Innovation of Ultrafine Structured Alloy Coatings Having Superior Mechanical Properties and High Temperature Corrosion Resistance

High temperature protection requires full coating density, high adhesion, minor oxide inclusions, and preferably fine grains, which is not achievable in most thermal spray processes. High velocity oxygen fuel (HVOF) thermal spray process has been applied extensively for making such coatings with the highest density and adhesion strength, but the existence of not melted or partially melted particles are usually observed in the HVOF coatings because of relatively low flame temperature and short particle resident time in the process. This work has investigated the development of an innovative HVOF process using a liquid state suspension/slurry containing small alloy powders. The advantages of using small particles in a HVOF process include uniform coating, less defective microstructure, higher cohesion and adhesion, full density, lower internal stress, and higher deposition efficiency. Process investigations have proven the benefits of making alloy coatings with full density and high bond strength attributing to increased melting of the small particles and the very high kinetic energy of particles striking on the substrate. High temperature oxidation and hot corrosion tests at 800 °C have demonstrated that the alloy coatings made by novel LS-HVOF process have superior properties to conventional counterpart coatings in terms of oxidation rates and corrosion penetration depths.     

热喷涂Ni基复合涂层重熔处理的研究现状

热喷涂Ni基复合涂层因具有耐磨、耐腐蚀及耐高温等特点,被广泛应用于机械零件的表面修复和保护。但是,热喷涂层为典型的层状结构,具有微缺陷含量较高、与基体结合强度低等特点,难以适应苛刻的工作环境,其应用和发展受限。重熔处理可以消除热喷涂层的层状结构,消除或部分消除孔隙、裂纹等微缺陷,使涂层与基体形成冶金结合,提高涂层的使用性能。本文首先介绍了几种适用Ni基复合涂层的重熔技术(即激光重熔、火焰重熔、感应重熔等),随后介绍了重熔处理对Ni基复合涂层表面完整性(即微缺陷、结合强度和硬度)的影响,接着分析了重熔处理对Ni基复合涂层两种服役性能(即耐磨性、耐腐蚀性能)的影响,最后总结了目前在关于Ni基复合涂层重熔技术研究中存在的问题,进而探讨了相应的解决方案,并指出挖掘新的表面重熔技术和对不同的材料体系进行针对性研究是未来重点发展的方向。     

Improving corrosion properties of high-velocity oxy-fuel sprayed inconel 625 by using a high-power continuous wave neodymium-doped yttrium aluminum garnet laser

Thermal spray processes are widely used to protect materials and components against wear, corrosion and oxidation. Despite the use of the latest developments of thermal spraying, such as high-velocity oxy-fuel (HVOF) and plasma spraying, these coatings may in certain service conditions show inadequate performance,e.g., due to insufficient bond strength and/or mechanical properties and corrosion resistance inferior to those of corresponding bulk materials. The main cause for a low bond strength in thermalsprayed coatings is the low process temperature, which results only in mechanical bonding. Mechanical and corrosion properties typically inferior to wrought materials are caused by the chemical and structural inhomogeneity of the thermal-sprayed coating material. To overcome the drawbacks of sprayed structures and to markedly improve the coating properties, laser remelting of sprayed coatings was studied in the present work. The coating material was nickel-based superalloy Inconel 625, which contains chromium and molybdenum as the main alloying agents. The coating was prepared by HVOF spraying onto mild steel substrates. High-power continuous wave Nd:YAG laser equipped with large beam optics was used to remelt the HVOF sprayed coating using different levels of power and scanning speed. The coatings as-sprayed and after laser remelting were characterized by optical microscopy and scanning electron microscopy (SEM). Laser remelting resulted in homogenization of the sprayed structure. This strongly improved the performance of the laser-remelted coatings in adhesion, wet corrosion, and high-temperature oxidation testing. The properties of the laser-remelted coatings were compared directly with the properties of as-sprayed HVOF coatings and with plasma-transferred arc (PTA) overlay coatings and wrought Inconel 625 alloy.     

沉积温度对高性能TiAlN涂层微观结构和力学性能的影响

采用真空电弧离子镀（AIP）技术在不同沉积温度下TiAlN涂层,用于高性能制造,并研究了沉积温度与表面性能的关系。结果表明,由于离子轰击作用,表面大颗粒随沉积温度的升高而减少。随着沉积温度的升高,涂层表面的晶粒尺寸先急剧减小后逐渐增大。此外,沉积温度对合成涂层的相组成和化学成分影响不大。随着沉积温度的升高,硬度和粘结强度先迅速增加,后逐渐降低。当沉积温度在450℃左右时,沉积的TiAlN涂层硬度最高,粘结强度最大。上述现象的发生机理与沉积过程中表面与界面之间的微观组织和残余应力的变化有关。合成的涂层在高达900℃的空气中具有良好的热稳定性。     

Adhesion Strength of HVOF Sprayed IN718 Coatings

The adhesion strength of high-velocity oxyfuel thermally sprayed coatings is of prime importance when thick coatings are to be sprayed in repair applications. In this study, relationships between process parameters, particle in-flight characteristics, residual stresses, and adhesion strength were explored. The most important process parameters that influence HVOF sprayed IN718 coating adhesion strength on IN718 substrate material were identified. Residual stress distributions were determined using the modified layer removal method, and adhesion strength was measured using an in-house-developed tensile test. Relationships between process parameters, particle in-flight characteristics, coating microstructure, and adhesion strength were established. Particle temperature, particle velocity, substrate preparation, and deposition temperature were identified as critical parameters to attain high adhesion strength. Controlling these parameters can significantly improve the adhesion strength, thus enabling thick coatings to be sprayed for repair applications.     

Effect of remelting process on characterization of air-plasma sprayed Fe67.5Ni23.5B9 alloy coatings onto 1Cr18Ni9Ti stainless steel

To develop a composite material with good mechanical and radiation shielding properties, the Fe–Ni–B (Fe_67.5Ni_23.5B₉, wt. %) coatings onto ₁Cr₁₈Ni₉Ti stainless steel substrate (SS, same as below) were prepared using air-plasma spraying (APS) technique in this work. A remelting process (1050 °C/2 h) was performed on the Fe–Ni–B coatings laminated composite under vacuum condition. The microstructure, phase composing, adhesion strength, Vickers hardness distribution and residual stress of Fe–Ni–B coatings before and after the remelting process were contrastively characterized. The results show that the remelting process decrease the coating defects and make the coating more cohesive and stable. The element diffusion and new compounds formation within the coating and interface area improves the adhesion and thermal fatigue of Fe–Ni–B coatings. In addition, the drop of variability of Vickers hardness data and residual stress level qualitatively identify that the Fe–Ni–B coatings possess more consistent microstructure and mechanical integrity after the remelting process.     

Effect of Substrate Temperature on CaHPO4 Coating on HT-C/C Composites Prepared by Ultrasonic Induction Heating Method

采用超声感应加热法在H2O2水热处理C/C复合材料表面沉积了CaHPO4涂层,借助SEM、XRD、FTIR、EDS等手段,研究了衬底温度对涂层的微观结构的影响,并通过划痕测试评价涂层与C/C基体之间的结合强度,同时运用分析天平测量质量以研究涂层的沉积动力学。结果显示,所制得的CaHPO4涂层钙磷比为1.2左右,晶格中出现碳离子。涂层形貌无明显变化,但是伴随温度的升高,涂层致密度降低。涂层与基体之间的结合强度随温度升高而增强,但内聚强度随温度升高而减弱。CaHPO4涂层的感应加热沉积过程受表面化学反应控制,沉积活化能为46.7 kJ/mol。     

Bonding,Reactivity, and Mechanical Properties of the Kinetic-Sprayed Deposition of Al for a Thermally Activated Reactive Cu Liner

Pure Al coatings were fabricated on Cu substrates via kinetic spraying to produce a thermally activated reactive Cu liner. The coatings need to endure high-strain rate severe plastic deformation and react with oxygen during penetration or after penetration of the liner. In this study, the Al powder underwent large exothermic reactions with a small particle size and fast heating rate, as determined from the differential scanning calorimetric analysis. Process optimization of the Al deposition was facilitated by defining the “critical velocity” of an Al particle in the kinetic spraying process based on numerical modeling and computations using ABAQUS finite element codes. The simulation results revealed that the critical velocity of an Al particle at room temperature (RT) is 780 m/s and it decreases as the particle temperature increases. Certain process conditions resulted in improved coating properties as the temperature of the particles was affected by the process gas temperature and pressure. The mechanical properties such as the bond strength of the coatings formed under various process conditions were evaluated and compared. The relationships between the resulting properties, processing conditions, and the structures of the coatings are discussed.     

Injection molding of products with functional surfaces by micro-structured, PVD coated injection molds

Molding of micro structures by injection molding leads to special requirements for the molds e.g. regarding wear resistance and low release forces of the molded components. At the same time it is not allowed to affect the replication precision. Physical vapor deposition (PVD) is one of the promising technologies for applying coatings with adapted properties like high hardness, low roughness, low Young’s modulus and less adhesion to the melt of polymers. Physical vapor deposition technology allows the deposition of thin films on micro structures. Therefore, the influence of these PVD layers on the contour accuracy of the replicated micro structures has to be investigated. For this purpose injection mold inserts were laser structured with micro structures of different sizes and afterwards coated with two different coatings, which were deposited by a magnetron sputter ion plating PVD technology. After deposition, the coatings were analyzed by techniques regarding hardness, Young’s modulus and morphology. The geometries of the micro structures were analyzed by scanning electron microscopy before and after coating. Afterwards, the coated mold inserts were used for injection molding experiments. During the injection molding process, a conventional and a variothermal temperature control of the molds were used. The molded parts were analyzed regarding roughness, structure height and structure width by means of laser microscopy.     

High-Performance Molybdenum Coating by Wire–HVOF Thermal Spray Process

Coating deposition on many industrial components with good microstructural, mechanical properties, and better wear resistance is always a challenge for the thermal spray community. A number of thermal spray methods are used to develop such promising coatings for many industrial applications, viz. arc spray, flame spray, plasma, and HVOF. All these processes have their own limitations to achieve porous free, very dense, high-performance wear-resistant coatings. In this work, an attempt has been made to overcome this limitation. Molybdenum coatings were deposited on low-carbon steel substrates using wire–high-velocity oxy-fuel (W-HVOF; WH) thermal spray system (trade name HIJET 9610^®). For a comparison, Mo coatings were also fabricated by arc spray, flame spray, plasma spray, and powder-HVOF processes. As-sprayed coatings were analyzed using x-ray diffraction, scanning electron microscopy for phase, and microstructural analysis, respectively. Coating microhardness, surface roughness, and porosity were also measured. Adhesion strength and wear tests were conducted to determine the mechanical and wear properties of the as-sprayed coatings. Results show that the coatings deposited by W-HVOF have better performance in terms of microstructural, mechanical, and wear resistance properties, in comparison with available thermal spray process (flame spray and plasma spray).     

The Effect of Deposition Conditions on Adhesion Strength of Ti and Ti6Al4V Cold Spray Splats

Cold spray is a complex process where many parameters have to be considered in order to achieve optimized material deposition and properties. In the cold spray process, deposition velocity influences the degree of material deformation and material adhesion. While most materials can be easily deposited at relatively low deposition velocity (<700 m/s), this is not the case for high yield strength materials like Ti and its alloys. In the present study, we evaluate the effects of deposition velocity, powder size, particle position in the gas jet, gas temperature, and substrate temperature on the adhesion strength of cold spayed Ti and Ti6Al4V splats. A micromechanical test technique was used to shear individual splats of Ti or Ti6Al4V and measure their adhesion strength. The splats were deposited onto Ti or Ti6Al4V substrates over a range of deposition conditions with either nitrogen or helium as the propelling gas. The splat adhesion testing coupled with microstructural characterization was used to define the strength, the type and the continuity of the bonded interface between splat and substrate material. The results demonstrated that optimization of spray conditions makes it possible to obtain splats with continuous bonding along the splat/substrate interface and measured adhesion strengths approaching the shear strength of bulk material. The parameters shown to improve the splat adhesion included the increase of the splat deposition velocity well above the critical deposition velocity of the tested material, increase in the temperature of both powder and the substrate material, decrease in the powder size, and optimization of the flow dynamics for the cold spray gun nozzle. Through comparisons to the literature, the adhesion strength of Ti splats measured with the splat adhesion technique correlated well with the cohesion strength of Ti coatings deposited under similar conditions and measured with tubular coating tensile (TCT) test.     

用激光重熔法提高铝硅合金的耐磨性

研究了激光重熔3种火焰喷涂层的强化效果。分析了激光重熔前后涂层的化学成分、显微组织、相结构以及显微硬度变化，进行了涂层的磨损试验。结果表明，激光重熔使涂层显微组织细化，质量明显改善，耐磨性能明显提高。     

Corrosion behavior of HVOF-sprayed and Nd-YAG laser-remelted high-chromium,nickel-chromium coatings

Thermal spray processes are widely used to deposit high-chromium, nickel-chromium coatings to improve high temperature oxidation and corrosion behavior. However, despite the efforts made to improve the present spraying techniques, such as high-velocity oxyfuel (HVOF) and plasma spraying, these coatings may still exhibit certain defects, such as unmelted particles, oxide layers at splat boundaries, porosity, and cracks, which are detrimental to corrosion performance in severe operating conditions. Because of the process temperature, only mechanical bonding is obtained between the coating and substrate. Laser remelting of the sprayed coatings was studied in order to overcome the drawbacks of sprayed structures and to markedly improve the coating properties. The coating material was high-chromium, nickel-chromium alloy, which contains small amounts of molybdenum and boron (53.3% Cr, 42.5% Ni, 2.5% Mo, 0.5% B). The coatings were prepared by HVOF spraying onto mild steel substrates. A high-power, fiber-coupled, continuous-wave Nd:YAG laser equipped with large beam optics was used to remelt the HVOF-sprayed coating using different levels of scanning speed and beam width (10 or 20 mm). Coating that was remelted with the highest traverse speed suffered from cracking because of the rapid solidification inherent to laser processing. However, after the appropriate laser parameters were chosen, nonporous, crack-free coatings with minimal dilution between coating and substrate were produced. Laser remelting resulted in the formation of a dense oxide layer on top of the coatings and full homogenization of the sprayed structure. The coatings as sprayed and after laser remelting were characterized by optical and electron microscopy (OM, SEM, respectively). Dilution between coating and substrate was studied with energy dispersive spectrometry (EDS). The properties of the laser-remelted coatings were directly compared with properties of as-sprayed HVOF coatings.     

Effect of Powder Characteristics on Properties of Warm-Sprayed WC-Co Coatings

In high-velocity oxy-fuel (HVOF) spraying of WC-Co coatings, the decomposition and decarburization of WC during deposition are responsible for their much lower toughness compared with a sintered bulk WC-Co. In a previous study, Warm Spray (WS) process, which is capable to control the flame temperature used to propel powder particles, was successfully applied in an attempt to suppress such detrimental reactions by keeping particles’ temperature lower than their melting point. The coatings deposited by WS process showed no or little formation of W₂C and η phases and demonstrated moderately improved fracture properties. However, there is still a gap in fracture toughness between WS coatings and the corresponding sintered bulk. In order to optimize the properties of the WS coatings, the effect of original powder sizes were investigated. Microstructural characterization and phase analysis were carried out on deposited coatings by SEM and XRD. The results show that the feedstock powder size has substantial effects on the properties of the coatings, i.e., the smaller powder showed improved properties.     

激光重熔参数对镍基纳米TiN复合电沉积镀层性能的影响

目的：在NiCr20 TiAl基体材料上进行镍基纳米TiN电沉积复合镀后再开展激光重熔工艺,研究激光重熔参数对镀层表面质量、结合力及硬度的影响。方法采用正交实验,研究不同激光重熔参数(扫描速率、搭接量、离焦量等)对重熔镀层的影响,采用显微硬度计、扫描电镜和划痕仪进行硬度、表面形貌和结合力检测,以得到较优工艺参数。结果通过控制重熔参数对镀层表面能量和表面形貌的影响,以降低表面性能差异,以得到了激光重熔较佳工艺参数为：电流115 A,脉宽为8 ms,频率为10 Hz,离焦量15 mm,扫描速度230 mm/min,使获得的镀层表面形貌比较平整,结合力提高到大于60 N,硬度值平均为632HV,并且硬度分布均匀。结论激光重熔工艺可消除纳米复合电沉积过程中产生的间隙,纳米复合镀层致密均匀,镀层与基体之间产生良好的冶金结合,镀层表面硬度分布均匀,力学性能趋近一致。     

Relationships Between Process Parameters, Microstructure, and Adhesion Strength of HVOF Sprayed IN718 Coatings

Fundamental understanding of relationships between process parameters, particle in-flight characteristics, and adhesion strength of HVOF sprayed coatings is important to achieve the high coating adhesion that is needed in aeronautic repair applications. In this study, statistical Design of Experiments (DoE) was used to identify the most important process parameters that influence adhesion strength of IN718 coatings sprayed on IN718 substrates. Special attention was given to the parameters combustion ratio, total gas mass flow, stand-off distance and external cooling, since these parameters were assumed to have a significant influence on particle temperature and velocity. Relationships between these parameters and coating microstructure were evaluated to fundamentally understand the relationships between process parameters and adhesion strength.     

火焰重熔高硬度镍基自熔性合金组织及性能研究

研究了火焰重熔火焰加热温度对镍基自熔性合金涂层显微组织的影响,测定并分析了基材至涂层的显微硬度分布.研究结果表明,氧-乙炔焰中性焰下火焰重熔涂层与基体形成了良好的冶金结合,且平均硬度达到830 HV,与基材相比提高了1.5倍.     

Laser Surface Remelting of Fe-based Alloy Coating Deposited by APS

The Fe-based amorphous alloy coatings with different porosities were deposited on Q235 steel substrates by means of atmospheric plasma spraying(APS).The as-sprayed coatings were remelted by the facility of a Nd:YAG laser to further enhance their compactness and bonding strength via orthogonal experiment design.The effects of laser remelting on the microstructure,phase compositions and mechanical properties of the as-sprayed coatings were investigated by optical microscopy,scanning electron microscope,X-ray diffraction and Vickers microhardness tester.The corrosion performance of the coatings was evaluated by both potential dynamic measurements(PDM)and electrochemical impedance spectroscopy(EIS)in a 10%NaOH solution.The results indicate that laser power of 700 W,scanning velocity of 4 mm/s,beam size of 3 mm and porosity of 1.19%are the optimized remelting process parameters.The laser-remelted coatings exhibite more homogenous structure as strong metallurgical bonding to substrates.The amorphous phases in the as-sprayed coatings crystallize toα-Fe,Fe2Si,Fe3.5B,and Fe2W phases for the high temperature and rapid solidification in the remelting process.The microhardness values of as-sprayed are in the range of 700-800 HV0.1,while the microhardness values of the remelted coatings are enhanced slightly to 750-850 HV0.1.Both PDM and EIS analysis results show that the remelted coatings exhibite relatively excellent corrosion resistance compared with the stainless steel 1Cr18Ni9Ti,however the corrosion resistance of the remelted coatings is inferior to the as-sprayed amorphous coatings.     

沉积温度对高功率脉冲磁控溅射AlCrSiN涂层结构和性能的影响*

采用高功率脉冲磁控溅射(HiPIMS)技术在不同沉积温度下制备了Al-Cr-Si-N涂层。系统研究了沉积温度对涂层结构、成分、显微形貌、力学和摩擦学性能的影响。结果表明:随着沉积温度由100℃升至350℃,涂层内部开始由非晶向纳米晶转化,300℃时出现fcc-AlN相;涂层平整性和致密性逐步改善,膜/基结合强度逐渐提高,在300℃达到最大值77 N,但温度继续升高至350℃时,严重的轰击刻蚀作用使临界载荷骤降至25 N;涂层硬度逐渐增加,在350℃达到最大值19.4GPa;涂层内应力整体呈下降趋势,由–0.8 GPa逐渐降低至–0.4 GPa左右。     

Effect of Substrate Temperature on Cold-Gas-Sprayed Coatings on Ceramic Substrates

This study focuses on cold-gas-sprayed deposition of metallic coatings onto ceramic substrates for application in power electronics. In order to achieve the required surface activation for bonding, the substrate is heated during spraying. The effects of substrate temperature on bond strength and coating properties are investigated for cold-gas-sprayed coatings of copper and aluminum on Al₂O₃. It is found that the adhesion strengths of the cold-gas-sprayed coatings and that of the single-impacting particles increase with the increasing temperature and roughness of the substrate. Coatings sprayed on heated substrates show relatively low compressive stresses and low hardness, while their electrical conductivity reaches high values of over 90% IACS. Overall, a higher substrate temperature is found to improve the coating properties significantly.