《Tungsten》2022年第一期

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封面：Preparation of the highly dense ceramic–metal fuel particle with fine-grained tungsten layer by chemical vapor deposition for the application in nuclear thermal propulsion

封面设计: 林俊，张锋（中科院上海应用物理研究所）

本期共发表8篇研究型文章

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文章简介

1.Preparation of the highly dense ceramic–metal fuel particle with fine-grained tungsten layer by chemical vapor deposition for the application in nuclear thermal propulsion

核热推进高致密细晶化金属陶瓷燃料颗粒的制备及热力学性能研究

Li-Hua Guo, Feng Zhang*（张锋，中科院上海应用物理研究所）, Lin-Yuan Lu, Yan You, Jun-Qiang Lu, Li-Bing Zhu & Jun Lin* （林俊，中科院上海应用物理研究所）

原文网址：https://link.springer.com/article/10.1007/s42864-021-00117-2

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摘要：本文通过喷动床化学气相沉积法在燃料颗粒表面制备了纯相、厚度均匀（约10μm）、致密（19.24g/cm³）的钨层，并研究了其微观结构和热导率等性能。这些工作为研究钨包覆燃料颗粒在高功率密度、快速升降温工况下的性能建立了基础。

图1  1173 K沉积温度制备的钨包覆燃料颗粒及其截面图

2. Deuterium retention in chemically vapor deposited tungsten carbide coatings and hot-rolled tungsten exposed to low-energy deuterium plasma

Vladimir Kh. Alimov*（Russian Academy of Sciences）, Joachim Roth 

原文网址：https://link.springer.com/article/10.1007/s42864-021-00120-7

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Abstract: Samples of chemically vapor deposited (CVD) coatings of tungsten carbides W₄₅C₅₅ and W₆₀C₄₀ and samples of hot-rolled tungsten were exposed to deuterium (D) plasma at sample temperatures ranging from 323 to 813 K, as a result of which the samples were irradiated with D ions with an energy of about 200 eV per D particle at a flux of D particles of about 1.1 × 10²¹ D·m⁻²·s⁻¹ to a fluence of about 2 × 10²⁴ D·m⁻². The concentration of deuterium in these samples was examined by the D(₃He,p)₄He nuclear reaction. Based on the measured deuterium depth profiles and assuming that these profiles are determined by diffusing D atoms , the diffusion coefficients of deuterium in the CVD tungsten carbide coatings were determined. Using these diffusion coefficients, an estimate of the Arrhenius relation for the diffusion coefficients of deuterium in CVD tungsten carbide coatings was obtained: D = 2.5 × 10^-3 exp(− 1.12 eV/kT) m²·s⁻¹, where T is temperature expressed in Kelvin, and k is the Boltzmann constant. The concentration of trapped deuterium in the bulk of CVD tungsten carbide coatings is practically independent of the stoichiometry of the coatings. It decreases from about 5 × 10^-2 to about 7 × 10^-4 D/(W + C) with an increase in the deuterium plasma exposure temperature from 373 to 813 K. The concentration of trapped deuterium in hot-rolled tungsten, expressed in units of the D/W atomic ratio, is more than an order of magnitude lower than the concentration of deuterium in tungsten carbides, and also decreases with increasing plasma exposure temperature. 

Fig.2 Comparison of the Arrhenius relations for the diffusion coefficients of deuterium in CVD tungsten carbide coatings W₄₅C₅₅ and W₆₀C₄₀ , as well as in hot-rolled tungsten samples, estimated in this work. In addition, the data on the diffusion of hydrogen (protium) in tungsten

3. Strengthening of tungsten by coherent rhenium precipitates formed during low fluence irradiation

Yuri Osetsky （Oak Ridge National Laboratory）

原文网址：https://link.springer.com/article/10.1007/s42864-021-00088-4

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Abstract: Experimental data show that the accumulation of rhenium and osmium from transmutation reactions severely affect the microstructural evolution and property degradation of tungsten-based materials under neutron irradiation. Theory and modeling have confirmed that Re atom transport in W is by irradiation-produced migrating self-interstitial atoms. With this diffusion mode in operation, a specific microstructure evolution is realized when at relatively low neutron fluence the Re-rich precipitates are formed, while the void and interstitial loop population development is suppressed, affecting the mechanical properties. This research shows the effect of small coherent Re-rich precipitates on the dislocation glide under stress, investigated using the molecular dynamics approach with empirical interatomic potentials. The results are compared with an earlier simulation of void hardening in W. It is demonstrated that small coherent Re-rich precipitates of less than 6 nm diameter represent relatively weak obstacles for moving edge dislocations. The implication of these results on the interpretation of experimental results is discussed.

Fig.3 (Left) Stress–strain curves during dislocation passing through precipitates containing 100 and 50 at.% Re with D_prpt= 9 nm; (right) the dislocation line shape around 50 at.% Re precipitate at the critical stress

4. Heteropolyacids supported on hierarchically macro/mesoporous TiO₂: efficient catalyst for deep oxidative desulfurization of fuel

Ta-Nb-Zr-Ti-Al难熔高熵合金中Ta/Ti含量对组织结构与力学性能的影响分级大孔/介孔磷钨酸/TiO₂复合材料：高效燃油深度氧化脱硫催化剂

Gao-Chen Yang, Qi-Yun Pan, Peng Yang, Yi-Si Liu, Yue Du* & Kai Wang* （王楷， 湖北师范大学）

原文网址：https://link.springer.com/article/10.1007/s42864-021-00125-2

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摘要 采用胶体晶体模板法制备了一系列分级大孔/介孔磷钨酸(HPW)/TiO₂复合材料，并用作燃油中的深度脱硫催化剂。该方法以尺寸均一的聚苯乙烯胶晶为大孔模板，配置稳定的钛酸四丁酯、磷钨酸溶胶，通过溶胶-凝胶法构筑了分级孔结构HPW/TiO₂复合材料。所制备的催化剂大孔结构高度有序，孔道间通过窗口孔相连接，而无序的介孔嵌入在大孔孔壁上。此外，Keggin型的HPW均匀分散在TiO₂基质上。作为燃油深度脱硫催化剂，分级大孔/介孔HPW/TiO2展现出了优异的催化性能，在优化的条件下模拟油中二苯并噻吩的脱除率达到99%，远高于纯介孔HPW/TiO₂材料。上述研究结果表明，以噻吩类大分子硫化物为反应物的催化体系中，分级孔结构的构筑有利于提高其催化氧化效率。

图4   SEM images of a M/m-HPW/TiO₂-10, b M/m-HPW/TiO₂-20, c M/m-HPW/TiO₂-30, and d magnified SEM image of M/m-HPW/TiO₂-20; TEM images of e, f M/m-HPW/TiO₂-20

5. Preparation of tungsten–iron composite oxides and application in environmental catalysis for volatile organic compounds degradation

钨铁复合氧化物的制备及其应用于环境催化领域降解挥发性有机物的研究

Jiang Liu, Song-Lin Wang, Ji-Li Xuan, Bo-Fang Shan, Hong Luo, Li-Ping Deng, Peng Yang*（杨鹏，绍兴文理学院） & Chen-Ze Qi 

原文网址：https://link.springer.com/article/10.1007/s42864-021-00128-z

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摘要 该研究工作合成了一系列具有不同比例和制备方法的钨铁复合氧化物，首次用于氯苯和甲苯的无焰催化降解。研究发现，钨铁元素之间存在强相互作用，氧化钨和氧化铁可抑制彼此的结晶，这有利于钨铁组分的均匀分散和氧化还原性能的改善。与单组分氧化物相比，钨铁复合氧化物的形成影响了其微观结构，改善了比表面积，优化了材料的孔隙结构。催化性能试验结果表明，以柠檬酸基溶胶-溶胶法制备的钨铁复合氧化物（FeWO₄-0.5Fe₂O₃，钨与铁的摩尔比为1/2）在320 ℃时对氯苯的催化降解效率可达到90%，对甲苯的催化降解效率可达到83%，且可维持至少60h，无明显失活，并对HCl和CO₂的形成具有较高的选择性。

图5 W-Fe-O催化剂的催化燃烧性能

6. Z-scheme systems of ASi₂N₄ (A = Mo or W) for photocatalytic water splitting and nanogenerators

用于光催化水分解和纳米发电机的ASi₂N₄（A=Mo, W）Z-型系统

Jian Zeng, Liang Xu*（许梁，江西理工大学）, Xin Luo, Tong Chen, Shuai-Hao Tang, Xin Huang & Ling-Ling Wang

原文网址：https://link.springer.com/article/10.1007/s42864-021-00116-3

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摘要：本文基于MoSi₂N₄和WSi₂N₄两种二维材料，构建了MoSi₂N₄/MoSi₂N₄，WSi₂N₄/WSi₂N₄和 MoSi₂N₄/WSi₂N₄三种Z-型光催化系统。理论计算表明ASi₂N₄（A=Mo或W）Z-型系统具有良好的可见光催化性能和滑动铁电性，极大地提高了二维材料的光生电子-空穴对的分离效率，增强了可见光光吸收。更重要的是实现了更强的氧化还原能力，并满足pH=0-7范围内水裂解的条件。此外，通过系统内层间滑动便可获得相反的内建电势，驱动不同方向的电荷转移，这有望用于未来的纳米发电机领域。

图6 最优化的ASi₂N₄（A =Mo 或 W）的系统结构，以及单层MoSi₂N₄和WSi₂N₄原子结构模型

7. Preparation of nano-crystalline tungsten powders from gaseous WO₂(OH)₂

Markus Ostermann, Valentin Dalbauer, Wolf-Dieter Schubert & Roland Haubner*(TU Wien)

原文网址：https://link.springer.com/article/10.1007/s42864-021-00118-1

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Abstract: The industrial production of tungsten powder is carried out by the reduction of tungsten oxide powder via hydrogen. In this process, the size of the W particles is limited to particle sizes larger than 100 nm. To get below this limit, alternative processes are needed. In the current work, the possibility of preparing W powder below 100 nm via a vapour phase reduction of volatile WO₂(OH)₂ by hydrogen was investigated. The process consists of two stages. In the first stage WO₂(OH)₂ is formed by reacting WO₃ with water vapour at temperatures of 1000–1100 °C. In the second stage, WO₂(OH)₂ is reduced by hydrogen at about 1000 °C to form metallic tungsten. The influence of process parameters such as furnace temperature, humidity and gas flow on the WO₂(OH)₂ evaporation and formation of tungsten powder was investigated. The characterization of the resulting powders was performed by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). By optimization of the reaction conditions, powder with a metallic tungsten content of about 70 at% besides tungsten oxides was produced with metal particle sizes down to 5 nm. Further optimization should lead to a high tungsten content and a high product yield. Due to the small particle size, applications in catalysis might be possible, although an industrial realization of the process seems unrealistic at moment.

图7 Experimental setup for the production of nano-sized tungsten powder via the CVT reaction from WO₃ (yellow material in quartz tube)

8. Selective laser melting of lanthanum oxide-reinforced tungsten composites: microstructure and mechanical properties

选区激光熔化氧化镧增强钨基复合材料的微观结构及力学性能研究

Shen-Yu Wei, Li-Na Ji*（纪丽娜，中国科学院重庆绿色智能技术研究院）, Wen-Jie Wu & Hong-Lin Ma

原文网址：https://link.springer.com/article/10.1007/s42864-021-00127-0

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摘要：本文将氧化镧（La₂O₃）纳米颗粒引入钨基体中以优化SLM钨的微观结构和性能。该工作通过选区激光熔化方法成形了具有不同La₂O₃质量分数的W-La₂O₃复合材料，并对其微观组织及机械性能进行了表征。结果表明，与纯钨相比，W-1wt% La₂O₃和W-2wt% La₂O₃的平均晶粒尺寸减小了51.3%以上，内部缺陷明显减少。SLM W-2wt% La₂O₃样品的显微硬度和抗压强度分别达到455HV和2194MPa。

图8 粉末能谱仪（Energy Dispersive Spectrometer，EDS）元素分析图像：（a）纯钨粉末；（b）W-0.5wt% La₂O₃；（c）W-1wt% La₂O₃；（d）W-2wt% La₂O₃。

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