameters. It would be interesting to apply the model to real structures, with misfit and interfacial dislocations.     

Effect of γ′ precipitation during hot isostatic pressing on the mechanical property of a nickel-based superalloy

The effect of the precipitation of γ′ phase during hot isostatic pressing (HIPing) on the mechanical property of a nickel-based superalloy, GTD-111, was evaluated by conducting tensile and creep-rupture tests at 871 °C. In the 4-h two-step HIP process, the coupons were isostatically compressed (at 120 MPa) and heated to 1230 °C, well above the dissolution temperature of γ′ precipitates into the γ matrix, for the first 2 h, and cooled down to a temperature to induce the precipitation of γ′ phase and held for the last 2 h at 120 MPa or at ambient pressure. The precipitates were controlled in size by varying the temperature for the last half of the process. According to the result of the tensile test, the mechanical properties of the alloy were varied upon the microstructural evolution, and improved more than 40%, compared to those of the untreated ones. The precipitation of γ′ phase under high pressure further improved in the properties, suggesting that the precipitation of γ′ phase at high pressure provides an advantage for the rigidity of the structure. Based on these findings, a 6-h three-step HIP process was tried, and proved to be an effective substitute for the normal heat treatment, especially in terms of creep properties. This feature was mostly attributed to the homogenized microstructure of HIPed ones, as evidenced by the X-ray diffraction patterns.     

γ-NaxCoO2粉体的聚丙烯酸钠凝胶法制备及其表征

本研究发展了一种用于制备氧化物热电材料γ-Na_xCoO₂粉体的化学合成方法——聚丙烯酸钠(PAAS)凝胶法。主要研究了PAAS/Co²⁺摩尔比、原料浓度和煅烧温度对产物相组成及微观形态的影响规律, 探讨了物相形成机制, 同时用该方法结合SPS制备了不同Na离子浓度的Na_xCoO₂多晶样品, 并对其热电性能进行了表征。结果表明, PAAS/Co²⁺摩尔比对产物相组成产生了显著影响, 随着PAAS/Co²⁺摩尔比的增加, 样品的相组成由Co₃O₄相向单相γ-Na_xCoO₂转变, 合适的PAAS/Co²⁺摩尔比为0.8~1.1。而反应原料浓度对产物相组成的影响存在一个临界值(0.025 mol/L), 大于临界值抑制单相形成, 小于临界值促进单相形成。煅烧温度的升高有助于γ-Na_xCoO₂单相的形成, 800℃煅烧得到γ-Na_xCoO₂单相, 晶粒形态呈片状, 平均厚度约200 nm, 片状方向的尺寸在1~4 μm之间。随着Na含量的增加, 样品的Seebeck系数增大, 电导率增加, 热导率降低, 最终导致ZT值大幅增加。     

Characterization and body distribution of beta-elemene solid lipid nanoparticles (SLN)

Solid lipid nanoparticles (SLN) containing β-elemene, a volatile oil used for the treatment of cancer, were prepared by the method combining probe sonication and membrane extrusion. Effects of the formulations and procedures on the characteristics of SLN were investigated. Body distribution of β-elemene SLN in rats after intravenous administration was compared with that of the commercial emulsion. The results showed that dispersing the surfactant in the melted lipid matrix could obtain smaller particles than that dispersing in the water phase. Increasing the ratio of monostearin in the lipid matrix or the concentration of surfactant reduced the mean volume size of the SLN. Optimized formulation was composed of monostearin and precirol ATO 5 at a mass ratio of 3:7, which was quite stable for 8 months at room temperature. In vitro release of β-elemene from the SLN was slow and stable without obvious burst release and was found to follow the Higuich equation. After intravenous administration, the β-elemene levels after 5 min injection of SLN formulation were 1.5, 2.9, and 1.4 times higher than those of β-elemene emulsion in liver, spleen, and kidney, respectively, while the concentrations of β-elemene were decreased 30% in heart and lung. Therefore, the SLN containing β-elemene might be an attractive candidate for the treatment of liver cancer.     

高居里温度BaTiO3-(Bi0.5Na0.5)TiO3无铅正温度系数电阻陶瓷的制备

用传统的固相反应烧结法制备了(1-xmol%)BaTiO₃-xmol%(Bi_0.5Na_0.5)TiO₃(BBNTx)高温无铅正温度系数电阻( positive temperature coefficient of resistivity, PTCR)陶瓷。X射线衍射表明所有的BBNTx陶瓷形成了单一的四方钙钛矿结构。SEM分析结果显示随着BNT含量的增加, 陶瓷晶粒尺寸减小。空气中烧结的0.2mol% Nb掺杂的BBNT1陶瓷, 室温电阻率为~10² Ω·cm, 电阻突跳为~4.5个数量级, 居里温度为~150℃。氮气中烧结的0.3mol% Nb掺杂的BBNTx(10≤x≤60)陶瓷, 同样具有明显的PTCR效应, 居里温度在180~235℃之间。随着BNT含量的增加, 材料的室温电阻率增大, 同时陶瓷的电阻突跳比下降。     

MgO/Eu2O3共掺杂对Al2O3陶瓷微波介电性能的影响

利用湿化学法制备了MgO/Eu₂O₃共掺Al₂O₃陶瓷, 研究了不同的MgO/Eu₂O₃掺杂量对Al₂O₃陶瓷物相组成、显微结构和微波介电性能的影响。结果表明: 适量的MgO/Eu₂O₃共掺有助于Al₂O₃的致密化和晶粒生长。在介电性能方面, MgO/Eu₂O₃共掺对Al₂O₃陶瓷的介电常数没有明显的影响, 但对介电损耗的影响显著。随着Eu₂O₃含量的增加, Al₂O₃陶瓷的Q×f值会呈现先增加后下降的变化趋势。0.05wt% MgO/0.10wt% Eu₂O₃共掺的样品在1590℃下保温4 h获得的微波介电性能最佳, ε_r~9.82, Q×f ~225, 225 GHz。Q×f值的这种变化可能与样品微观结构的变化相关。先是随着MgO/Eu₂O₃共掺量的增加, 晶粒尺寸不断增加, 晶界不断减少, 这有利于Q×f值的提高; 接着, 当MgO/Eu₂O₃共掺量进一步增加时, 晶粒尺寸不断下降, 晶界增多, 这会导致样品Q×f值的降低。另外, 应力和第二相也可能对Q×f值的变化产生影响。     

A linear θ time-marching algorithm in 3D BEM formulation for elastodynamics

A time-marching process similar to the well-known Wilson θ-method is used in order to develop an algorithm for carrying out the 3D time domain analyses with the boundary element method (BEM). The scheme described here, when incorporated to existing BE algorithms, can improve substancially the stability of the tractions time responses for both: bounded and unbounded domain applications. In order to conclude in fact that the proposed time-marching scheme makes possible to broaden the choice of the time step length, the BE time domain response for a classical example is discussed. For this analysis linear time interpolation functions for displacements and tractions are employed. In addition, to the basic idea of the θ time-marching scheme presented here an analysis of stability by numerical experimentation and computational aspects of the time domain BEM algorithm are other topics discussed.     

Study on surface and mechanical fiber characteristics and their effect on the adhesion properties to a polycarbonate matrix tuned by anodic carbon fiber oxidation

Polyacrylonitrile (PAN) based high strength carbon fibers were anodically oxidized using the galvanostatic mode in alkaline electrolyte solutions to influence the chemical surface composition. The change of chemical and physical properties was investigated using scanning electron microscopy (SEM), photoelectron spectroscopy (XPS), energy dispersive X-ray analysis (EDX) and contact angle as well as zeta (ζ)-potential measurements.

An initially improved wettability for polar liquids, particularly water, was observed for oxidized carbon fibers. This result was confirmed by ζ-potential measurements. The chemical state of the oxygen containing surface groups changes during anodic oxidation in K₂CO₃/KOH due to further oxidation of C–OH and C=O groups to COOH groups. Therefore the surface acidity increases, which leads to a shift of the isoelectric point to lower pH values and increases the negative ζ_plateau value. The ζ–pH as well as the ζ–concentration dependence show the same tendency. During anodic oxidation of carbon fibers in KNO₃/KOH electrolyte solution beside ‘normal’ (like C–OH, C=O and COOH) surface oxides also carboxylate groups (COO⁻K⁺) were formed at the fiber surface in contrast to an oxidation in K₂CO₃/KOH which introduces ‘normal' surface oxides. No influence could be observed of such an anodic oxidation on the single fiber tensile strength. Contact angle measurements of polycarbonate melt droplets onto single carbon fibers show no dependence of the surface composition. The interfacial shear strength, measured using the microdroplet pull-off test were compared with the thermodynamic work of adhesion. The calculated as well as the measured adhesion show the same absence of any influence of fiber treatment.