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.

Microwave-induced synthesis and characterization of nanometer Ce_(0.5)Zr_(0.5)O_2 solid solution for the acidic catalytic reaction

Ce0.5Zr0.5O2 solid solution was successfully synthesized using cerium nitrate, zirconium nitrate, and urea as raw materials by the microwave irradiation method and characterized by X-ray diffraction, fluorescence spectrum, transmission electron microscopy, and infrared spectrum. Its acid catalytic activity was evaluated in the esterification reaction of acetic acid and n-butyl alcohol. The results show that Ce0.5Zr0.5O2 solid solution has cubic fluorite structure, and its particle diameter is in the nanometer scale. As a sort of solid acid, it possesses a higher acid catalytic activity and can be easily separated from reaction liquids. It can be used for several times, and basically, its activity keeps constant. The proton acid sites and Lewis acid sites exist in the structure of Ce0.5Zr0.5O2 solid solution.

Formation Kinetics of Unsaturated (Ti, W)C Solid Solution

The effects of temperature (1650-2250°C), time (20-180 min), particle size of WC (1-13 μm) and that of TiO2 (1-7 μm) on the formation process of solid solution Ti0.5W0.5C have been investigated by X-ray diffraction, optical microscopy, SEM and EPMA methods. It is found that the formation of (Ti, W)C is controlled by diffusion process between WC and disequilibrium (Ti, W)C. According to Jander and Arrhenius equation, the apparent activation energy was calculated to be 318-380 kJ/mol (for T<1850°C) and 100-117 kJ/mol (for T≥1850°C). The diffusion model for different temperature interval was proposed. An X-ray diffraction calculating index H was also developed to examine the micro-inhomogeneity of (Ti, W)C. The H value variation agrees well with the experimental results.

Solid Solution Characteristics of Pb(B_(1/3)Nb_(2/3))O_(3)-based Composite Ceramics

The solid solution characteristics of Pb（B1/3Nb2/3）O3-based （B=Zn^2＋, Mg^2＋, Ni^2＋） composite ceramics prepared by two-phase mixed-sintering method were developed based on dielectric measurements. Results show that there are double dielectric peaks for PZN-based composite ceramic, implying two phases coexist. However single dielectric peak was presented in PMN- and PNN-based composite ceramics, respectively. It is indicated that obvious solid solution reaction exists during the sintering process of these two systems. The effects of B-site ion difference on the solid solution characteristics were discussed by crystal chemistry. SEM was employed to investigated the microstructures of composite ceramics. The influences of solid solution reaction on grain growth were discussed.

In situ regulating intimately connected heterostructure by decomposition of solid solution oxides toward high-efficient water oxidation

Heterogeneous interfaces produced by interdomain interactions on a nanoscale performs a crucial role in boosting the properties of an electrocatalyst toward oxygen evolution reaction(OER)process.Herein,a series of dual-phase electrodes with intimately connected heterointerfaces are prepared by in situ decomposing solid solution oxide of Ni_(x)Co_(y)Fe_(100-x-y)O,which grew on Ni foam massively via an ultrafast combustion approach.Particularly,with high-reaction kinetics caused by the reduction treatment at 450℃,the less electronegative Fe and Co are more oxyphilic than Ni,which facilitated their co-exsolution and formation of CoFe_2O_4/NiO oxide with enriched oxygen vacancies.Benefiting from the nanoporous framework,heterojunction structure,and oxygen defects,the self-supporting electrodes present rapid charge/mass transmission and provide abundant active sites for OER.The optimized sample(R-SNCF4.5)shows low overpotentials of 226 and 324 mV at 10 and100 mA·cm^(-2),a small Tafel slope(46.7 mV·dec^(-1)),and excellent stability.The assembled R-SNCF4.5//Pt/C/NF electrolyzer demonstrates continuous electrolysis over 50 h at a current density of 10 mA·cm^(-2),under 1.51 V.Density functional theory(DFT)calculations verify that the strong electronic modulation plays a critical part in the CoFe_2O_4/NiO hybrid by lowering the energy barriers for the ratedetermining steps,and Fe sites are the most active OER sites.

Morphology effects in MnCeO_(x)solid solution-catalyzed NO reduction with CO:Active sites,water tolerance,reaction pathway

Morphological effects of nanoparticles are crucial in many solid-catalyzed chemical transformations.We herein prepared two manganese-ceria solid solutions,well-defined MnCeO_(x)nanorods and MnCeO_(x)-nanocubes,exposing preferentially(111)and(100)facets of ceria,respectively.The incorporation of Mn dopant into ceria lattice strongly enhanced the catalytic performance in the NO reduction with CO.MnCeO_(x)(111)catalyst outperformed MnCeO_(x)(100)counterpart due to its higher population density of oxygen vacancy defects.In-situ infrared spectroscopy investigations indicated that the reaction pathway over MnCeO_(x)and pristine CeO_(2)is similar and that besides the direct pathway,an indirect pathway via adsorbed hyponitrite as an intermediate cannot be ruled out.X-ray photoelectron and Raman spectroscopies as well as first-principles density functional theory(DFT)calculations indicate that the enhanced catalytic performance of MnCeO_(x)can be traced back to its“Mn–OL(VÖ)–Mn–OL(VÖ)–Ce”connectivities.The Mn dopant strongly facilitates the formation of surface oxygen vacancies(VÖ)by liberating surface lattice oxygen(OL)via CO*+OL→CO_(2)*+VÖand promotes the reduction of NO,according to NO*+VÖ→N*+OL and 2N*→N_(2).The Mn dopant impact on both the adsorption of CO and activation of OL reveals that a balance between these two effects is critical for facilitating all reaction steps.

使固态化学反应100%完成的方法

无溶液形成的固态化学反应具有“一旦发生,就必完全”的特质,但因为固体的非流动性,它常常会因严重的传质困难而有始无终。为了克服这个困难,作者提出了少溶剂固态化学反应(LSR)的概念,即通过使用少量的溶剂赋予固体流动性,使反应物固体部分溶解,再使用搅拌反应器解决其“三传”问题,使之完全反应,从而达到使一些化学工业过程绿色化的目的。本文用平衡热力学数值计算的方法图解了几种代表性LSR的Gibbs自由能随反应进度的关系,进而指出:LSR的中间阶段如同没有溶液形成的固态化学反应,两端像溶液化学反应,因此,LSR虽继承了混合自由能导致的化学平衡,但其平衡点比溶液化学反应更接近100%完全。特别地,在LSR即将结束时,通过逐步移除溶剂以使反应物和产物固体持续存在而延长中段,能推动反应达到100%完全;对于连串反应,LSR仍有可能通过控制反应物的物质的量之比来获得中间产物;对于Δ_rG_m~?略小于零的反应,可以通过使用较多的溶剂跨越可能的早期平衡态,或者使用大量的产物固体“种子”使所有的产物一直与其饱和溶液平衡,最终通过逐渐蒸发溶剂推动反应进行到底;LSR的反应速度与反应物或产物的溶解度关系不大,但与反应物的溶解速度、化学反应速度和产物的结晶速度紧密相关。本文还讨论了使一些竞争反应、非自发反应进行到底的方法,获得高度的反应控制能力。

Ni^(3+)抑制具有阴离子氧化还原活性钠离子电池正极材料的电压衰减

由于钠资源丰富,钠离子电池在大规模储能方面显示出巨大的潜力。随着近年来研究的深入,在正极材料中引入适量的阴离子氧化还原可以有效地提升钠离子电池的能量密度,同时减少高成本过渡金属元素如V、Co和Ni等的用量。有研究表明,材料循环过程中不可逆的氧损失以及Mn^(4+)/Mn^(3+)氧化还原的激活,导致了层状氧化物正极材料持续的电压衰减。本工作通过在Na_(x)[Li,Ni,Mn]O_(2)基钠离子电池正极材料中引入Ni^(3+)作为Mn^(4+)/Mn^(3+)氧化还原屏障,利用Ni^(3+)/Ni^(2+)的氧化还原代替Mn^(4+)/Mn^(3+)的氧化还原,成功抑制了材料的电压衰减。电化学测试结果显示,改性材料在不损失容量的前提下,循环稳定性得到明显提升。X射线光电子能谱结果也验证了Ni3^(+)的引入有利于维持材料多周循环后Mn价态的稳定。

泡沫镍负载CeO_(2)改性CuO催化剂的碳烟燃烧性能研究

通过在泡沫镍基底上预沉积CeO_(2)晶核,采用水热法成功合成出泡沫镍负载CeO_(2)改性CuO催化剂(xCeO_(2)-CuO/NF),同未加入CeO_(2)的催化剂(CuO/NF)相比,其碳烟氧化活性显著提高。随着催化剂中CeO_(2)含量的增加,Ce/Cu质量比不断增大直至趋于平稳,催化剂的催化活性随之提高直至基本不变。其中,6.5CeO_(2)-CuO/NF的催化活性最好,T_(50)(383℃)最低,比CuO/NF催化剂低32℃。研究结果表明,预沉积CeO_(2)晶核一方面可促进CuO微纳结构的生长,提高碳烟颗粒与催化剂活性位点的接触效率;另一方面,xCeO_(2)-CuO/NF中形成的Cu_(x)Ce_(1-x)O固溶体增强了铜铈之间的相互作用,通过Ce^(3+)/Ce^(4+)和Cu^(2+)/Cu^(+)之间氧化还原耦合循环促使活性氧物种的生成,并提升了其本征活性,从而极大地提高了其催化碳烟氧化的能力。

In-situ assembly of 2D/3D porous nickel cobalt sulfide solid solution as superior pre-catalysts to boost multi-functional electrocatalytic oxidation

In this work,we fabricated an efficient pre-catalyst based on(Ni,Co)S2solid solution with hierarchical architecture and high porosity to boost urea oxidation reaction and electrocatalytic oxidation of organic small molecules.The interaction between Ni and Co can optimize the electronic structure,resulting in the improved conductivity and accelerated charge transfer rate.The 2D/3D architecture can enrich more active species and endow the mass and electron transport to facilitate the surface oxidation and the following catalytic process.Post-structure and catalytic characterizations confirm the surface oxidation of(Ni,Co)S_(2)during the stability test,and the in-situ formed Co(Ni)based(oxy)hydroxides exhibit superior catalytic activity and facilitated charge transfer ability.As a result,the optimal(Ni,Co)S_(2)solid solution pre-catalyst displays facilitated catalytic behavior and good stability for multifunctional electrocatalytic oxidation,in which a high conversion of benzyl alcohol(97.50%),a good selectivity to benzoic acid(93.78%)and a satisfied faraday efficiency(91.86%)can be achieved.

Facile synthesis of Fe/Ni bimetallic oxide solid-solution nanoparticles with superior electrocatalytic activity for oxygen evolution reaction

The sluggish oxygen evolution reaction （OER） is an important half-reaction of the electrochemical water-splitting reaction. Amorphous Fe/Ni composite oxides have high activity. In this work, we modified the aerosol spray-assisted approach and obtained amorphous Fe-Ni-Ox solid-solution nanoparticles （Fe-Ni-Ox-NPs） approximately 20 nm in size by choosing iron/nickel acetylacetonates as raw materials instead of inorganic salts. The small-sized Fe-Ni-Ox-NPs were characterized by scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, X-ray diffraction （XRD） analysis, energy-dispersive X-ray spectroscopy （EDX）, and X-ray photoelectron spectroscopy （XPS）. Furthermore, an investigation of electrochemical OER performance suggests that the small-sized Fe-Ni-Ox-NPs have higher activity than the large-sized Fe-Ni-Ox-MPs. A small overpotential of 0.315 V was demanded to obtain a working current density of 50 mA/cm2, and the Tafel slope was as low as 38 mWdec.

Chromium-ruthenium oxide solid solution electrocatalyst for highly efficient oxygen evolution reaction in acidic media

With the support of the National Natural Science Foundation of China and the aided program for Science and Technology Innovative Research Team of Ningbo Municipality,the research team led by Prof.ChenLiang(陈亮)at Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences,reported a chromium-ruthenium oxide solid solution electrocatalyst for the highly efficient oxygen evolution reaction(OER)in acidic media.

Effects of Carrier on CuO/TiO_2 and CuO/Ti_(0.5)Zr_(0.5)O_2 Catalysts in the NO+CO Reaction

Using TiO2 and Ti0.5Zr0.5O2 as carriers, the CuO/TiO2 and CuO/Ti0.5Zr0.5O2 catalystswere prepared by the impregnation method with Cu(NO3)2 as active component. The catalyticactivities in NO+CO reaction were investigated using a microreactor-GC system, and structure andreducibility of catalysts were characterized by means of physical adsorption, TPR, XRD, NO-TPDtechnologies. It was found that the activity of CuO/Ti0.5Zr0.5O2 catalyst was higher than that ofCuO/TiO2, probably due to the large specific surface area of Ti0.5Zr0.5O2 that played an importantrole in NO+CO reaction.

反应温度和固液质量比对磷石膏脱水转晶的影响

为提高磷石膏的利用率和附加值,利用磷石膏在20%NaCl溶液中脱水转晶制备α-半水石膏,研究了反应温度和固液质量比对磷石膏脱水行为、转晶效率、矿相组成和微观形貌的影响。结果表明,当反应温度为80~95℃时,随着温度的升高,磷石膏的转晶速率加快,α-半水石膏的诱导成核时间和晶体生长时间均逐渐减少,总转化时间缩短。过低或过高的固液质量比均会影响磷石膏在盐溶液中的分散程度,在一定程度上阻碍磷石膏的脱水转晶,导致α-半水磷石膏的转晶时间随着固液质量比的减小呈现先减小后增大的变化趋势。在反应温度为90℃和固液质量比为1∶4的20%NaCl溶液中,磷石膏仅需常压水热反应1.34 h即可完全脱水形成长棒状α-半水石膏。

固溶反应对MA-Al_(2)O_(3)材料结构和性能的影响

以电熔镁铝尖晶石为主要原料并加入少量烧结刚玉细粉部分替代尖晶石细粉,或以白刚玉为主要原料并加入少量电熔镁铝尖晶石细粉替代白刚玉细粉,制备了两组MA-Al_(2)O_(3)材料。研究刚玉与镁铝尖晶石之间的固溶反应对材料性能及显微结构的影响。结果表明:1)在两组材料中均发生了固溶反应,使得镁铝尖晶石的富铝程度增大,镁铝尖晶石中的氧化铝含量(w)由约76%增加到80%以上,从而加强了试样骨料与基质的结合,减少结构缺陷,改善了材料的高温性能;2)在以镁铝尖晶石为主要原料的MA-Al_(2)O_(3)材料中,加入烧结刚玉可使其常温耐压强度增大,改善其高温抗蠕变性和抗热震性;3)在以白刚玉为主要原料的MA-Al_(2)O_(3)材料中,加入镁铝尖晶石细粉,其常温耐压强度、高温抗蠕变性和高温抗折强度均有大幅度提高。

制备方法对铈锰固溶体催化燃烧甲苯性能的影响

以甲苯为代表的挥发性有机化合物的排放,导致大气污染问题加剧。为了开发一种高效的用于甲苯催化燃烧反应的催化剂,采用水热法、热分解法和共沉淀法制备3种Ce_(0.7)Mn_(0.3)O_(2)样品,分别用于催化甲苯燃烧反应,并通过X射线衍射、扫描电镜、透射电镜、氮气物理吸附-脱附、X射线光电子能谱、H_(2)程序升温还原、原位红外光谱测试对3种样品进行表征,探究制备方法对Ce_(0.7)Mn_(0.3)O_(2)催化剂结构、形貌、化学性质和催化燃烧甲苯性能的影响。结果表明:3种方法制备的Ce_(0.7)Mn_(0.3)O_(2)均为纳米颗粒;相较于其他2种方法,采用水热法制备的Ce_(0.7)Mn_(0.3)O_(2)具有更丰富的表面Mn3+、表面氧空位以及较强的低温可还原性,因此在甲苯催化燃烧反应中表现出良好的催化活性,在218℃时甲苯的转化率达到90%;此外,该样品具有优异的稳定性,在218℃下进行50h的稳定性测试后,仍能保持较高的甲苯转化率(约为90%);原位红外测试表明,水热法制备的Ce_(0.7)Mn_(0.3)O_(2)样品表面的催化燃烧甲苯反应遵循Marse-van Krevelen机制。

界面密排六方固溶体提高Au-Ge/Cu焊点的剪切强度

系统研究界面产物形貌、化学成分、力学性能及其对Au−Ge/Cu焊点剪切强度的影响。结果表明,在400℃下钎焊5~60 min后,焊点界面生成密排六方结构固溶体相(HCP)。该HCP相成分为78%~46%Cu,9%~42%Au和~12%Ge(摩尔分数),杨氏模量为105~112 GPa,硬度为4.3~4.7 GPa。钎焊5 min焊点的剪切强度为57 MPa,但钎焊60 min后焊点的剪切强度上升至68 MPa。焊点强度的提高可归因于塑性HCP相的生成及其对脆性(Ge)相的消耗。这说明生成塑性HCP界面产物是一种能有效提高钎焊焊点剪切强度的方法。

Preparation of ceria-zirconia solid solution with enhanced oxygen storage capacity and redox performance

A new method called ultrasonic-assisted membrane reaction(UAMR)was reported for the fabrication of ceria-zirconia solid solution.A series of ceria-zirconia solid solutions with different Ce/Zr molar ratios were prepared by the UAMR method and characterized by Xray diffraction(XRD),N2 adsorption,hydrogen temperature-programmed reduction(H2-TPR),scanning electron microscope(SEM),and transmission electron microscopy(TEM)techniques.The UAMR method proved to be superior,especially when the Ce/Zr molar ratio was lower than 1,in fabricating ceria-zirconia solid solutions with large BET surface area,high oxygen storage capacity(OSC),and low reduction temperature.

High-pressure synthesis and properties of CeO_2-ZrO_2 solid solution

Using nanoparticles of CeO2 and ZrO2 prepared by the chemical precipitation method as starting materials, the single-phase cubic Ce0.5Zr0.5O2 solid solution (c-Ce0.5Z0.5O2) has been synthesized under 3.1 GPa at 1073 K for the first time. The structure of the c-Ce0.5Zr0.5O2 has not been changed before and after annealing at 773 K for 1 h. Only an unknown EPR signal (g =1.990) has been observed in the c-Ce0.5Zr0.5O2 and not varied after annealing at 773 K for 1 h, which exhibited that there exists no Ce3+ in the c-Ce0.5Zr0.5O2 and the Ce4+ has not been reduced into Ce3+ after annealing. The transport mechanism is ionic for the c-Ce0.5Zr0.5O2. The bulk conductivity (a =1.2×10-5 S/cm at 823 K, σ=2.1 ×10-3 S/cm at 1123 K) is the same as that of CeO2, but smaller than that of Y2O3-stabilized ZrO2. A marked curvature at T = 823 K has been observed in the Arrhenius plot of the bulk conductivity. The activation energy below 823 K is lower than that above 823 K, and the reason has been discussed.

Incubation of PbSe Thin Films in a Tin(Ⅱ) Salt Aqueous Solution:Modification and Ion-Exchange Reactions

Topochemical ion-exchange reactions between solid micro- and nanostructured metal chalcogenides and aqueous salt solutions are generally used for formation of composite structures based on initial metal chalcogenides and products of their ion-exchange transformation. However, ion exchange has promises as a route to obtaining both composites and solid solutions based on the initial and the end chalcogenide phases. With the help of the ion-exchange technique, single-phase films of Phi xSnxSe substitutional solid solutions with a tin content up to -2 at.%, which are promising for mid- and long-wavelength infrared radiation （IR） optoelectronics, have been obtained at the interface between PbSe poly- crystalline thin films and SnCl2 aqueous solutions containing sodium citrate. It has been shown that the pH value and temperature of the reaction system play an important role in the ion-exchange process. Incubation of lead selenide （PbSe） films in a tin（II） salt aqueous solution also leads to their modification with oxygen-containing tin compounds to a depth of-3 nm. Differences in the film structure, such as changes in the coherent scattering region sizes and orientation of crystallites along the [220] direction, which arise during the contact with citrate-containing SnCl2 solutions, have also been revealed. For the first time, an idea of the existence of a relatively wide reaction zone of an intragranular topochemical ion-exchange reaction in an aqueous solution, within which substitutional solid solutions can form in micro- and nanostructured systems, has been set forth.