Characterization of nanostructured TiN coatings fabricated by reactive plasma spraying

The nanostructured TiN coatings are fabricated by means of reactive plasma spraying micrometers titanium powders in the atmosphere, and the microstructure and performance of the coatings are analyzed by XRD, SEM and TEM. The experimental results show that the coatings are mainly composed of TiN and Ti₃O phases, and the coatings have the typical sprayed lamellae structures. In parallel to substrate surface direction, the nanoscale grains with particle diameters ranging from 60 to 120nm are observed in the coatings, and both fine equiaxed and columnar grains are found in some zones of the nanostructured TiN coatings. But in vertical to substrate surface direction, the contrary is the case. Thus it can be concluded that the TiN coatings are composed of the columnar grains, and the columnar grains are nanostructural equiaxed grains in their cross-section. In addition, a large number of deformation twins caused by the stresses concentration are found in TiN coatings. Meanwhile, the nanostructured TiN coatings have a higher bonding strength and better fracture toughness than other observed as-sprayed coatings.     

CrN/CrAlSiN涂层海水环境下的摩擦学性能

为提高海洋装备摩擦零部件的摩擦学性能,采用多弧离子镀技术在316L不锈钢上制备了CrN/CrAlSiN涂层。通过XRD、XPS表征涂层的物相及成分,SEM和TEM表征涂层的形貌和微观结构,并用纳米压痕仪测试其硬度,采用摩擦磨损试验机对涂层在大气和海水环境中的摩擦磨损性能进行测试。结果表明:CrN/CrAlSiN涂层的微观结构主要有CrN相、AlN相以及非晶态Si_3N_4包裹CrN、AlN相,(111)择优取向最为明显;基于微观结构与CrN过渡层的设计,CrAlSiN涂层硬度高达35.5 GPa;较之于316L基底,涂层致密的结构使其在海水环境下表现出更好的耐腐蚀性能;在大气和海水环境下,CrN/CrAlSiN涂层的摩擦因数及磨损率均明显降低,在海水环境下达到最优。     

Electrospark coatings produced by ceramic nanostructured SHS electrode materials

The paper considers the possibility to expand the number of materials used for electrospark alloying. Ceramic nanostructured TiB₂–TiC–Al₂O₃–ZrO₂-based materials produced by means of SHS extrusion are used as electrodes. The regularities of the alloyed layer formation with electrospark alloying (ESA) are studied. Three different modes of anode erosion and cathode gain are observed for single pulse energies ranging from 0.05 to 2.5 J. The microstructure of the coatings is studied. It is shown that, in the case of ESA by ceramic SHS electrodes, nanosized crystallites are formed. The microhardness of the alloyed layer is 1250 HV. The tribological tests of the protective coatings demonstrate a high wear resistance (10^–5 mm³/N/m) and low friction coefficient (0.2).     

Thermal Spray Coatings Engineered from Nanostructured Ceramic Agglomerated Powders for Structural,Thermal Barrier and Biomedical Applications: A Review

Thermal spray coatings produced from nanostructured ceramic agglomerated powders were tailored for different applications, some of which required almost completely opposite performance characteristics (e.g., anti-wear and abradable coatings). The influence of nanostructured materials on important areas, such as, thermal barrier coatings (TBCs) and biomedical coatings was also investigated. It was determined that by controlling the distribution and character of the semi-molten nanostructured agglomerated particles (i.e., nanozones) embedded in the coating microstructure, it was possible to engineer coatings that exhibited high toughness for anti-wear applications or highly friable for use as abradables, exhibiting abradability levels equivalent to those of metallic-based abradables. It is shown that nanozones, in addition to being very important for the mechanical behavior, may also play a key role in enhancing and controlling the bioactivity levels of biomedical coatings via biomimetism. This research demonstrates that these nanostructured coatings can be engineered to exhibit different properties and microstructures by spraying nanostructured ceramic agglomerated powders via air plasma spray (APS) or high velocity oxy-fuel (HVOF). Finally, in order to present readers with a broader view of the current achievements and future prospects in this area of research, a general overview is presented based on the main papers published on this subject in the scientific literature.     

Deposition of Al2O3-TiO2 Nanostructured Powders by Atmospheric Plasma Spraying

Al₂O₃-13%TiO₂ coatings were deposited on stainless steel substrates from conventional and nanostructured powders using atmospheric plasma spraying (APS). A complete characterization of the feedstock confirmed its nanostructured nature. Coating microstructures and phase compositions were characterized using SEM, TEM, and XRD techniques. The microstructure comprised two clearly differentiated regions. One region, completely fused, consisted mainly of nanometer-sized grains of γ-Al₂O₃ with dissolved Ti⁺⁴. The other region, partly fused, retained the microstructure of the starting powder and was principally made up of submicrometer-sized grains of α-Al₂O₃, as confirmed by TEM. Coating microhardness as well as tribological behavior were determined. Vickers microhardness values of conventional coatings were in average slightly lower than the values for nanostructured coating. The wear resistance of conventional coatings was shown to be lower than that of nanostructured coatings as a consequence of Ti segregation. A correlation between the final properties, the coating microstructure, and the feedstock characteristics is given.     

Novel processing in inert atmosphere and in air to manufacture high‐activity slurry aluminide coatings modified by Pt and Pt/Ir

Slurry‐derived coatings are an interesting alternative method to pack aluminization of nickel‐base superalloys, which provide similar properties and protection at high temperatures. For highest performance, these aluminide coatings are modified by the addition of Pt or, as recent research suggests, with Pt/Ir. While the combination of Pt and Pt/Ir with an out‐of‐pack process is state of the art, slurry coatings are of special interest as a repair method for turbine blades. In this study, the microstructural evolution of slurry‐derived coatings manufactured on CM 247 in inert atmosphere as well as in air was investigated. Layers of Ni, Pt, and Pt/Ir mixtures were electrodeposited. After annealing, a diffusion heat‐treatment with a slurry containing aluminum or aluminum–silicon powder was applied on the samples. The addition of silicon is well known to be beneficial for hot corrosion environments. The reaction and interdiffusion behavior of aluminum/aluminum–silicon determines the microstructural evolution of the coatings. Depending on the initial electroplated layer on the surface, different microstructures can be obtained, such as the Pt/Ir‐modified beta phase (Ni,Pt)Al or two‐phase layers of PtAl₂ and NiAl. Additionally, the reactivity between the elements at the surface and those from the slurry was shown to determine homogeneity and surface roughness of the diffusion coating, also depending on the atmosphere used during slurry aluminization. Finally, it was demonstrated that iridium has a high influence on the diffusion behavior and especially the distribution of platinum in the coatings. Such new coatings have the potential to overcome some disadvantages of conventionally manufactured high‐activity aluminide coatings, as the combination of Pt/Ir‐electroplating with the slurry process results in less detrimental substrate elements like molybdenum or tungsten close to the surface.     

Influence of pore structure on ion diffusion property in porous TiO2 coating and photovoltaic performance of dye-sensitized solar cells

The ion diffusion in porous TiO₂ coating determines the limiting current density and the photovoltaic performance of a dye-sensitized solar cell. Nano-TiO₂ coatings with unimodal nano-size distribution and bimodal size distribution were deposited by vacuum cold spray to examine the effects of the pore structure on the ion diffusion property and cell performance. Results show that the I₃⁻ ion diffusion coefficient increased with the increase in the mean pore size. The bimodal size distribution of nanometer-sized and submicrometer-sized pores in the coating was found to have a synergistic enhancement effect on the ion diffusion. Better ion diffusion performance contributed to a higher open circuit voltage. The optimal coating thickness (~ 30 μm) was nearly doubled in the cells with bimodal pore size distribution, compared with the previously reported optimal coating thickness (~ 15 μm) in the cell with unimodal pore size distribution. The reason is attributed to the high ion diffusion coefficient which allows a high limiting current density.     

Finite element modeling of ultrasonic surface rolling process

Ultrasonic surface rolling (USRP) is a newly developed process in which ultrasonic vibration and static force are applied on work-piece surface through the USRP operator to generate a nanostructured surface layer with mechanical behaviors highly improved. Compared with other surface severe plastic deformation (S²PD) methods, it can realize mechanized machining and be directly used for preparing final product. Notwithstanding the excellent performance of USRP, elaborate relation between process parameters and surface layer characteristics is still inadequacy due to inconvenient and costly experimental evaluation. Therefore, in this paper a three-dimensional finite element model (FEM) has been developed to predict the treatment conditions that lead to surface nanocrystallization. Simulated results of surface deformation, stress and strain are investigated to assess the formation of nanostructured layer. The numerical results from the FEM corresponds well with the values measured experimentally, indicating that this dynamic explicit FEM is a useful tool to predict the processing effects and to relate the treating parameters with the surface layer in terms of the size of nanostructured layer, residual stress and work hardening.     

Manufacturing Process of Nanostructured Alumina Coatings by Suspension Plasma Spraying

This paper describes the formation process of nanostructured alumina coatings and the injection system obtained by suspension plasma spraying (SPS), an alternative to the atmospheric plasma spraying technique in which the material feedstock is a suspension of the nanopowder to be sprayed. The nanoscale alumina powders (d ≈ 20 nm) were dispersed in distilled water or ethanol and injected by a peristaltic pump into plasma under atmospheric conditions. Optical microscopy (OM), scanning electron microscopy (SEM), and x-ray diffraction (XRD) analyses were performed to study the microstructure of the nanostructured alumina coatings. The results showed that the nanoscale alumina powders in suspension were very easily adsorbed at the inner surface of injection, which caused the needle to jam. The rotation of the pump had a great effect on the suspension injection in the plasma. The very small resistance of the thin plasma boundary layer near the substrate can drastically decrease the impacting velocity of nanosize droplets. The concentration of suspension also has a significant influence on the distribution of the size of the droplet, the enthalpy needed for spraying suspension, and the roughness of the coating surface. The phase structures of alumina suspension coatings strongly depend on the plasma spraying distance. A significant nanostructured fine alumina coating was obtained in some areas when ethanol was used as a solvent. The microstructures of the coating were observed as a function of the solvent and the spraying parameters.     

基于熔融因子的纳米结构涂层制备工艺优化EI北大核心CSCD

在热喷涂制备微米/纳米双结构涂层的工艺优化研究中缺乏对颗粒状态与喷涂工艺和涂层结构性能之间关系的综合分析。针对大气等离子喷涂制备双模态微观结构的热障涂层过程开展工艺参数优化研究。首先基于试验测量和数值仿真模拟所获得的颗粒状态以及射流信息,计算可表征飞行粒子受热状态的熔融因子分布,同时开展试验研究获得给定喷涂工况下涂层微观结构和沉积效率。最后以熔融因子为中间参数,研究并建立喷涂工艺-飞行粒子状态-涂层结构特性相关关系。结果表明,数值仿真模拟得到的纳米团聚颗粒状态与试验测量结果基本一致。纳米结构涂层微观结构主要缺陷为未熔纳米团聚粒子及微裂纹。在纳米结构涂层制备过程中,随着喷涂距离增加,飞行粒子的熔融因子先增大后减小,涂层沉积效率先增加后降低,孔隙率和未熔粒子数则先减小后增大。主气流量的增加则会导致熔融因子减小。在喷涂功率相近情况下,采用低电流高电压的组合会使得飞行粒子熔融因子分布取值较大,进而使得涂层沉积效率增加、孔隙率降低。使用熔融因子分析喷涂工艺参数对纳米团聚粉末颗状态和涂层结构特性的影响关系,可用于指导纳米双结构涂层制备过程工艺控制。     

Structure and mechanical properties of plasma sprayed nanostructured alumina and FeCuAl-alumina cermet coatings

Nanostructured alumina (Al₂O₃) and nanostructured cermet coatings containing alumina dispersed in a FeCu or FeCuAl matrix, were deposited by atmospheric plasma spraying (APS) from nanostructured powders. These coatings were characterized by SEM, EDAX, TEM, XRD and nanoindentation. Friction and wear behaviour were investigated by sliding and abrasion tests. TEM and XRD revealed that a nanostructuring was retained in the APS deposited coatings.The nanostructured ceramic and cermet coatings were compared in terms of coefficient of friction and wear resistance. Nanostructured cermet coatings appeared to offer a better wear resistance under sliding and abrasion tests than nanostructured Al₂O₃ coatings. The role of Fe, Cu, and Al additions to the Al₂O₃ coatings on friction and wear behaviour, was investigated.In the case of FeCu- and FeCuAl-based cermet coatings containing alumina, though the starting material consist of only two compounds, the coatings contain up to four different phases after plasma spraying. The mechanical properties of these different phases namely crack sensitivity and elasto-plastic deformation was determined by nanoindentation. The failure mechanisms were investigated and an attempt was made to establish a ‘structure-property’ relationship. It was shown that an appropriate balance between hard and soft phases results in optimum tribological properties of the nanostructured cermet coatings.     

Synthesis and oxidation behavior of nanocrystalline MCrAlY bond coatings

Thermal barrier coating systems protect turbine blades against high-temperature corrosion and oxidation. They consist of a metal bond coat (MCrAlY, M = Ni, Co) and a ceramic top layer (ZrO₂/Y₂O₃). In this work, the oxidation behavior of conventional and nanostructured high-velocity oxyfuel (HVOF) NiCrAlY coatings has been compared. Commercially available NiCrAlY powder was mechanically cryomilled and HVOF sprayed on a nickel alloy foil to form a nanocrystalline coating. Freestanding bodies of conventional and nanostructured HVOF NiCrAlY coatings were oxidized at 1000 °C for different time periods to form the thermally grown oxide layer. The experiments show an improvement in oxidation resistance in the nanostructured coating when compared with that of the conventional one. The observed behavior is a result of the formation of a continuous Al₂O₃ layer on the surface of the nanostructured HVOF NiCrAlY coating. This layer protects the coating from further oxidation and avoids the formation of mixed oxide protrusions present in the conventional coating. The original version of this article was published as part of the ASM Proceedings, Thermal Spray 2003: Advancing the Science and Applying the Technology, International Thermal Spray Conference (Orlando, FL), May 5–8 2003, Basil R. Marple and Christian Moreau, Ed., ASM International, 2003.     

Three-dimensional simulation of thermal plasma spraying of partially molten ceramic agglomerates

Thermal plasma spraying of agglomerated nanostructured ceramic particles has been studied using computational fluid dynamics. The plasma jet is modeled as a mixture of Ar-H₂ plasmas issuing into a quiescent atmosphere. The particles, modeled as micron-sized spheres, are introduced into the jet outside the plasma gun exit with radial injection. The existence of a simple target in front of the plasma gun is taken into account. The trajectories and state histories of particles of various sizes during their flight through the jet are presented. Moreover, the solid-liquid interface within the particles is tracked in an attempt to predict the amount of unmelted material retained in these particles at various axial distances from the gun exit. The effects of turbulence in the jet on these particle histories are accounted for. It is shown that, for the range of particle sizes and the plasma gun operating conditions studied, both the deposition location and the retained unmolten fraction are strongly affected by the size of the particles. The predictions are significant in terms of showing general trends, which will be useful in identifying processing windows for producing optimally nanostructured coatings.     

Microstructure and properties of Al2O3-13%TiO2 coatings sprayed using nanostructured powders

The microstructure and wear performance of M203-13% TiO2 coatings prepared by plasma spraying of agglom- erated nanoparticle powders were investigated. SEM analysis showed that the as-sprayed Al2O3-TiO2 coatings comprise of two kinds of typical region： fully melted region and unmelted/partially melted nanostructured region, which is different than the conventional coating with lamellar structure. It is shown that the microhardness of the nanostructured coatings was about 15%-30% higher than that of the conventional coating and the wear resistance is significantly improved, especially under a high wear load. The nanostructured coating sprayed at a lower power shows a lower wear resistance than the coatings produced at a higher power, because of the presence of pores and microstructural defects which are detrimental to the fracture toughness of the coatings.     

Microstructure and Thermal Properties of Nanostructured 4?wt.%Al2O3-YSZ Coatings Produced by Atmospheric Plasma Spraying

Microstructure and phase composition of the nanostructured Al₂O₃ doped YSZ coatings by atmospheric plasma spraying method have been characterized with XRD, TEM and SEM. The nanostructured 4AlYSZ coatings consist mainly of t-ZrO₂, crystalline Al₂O₃ phase is absent in the coatings and the grain size of the 4AlYSZ coating is about 65 nm. The APS 4AlYSZ coating is characterized by nanozones, dense area and voids. After doping, the coefficient of thermal expansion of YSZ is decreased to 10.928 × 10⁻⁶/K. The addition of Al₂O₃ has a great influence on decreasing the thermal conductivity of nano-YSZ, which is mainly caused by the point defect scattering and grain-boundary scattering. The lifetime of nanostructured 4AlYSZ coating is about 1000 cycles at 1100 °C.     

等离子喷涂制备ZrB2/SiC/Ta2O5涂层抗烧蚀性能研究

为了提高C/C复合材料的抗烧蚀性能,通过等离子喷涂法在C/C表面制备了SiC/Al₂O₃内层和ZrB₂/SiC/Ta₂O₅外层的双层涂层,通过XRD,SEM和EDS分析了涂层烧蚀前后的物相组成、微观结构和成分分布。烧蚀前涂层表面没有裂纹并且内层与基体、内层与外层之间结合良好。元素Zr、Si、Ta在涂层表面的分布相近,涂层表面成分分布均匀性良好。通过氧乙炔火焰在1800 ℃下对涂层的抗烧蚀性能进行考核。烧蚀过程中形成的镶嵌结构有利于阻挡氧气的渗入,Ta-Si-O玻璃层的形成封填了涂层孔隙,对基体有良好的保护效果,涂层表现出了较好的抗烧蚀性能。     

Finely grained nanometric and submicrometric coatings by thermal spraying: A review

Technology, microstructure and properties of nanostructured coatings obtained using different feedstock including: (i) powders composed of agglomerated nanocrystals; (ii) solutions; and (iii) suspensions are discussed. The methods of nanostructured coarse powders manufacturing are reviewed together with the problems related to formulation of solutions and suspensions. A particular attention is paid to the key problem at liquid feedstock spraying, namely to their delivery and injection into jets or flames. The physical and chemical phenomena occurring at flight of injected liquid droplet of solution and suspension are shown and related to the formation of coatings and their microstructure. Some microstructural, chemical, mechanical and electrical properties of coatings are collected and related to the operational processing parameters by regression equations derived from the design of spray experiments. Finally, the possible applications of nanostructured coatings are briefly discussed.     

Thermal stability of nanostructured Cr3C2-NiCr coatings

The thermal stability behavior of nanostructured Cr₃C₂-NiCr coatings was investigated. The nanostructured Cr₃C₂-NiCr coatings, synthesized using mechanical milling and high-velocity oxygen fuel (HVOF) thermal spraying, were thermally exposed in air at 473, 673, 873, and 1073 K for 8 h. The results show that microhardness of the conventional coating increased slightly with increasing temperature, while that of the nanostructured coating drastically increased from 1020 to 1240 HV₃₀₀ for the same temperature increases. Heat treatment led to increases in scratch resistance and decreases in the coefficient of friction for the nanostructured Cr₃C₂-NiCr coatings. A high density of Cr₂O₃ oxide particles with average size of 8.3 nm was found in the nanostructured coatings exposed to high temperatures, which is thought to be responsible for the observed increase in microhardness and scratch resistance and the decrease in the coefficient of friction of the nanostructured coatings.     

Structure,texture, and properties of superconductive electrolytic niobium coatings on glassy carbon

Superconductive electrolytic niobium coatings 0.1–100 μm thick are prepared via electrochemical deposition onto SU-2000 glassy carbon substrates in (LiF + NaF + KF)_eut–K₂NbF₇ molten salt. Their structure, texture, and residual stresses are investigated by X-ray diffraction methods. It is shown that, when depositing the coatings, the diffusion superconductive layer of niobium carbide is formed at the substrate–coating interface. The sequence of changes in the axis of the texture of niobium coating from 〈100〉 through 〈211〉 to a textureless state with an increase in their thickness is established. It is found that, in the interval 0.5–5 μm, the sign of the stress changes (compressive stresses change into tensile stresses) and it reaches its maximum value. With an increase in the coating thickness from 5 to 100 μm, tensile stresses decrease from 345 to 80 MPa. It is shown that the coatings formed can be used as the material for creating a working layer of a superconducting cryogenic gyroscope rotor.     

Formation of nanostructured YSZ/Ni anode with pore channels by plasma spraying

YSZ/Ni is the conventionally most used material for making the anode of a solid oxide fuel cell. Agglomerated nanostructured YSZ/NiO powders and plasma spray are applied to produce nanostructured YSZ/NiO coatings on porous support substrates. After reduction in an ambient atmosphere of 7% hydrogen and 93% argon at about 800 °C for 4 hours, a novel SOFC anode with nanostructured characteristics such as nano YSZ particles, nano Ni particles, nano pores and nano pore channels is produced. This new YSZ/Ni anode provides larger triple phase boundaries for hydrogen oxidation reactions. X-ray diffraction patterns of these YSZ/NiO coatings after 1 h of heat treatment at temperatures from 700 to 1100 °C are obtained and Scherrer analysis is conducted to study the effect of temperature on grain size. The results obtained from SEM, TEM, XRD and EDX measurements and analyses are presented in this investigation.