Development and microstructure optimization of atmospheric plasma-sprayed NiO/YSZ anode coatings for SOFCs

In this paper, preparation and characterization of porous anode layers with uniform phase distribution are discussed for solid oxide fuel cell (SOFC) application. The Ni/8YSZ cermet coatings were fabricated by atmospheric plasma spray (APS) process using oxidized nickel coated graphite (Ni-graphite) and 8 mol% yittria — stabilized zirconia (8YSZ) blend as feedstock. To control the microstructure of the coating, the nickel coated graphite with low density was used as a starting feedstock instead of conventional pure nickel (Ni) powder. To balance the conductivity, uniform porosity, and structural stability of the coatings, the effects of process parameters such as hydrogen gas flow rate, stand off distance and pore formation precursor (graphite) addition on the microstructures of the resulting coatings are investigated. The results show that the anode coatings with high conductivity, structural stability and porosity could be deposited with moderate hydrogen gas flow rate and short stand off distance.     

水性集装箱涂料应用现状及研究进展

总结了水性集装箱涂料在国内外的应用现状和最新研究进展,指出随着人们环保意识的不断增强,国际社会对集装箱用涂料在环保方面提出了更高要求,集装箱涂料水性化成为一种必然,且实践证明集装箱涂料水性化是可行的。水性集装箱涂料具有环保、安全的优点,今后必然在集装箱涂料应用领域中产生变革性的影响。对不同体系集装箱涂料的膜厚规范,以及溶剂型涂料体系与水性集装箱涂料体系的综合性能进行了对比,综述了三涂层体系和二涂层体系为现有水性集装箱涂料的2种主流配套体系,并对2种体系的基本组成及各涂层的功能进行分析,讨论了不同集装箱涂层体系的优缺点,指出国内水性集装箱用涂料的技术瓶颈,列举了近年来在水性集装箱涂料方面的主要研究方向及最新研究成果,最后结合目前国内水性集装箱涂料应用的发展水平,提出在水性集装箱涂料的制备过程中,可在涂料用树脂或者基料的合成、改性方面进行更深入的研究和探索,努力提高涂料的综合力学性能,从而实现水性集装箱涂料行业的可持续发展。     

Microstructural Characteristics and Residual Stresses in Arc-Sprayed Cermet Coatings Using Different Carbide Grain Size Fractions

Different studies have emphasized the technological relevance of residual stresses in engineered surfaces, such as thermally sprayed coatings, and their effect on the fracture and fatigue behavior. In arc-sprayed coatings, the microstructural characteristics and resulting residual stresses are determined primarily by the inherent process characteristics and feedstock material. With the scope of this work, a study on the residual stress field in coatings formed by an arc spraying process for different electric parameter settings has been carried out using different wire configurations. Thus, iron-based cored wires with different grain-sized tungsten carbides as filler material were used as feedstock. The coatings are mainly composed of eutectic carbides, and eta carbides such as M₆C, M₁₂C, or M₂₃C and some iron-rich oxide phases, as well as characterized by an inhomogeneous, lamellar microstructure. The results demonstrated that the magnitude of the residual stresses in the coating depends on the carbide grain size fraction used as filling for cored wires. A smaller carbide grain size leads to a more pronounced dissolution of eutectic carbides, resulting in the formation of eta carbides, which in turn is accompanied by decreased tensile residual stresses across the coating. With respect to the spray parameter settings, reduced tensile residual stresses are observed when an increased voltage is applied, which can be attributed to phase evolution phenomena during spraying and thermal effects on the substrate-coating system.     

Plasma spraying of functionally graded yttria stabilized zirconia/NiCoCrAlY coating system using composite powders

Pre-alloyed and plasma spheroidized composite powders were used as the feedstock in the plasma spraying of functionally graded yttria stabilized zirconia (YSZ)/NiCoCrAlY coatings. The ball milling parameters of the composite powders and the plasma spraying parameters for preparing functionally graded materials (FMGs) coatings were optimized to obtain the best performance for the thermal barrier coatings (TBCs). Microstructure, physical, mechanical, and thermal properties of YSZ/NiCoCrAlY FGMs coatings were investigated and compared with those of traditional duplex coatings. Results showed that the advantages of using pre-alloyed composite powders in plasma spraying were to ensure chemical homogeneity and promote uniform density along the graded layers. Microstructure observation showed the gradient distribution of YSZ and NiCoCrAlY phases in the coating, and no clear interface was found between two adjacent different layers. Oxidation occurred during plasma spray and the resultant aluminum oxide combines with YSZ in a wide range of proportions. The bond strength of functionally graded coatings was about twice as high as that of the duplex coatings because of the significant reduction of the residual stresses in the coatings. The thermal cycling resistance of functionally graded coating was much better than that of duplex coating.     

Process Conditions and Microstructures of Ceramic Coatings by Gas Phase Deposition Based on Plasma Spraying

Plasma spraying at very low pressure (50-200 Pa) is significantly different from atmospheric plasma conditions (APS). By applying powder feedstock, it is possible to fragment the particles into very small clusters or even to evaporate the material. As a consequence, the deposition mechanisms and the resulting coating microstructures could be quite different compared to conventional APS liquid splat deposition. Thin and dense ceramic coatings as well as columnar-structured strain-tolerant coatings with low thermal conductivity can be achieved offering new possibilities for application in energy systems. To exploit the potential of such a gas phase deposition from plasma spray-based processes, the deposition mechanisms and their dependency on process conditions must be better understood. Thus, plasma conditions were investigated by optical emission spectroscopy. Coating experiments were performed, partially at extreme conditions. Based on the observed microstructures, a phenomenological model is developed to identify basic growth mechanisms.     

Fabrication of TiAl intermetallic phases by heat treatment of warm sprayed metal precursors

Warm Spraying is an atmospheric coating process based on high-velocity impact bonding of powder particles. By decreasing the temperature of combustion gas via mixing with nitrogen the oxidation of feedstock powder can be effectively controlled. This is particularly important for Ti-based coating materials, which rapidly oxidize at elevated temperatures.In this study, Ti–Al composite coatings were fabricated by the Warm Spray process using a mixture of titanium and aluminum powders as a feedstock and applying a two-stage heat treatment at 600 and 1000 °C to obtain intermetallic phases. The microstructure, chemical and phase composition of the deposited and heat-treated coatings were investigated using SEM, EDS and XRD. The experimental results show that TiAl₃ was the first intermetallic phase formed during the first-stage heat treatment. The growth of TiAl₃ layer occurred mainly by diffusion of Al into Ti particles. Significant porosity that developed during the heat treatment was caused mainly by Kirkendall effect. After the second-stage heat treatment, a coating layer with TiAl as the dominant phase was obtained with about 20 vol % porosity.     

还原性气氛制备Zr-B-N纳米复合涂层的结构及性能分析

目的 制备高纯度、超硬、高耐磨的Zr-B-N纳米复合涂层。方法 在反应气体中掺入还原性气体H2,利用氢元素强还原性去除真空室以及反应气氛中残留的O杂质,采用脉冲直流磁控溅射技术,通过调节N2+H2混合气体流量制备高纯度Zr-B-N涂层。利用扫描电镜、纳米压痕仪、摩擦磨损试验机等设备对涂层的微观结构、力学性能和摩擦性能进行测试,并分析其变化机理。结果 随着N2+H2流量的增加,Zr-B-N涂层内N含量在N2+H2流量为10 mL/min时达到最高。从截面形貌可以看出,涂层结构由粗大的柱状晶逐步转变为玻璃状细小柱状晶结构,涂层更加致密,呈现典型的纳米复合结构。微量H元素的掺入,减少了涂层制备过程中O相关化学键的生成,制备出的Zr-B-N涂层晶粒的生长环境得到改善。在N2+H2流量为 10 mL/min时,涂层的硬度和弹性模量达到最大值40.26 GPa和532.98 GPa,临界载荷最大约为60.1 N,摩擦系数较小,为0.72,磨损率在此时最低,为1.12×10^–5mm³/(N.m)。结论 当N2+H2流量为10 mL/min时,制备出了超硬Zr-B-N纳米复合涂层。适量氢元素的掺入,充分去除真空室内氧杂质,改善了涂层中晶粒的生长环境,有效地提高涂层的硬度及摩擦磨损性能。     

WC-based composite coatings prepared by the pulsed gas dynamic spraying process: Effect of the feedstock powders

WC-based cermet coatings are typically produced using the HVOF process, due to high particle velocity and the lower heating characteristic of this technique. Despite the effort of optimisation of the coating process, degradation of the feedstock materials such as decarburisation of WC and amorphization of the metallic phase still occurs. It is known that the coating properties do not depend only on the spray process and its parameters, but also on the feedstock powder characteristics such as its chemistry, carbide size, particle morphology and production method. The work presented here is part of a research program aimed at exploring the possible advantages of the Pulsed Gas Dynamic Spray (PGDS) process, as an alternative technique for the preparation WC-based cermet coatings. In this paper, WC-based coatings have been prepared using six different types of cermets powders. In order to study the effects of the feedstock powder on the coatings microstructures and hardness, the selected starting powders differed not only in microstructural features such as size and morphology but also in the chemistry and phases. Using different analysis technique (OM, SEM, XRD, and HV), a detailed comparison of powders and coatings microstructures, phase compositions, and hardness are presented and discussed in detail. It was found that the PGDS process preserves the microstructure of the starting cermet powders in such a way that no significant degradation of the phase composition, even those that show the pre-existence of complex carbides, has been observed. Furthermore, although the same spray parameters were used, the thickness, deposition efficiency, porosity, and micro-cracks within the coatings are different from one type of cermet to another, suggesting that PGDS optimum process parameters are material dependant.     

Plasma spraying of combustion flame spheroidized hydroxyapatite (HA) powders

Tailoring powder characteristics to suit the plasma spray process can alleviate difficulties associated with the preparation of hydroxyapatite (HA) coatings. Commercial HA feedstock normally exhibit an angular morphology and a wide particle size range that present difficulties in powder transport from the powder hopper to the plasma spray gun and in nonuniform melting of the powders in the plasma flame. Hence, combustion flame spheroidized hydroxyapatite (SHA) was used as the feedstock for plasma spraying. Spherical particles within a narrow particle size range are found to be more effective for the plasma spray processes. Results show coatings generated from spheroidized HA powders have unique surface and microstructure characteristics. Scanning electron microscope (SEM) observation of the coating surface revealed well-formed splats that spread and flatten into disc configurations with no disintegration, reflecting adequate melting of the HA in the plasma and subsequent deposition consistency. The surface topography is generally flat with good overlapping of subsequent spreading droplets. Porosity in the form of macropores is substantially reduced. The cross-section microstructure reveals a dense coating comprised of randomly stacked lamellae. The tensile bond strengths of the SHA coatings, phase composition, and characteristics of the coatings generated with different particle sizes (125 to 75 μm, 45 to 75 μm, 20 to 45 μm, and 5 to 20 μm) showed that a high bond strength of ∼16 MPa can be obtained with SHA in the size range from 20 to 45 μm. This can be improved further by a postspray treatment by hot isostatic pressing (HIP). However, larger particle size ranges exhibited higher degrees of crystallinity and relatively higher HA content among the various calcium phosphate phases found in the coatings.     

Microstructure and composition analysis in plasma sprayed coatings of Al2O3/ZrSiO4 mixtures

Plasma spraying of Al₂O₃/ZrSiO₄ was performed using spray dried and plasma spheroidised powder feedstock. The mixtures were sprayed using different spray stand-off distances and plasma power levels. X-Ray diffraction (XRD) was used to characterise the phase composition and scanning electron microscopy (SEM) examined the morphology of the sprayed surface and polished cross-sections. The results showed that the plasma spray process parameters played an important role in the final outcome of microstructures of the coatings. The coatings produced with spheroidised powders displayed a much denser structure than those produced with the spray-dried powders. The phase composition analysis showed the presence of amorphous phases in addition to crystalline alumina, zircon and tetragonal (t) zirconia (ZrO₂). Transmission electron microscopy (TEM) showed that amorphous phases and t-ZrO₂ crystals with particle size 100–200 nm could coexist within a single splat due to the relatively low local cooling rate.     

Optimisation of flow balance and isothermal extrusion of aluminium using finite-element simulations

There is significant demand to reduce variations in the shape and mechanical properties of the aluminium extrusion process to meet tighter tolerance requirements. To reduce variations, the flow and temperature evolution in the container and die must be controlled. To study how the process parameters influence the temperature evolution and the material flow, the effects of ram speed, initial temperature distribution in the billet and container cooling rate have been studied. This work is divided into three parts which examine the different aspects of the extrusion process. (1) To minimize the radial variations of temperature and velocity fields over multiple press cycles. (2) To obtain isothermal extrusion of aluminium. (3) To understand and formulate the effect of an undesired lateral temperature gradient in the billet on the exit velocity of the aluminium sections. In each part, the effect of different process parameters on the flow balance and temperature evolution of the extruded sections is shown and discussed.     

A Novel Hybrid Axial-Radial Atmospheric Plasma Spraying Technique for the Fabrication of Solid Oxide Fuel Cell Anodes Containing Cu, Co, Ni, and Samaria-Doped Ceria

Composite coatings containing Cu, Co, Ni, and samaria-doped ceria (SDC) have been fabricated using a novel hybrid atmospheric plasma spraying technique, in which a multi-component aqueous suspension of CuO, Co₃O₄, and NiO was injected axially simultaneously with SDC injected radially in a dry powder form. Coatings were characterized for their microstructure, permeability, porosity, and composition over a range of plasma spray conditions. Deposition efficiency of the metal oxides and SDC was also estimated. Depending on the conditions, coatings displayed either layering or high levels of mixing between the SDC and metal phases. The deposition efficiencies of both feedstock types were strongly dependent on the nozzle diameter. Plasma-sprayed metal-supported solid oxide fuel cells utilizing anodes fabricated with this technique demonstrated power densities at 0.7 V as high as 366 and 113 mW/cm² in humidified hydrogen and methane, respectively, at 800 °C.     

Suspension Plasma Spraying: Process Characteristics and Applications

Suspension plasma spraying (SPS) offers the manufacture of unique microstructures which are not possible with conventional powdery feedstock. Due to the considerably smaller size of the droplets and also the further fragmentation of these in the plasma jet, the attainable microstructural features like splat and pore sizes can be downsized to the nanometer range. Our present understanding of the deposition process including injection, suspension plasma plume interaction, and deposition will be outlined. The drawn conclusions are based on analysis of the coating microstructures in combination with particle temperature and velocity measurements as well as enthalpy probe investigations. The last measurements with the water cooled stagnation probe gives valuable information on the interaction of the carrier fluid with the plasma plume. Meanwhile, different areas of application of SPS coatings are known. In this paper, the focus will be on coatings for energy systems. Thermal barrier coatings (TBCs) for modern gas turbines are one important application field. SPS coatings offer the manufacture of strain-tolerant, segmented TBCs with low thermal conductivity. In addition, highly reflective coatings, which reduce the thermal load of the parts from radiation, can be produced. Further applications of SPS coatings as cathode layers in solid oxide fuel cells (SOFC) and for photovoltaic (PV) applications will be presented.     

粉末原料粒径对WC-17Co涂层性能的影响

本文利用超音速火焰喷涂技术喷涂四种不同粒径的WC-17Co粉末,评价粉末粒径对涂层机械性能和抗磨粒磨损性能的影响。结果表明,粉末的粒径越小,在超音速焰流作用下获得的速度和温度越高,形成的涂层越致密,颗粒间的粘接强度越高,同时涂层的显微硬度也越高。WC-17Co粉末的粒径越小,获得涂层的孔隙直径越小,颗粒间的粘接缺陷越少,因此涂层的抗磨粒磨损性能越好。但是当WC-17Co粉末的粒径过于微小时,涂层的断裂韧性将受到影响。在本文研究的四种粒径分布的WC-17Co粉末中,中间粒径且分布范围集中的粉末制得的涂层兼具良好的机械性能和抗磨粒磨损性能。     

Fabrication of nano-sized oxide composite coatings and photo-electric conversion/electron storage characteristics

Titanium dioxide TiO₂ can be used as a photo-anode to give generated electrons to the metal substrate under illumination. The transition metal oxide such as iron oxide Fe₂O₃ can be used to store electrons generated by the photo-electric conversion function of TiO₂ under the illuminated situation while the electrons are discharged from the transition metal oxide to the metal substrate in the dark. In this paper, coatings of nano-sized composite of TiO₂ and Fe₂O₃ were fabricated by the Warm Spray process, in which the feedstock powder is accelerated by a supersonic gas jet with speed above 1.0 km s^- 1 and temperature between 800 and 2500 K, and then impacted onto the target substrate continuously to form coatings. The coatings of TiO₂ and Fe₂O₃ nano-composite fabricated by Warm Spray showed no thermal deterioration such as phase transformation and particle growth of the feedstock during the spray process. The coatings fabricated by the Warm Spray had larger photo-current and the electron charge/discharge capacity than that by a conventional HVOF process. In addition, these characteristics were improved by decreasing the primary particle size of TiO₂ and Fe₂O₃.     

Phase Stability of Al-5Fe-V-Si Coatings Produced by Cold Gas Dynamic Spray Process Using Rapidly Solidified Feedstock Materials

In this study, aluminum alloy Al-5Fe-V-Si (in wt.%) feedstock powder, produced by rapid solidification (RS) using the gas atomization process, was selected to produce high-temperature resistant Al-alloy coatings using the cold gas dynamic spraying process (CGDS). The alloy composition was chosen for its mechanical properties at elevated temperature for potential applications in internal-combustion (IC) engines. The CGDS spray process was selected due to its relatively low operating temperature, thus preventing significant heating of the particles during spraying and as such allowing the original phases of the feedstock powder to be preserved within the coatings. The microstructure and phases stability was investigated by means of Scanning Electron Microscopy, transmission electron microscopy, X-ray diffraction and differential scanning calorimetery techniques. The coatings mechanical properties were evaluated through bond strength and microhardness testing. The study revealed the conservation of the complex microstructure of the rapid solidified powder during the spray process. Four distinct microstructures were observed as well as two different phases, namely a Al₁₃(Fe,V)₃Si silicide phase and a metastable (Al,Si) _x (Fe,V) Micro-quasicrystalline Icosahedral (MI) phase. Aging of the coating samples was performed and confirmed that the phase transformation of the metastable phases and coarsening of the nanosized precipitates will occurs at around 400 °C. The metastable MI phase was determined to be thermally stable up to 390 °C, after which a phase transformation to silicide starts to occur.     

WC-Co复合粉末的原位合成及于硬质合金涂层制备中的应用

目的为解决超细/纳米WC-Co热喷涂时易于脱碳等瓶颈问题,制备具有高的硬度、断裂韧性、耐磨性和表面质量等优异综合性能的超细及纳米结构硬质合金涂层,并推广其在工业领域中的应用。方法以原位合成技术批量制备的超细/纳米WC-Co复合粉末为原料,利用团聚造粒技术制备得到具有高球形度和致密性,并保持原有超细/纳米结构的喷涂喂料粉末,利用超音速火焰喷涂工艺制备低脱碳、高致密的超细结构WC基涂层。结果降低喂料粉末孔隙度可有效减少涂层中W2C等脱碳相的含量,在优化工艺下制备的超细结构WC基涂层的硬度达到1450HV0.3以上,韧性相对于常规微米结构涂层提高40%以上,在两种载荷和磨料条件下均表现出更高的耐磨性。结论利用原位反应技术批量合成的超细/纳米WC-Co复合粉制备的硬质合金涂层具有优良的综合性能,可应用于对涂层的硬度、耐磨性、强韧性配合和表面质量有较高要求的工况。     

UBET analysis of process of extruding aluminum alloy ribbed thin-wall pipes through a porthole die

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Electrodeposition of gold–indium alloys

The gold–indium alloy system has a number of intermetallic, differently coloured phases, of interest to the jewellery industry, and giving rise to the name blue gold. The present study is aimed at finding out the effect of electrolysis conditions on the morphology, elemental and phase composition of the Au–In alloy coatings from different electrolytes – with cyanide, acetate and glycine – as well as establishing the conditions for formation and observation of spatio-temporal structures on the surface of the electrode, similar to those observed during the electrodeposition of other indium alloys with silver, cobalt and palladium. It was established, that blue coloured matt coatings could be obtained from acetate–citrate electrolytes and the process of electrodeposition of gold–indium alloy from glycine electrolytes is a very promising one because of the possibility to obtain a variety of spatio-temporal structures on the surfaces of the electrode which could allow the comparison with other known cases of electrodeposition of similar structures in many other alloy systems.     

可轴向振动挤压模体精锻过程中振幅影响的数值模拟

齿形填充不满和最后阶段的成形力过高是齿轮闭式冷锻方案的主要缺陷。型腔壁对于坯料的摩擦阻力是影响金属流动的主要因素之一，通过变摩擦阻力为动力可以改善金属的塑性流动。采用可轴向振动挤压模体新工艺和DEFORM-3D有限元分析软件，对挤压模体在不同振幅下的振动进行模拟。从数值模拟结果中获得载荷随时间变化的曲线图．并找到了载荷力随着振幅的变化规律，得出一种最优方案。