Synthesis of Commercial-Scale Tungsten Carbide-Cobalt (WC/Co) Nanocomposite Using Aqueous Solutions of Tungsten (W), Cobalt (Co), and Carbon (C) Precursors

This paper reports the chemical synthesis of tungsten carbide/cobalt (WC/Co) nanocomposite powders via a unique chemical processing technique, involving the using of all water soluble solution of W-, Co- and C-precursors. In the actual synthesis, large quantities of commercial-scale WC-Co nanocomposite powders are made by an unique combination of converting a molecularly mixed W-, Co-, and C-containing solutions into a complex inorganic polymeric powder precursor, conversion of the inorganic polymeric precursor powder into a W-Co-C-O containing powder intermediates using a belt furnace with temperature at about 500°C - 600°C in an inert atmosphere, followed by carburization in a rotary furnace at temperature less than 1000°C in nitrogen. Liquid phase sintering technique is used to consolidate the WC/Co nanocomposite powder into sintered bulk parts. The sintered parts have excellent hardness in excess of 93 HRA, with WC grains in the order of 200 - 300 nm, while Co phase is uniformly distributed on the grain boundaries of the WC nanoparticles. We also report the presence of cobalt Co precipitates inside tungsten carbide WC nanograins in the composites of the consolidated bulk parts. EDS is used to identify the presence of these precipitates and micro-micro-diffraction technique is employed to determine the nature of these precipitates.

Jet formation and penetration performance of a double-layer charge liner with chemically-deposited tungsten as the inner liner

This paper proposes a type of double-layer charge liner fabricated using chemical vapor deposition(CVD)that has tungsten as its inner liner.The feasibility of this design was evaluated through penetration tests.Double-layer charge liners were fabricated by using CVD to deposit tungsten layers on the inner surfaces of pure T2 copper liners.The microstructures of the tungsten layers were analyzed using a scanning electron microscope(SEM).The feasibility analysis was carried out by pulsed X-rays,slug-retrieval test and static penetration tests.The shaped charge jet forming and penetration law of inner tungsten-coated double-layer liner were studied by numerical simulation method.The results showed that the double-layer liners could form well-shaped jets.The errors between the X-ray test results and the numerical results were within 11.07%.A slug-retrieval test was found that the retrieved slug was similar to a numerically simulated slug.Compared with the traditional pure copper shaped charge jet,the penetration depth of the double-layer shaped charge liner increased by 11.4% and>10.8% respectively.In summary,the test results are good,and the numerical simulation is in good agreement with the test,which verified the feasibility of using the CVD method to fabricate double-layer charge liners with a high-density and high-strength refractory metal as the inner liner.

Trace elements in magmatic and hydrothermal quartz:Implications on the genesis of the Xingluokeng Tungsten Deposit,South China

The Xingluokeng deposit is the largest gran-ite-related tungsten deposit within the Wuyi metallogenic belt in South China.The Xingluokeng intrusion primarily consists of porphyritic biotite granite,biotite granite,andfine-grained granite.The deposit is represented by veinlet-disseminated mineralization with K-feldspathization and biotitization,alongside quartz-vein mineralization with gre-isenization and sericitization.This study investigates in-situ analyses of quartz compositions from both the intrusion and hydrothermal veinlets and veins.Trace element correlations indicate that trivalent Al^(3+)and Fe^(3+)replace Si^(4+)within the quartz lattice,with monovalent cations(such as Li^(+),Na^(+),and K^(+))primarily serving as charge compensators.Low Ge/Al ratios(<0.013)of quartz from granites suggest a mag-matic origin.The low Al/Ti and Ge/Ti ratios,accompanied by high Ti contents in quartz,suggest that the porphyritic biotite granite and biotite granite are characterized by rela-tively low levels of differentiation and high crystallization temperatures.In contrast,thefine-grained granite exhibits a higher degree of fractionation,lower crystallization tem-peratures,and a closer association with tungsten miner-alization.Ti contents in quartz from quartz veins indicate Qz-Ⅰformed at temperatures above 400°C,while Qz-Ⅱto Qz-Ⅴformed at temperatures below 350°C.Variations in different generations of quartz,as indicated by Al content and(Al+Fe)/(Li+Na+K)ratio,suggest that Qz-Ⅰprecipi-tated from a less acidicfluid with a stable pH,whereas Qz-Ⅱto Qz-Ⅴoriginated from a more acidicfluid with notable pH variations.Consequently,alkaline alteration and acidic alteration supplied the essential Ca and Fe for the precipita-tion of scheelite and wolframite,respectively,highlighting a critical mechanism in tungsten mineralization at the Xin-gluokeng deposit.

Cerium-tungsten oxides supported on activated red mud for the selective catalytic reduction of NO_(x)

Activated red mud(RM)has been proved to be a promising base material for the selective catalysis reduction(SCR)of NOx.The inherent low reducibility and acidity limited its low-temperature activity.In this work,molybdenum oxide,tungsten oxide,and cerium oxide were used to reconfigure the redox sites and acid sites of red mud based catalyst.When activated red mud was reconfigured by cerium-tungsten oxide(Ce-W@RM),the NOx conversion kept above 90%at 219-480℃.The existence of Ce^(3+)/Ce^(4+) redox electron pairs provided more surface adsorbed oxygen(O_(α)) and served as a redox cycle.Positive interactions between Ce,W species and Fe oxide in red mud occurred,which led to the formation of unsaturated chemical bond and promoted the activation of adsorbed NH_(3) species.WO_(3) and Ce_(2)(WO_(4))_(3)(formed by solid-state reaction between Ce and W species)could provide more Brønsted acid sites(W-O modes of WO_(3),W=O or W-O-W modes of Ce_(2)(WO_(4))_(3)).CeO_(2) species could provide more Lewis acid sites.The Langmuir-Hinshelwood(L-H)routes and Eley-Rideal(E-R)routes occurred in the low-temperature SCR reaction on the Ce-W@RM surface.NH_(4)^(+) species on Brønsted acid sites,NH_(3) species on Lewis acid sites,bidentate nitrate and bridging nitrate species were key active intermediates species.

Plasma synthesis of various polymorphs of tungsten trioxide nanoparticles using gliding electric discharge in humid air:characterization and photocatalytic properties

A gliding electric arc(glidarc)discharge generates a low-temperature plasma at atmospheric pressure.When the discharge occurs in humid air as the feed gas,the chemistry of a glidarc plasma consists of in situ formation of HO°and NO°as the primary chemical species.Tungsten trioxide(WO_(3))nanoparticles were successfully prepared by exposure of a liquid precursor to glidarc plasma.The WO_(3)samples were calcined at three different temperatures(300℃,500℃and 800℃),resulting in different pure polymorphs:γ-WO_(3)(at 300℃),β-WO_(3)(at 500℃)andα-WO_(3)(at 800℃)according to x-ray diffraction analysis.The identification of WO_(3)compounds was also confirmed by attenuated total reflection Fourier transform infrared spectroscopy analysis.Increase in the calcination temperature of WO_(3)induced a decrease in its specific surface area according to Brunauer–Emmett–Teller nitrogen physisorption analysis.The UV-visible results showed that the absorption bands of plasma-WO_(3)samples were more intense than those of WO_(3)samples obtained by a precipitation route,a classical method used for comparison.Consequently,this parameter can improve the photocatalytic properties of WO_(3)under visible light.The photodegradation(in sunlight conditions)of gentian violet,chosen as a model pollutant,confirmed the photocatalytic properties of plasma-WO_(3)samples.This novel synthesis method has great potential to improve the efficiency of advanced tungsten trioxide-based functional material preparation,as well as in pollution-reducing and energy-saving tungsten extractive metallurgy.

Giant saturation absorption of tungsten trioxide film prepared based on the seedless layer hydrothermal method

Nonlinear materials have gained wide interest as saturable absorbers and pulse compression for pulsed laser applications due to their unique optical properties.This work investigates the third-order nonlinear phenomenon of tungsten trioxide(WO_(3))thin films.The giant nonlinear absorption and nonlinear refractive index of WO_(3)thin films were characterized by Z-scan method at 800 nm.We experimentally observed the giant saturable absorption(SA)and nonlinear refractive index of WO_(3)thin films prepared by the seedless layer hydrothermal method,with SA coefficient being as high as-2.59×105cm·GW^(-1).The SA coefficient is at least one order of magnitude larger than those of the conventional semiconductors.The nonlinear refractive index n_(2)of WO_(3)film has been observed for the first time in recent studies and the corresponding coefficient can be up to 1.793 cm^(2)·GW^(-1).The large third-order nonlinear optical(NLO)response enables WO_(3)thin films to be promising candidates for optoelectronic and photonic applications in the near-infrared domain.

Sol-gel-based porous Ti-doped tungsten oxide films for high-performance dual-band electrochromic smart windows

Dual-band electrochromic smart windows(DESWs)with independent control of the transmittance of near-infrared and visible light show great potential in the application of smart and energy-saving buildings.The current strategy for building DESWs is to screen materials for composite or prepare plasmonic nanocrystal films.These rigorous preparation processes seriously limit the further development of DESWs.Herein,we report a facile and effective sol-gel strategy using a foaming agent to achieve porous Ti-doped tungsten oxide film for the high performance of DESWs.The introduction of foaming agent polyvinylpyrrolidone during the film preparation can increase the specific surface area and free carrier concentration of the films and enhance their independent regulation ability of near-infrared electrochromism.As a result,the optimal film shows excellent dual-band electrochromic properties,including high optical modulation(84.9%at 633 nm and 90.3%at 1200 nm),high coloration efficiency(114.9 cm^(2) C^(-1) at 633 nm and 420.3 cm^(2) C^(-1) at 1200 nm),quick switching time,excellent bistability,and good cycle stability(the transmittance modulation losses at 633 and 1200 nm were 11%and 3.5%respectively after 1000 cycles).A demonstrated DESW fabricated by the sol-gel film showed effective management of heat and light of sunlight.This study represents a significant advance in the preparation of dual-band electrochromic films,which will shed new light on advancing electrochromic technology for future energy-saving smart buildings.

Tungsten combustion in impact initiated W-Al composite based on W(Al) super-saturated solid solution

Element W can effectively improve the density of energetic structural materials. However, W is an inert element and does not combust in air. To change the reaction characteristics of W, 60 at.% Al was introduced into W through mechanical alloying. XRD analysis shows that after 50 h of ball milling, the diffraction peak of Al completely disappears and W(Al60) super-saturated solid solution powder is obtained. Further observation by HAADF and HRTEM reveals that the W(Al60) super-saturated solid solution powder is a mixture of solid solution and amorphous phase. Based on the good thermal stability of W(Al60) alloy powder below 1000℃, W(Al60)-Al composite was synthesized by hot pressing process.Impact initiation experiments suggest that the W(Al60)-Al composite has excellent reaction characteristics, and multiple types of tungsten oxides are detected in the reaction products, showing that the modified W is combustible in air. Due to the combustion of tungsten, the energy release rate of the W(Al60)-Al composite at speed of 1362 m/s reaches 2.71 kJ/g.

Preparation of Spherical Tungsten Particles Assisted by Hydrothermal Method

We presented a strategy to prepare spherical tungsten powder by the combination of hydrothermal method and H2reduction process.In hydrothermal process,the micelle of tetraethylammonium bromide(TEAB)act as spherical templates for the deposition of tungsten oxide,whereas the excessive TEAB inhibit the formation of spherical tungsten oxide due to the dense molecular layer of TEAB on the tungsten oxide particles.Citric acid(CA)can control the formation rate and structure of the tungsten oxide when its concentration is more than 0.2 mol/L,because of its ability to coordinate with tungsten atoms.The synergistic effect of TEAB and CA facilitates the formation of spherical tungsten oxide with nanorod crown.After being treated by H_(2)at 600 and 650℃,the tungsten oxide particles are reduced to tungsten particles,which maintain the spherical structure of tungsten oxide and have porous structure.

Crushing Mechanism of Spherical Tungsten Alloy Fragments Penetrate Thick Steel Plate Target

Against protection requirements for high-speed fragments on the ground weapons,we carried out the research work of crushing mechanism at different impact speeds ofφ8.7 mm spherical tungsten alloy,the penetration to 603 armor steel was completed by 20 mm ballistic gun,and the ANSYS/LS-DYNA software was used to complete the numerical calculation of the penetration.We find that there are different crushing mechanisms of spherical tungsten alloy with different speeds and low speed,the crushing mechanism of fragment is mainly controlled by overall plastic deformation,shearing stripping,and squeezing at a high pressure and a high speed.The crushing mechanism will have a spallation phenomenon in addition to the crushing mechanism under high pressure.

钨矿碱分解工艺制备仲钨酸铵全流程仿真计算

以钨矿碱分解工艺制备仲钨酸铵全流程为对象,基于质量守恒、化学平衡、元素分配约束和指标约束等原理,构建钨矿配矿、磨矿、碱分解、脱磷、离子交换、除钼和蒸发结晶的热力学模型,进而根据各工序物料的迁移传递关系,应用MetCal软件平台,开发钨矿碱分解工艺制备仲钨酸铵全流程仿真计算系统,并采用典型工况下的实际值对模型计算的可靠性进行实例验证。研究结果表明:碱分解浓料中WO_(3)和P质量分数计算值与实际值的相对误差分别为-5.755%和-12.195%,钨渣中WO3、P、Fe、Mn和Ca质量分数的相对误差分别为-2.026%、-5.439%、-14.819%、-14.971%和11.826%;脱磷后液中WO3和P质量分数的相对误差分别为5.513%和-7.692%,脱磷渣中WO_(3)、P和Ca质量分数的相对误差分别为-5.834%、3.337%和7.113%;除钼后液中WO3和Mo质量分数的相对误差分别为-1.627%和-9.375%,除钼渣中WO_(3)、Mo、S和Cu质量分数的相对误差分别为2.547%、-8.827%、8.686%和9.692%。

Exciting News from Indentations onto Silicon, Copper, and Tungsten

Indentations onto crystalline silicon and copper with various indenter geometries, loading forces at room temperature belong to the widest interests in the field, because of the physical detection of structural phase transitions. By using the mathematically deduced FNh3/2 relation for conical and pyramidal indentations we have a toolbox for deciding between faked and experimental loading curves. Four printed silicon indentation loading curves (labelled with 292 K, 260 K, 240 K and 210 K) proved to be faked and not experimental. This is problematic for the AI (artificial intelligence) that will probably not be able to sort faked data out by itself but must be told to do so. High risks arise, when published faked indentation reports remain unidentified and unreported for the mechanics engineers by reading, or via AI. For example, when AI recommends a faked quality such as “no phase changes” of a technical material that is therefore used, it might break down due to an actually present low force, low transition energy phase-change. This paper thus installed a tool box for the distinction of experimental and faked loading curves of indentations. We found experimental and faked loading curves of the same research group with overall 14 authoring co-workers in three publications where valid and faked ones were next to each other and I can thus only report on the experimental ones. The comparison of Si and Cu with W at 20-fold higher physical hardness shows its enormous influence to the energies of phase transition and of their transition energies. Thus, the commonly preferred ISO14577-ASTM hardness values HISO (these violate the energy law and are simulated!) leads to almost blind characterization and use of mechanically stressed technical materials (e.g. airplanes, windmills, bridges, etc). The reasons are carefully detected and reported to disprove that the coincidence or very close coincidence of all of the published loading curves from 150 K to 298 K are constructed but not experimental. A tool-box for distinction of experimental from faked indentation loading curves (simulations must be indicated) is established in view of protecting the AI from faked data, which it might not be able by itself to sort them out, so that technical materials with wrongly attributed mechanical properties might lead to catastrophic accidents such as all of us know of. There is also the risk that false theories might lead to discourage the design of important research projects or for not getting them granted. This might for example hamper or ill-fame new low temperature indentation projects. The various hints for identifying faked claims are thus presented in great detail. The low-temperature instrumental indentations onto silicon have been faked in two consecutive publications and their reporting in the third one, so that these are not available for the calculation of activation energies. Conversely, the same research group published an indentation loading curve of copper as taken at 150 K that could be tested for its validity with the therefore created tools of validity tests. The physical algebraic calculations provided the epochal detection of two highly exothermic phase transitions of copper that created two polymorphs with negative standard energy content. This is world-wide the second case and the first one far above the 77 K of liquid nitrogen. Its existence poses completely new thoughts for physics chemistry and perhaps techniques but all of them are open and unprepared for our comprehension. The first chemical reactions might be in-situ photolysis and the phase transitions can be calculated from experimental curves. But several further reported low temperature indentation loading curves of silicon were tested for their experimental reality. And the results are compared to new analyses with genuine room temperature results. A lot is to be learned from the differences at room and low temperature.

钨粉制备及其对钨合金性能影响的研究进展

金属钨因具有高熔点、高硬度、耐腐蚀、耐磨和热膨胀系数小等优点而被广泛应用于制备各种合金材料。本研究综述了钨粉的制备方法,如熔盐电解法、溶胶凝胶法、高能球磨法和氢气还原法。针对钨粉均匀性问题,重点阐述了目前使用最广泛的氢气还原法的研究现状,其中,调控氢气中水蒸气分压有利于提高钨粉均匀性;气流磨和球化等钨粉的处理工艺有助于提高钨粉均匀性和分散性。另外,介绍了钨粉粒度和分散性等对钨合金性能的影响,均匀分散的钨粉对制备组织均匀的钨合金优势巨大。针对钨粉和钨合金中钨晶粒之间的相关性介绍了晶粒细化的相关研究。简要介绍了钨粉性能对增材制造钨合金性能的影响。

赣南铁山垅钨矿田花岗斑岩地球化学特征、锆石U-Pb年龄及Hf同位素特征

赣南铁山垅钨矿田位于南岭钨锡多金属成矿带东段,已探获黑钨矿资源量超10万吨。铁山垅复式岩体包括主体似斑状黑云母花岗岩和补体细粒二云母花岗岩两部分,花岗斑岩呈脉状分布。矿田内花岗岩具有相似的地球化学特征,都属过铝质高钾钙碱性花岗岩类,表现出高硅、富铝、富碱、高钾、富成矿元素(W、Sn、Cu、Mo)和亏损Ba、Sr、Ti、P、REE、Eu,稀土配分曲线呈典型的“海鸥式”分布和M型四分组效应等特征。利用LA-ICP-MS锆石U-Pb定年方法获得花岗斑岩^(206)Pb/^(238)U年龄为146.7±0.5 Ma(MSDW=0.5),成岩时代属晚侏罗世。锆石的n(^(176)Lu)/n(^(177)Hf)=0.000973~0.001989,f_(Lu/Hf)=-0.97~-0.94,ε_(Hf)(t)=-17.9~-10.3,二阶段模式年龄(TDM2)为1.86~2.33 Ga,显示原岩为古元古代地壳。综合分析认为,铁山垅矿田岩浆活动可划分为170~155 Ma、155~150 Ma、150~145 Ma三个阶段,钨锡矿成矿主要集中在第二阶段,且第三阶段花岗斑岩与铜多金属矿成矿关系密切,推测铜岭矿区深部具有较大的找矿前景。

钨渗铜样件烧蚀裂纹产生机理探讨

以烧蚀后的钨渗铜样件(牌号W-7Cu)为研究对象,针对特定环境条件下烧蚀试验后钨渗铜样件表面裂纹进行了形貌特征分析并对裂纹产生的机理进行了探讨。表面形貌及能谱分析结果表明,3000℃高温环境试验后,表面存在Cu析出且在高温粒子冲刷后留下烧蚀坑,嵌入基体的颗粒中含有大量C、O、Al等元素;物相分析表明,烧蚀产物的主要相为WC、W6C2.54脆性相,推测Cu相挥发后铜基体上形成连通孔隙,推进剂或者环境中的C进入钨骨架孔隙中,与钨渗铜件中的W形成碳化钨脆性相导致烧蚀过程中形成小裂纹继而分层剥离,是烧蚀裂纹产生的主要原因。

钨纤维增韧钨基复合材料的研究进展

钨纤维增韧钨基复合材料作为一种理想的面向等离子体材料,可以不需要引入其他合金元素,通过充分发挥钨纤维本身的优异性能而提升其韧性。对钨纤维增韧钨基复合材料的增韧机理、增韧相类型、制备方法的研究现状进行了综述,重点介绍了钨纤维表面改性、钨纤维体积分数以及烧结温度对复合材料性能的影响,指出了该复合材料今后的研究方向。

晶粒尺寸对铌钨合金力学性能的影响

本文以铌钨合金为研究对象,通过熔炼、挤压、锻造制备了两种不同晶粒尺寸的铌钨合金棒材,研究了初始晶粒尺寸对经过热处理后棒材的显微组织和力学性能的影响,研究结果将为制备有特殊性能要求的铌合金材料提供一定参考。结果表明,经过相同热处理工艺处理后,初始晶粒尺寸细小的Φ43 mm棒材形成均匀细小的等轴晶,而初始晶粒尺寸粗大的Φ89 mm棒材形成不均匀且粗大的部分再结晶组织。无论是室温拉伸还是高温(1100℃)拉伸,晶粒细小的Φ43 mm棒材均呈现较好的屈服强度,分别为401 MPa和272 MPa。因此,铌钨合金的屈服强度与棒材初始晶粒尺寸有关。铌钨合金棒材的屈服强度要求越高,越需制备具有细小初始晶粒的棒材。

钴含量对Ni-W-Co合金镀层耐蚀性的影响

[目的]研究镀层Co含量对Ni-W-Co合金镀层耐蚀性的影响。[方法]通过调节镀液的钴盐(Co SO_(4)·7H_(2)O)用量,在N80钢表面直流电沉积得到不同Co含量的Ni-W-Co合金。通过镀层厚度测量、成分分析、形貌观察、全浸腐蚀试验、动电位极化曲线测试等方式研究了钴盐质量浓度对沉积速率及合金镀层成分、形貌和耐蚀性的影响。[结果]随着镀液中钴盐质量浓度的增大,沉积速率增大,镀层的Co质量分数增大,表面变得粗糙,耐蚀性先变好后变差。Co SO_(4)·7H_(2)O的质量浓度为2.0 g/L时获得的Ni-W-Co合金镀层在5%Na Cl溶液和土酸溶液(由10%盐酸与5%氢氟酸组成)中的腐蚀速率最低,耐蚀性最佳。[结论]通过调整镀液的钴盐用量可电沉积得到适用于油田环境的耐腐蚀Ni-W-Co合金镀层。

大宝山含钨褐铁矿中钨的赋存状态与嵌布特征

通过多种分析方法,探究广东大宝山含钨褐铁矿的物相组成、元素分布等工艺矿物学特征,以揭示矿石中关键金属钨的赋存状态与嵌布特征。X射线荧光分析(XRF)、粉末X射线衍射(XRD)以及扫描电子显微镜和能谱(SEM-EDS)结果表明:矿石中主要矿物为含钨褐铁矿和石英,关键金属钨品位为1.35%。微区X射线衍射(Micro-XRD)和矿物解离度分析仪(MLA)结果表明:钨主要赋存于高铁钨华((W,Fe)(O,OH)_(3))中,而高铁钨华则以剥离和带状形式紧密分布在褐铁矿中。同时,还定量分析了有价元素在各主要矿物中的赋存和分布情况,并讨论了含钨褐铁矿风化演变和形成机制。最终提出了一种选冶联合分选回收流程,为高效回收含钨褐铁矿中关键金属钨提供理论基础。

弹体材料性能对超高速侵彻深度的影响规律

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