钾掺杂钨合金中气相热充氘的热脱附行为

钾(K)掺杂钨(W)合金已经表现了优异的高温力学性能,成为最有希望的PFMs备选材料之一。为评估氢同位素在W-K合金中的滞留情况,采用放电等离子烧结技术(SPS),制备了纯W及K含量82μg/g的W-K合金,通过气相热充法引入氘(D)元素,考察热脱附行为。研究表明,气相热充氘释放温区从600K延伸至1200K,掺杂K后,D脱附活化能从0.86 eV下降到0.68 eV;纯W样品D滞留量在1×10^-6(原子比)左右,掺杂K后有所提高,但依然大大优于商用ITER级纯W。     

锆表面磁过滤阴极真空弧离子镀Cr涂层高温蒸汽氧化行为研究

采用磁过滤阴极真空弧离子镀(FCVAD)技术在纯锆表面制备了厚度约为4μm的Cr金属层,对比研究了它们在不同温度水蒸汽环境中的氧化行为,并利用XRD、XPS、SEM及EDS分析了Cr涂层及氧化膜的物相组成、微观结构及成分分布。结果表明,在900、1000和1100℃水蒸汽环境中,镀Cr涂层大幅度降低了锆的氧化速率,其单位面积氧化增重仅为同一温度下锆基体的1/4、1/6和4/9。氧化初期,Cr涂层表面生成一层均匀致密的Cr_2O_3膜,当Cr层被消耗完后,Cr_2O_3/Zr界面上部分Cr_2O_3被Zr还原成金属Cr,锆基体氧化生成ZrO_2。镀Cr涂层样品的氧化激活能达293.17 kJ/mol。     

Effect of post-weld heat treatment and electrolytic plasma processing on tungsten inert gas welded AISI 4140 alloy steel

Post-weld heat treatment (PWHT) is commonly adopted on welded joints and structures to relieve post-weld residual stresses; and restore the mechanical properties and structural integrity. An electrolytic plasma process (EPP) has been developed to improve corrosion behavior and wear resistance of structural materials; and can be employed in other applications and surface modifications aspects. In this study the effects of PWHT and EPP on the residual stresses, micro-hardness, microstructures, and uniaxial tensile properties are explored on tungsten inert gas (TIG) welded AISI-4140 alloys steel with SAE-4130 chromium–molybdenum alloy welding filler rod. For rational comparison all of the welded samples are checked with nondestructive Phased Array Ultrasonic Testing (PAUT) and to ensure defect-free samples before testing. Residual stresses are assessed with ultrasonic testing at different distances from weld center line. PWHT resulted in relief of tensile residual stress due to grain refinement. As a consequence higher ductility but lower strength existed in PWHT samples. In comparison, EPP-treated samples revealed lower residual stresses, but no significant variation on the grain refinement. Consequently, EPP-treated specimens exhibited higher tensile strength but lower ductility and toughness for the martensitic formation due to the rapid heating and quenching effects. EPP was also applied on PWHT samples, but which did not reveal any substantial effect on the tensile properties after PWHT at 650 °C. Finally the microstructures and fracture morphology are analyzed using scanning electron microscopy (SEM) and optical microscope to study the evolution of microstructures.     

Well-dispersed Rh nanoparticles with high activity for the dry reforming of methane

Rh catalysts with low Rh content were prepared by incipient wetness impregnation using [NH₄]₃[RhCl₆]·3H₂O or RhCl₃·3H₂O as precursor salts, on CaO–SiO₂ supports. All solids showed a high stability after 48 h on stream for the dry reforming of methane with low carbon content, which made them suitable for obtaining ultrapure hydrogen in a membrane reactor. The methane conversion and hydrogen recovery were measured increasing the sweep gas flow rates to rise the driving force for hydrogen permeation. The catalyst with 0.36 wt.% of Rh showed a slight deactivation. However, the Rh(0.6)/CaO–SiO₂ solid, in which the Rh impregnation was performed using [NH₄]₃[RhCl₆]·3H₂O, exhibited an increase on CH₄ conversion of 77% and a hydrogen recovery equal to 84%.Nanoparticles of about 1.4–1.7 nm surface average diameter were detected for the reduced and used solids indicating that Rh is well dispersed and sintering was not produced after the catalytic tests. Rh particle sizes calculated by CO chemisorption were coincident with those measured by Transmission Electron Microscopy. Characterization by this technique and Laser Raman Spectroscopy of the solids used in membrane reactor revealed the formation of scarce carbon filaments. However, a surface re-oxidation was detected in the low loading catalyst used in the membrane reactor suggesting that it is the main cause for the decrease in the activity of the highly dispersed catalyst.     

Optimal design of catalytic distillation columns: A case study on synthesis of TAEE

The design of catalytic distillation (CD) columns is a challenging task because of the superposition of chemical reaction and distillation in one apparatus. In this work, a method to design a cost-optimal CD column for chemical systems with large number of components and chemical reactions is presented. The method is based on the following steps: (1) estimation of the number of theoretical stages and catalyst volume by the decomposition of the CD column into a sequence of chemical reactors and non-reactive distillation columns, (2) estimation of the column diameter and operating conditions using an equilibrium stage model, and (3) design of the column applying an optimisation algorithm and using a rigorous non-equilibrium stage model to represent the CD process. The method is applied to determine the optimal column configuration and operating conditions for the synthesis of tert-amyl ethyl ether from ethanol and isoamylenes. Eight components and four chemical reactions were selected to represent the chemical system in the simulations.     

Densification behavior,mechanical properties and thermal shock resistance of tungsten alloys fabricated at low temperature

The low-temperature shrinkage of tungsten was greatly accelerated by the addition of trace Nb and Ni, and the addition of trace Nb and Ni also significantly promoted the final sintering density. The 99.1% of theory density for W–0.1 wt.%Nb–0.1 wt.%Ni material sintered at 1600 °C was obviously greater than 93.7% of theory density for W material sintered at 2000 °C. Ball milling treatment played an important role in promoting the sintering densification of W–0.1 wt.%Nb–0.1 wt.%Ni powder, and the powder milled for 10 h (W10) could be sintered to near full density (99.4% of theory density) at 1600 °C. The ball milling for 15 h has no effect in improving the sintering density, but it induced rapid growth of tungsten grains. The microhardness and tensile strength of the sintered tungsten alloys were highly dependent on its sintering density and grain size. Improving the sintering density while controlling the grain growth could effectively promote the microhardness and tensile strength. Furthermore, the improvement of thermal shock resistance of the W10 alloy was due to good microstructure and the increase in the tensile strength.     

Polycrystalline behavior analysis of pure magnesium by the homogenization method

In this study, mechanical behaviors of pure magnesium polycrystals are numerically investigated. The homogenization method, which combines the crystal and macroscopic scales, is introduced to include the effect of crystalline scale behaviors. The polycrystal plasticity model modified for pure magnesium, in which twinning is considered as asymmetric slip-like deformation, is utilized as a constitutive equation. Within this framework, numerical convergence analyses are conducted, and a representative volume element to present realistic deformation of pure magnesium is investigated. Second, polycrystalline behaviors of pure magnesium are investigated. The present approach is shown to reproduce the typical phenomena induced by crystalline scale structure in pure magnesium: nonuniform strain distribution, asymmetric crystal lattice orientation, strength differential effect, and strongly anisotropic initial and subsequent yield surfaces.     

Decalcification of activated paper sludge – Fly ash-Portland cement blended pastes in pure water

Decalcification in pure water of ternary Portland cement (TPC) pastes, containing thermally activated paper sludge and fly ash, has been evaluated from the leaching of Ca²⁺ in pure water at the temperature of 20 °C during 90 days. Monitoring of calcium loss showed that the leaching kinetics are controlled by diffusion. The degradation of the material over time is estimated from the calcium effective diffusivity. A similar study of plain ordinary Portland cement (OPC) pastes was carried out for comparison. The results showed lower effective diffusion coefficients of calcium in the case of the TPC pastes. This behaviour is related to its microstructure, which is denser than that of OPC as a result of the pozzolanic activity of both additions.     

Hot wire chemical vapor deposition: limits and opportunities of protecting the tungsten catalyzer from silicide with a cavity

Hot Wire Chemical Vapor Deposition (HW-CVD) is one of the most promising techniques for depositing the intrinsic microcrystalline silicon layer for the production of micro-morph solar cells. However, the silicide formation at the colder ends of the tungsten wire drastically reduces the lifetime of the catalyzer, thus limiting its industrial exploitation. A simple but interesting strategy to decrease the silicide formation is to hide the electrical contacts of the catalyzer in a long narrow cavity which reduces the probability of the silane molecules to reach the colder ends of the wire. In this paper, the working mechanism of the cavity is elucidated. Measurements of the thickness profile of the silicon deposited in the internal walls of the cavity have been compared with those predicted using a simple diffusion model based on the assumption of Knudsen flow. A lifetime study of the protected and unprotected wires has been carried out. The different mechanisms which determine the deterioration of the catalyzer have been identified and discussed.     

Electrochromism in nickel oxide and tungsten oxide thin films: Ion intercalation from different electrolytes

Electrochromic (EC) NiO_z and WO_y thin films were prepared by sputtering and were used in a feasibility study aimed at investigating mixtures of these two oxides. The object was to identify a suitable electrolyte, compatible with both NiO_z and WO_y. To that end we carried out cyclic voltammetry (CV) in potassium hydroxide (KOH), propionic acid, and lithium perchlorate in propylene carbonate (Li-PC). WO_y could be coloured in propionic acid and Li-PC, while NiO_z could be coloured only in KOH. Both films showed best stability in Li-PC, which hence is well suited for further studies of mixed NiO_z and WO_y.