Development of ultrafine-grained tungsten-based materials for applications under conditions of high-velocity impact

The effect of green porosity of powder specimens and dispersion of nanostructured tungsten powder specimens on the density of sintered alloys of the tungsten – nickel system is investigated. It is shown that the maximum density of the alloys is achieved during liquid-phase sintering of powder compacts for one hour irrespective of their initial porosity within the range from 30 to 65 vol.%. Dispersion of the nanostructured tungsten powders also affects the final porosity. Using the calculations and experimental studies, the effective penetration of cylindrical striker bars made from the WNi-91 tungsten-nickel alloy into steel plates is investigated.     

Preparation and characterization of scandia and Re doped tungsten matrix impregnated cathode

The paper describes the preparation and emission property of scandia and Re doped tungsten matrix impregnated cathode. By an easy and reproducible way, solid-liquid doping combined with two-step reduction, powders of tungsten particles covered with scandium oxide were obtained. Compared with scandia mixed tungsten powders prepared by mechanically mixing, scandia and rhenium doped tungsten powders had smaller particle size, for example, scandia (3 wt%) and Re (5 wt%) doped tungsten powders had the average size of about 50 nm in diameter. Based on this kind of powder, scandia and Re doped tungsten matrix with the sub-micrometer sized tungsten grains and a more uniform distribution of Sc₂O₃ were obtained in this paper. Scandia and Re doped tungsten matrix impregnated cathode had shown excellent emission property and good emission uniformity. The space charge limited current densities of more than 58A/cm² at 900 °C_b could be obtained and the work function of this cathode was as low as 1.18 eV.     

Physical Characteristics and Sintering Behavior of MgO-Doped ZrO2nanoparticles

Nanosized particles of 13mol% MgO-doped ZrO₂ with a narrow distribution of pore sizes were prepared by the coprecipitation technique using optimized parameters of synthesis. Transmission electron microscopy analysis of the calcined powder reveals that the majority of the particles have grain sizes in the 10–20nm range. From nitrogen adsorption analysis an average particle size of 13nm was estimated, which is similar to the average pore size diameter (12nm). Besides the unimodal distribution of pore sizes, the linear shrinkage curve of a powder compact exhibits several inflexions indicating different rates of densification up to 1600°C. After sintering at 1600°C for 2h, the microstructure features of a compact are characteristics of the intermediate stage with interconnected porosity preferentially observed at grain boundaries. These results are explained as a size effect of nanoparticles of magnesia-doped zirconia during sintering.     

Influence of a plasma jet on different types of tungsten

The influence of a plasma producing nonstationary thermal loads akin to edge-localized modes in a tokamak on different types of tungsten is investigated. Tungsten is irradiated by a jet of a hydrogen plasma generated in a plasma gun. The plasma density and velocity are on the order of 10²² m^?3 and 100–200 km/s, respectively, and the irradiation time is 10 μs. Two plasma flux densities, 0.70 and 0.25 MJ/m², are used. Structural modifications in irradiated single-crystal and hot-rolled tungsten samples, as well as in V-MP and ITER_D_2EDZJ4 tungsten powders, are examined. It is found that the plasma generates a regular crack network with a period of about 1 mm on the surface of the single-crystal, hot-rolled, and V-MP powder samples, while the surface of the ITER_D_2EDZJ4 powder is more cracking-resistant. The depth of the molten layer equals 1–3 μm, and the extension of intense thermal action is 15–20 μm. The material acquires a distinct regular structure with a typical grain size of less than 1 μm. X-ray diffraction analysis shows that irradiation changes the crystal lattice parameters because of the melting and crystallization of the surface layer. The examination of the V_MP tungsten powder after cyclic irradiation by a plasma with different energy densities shows that high-energy-density irradiation causes the most significant surface damage, whereas low-energy-density irradiation generates defects that are small in size even if the number of cycles is large.     

钡-钨阴极的组织特性与热电子发射性能

利用正交试验探讨了放电等离子技术工艺参数（温度、压力、保温时间）对钡-钨（Ba-W）阴极中的W的孔隙度的影响规律,获得了孔隙率在23%～30%内变化时所需要的最佳工艺参数。在此基础上,制备出了具有不同孔隙度的球形W基体和普通不规则的W基体。研究表明:球形多孔W颗粒间堆积、排列有序,无闭孔,孔径分布集中而均匀,在26.3%的孔隙度下中值孔径为1.41 μm;机械性能方面,球形钨粉基体维氏硬度低于传统普通不规则钨多孔体。在脉宽10 μs、频率1000 Hz的条件下,阴极脉冲发射电流密度随着孔隙度的增大,先增大后减小。当基体孔隙度为26.3%时,阴极电流发射密度最大,在1050 ℃,偏离点发射电流密度可达24.62 A/cm2,零场发射电流密度为7.62 A/cm2,功函数为1.95 eV。     

钨粉的平面动载压实

 本文研究了粒度为3 μm与20 μm两种钨粉的平面动载压实。证明粒度较小的钨粉在压实后分层严重，中层疏松。要得到良好的压实件，钨粉要有一定值以上的粒度，碰撞速度要在1 100 m/s以上，钨粒中要配以一定量的钴、镍、铁粘结相。这些能用Carroll和Holt的球壳模型作的数值模拟计算清楚说明。     

Model for milling of powders

A model is proposed for mechanical milling of powders that relates the applied energy to average particle size D in the powders. It is shown that the milling energy is consumed for the rupture of interatomic bonds in crystalline particles and for the creation of an additional surface during powder fragmentation. The appearance of microstrains ɛ retards powder fragmentation. Average particle size D after milling decreases with increasing milling time t and decreasing particle size in the initial powder or its mass M. The calculated results are compared to the experimental data obtained on a tungsten carbide WC powder.     

Plasma synthesis of nanosized W–Co composite powder followed by carburization with a methane–hydrogen mixture

Nanosized tungsten carbide and cobalt composite powder was synthesized by a two-step reaction via a thermal plasma process. Ammonium paratungstate (APT) and cobalt oxide were used as the precursors. The injected precursors were vaporized in the plasma flame and the subsequent reduction of the vaporized precursors produced uniformly mixed nanosized tungsten and cobalt composite powder. The subsequent carburization of this powder by CH₄–H₂ mixture resulted in the formation of nanosized WC–Co composite powder with a particle size <110 nm. This new method represents an alternative route that avoids the post-treatment required for the WC_1?x produced when methane was used for direct carburization in the powder production step.     

Combustion synthesis of nano-sized tungsten carbide powder and effects of sodium halides

The synthesis of nano-size tungsten carbide powder has been investigated with a WO₃ + Mg + C + carbonate system using alkali halides. The effects of different types of alkali halides on combustion temperature and tungsten carbide formation were discussed. Sodium fluoride had a notable effect on the particle size of the product and the degree of transformation from the initial mixture. A small amount of ammonium carbonate activated the carburization of tungsten carbide by the gas phase carbon transportation. X-ray diffraction data and particle analysis showed that the final product synthesized from a WO₃–Mg–C–(NH₄)₂CO₃–NaF system contains pure-phase tungsten carbide with a particle size of 50–100 nm.     

Synthesis and characterization of nanoparticulate films for intermediate temperature solid oxide fuel cells

Nanocrystalline strontium-doped lanthanum manganite (LSM) with a high specific surface area of 70 m²/g was synthesized via spray pyrolysis. The as prepared powder was characterized by ex-situ X-ray diffraction (XRD), in-situ high temperature X-ray diffraction (HTXRD), ex-situ nitrogen adsorption and high resolution scanning electron microscopy (HRSEM). LSM nanopowders with a mean particle size of 40 nm were dispersed in water-based media using ultrasonication. Nanocomposite LSM-GDC (gadolinium doped ceria) thin films were prepared by single step spin coating of co-stabilized LSM and GDC dispersions. The thickness of these thin films (≤ 1 μm) is more than 10 times lower than conventional cathode layers prepared by screen printing. The interfacial polarization resistances were 68, 118 and 220 mΩ cm² at 850, 800 and 750 °C, respectively. The high performance is attributed to small grain size, high porosity and large specific surface area. This method offers a very cost effective approach for the preparation of electrochemically highly active porous thin films, particularly applicable for micro solid oxide fuel cells.     

Restricting the High-Temperature Growth of Nanocrystalline Tin Oxide

The sensitivity of tin oxide is dependent on various factors, one of which is the grain size. Three methods have been investigated with the aim of stabilising the grain size in the nanometer range, namely; (i) encapsulation within a silica matrix, (ii) coating the crystallites with hexamethyldisilazane and (iii) pinning the grain boundaries with a second metal oxide nanocrystal. The resulting materials have been characterised by X-ray powder diffraction (XRPD), Extended X-ray absorption fine structure (EXAFS) and conductivity measurements.     

Consolidation of cryomilled Al–Si using spark plasma sintering

Cryomilled eutectic aluminum–12% silicon powder was sintered using spark plasma sintering (SPS) to create bulk compacts. The cryomilling serves to break up and disperse the eutectic phase in the powder to create a well-distributed Si phase throughout the matrix and to modify the morphology of the Si phase from plate-like to spherical, whilst refining the aluminium grain size to the nanometric level. The effects of different sintering times and temperatures using SPS on the densification of the powder, the aluminium grain size evolution, the growth of the Si phase and the morphology change of the Si phase were investigated. The compacts were analysed using X-ray diffraction, scanning electron microscopy and optical microscopy. The initial stages of densification appear to be highly dependent on the yield strength of the powder. An estimate of the temperature gradient seen in the powder bed was made and calculated to be near 200?°C at the highest point. The Al and Si phase growth was investigated and it was observed that the Si coarsening rate is increased due to the increased volume of grain boundaries. As the Si coarsens, any pinning effect on the Al grains is lost, resulting in a highly unstable microstructure that coarsens rapidly.     

Mechanochemical synthesis and giant dielectric properties of CaCu3Ti4O12

CaCu₃Ti₄O₁₂ powder has been synthesized by mechanochemical milling (C-m) and solid-state reaction (C-ssr) techniques. C-m powder has a grain size of ~24 nm as determined from X-ray diffraction and FE-SEM measurements. The grain size of C-m ceramics has increased to 20 μm compared to a size of 3 μm for C-ssr ceramics after sintering at 1,050 °C for 10 h. Giant dielectric constant was observed in both ceramics with that of C-m larger than that of C-ssr. Impedance results show that the grain conductivity of C-m is more than two orders of magnitude lower than that of C-ssr, whereas its grain boundary conductivity is larger than that of C-ssr. These results are supported by the EDX results that show Cu-enriched grain boundaries in C-m ceramics.     

High frequency properties of composite membrane with in-plane aligned Sendust flake prepared by infiltration method

Composite membranes (with thickness around 100–200 μm) containing highly in-plane aligned Sendust flakes embedded in polyvinyl alcohol matrix were prepared with a novel infiltration method. As compared with tape-casting method, infiltration method results in enhanced magnetic permeability, which could be caused by better alignment and less porosity. Annealing process could modify the grain size, improve saturation magnetization and coercivity of Sendust flakes. Hence, the radio and quasi-microwave frequency permeability (between 10 MHz to 3 GHz) of composites membranes with annealed Sendust flakes could be enhanced significantly as compared with that of the as-prepared flakes. Infiltration method is especially suitable for composites with high concentration of flaky fillers. The composite membranes prepared have potential applications, including electromagnetic shielding, noise reduction and wave absorption.     

Anomalous porosity in certain aluminum alloys

Metallographic examination was used to study the formation of porosity in an aluminum alloy A1-4%Cu with grain size in ranges 1000-200 and 120-85 , in technical grade aluminum Al (grain size 80-60 ), and in type D1 alloy (grain size 30-10 ) during a thermal cycling treatment, each cycle of which included aging in water at 100 ° C. The character of porosity depends on alloy composition and grain size. In coarsely granular materials the pores are formed inside grains, have clearly defined form, and reach a size of 10–20 after 60 cycles. The pore size in finely granular materials is smaller by one order of magnitude; the pores are formed predominantly along grain boundaries with some pores formed in the grain interior. Pores formed in alloy D1 are of an irregular form and grow to sizes exceeding the grain size. Data on changes in the specimen length, diameter, and volume were obtained. The relative increase in specimen volume reaches 0.5–1.0% per cycle. In spite of differences revealed by metallographic examination, the phenomena taking place in specimens with large and small grain size are of the same nature.     

Fine crystal structure of porous corundum ceramics

The microstructure of corundum ceramics based on powders with a varying grain size has been investigated. Both commercial alumina powders and those fabricated by denitration of aluminum salts in a high-frequency discharge plasma were used. An increase in the plasma-chemical Al₂O₃ powder content in the sample was found to change the pore structure of the corundum ceramics from a high-porosity ceramic skeleton with a well-developed system of channel-forming pores to ceramics with isolated pores. The change in the pore structure was observed for 50% porosity and caused an increase in the level of crystal lattice microdistortions. An increase in the sintering temperature from 1200 to 1650°C is shown to be responsible for a two-fold increase in the average crystallite size and for annealing of lattice defects along grain boundaries.     

Disorder driven optical processes in nanocrystalline ZnO

A systematic study on the modification of optical properties in mechanically milled ZnO powder has been reported here. The average grain size of the powder becomes ～20 nm within 4 h of milling. Fluctuations of average grain size have been noticed at the initial stage of milling (within 15 min). Changes in grain morphology with milling have also been noticed in scanning electron micrographs of the samples. Room temperature optical absorption data shows a systematic red shift of absorption band edge (～3.25 eV). The band tail parameter (extracted from the optical absorption just below the band edge) follows a simple exponential relation with the inverse of the average grain size. Significant increase of the band tail parameter has been noticed at low grain size regime. It has been analyzed that high values of band tail parameter is a representative of V_Zn–V_O type divacancy clusters. Room temperature photoluminescence spectra show decrease (except for 120 min milling) of band edge emission intensity with increase of milling time. Subsequent decrease of sub-band edge emission is, however, less prominent. The variation of PL intensity ratio (intensity at band edge peak with that at 2.3 eV) follows simple exponential decrease with the increase of band tail parameter. This indeed shows that band edge emission in ZnO is related with the overall disorder in the system, not grain size induced only.     

Neutron depolarization study on the magnetic correlation length of nickel ferrite with different packing densities

The magnetic correlation length of a mixed nickel ferrite powder was studied by a newly commissioned depolarized neutron beamline at the W3 port of Tsing Hua Open Pool Reactor (THOR). In this work, Ni ferrite powder samples with different packing densities were studied. The magnetic correlation lengths of the sample were observed to be 2 μm at virgin state and about 3.1 μm at remanent state from the packing density of 20–60%. This magnetic domain size is smaller than particle size. No significant change of domain size at this packing density implies the domain wall motion is hindered by the porosity effectively up to at least 60% of packing density.     

Growth instability and surface phase transition of Ti thin film on Si(1 1 1): An atomic force microscopy study

Evolution of surface structure during the annealing of e-beam evaporated Ti films is studied by means of atomic force microscopy (AFM). Image variography and power spectral density analysis are used to study scaling properties of the films, ranging from 50 nm to 20 μm length scale. No particular grain size is observed up to 473 K. At 673 K, grain size of ∼250 nm are formed and coalesced to form bigger grain size upon further annealing. At 473 K, RMS roughness dropped at all length scale and became rougher at 673 K with an increasing trend up to 873 K. Clustering at 673 K indicates Kosterlitz-Thaouless [J.M. Kosterlitz, D.J. Thaouless, J. Phys. Chem. 6 (1973) 1181] type phase transition at the surface. The observed transition is also consistent with existing scaling laws.     

冷动力喷涂法制备钨和钨合金涂层 及其涂层的计算模拟

采用冷动力喷涂法以纯钨和钨-镍-铁合金为原料在铜合金基体上制备了钨涂层和钨-镍-铁涂层. 研究了冷喷涂过程中钨粉粒径、喷涂距离等因素对涂层性能的影响. 用扫描电子显微镜分析了涂层的表面、断面微观结构, 并用原子力显微镜测量了涂层的粗糙度. 此外, 计算了冷喷涂过程中粉末颗粒的实际速度, 并采用有限元分析软件ANSYS/LS-DYNA模拟了冷喷涂过程中颗粒撞击基体时的变形情况.