New horizon in mechanochemistry—high-temperature,high-pressure mechanical synthesis in a planetary ball mill—with magnesium hydride synthesis as an example

A new route of materials synthesis, namely, high-temperature, high-pressure reactive planetary ball milling (HTPRM), is presented. HTPRM allows for the mechanosynthesis of materials at fully controlled temperatures of up to 450 °C and pressures of up to 100 bar of hydrogen. As an example of this application, a successful synthesis of magnesium hydride is presented. The synthesis was performed at controlled temperatures (room temperature (RT), 100, 150, 200, 250, 300, and 325 °C) while milling in a planetary ball mill under hydrogen pressure ($>$50 bar). Very mild milling conditions (250 rpm) were applied for a total milling time of 2 h, and a milling vial with a relatively small diameter (φ = 53 mm, V = ～0.06 dm³) was used. The effect of different temperatures on the synthesis kinetics and outcome were examined. The particle morphology, phase composition, reaction yield, and particle size were measured and analysed by scanning electron microscopy, X-ray diffraction, differential scanning calorimetry (DSC) techniques. The obtained results showed that increasing the temperature of the process significantly improved the reaction rate, which suggested the great potential of this technique for the mechanochemical synthesis of materials.     

Complex study of protective Cr3C2–NiAl coatings deposited by vacuum electro-spark alloying,pulsed cathodic arc evaporation,magnetron sputtering,and hybrid technology

Coatings were obtained by vacuum electro-spark alloying (VESA), pulsed cathodic arc evaporation (PCAE), magnetron sputtering (MS) techniques and VESA-PCAE-MS hybrid technology using Cr₃C₂–NiAl electrodes. The structure of the coatings was analyzed using scanning and transmission electron microscopy, X-ray diffraction and energy-dispersive spectroscopy. Mechanical properties were determined by nanoindentation, while tribological properties were assessed using pin-on-disk tribometer. Corrosion resistance was estimated by voltammetry in 1 N H₂SO₄ and 3.5%NaCl solutions. Oxidation resistance tests were performed at 800°С in air. The VESA coating had the highest thickness, low friction coefficient and high wear resistance. PCAE coating demonstrated the highest hardness (24 GPa) and elastic recovery (59%), oxidation resistance and superior corrosion resistance both in 1 N H₂SO₄ (i_corr = 70 μА/cm²) and 3.5%NaCl (i_corr = 0.74 μА/cm²) solutions. The MS coating had average mechanical properties and low corrosion current density (71 μА/cm²) in 1 N H₂SO₄. Deposition of coatings using VESA-PCAE-MS hybrid technology led to an increase in corrosion and oxidation resistance at least by 1.5 times in comparison with the VESA coating.     

Alloying behavior and novel properties of CoCrFeNiMn high-entropy alloy fabricated by mechanical alloying and spark plasma sintering

An equiatomic CoCrFeNiMn high-entropy alloy was synthesized by mechanical alloying (MA) and spark plasma sintering (SPS). During MA, a solid solution with refined microstructure of 10 nm which consists of a FCC phase and a BCC phase was formed. After SPS consolidation, only one FCC phase can be detected in the HEA bulks. The as-sintered bulks exhibit high compressive strength of 1987 MPa. An interesting magnetic transition associated with the structure coarsening and phase transformation was observed during SPS process.     

多元合金化大断面球墨铸铁组织和性能的分析

为了提升大断面球墨铸铁综合力学性能，通过复合添加微量合金元素铜、锑、锡、钼对大断面球墨铸铁进行微合金化处理，借助金相显微镜(OM)、扫描电子显微镜(SEM)及力学性能测试等手段，研究了Cu Sb Sn Mo复合微合金化大断面球墨铸铁微观组织和力学性能。结果表明，试验球墨铸铁具有良好的综合力学性能。大断面球墨铸铁中添加铜、锑、锡、钼后优化了材料的组织结构，基体组织为珠光体＋少量牛眼状铁素体；试样石墨组织细小、圆整，分布均匀。同时，合金元素的复合加入使得其抗拉强度达到800 MPa以上，硬度约为280HB，伸长率达到5%以上。拉伸断口分析表明，微合金化大断面球墨铸铁断裂模式以解理断裂为主，伴有少量的塑性变形。     

Mechanism of methanol decomposition on the Pd/WC(0001) surface unveiled by first-principles calculations

In this study, the decomposition of methanol into the CO and H species on the Pd/tungsten carbide (WC)(0001) surface is systematically investigated using periodic density functional theory (DFT) calculations. The possible reaction pathways and intermediates are determined. The results reveal that saturated molecules, i.e., methanol and formaldehyde, adsorb weakly on the Pd/ WC(0001) surface. Both CO and H prefer three-fold sites, with adsorption energies of −1.51 and −2.67 eV, respectively. On the other hand, CH₃O stably binds at three-fold and bridge sites, with an adsorption energy of −2.58 eV. However, most of the other intermediates tend to adsorb to the surface with the carbon and oxygen atoms in their sp³ and hydroxyl-like configurations, respectively. Hence, the C atom of CH₂OH preferentially attaches to the top sites, CHOH and CH₂O adsorb at the bridge sites, while COH and CHO occupy the three-fold sites. The DFT calculations indicate that the rupture of the initial C–H bond promotes the decomposition of CH₃OH and CH₂OH, whereas in the case of CHOH, O–H bond scission is favored over the C–H bond rupture. Thus, the most probable methanol decomposition pathway on the Pd/WC(0001) surface is CH₃OH → CH₂OH → trans-CHOH → CHO → CO. The present study demonstrates that the synergistic effect of WC (as carrier) and Pd (as catalyst) alters the CH₃OH decomposition pathway and reduces the noble metal utilization.     

氮化硅/石墨激光合金化涂层的组织结构与性能研究

为获得金属表面特别是高副接触金属表面含自润滑特性且具有高硬度耐磨特性的功能材料 ,研究了 45 # 钢表面激光合金化氮化硅 /石墨复合涂层的工艺方法、组织特征、界面形态及其形成机制 ,利用光学显微镜、扫描电镜和X射线能谱对所形成合金化层的元素分布和含量进行了分析 ,并对试样硬度进行了测定。结果表明 ,合金化层中元素Fe ,Co ,Si,C分布均匀 ;C含量达到了 15 6 9%,大部分以石墨的形式存在 ,具有一定的自润滑性能 ;但在形成合金化层的温度条件下 ,氮化硅分解严重 ;合金化层硬度提高的主要原因是Si Fe ,Co Fe固溶体的强化作用及高碳马氏体的生成和高硬度碳化物的存在。     

WC/Cu复合材料制备及其高温性能

用机械合金化法结合冷变形，制备了WC／Cu复合材料，研究了冷变形后复合材料的组织特征和高温退火时韵性能变化。结果表明：烧结后的材料经冷变形，组织呈显著纤维状，WC颗粒弥散分布，密度明显提高，达到理论密度的99．2％；复合材料经600～900℃高温退火，强度和硬度略有下降，塑性则有大幅提高；900℃退火时未发生明显的再结晶，界面结合良好；所制备的WC／Cu复合材料有优良的综合性能。     

机械合金化Fe-Ni粉末的相结构

使用XRD和Moessbauer等方法，研究了在Ar气氛下机械合金化Fe—Ni粉末相结构的变化．结果表明，在机械合金化Fe64-Ni36粉末过程中，fcc相的数量随着球磨时间的增加先增加然后减少，与加乙醇球磨Fe64-Ni36的情形相同．当Ni的含量(原子分数)大于50％时，有fcc相、顺磁相和FeNi3形成，当Ni的含量低于50％时，bcc相的数量随着Ni含量减少而增加．Moessbauer谱的结果表明，因球磨时间或Fe、Ni比例的不同，Fe—Ni球磨粉末固溶体具有不同结构的原子配比。     

激光熔敷合金层组织及腐蚀磨损特性研究

利用ＣＯ＿２连续激光器在４５钢表面进行了激光熔敷镍基合金、镍基Ｃｒ＿２Ｏ＿３合金和镍基ＷＣ合金，以２Ｃｒ１３不锈钢为对比材料，系统地研究了激光熔敷层在不同冲击速度和腐蚀介质浓度下的腐蚀磨损特性，并根据组织分析、显微硬度测试及腐蚀磨损后的表面形貌观察，探讨了激光熔敷层的腐蚀磨损过程。结果表明：激光熔敷层的腐蚀磨损性能均比２Ｃｒ１３不锈钢好。     

机械合金化过程中Fe70B30粉末晶粒尺寸和微观应变的研究

用Ｘ射线和电镜研究了Ｆｅ＿（７０）Ｂ＿（３０）粉末经不同时间高能球磨后晶粒尺寸和微观应力的变化。在机械合金化过程中，粉末的Ｘ射线衍射谱的宽度随球磨时间的增加逐渐加宽，这是晶粒细化和内部微观应力共同作用的结果。Ｘ射线衍射结果表明：随着机械合金化的进行，粉末的晶粒尺寸逐渐减小，球磨初期晶粒尺寸下降较快，经１５ｈ球磨，晶粒尺寸为２５ｎｍ，机械合金化进行到一定时间后晶粒尺寸下降缓慢，８０ｈ球磨后晶粒尺寸可达５ｎｍ。在机械合金化过程中球磨所造成的微观应变不大，球磨初期粉末的内应力随球磨时间增加而增加，当粉末粒子尺寸很小时，随球磨的进行粉末中的微观应变显著下降。