Studies on influence of hydrogen and carbon monoxide concentration on reduction progression behavior of molybdenum oxide catalyst

Temperature programmed reduction (TPR) analysis was applied to investigate the chemical reduction progression behavior of molybdenum oxide (MoO₃) catalyst. The composition and morphology of the reduced phases were characterized by X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FE-SEM). The reduction progression of MoO₃ catalyst was attained with different reductant types and concentration (10% H₂/N₂, 10% and 20% CO/N₂ (%, v/v)). Two different modes of reduction process were applied. The first approach of reduction involved non-isothermal mode reduction up to 700 °C, while the second approach of reduction involved the isothermal mode reduction for 60 min at 700 °C. Hydrogen temperature programmed reduction (H₂-TPR) results showed the reduction progression of three-stage reduction of MoO₃ (Mo⁶⁺ → Mo⁵⁺ → Mo⁴⁺ → Mo⁰) with Mo⁵⁺ and Mo⁴⁺. XRD analysis confirmed the formation of Mo₄O₁₁ phase as an intermediate phase followed by MoO₂ phase. After 60 min of isothermal reduction, peaks of metallic molybdenum (Mo) appeared. Whereas, FESEM analysis showed porous crater-like structure on the surface cracks of MoO₂ layer which led to the growth of Mo phase. Meanwhile, the reduction of MoO₃ catalyst in 10% carbon monoxide (CO) showed the formation of unstable intermediate phase of Mo₉O₂₆ at the early stage of reduction. Furthermore, by increasing 20% CO led to the carburization of MoO₂ phase, resulted in the formation of Mo₂C rather than the formation of metallic Mo, as confirmed by XPS analysis. Therefore, the presented study shows that hydrogen gave better reducibility due to smaller molecular size, which contributed to high diffusion rate and achieved deeper penetration into the MoO₃ catalyst compared to carbon monoxide reductant. Hence, the reduction of MoO₃ in carbon monoxide atmosphere promoted the formation of Mo₂C which was in agreement with the thermodynamic assessment.     

Distribution of carbon contamination in MgAl2O4 spinel occurring during spark-plasma-sintering (SPS) processing: I – Effect of heating rate and post-annealing

Carbon contamination from the carbon paper/dies during spark-plasma-sintering (SPS) processing was examined in the MgAl₂O₄ spinel. The carbon contamination sensitively changes with the heating rate during the SPS processing. At the high heating rate of 100 °C/min, the carbon contamination having organized structures occurred over almost the entire area from the surface to deep inside the SPSed spinel disk. In contrast, at the slow heating rate of 10 °C/min, the carbon contamination having disordered structures occurred only around the surface area. The carbon phases transform into high pressure CO/CO₂ gases by post-annealing in air and lead to pore formation along the grain junctions. The pore formation significantly occurs at the high heating rate due to the large amount of the contaminant carbon phases. This suggests that if once the carbon contamination was formed in the materials, it is very difficult to remove the carbon phases from the materials.     

Influence of SiC content on the oxidation of carbon fibre reinforced ZrB2/SiC composites at 1500 and 1650 °C in air

The microstructure and the oxidation resistance in air of continuous carbon fibre reinforced ZrB₂–SiC ceramic composites were investigated. SiC content was varied between 5–20?vol.%, while maintaining fibre content at ～40?vol.%. Short term oxidation tests in air were carried out at 1500 and 1650?°C in a bottom-up loading furnace. The thickness, composition and microstructure of the resulting oxide scale were analysed by SEM-EDS and X-Ray diffraction. The results show that contents above 15?vol.% SiC ensure the formation of a homogeneous protective borosilicate glass that covers the entire sample and minimizes fibre burnout. The scale thickness is ～90?μm for the sample containing 5?vol.% SiC and decreases with increasing SiC content.     

工艺参数对超声辅助脉冲电沉积镍-氮化钛复合镀层的影响

在45钢表面以超声波辅助脉冲电沉积制备Ni-TiN复合镀层。研究了平均阴极电流密度、脉冲占空比、超声功率和TiN粒子(平均直径20~30 nm)添加量对复合镀层的TiN粒子含量和显微硬度的影响。得到较优的工艺参数为:NiSO4ꞏ6H2O 300 g/L,NiCl2ꞏ6H2O 30 g/L,H3BO330 g/L,十二烷基硫酸钠0.3 g/L,TiN 25 g/L,pH 4.1~4.3,温度40°C,平均阴极电流密度4 A/dm2,脉冲占空比40%,脉冲频率1000 Hz,超声功率300 W,机械搅拌速率200 r/min,时间60 min。该条件下所得Ni-TiN复合镀层的TiN质量分数为8.35%,显微硬度为819 HV,表面平整、致密,晶粒尺寸均匀。     

Nanocrystalline transition metal oxides and their composites with reduced graphene oxide and carbon nanotubes for photocatalytic applications

Transition metal oxide nanoparticles (CuO, ZnO & Fe₂O₃) and mixed metal oxides CuO. ZnO.Fe₂O₃ were fabricated by facile co-precipitation approach for photocatalytic treatment of organic dyes. The structural features, phase purity, crystallite size and morphology of individual and mixed metal oxides were analysed by X-rays diffraction patterns (XRD) and scanning electron microscopic (SEM) analysis. Electrical behaviour of CuO, ZnO, Fe₂O₃ and mixed metal oxides CuO. ZnO.Fe₂O₃ was explored by current-voltage (I-V) measurements. Functional groups present in the synthesized metal oxides were investigated by Fourier transform infrared spectroscopy (FTIR) which ensures the existence of M-O functional groups in the samples. The optical bandgap analysis was carried out by UV–visible spectroscopic technique which revealed that the blend of three different transition metal oxides reduced the bandgap energy of mixed metal oxides. The reason behind this reduced bandgap energy is formation of new electronic state which arises due to the metal-oxygen interactions. Moreover, the nanocomposites of CuO.ZnO.Fe₂O₃ with reduced graphene oxide (rGO) and carbon nanotubes (CNTs) were prepared to study the effect of the carbonaceous materials on the rate of photodegradation. These carbonaceous nanomaterials have plethora properties which can bring advancement in sector of photocatalytic treatment of wastewater. The photocatalytic experiments were performed using methylene blue (MB) as standard dye for comparative study of metal oxides and their composites with rGO and CNTs. The percentage degradation of methylene blue (MB) by nanocomposite CuO.ZnO.Fe₂O₃/rGO is 87% which is prominent among all samples. This result ascribed the photocatalytic aspects of reduced graphene oxide along with mixed metal oxides.     

轨腰仿生自分层防腐梯度涂料合成及影响因素和结构探究

目的仿荷藕结构及功能,制备一种自分层防腐涂料。方法合成聚氨酯改性环氧树脂(PU/EP)及氟硅改性丙烯酸树脂(氟硅改性PAA),将两种树脂共混形成自分层涂料。通过铅笔硬度测试、机械性能测试、接触角测试、耐老化测试、划格法附着力测试、电化学阻抗测试等,分别评价两种树脂比例、混合溶剂比例对涂膜自分层行为及性能的影响,并通过SEM-EDS、红外光谱等表征技术分析涂膜分层后的结构。结果当PU/EP∶氟硅改性PAA=1∶1时,接触角达到96.0°,柔韧性为0.5 mm,耐冲击为50 cm,附着力等级为1,失光率降至19%;乙酸丁酯(NBAC)∶正丁醇(NBA)=4∶6时,涂膜分层情况良好,接触角达到107.7°,浸泡水中48 h耐水性无变化,失光率降至17%。SEM-EDS、红外光谱分析表明,自分层涂膜上层为氟硅改性PAA、底层为PU/EP,中间存在过渡涂层,过渡层两种树脂中的─COOH、─OH、环氧基发生反应,使整个涂层更具稳定性。经由EIS分析,在3.5%NaCl溶液中浸泡40天后,腐蚀介质没有渗透涂膜到达基底金属界面。结论制备的轨腰仿生自分层涂膜的机械性能、附着力、疏水性、耐老化、防腐蚀性能优异,涂膜结构稳定。     

TC4合金表面Cu/石墨复合镀层的摩擦磨损行为

采用无氰电镀工艺在TC4合金表面制备了Cu/石墨复合镀层，研究了镀层的组织结构和摩擦磨损行为。结果表明，采用无氰电镀方法能够在TC4合金表面制备出组织致密且与基体结合紧密的Cu/石墨复合镀层，但增加镀层中石墨的含量会降低镀层与基体合金的结合强度，并导致硬度小幅下降。摩擦磨损实验结果表明，Cu/石墨复合镀层具有优良的摩擦磨损防护性能，归因于石墨有效降低了镀层的摩擦系数和磨损率；对镀层磨损形貌、磨损产物和摩擦系数的综合分析结果表明，纯铜镀层的摩擦磨损机制主要为犁削磨损、黏着磨损和剥层磨损，Cu/石墨复合镀层的磨损机制为轻微的削层磨损和疲劳磨损。     

Ni,Cr, and Fe surfaces corroded by molten ZnCl2

Understanding the corrosion of molten ZnCl₂ on metal surfaces is significant for the corrosion protection of metals, sustainable use of molten salts, preparation of ZnO coatings, and so on. In this paper, surfaces of pure Ni, Cr, and Fe corroded by molten ZnCl₂ were investigated. The results show that Ni suffered very slight corrosion, while Cr experienced more serious corrosion than Ni, but lighter corrosion than Fe. The morphology of the corrosion of Cr and Fe, respectively, presented pitting and intergranular corrosion characteristics. Furthermore, nanostructured ZnO coatings were obtained on the surfaces of Ni and Fe, but not on the surface of Cr. The ZnO coating on the Ni surface was doped with a small amount of Zn₅(OH)₈Cl₂, and the ZnO coating on the Fe surface was doped with ZnFe₂O₄ and Zn₂OCl₂. The coatings on the Ni and Fe surfaces had an average thickness of 1.5 and 50 μm, respectively.     

化学气相沉积钨涂层的研究现状与进展

化学气相沉积钨涂层具有工艺简单、技术成熟度高、涂层综合质量优异等特点，广泛应用于国防、航天、核工业等领域。首先介绍了化学气相沉积钨涂层的原理和特点，重点讨论了化学气相沉积钨涂层的工艺及应用研究现状，包括化学气相沉积钨涂层微观组织控制工艺及在耐辐射、耐磨耐蚀和高温防护领域的应用，同时对新型化学气相沉积钨涂层技术的发展进行了展望。一是改善现有工艺存在的反应气源与反应产物毒性大等问题，满足绿色环保的发展要求；二是改善现有工艺存在的沉积温度高、沉积速率偏低等问题，实现在不同衬底表面的高效、高质量沉积；三是改善现有化学气相沉积钨涂层结构与功能单一等问题，满足构件对钨涂层高性能和多功能的需求。