Thermal Spray Coatings for Fusion Applications—Review

Thermonuclear fusion is a potential source of cleaner and safer energy for the future. Its technological realization depends on the development of materials able to survive and function in extreme conditions. This article reviews the applications of thermally sprayed coatings for fusion reactor materials. First, the principle and purpose of fusion is briefly introduced, and technological objectives are mentioned. Material-environment interactions are summarized, together with materials requirements and the role of coatings. Then, specific applications—e.g., the plasma facing components—are reviewed, focusing on application issues as well as issues related to thermal spray processing and specific properties of the respective materials. An overview of specific materials testing methods is also provided.     

Fabrication and Characterization of Suspension Plasma-Sprayed Fluoridated Hydroxyapatite Coatings for Biomedical Applications

Fluoridated hydroxyapatite (FHA) coatings were prepared on a Ti substrate using a suspension plasma spraying technique. The crystalline phases and chemical compositions of the coatings were characterized using x-ray diffraction, Fourier transform infrared spectroscopy, and x-ray photoelectron spectroscopy. The analysis confirmed that the coating consisted of an FHA phase. The corrosion behavior in simulated body fluid was studied using potentiodynamic polarization tests, and the results indicated that the FHA coating greatly enhanced the corrosion resistance of the Ti substrate. The chemical stability of the FHA coatings was assessed by evaluating the release of Ca²⁺ ions. The results indicated that the substitution of fluorine into the hydroxyapatite (HA) structure had a positive effect on the dissolution resistance of the HA. The antibacterial activity was investigated using a surface-plating method; the results revealed that the antibacterial activity of the FHA coating was greater than that of the pure HA coatings. During cell culture tests, the FHA coating did not exhibit cytotoxicity toward the osteoblast cell line, and the cell proliferation was comparable with that of the HA coatings. The antibacterial activity and cell culture results suggested that the plasma-sprayed FHA coating possesses good antibacterial qualities, but is biocompatible with osteoblasts. The promising features of the FHA coating render it suitable for orthopedic and dental applications.     

高导热涂层制备及其性能研究进展

随着高集成技术、微电子封装技术、大功率LED技术以及超级计算机的迅猛发展,小型化、微型化与轻薄化成为现代及未来电子设备、电子电路的发展潮流,因此对散热要求越来越高.目前电子器件及设备主要应用导热硅脂、导热硅胶及复合材料来实现散热.若在器件及设备上制备一层具有高热导率、耐腐蚀、结合强度良好的导热涂层,可以更好地实现散热.从高导热涂层的应用背景及导热涂层的特点出发,阐述了制备方法和材料体系不同的三大类高导热涂层,重点介绍了以喷涂技术、磁控溅射技术、涂料技术制备高导热涂层的研究进展.对比这几种导热涂层制备技术可以发现,因为空气是热的不良导体,基于冷喷涂技术制备的涂层孔隙率低的特点,加之对涂层进行热处理后会更加致密,所以冷喷涂技术制备的导热涂层具有较高的热导率.但目前的喷涂粉末具有导电性,因此喷涂在电路及电器设备上应用还不够成熟.基于冷喷涂技术制备绝缘、高导热涂层,提高器件设备的导热性能,还有待进一步探索.     

Through-thickness residual stress evaluations for several industrial thermal spray coatings using a modified layer-removal method

Residual stresses are inherent in thermal spray coatings because the application process involves large temperature gradients in materials with different mechanical properties. In many cases, failure analysis of thermal spray coatings has indicated that residual stresses contribute to reduced service life. An estab-lished method for experimentally evaluating residual stresses involves monitoring deformations in a part as layers of material are removed. Although the method offers several advantages, applications are lim-ited to a single isotropic material and do not include coated materials. This paper describes a modified layer-removal method for evaluating through-thickness residual stress distributions in coated materials. The modification is validated by comparisons with three-dimensional finite-element analysis results. The modified layer-removal method was applied to determine through-thickness residual stress distributions for six industrial thermal spray coatings: stainless steel, aluminum, Ni-5A1, two tungsten carbides, and a ceramic thermal barrier coating. The modified method requires only ordinary resistance strain-gage measuring equipment and can be relatively insensitive to uncertainties in the mechanical properties of the coating material.     

Thermal Spray of Cemented Carbide Coatings in Off-Angle Spraying: Correlations Between Process,Coating Features/Characteristics and Performance

Oxidation or decomposition of thermally sprayed coatings during deposition may noticably impair the coating features and characteristics, i.e. the surface integrity of coated components, including coating porosity, phase, microhardness, elastic modulus and toughness, etc., having a profound influence on the final performance of components. Further degradations along with enhanced oxidation of the coatings were observed for an off-angle spraying scheme in industrial practice, where inconsistent results were previously reported for spray angle-dependent degradation of various thermal spray coatings, with the mechanism not being fully understood with the less controlled surface integrity. An improved off-angle HVOF thermal spray has been developed for cemented carbide coatings, using pretreated WC-Ni feedstock powders covered with a nanoscale capsulizing nickel layer. A comprehensive study on the formation of multiple surface integrity parameters and the correlative interactions between them is thus facilitated with controllable surface integrity generation using the capsulized powders. Decarburization is mainly attributed to the exposure of pristine WC grains causing enhanced porosity in inter-splats regions, and then microhardness depends mainly on porosity and partly on phase composition, while the elastic modulus depends on intra-splats cohesion and the indentation fracture toughness on inter-splats cohesion, respectively. Abrasive wear from mild to severe regime transition could be interpreted by the inter-splats and intra-splats cohesion correlation. It has been demonstrated by the improved off-angle thermal spray that a manufacturing process could be designed and optimized on the identified unique correlations between the processes, surface integrity and the final performance.     

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.     

Liquid-Solid Self-Lubricated Coatings

Self-lubricated coatings have been a major topic of interest in thermal spray in the last decades. Self-lubricated coatings obtained by thermal spray are exclusively based on solid lubricants (PTFE, h-BN, graphite, MoS₂, etc.) embedded in the matrix. Production of thermal spray coatings containing liquid lubricants has not yet been achieved because of the complexity of keeping a liquid in a solid matrix during the spraying process. In the present article, the first liquid-solid self-lubricating thermal spray coatings are presented. The coatings are produced by inserting lubricant-filled capsules inside a polymeric matrix. The goal of the coating is to release lubricant to the system when needed. The first produced coatings consisted solely of capsules for confirming the feasibility of the process. For obtaining such a coating, the liquid-filled capsules were injected in the thermal spray flame without any other feedstock material. Once the concept and the idea were proven, a polymer was co-sprayed together with the capsules to obtain a coating containing the lubricant-filled capsules distributed in the solid polymeric matrix. The coatings and the self-lubricated properties have been investigated by means of optical microscopy, Scanning Electron Microscopy, and tribological tests.     

热腐蚀和盐雾腐蚀影响氮化物涂层冲蚀行为的机制

金属氮化物涂层是目前重点关注的航空发动机压气机抗冲蚀涂层体系。为了兼顾热物理化学环境和应力环境的影响,进行涂层的腐蚀-冲蚀耦合行为研究十分重要。本研究对比了TiN/Ti涂层与TiN/ZrN涂层的原始状态、热腐蚀后和盐雾腐蚀后的冲蚀行为。结果表明,对于TiN/Ti涂层,在涂层的缺陷处盐雾腐蚀时形成点蚀坑,这是发生冲蚀的薄弱环节,盐雾腐蚀后TiN/Ti涂层的抗冲蚀能力及结合力低于原始涂层和热腐蚀后的涂层。对于TiN/ZrN涂层,热腐蚀过程中液滴表面形成疏松的腐蚀产物和氧化物,使其在冲蚀时更容易脱落,热腐蚀过程中产生的层间热应力削弱了涂层的结合力。热腐蚀涂层冲蚀后呈现严重的螺旋状剥落,热腐蚀后TiN/ZrN涂层的抗冲蚀能力及结合力低于原始涂层和盐雾腐蚀后涂层。     

Review on the Oxidation of Metallic Thermal Sprayed Coatings: A Case Study with Reference to Rare-Earth Permanent Magnetic Coatings

Thermal spray fabrication of rare-earth permanent magnetic coatings (PMCs) presents potential manufacturing routes for micro-magnetic devices. Despite this potential, thermal spray of PMCs is still not widely explored due to oxidation concerns. It was established that oxidation leads to the loss of ferromagnetic phases in these materials and results in deterioration of magnetic performance. Although this review focuses on a specific class of material, i.e., magnetic materials, there is significant technical crossover to all classes of feedstocks that are employed in thermal spray processing. The oxidation mechanisms and the associated influencing factors are explored in this work to implement effective processing techniques during the deposition process. This paper reviews the various stages and mechanisms of oxidation in thermal spray processes. The factors that influence the extent of oxidation depend on the type of oxidation that is dominant and rely on the type of spray system, powder injection position, and the particle size of feedstock. Among the aspects that are reviewed include the oxygen-fuel ratio for high velocity oxygen-fuel (HVOF), current intensity, gas flow rate, particle size, spray distance, and substrate temperature. Protection strategies to minimize oxidation in thermal spray processes, such as gas shrouding and shielding, are presented.     

等离子喷涂生物涂层对病理性骨缺损愈合的应用研究

患者代谢性疾病(如骨质疏松症、糖尿病、痛风等)不利于体内骨植入体与周围骨的结合。基于不同疾病患者骨折部位骨微环境的特点,采用等离子喷涂技术制备的抗氧化应激生物涂层(针对骨质疏松)、抗感染-促成骨功能的生物涂层(针对糖尿病)和骨免疫调控涂层(针对痛风)能提高骨科植入器械与骨组织接触界面处的成骨能力,是增强植入体与骨结合的有效方法。研究了骨植入生物涂层对不同病理状态下效应细胞的影响,总结了材料表面性质调控效应细胞行为以及骨形成的规律,可为新型骨植入生物涂层的设计提供依据。等离子喷涂技术制备的含氧化铈的生物抗氧化涂层,可催化分解生物体内的过量活性氧簇,保护骨细胞成骨分化能力免于氧化应激的负面影响,有利于提高骨质疏松症下骨植入体的愈合能力。具抗感染与促成骨功能的硅酸钙基生物涂层能够抑制细菌在其表面的粘附与生长,降低植入体相关感染的几率,另外,该类涂层还能促进骨细胞成骨分化与矿化,提高骨植入体的成骨能力,有望应用于骨折合并糖尿病患者。等离子喷涂钛涂层表面微纳多级结构的构建以及生物涂层中锶/硼/铈等元素的掺入,有利于提高骨免疫性能,并促进骨细胞成骨分化,可用作炎症疾病下的骨缺损修复材料。     

面向等离子体材料钨厚涂层的制备及表征

等离子体喷涂技术在面向等离子体材料钨涂层的制备中占据主导地位,本实验采用CuMo/MoW作为涂层的中间过渡层,分别以结晶钨粉和羰基钨粉为原料,用大气等离子体喷涂技术在CuCrZr合金基体(110 mm×130mm)上制备了3-4 mm厚的3种钨涂层.对钨涂层微观组织、力学性能和热学性能研究表明,羰基钨粉制备的钨涂层的综合性能优于结晶钨粉,且薄涂层的结合强度优于厚涂层.优化喷涂工艺后,金相法测得钨涂层孔隙率＜2％,涂层的结合强度最大值为10 MPa,EDS测得氧含量为6％左右,纯钨层热导率最大值为12.52 W/(m.K),涂层氧含量过高导致涂层热导率显著降低.研究表明采用大气等离子体喷涂技术在铜合金上制备3～4mm厚的钨涂层是可行的,该技术可为下一步低成本、高性能厚钨涂层的制备奠定基础.     

Multiple-Approach Evaluation of WSP Coatings Adhesion/Cohesion Strength

Adhesion/cohesion testing represents one of the most common methods for benchmarking and optimization of thermal spray coatings. However, owing to the inhomogeneous coating microstructure, such testing may be quite troublesome. In this study, adhesion/cohesion strength of representative metallic and ceramic coatings deposited by water-stabilized plasma (WSP) spraying was evaluated by four different methods: tensile adhesion test, pin test, tubular coating tensile test, and shear test. Combination of various methods enabled the evaluation of the coating adhesion/cohesion strength under different loading conditions. Limitations and benefits of each method for testing of WSP coatings are demonstrated. Dominating failure micromechanisms were determined by supplementary fractographic analysis.     

The Corrosion Behavior of Cold Sprayed Zinc Coatings on Mild Steel Substrate

Zinc and its alloy coatings have been used extensively for the cathodic protection of steel. Zinc coating corrodes in preference to the steel substrate due to its negative corrosion potential. Numerous studies have been conducted on the corrosion behavior of zinc and its alloy coatings deposited using several techniques viz., hot dip galvanizing, electrodeposition, metalizing or thermal spray etc. Cold spray is an emerging low temperature variant of thermal spray family which enables deposition of thick, dense, and pure coatings at a rapid rate with an added advantage of on-site coating of steel structures. In the present study, the corrosion characteristics of cold sprayed zinc coatings have been investigated for the first time. In addition, the influence of heat treatment of zinc coating at a temperature of 150 °C on its corrosion behavior has also been addressed.     

Fabrication and Oxidation Resistance of TiAl Matrix Coatings Reinforced with Silicide Precipitates Produced by Heat Treatment of Warm Sprayed Coatings

Ti-Al-based intermetallics are promising candidates as coating materials for thermal protection systems in aerospace vehicles; they can operate just below the temperatures where ceramics are commonly used, and their main advantage is the fact that they are lighter than most other alloys, such as MCrAlY. Therefore, Ti-Al-Si alloy coatings with five compositions were manufactured by spraying pure Ti and Al-12 wt.% Si powders using warm spray process. Two-stage hot pressing at 600 and 1000 °C was applied to the deposits in order to obtain titanium aluminide intermetallic phases. The microstructure, chemical composition, and phase composition of the as-deposited and hot-pressed coatings were investigated using SEM, EDS, and XRD. Applying of hot pressing enabled the formation of dense coatings with porosity around 0.5% and hard Ti₅(Si,Al)₃ silicide precipitates. It was found that the Ti₅(Si,Al)₃ silicides existed in two types of morphologies, i.e., as large particles connected together and as small isolated particles dispersed in the matrix. Furthermore, the produced coatings exhibited good isothermal and cyclic oxidation resistance at a temperature of 750 °C for 100 h.     

Ti65合金磷酸盐涂层抗高温氧化性能研究

目的通过表面涂层提高高温钛合金Ti65的抗高温氧化性能。方法采用喷涂法在Ti65合金基体上制备以磷酸铝为粘结剂、Al和Al/SiC为填料的两种磷酸盐抗高温氧化复合涂层。研究Ti65合金和涂层样品在650℃准等温、静态空气条件下的氧化动力学行为。用XRD和SEM/EDS分别对涂层样品氧化前后的物相组成、组织形貌和微区成分进行表征分析;用电子探针(EPMA)分析涂层样品的元素分布情况。结果650℃抗高温氧化实验结果表明,磷酸盐涂层样品的准等温氧化动力学曲线均符合抛物线规律,两种涂层样品的抛物线氧化速率常数kp分别为3.922×10^-2、1.768×10^-2 mg/(cm^2·h^1/2)和2.48×10^-2、3.385×10^-4 mg/(cm^2·h^1/2),均小于Ti65合金,氧化增重显著降低。以Al/SiC为填料的磷酸铝涂层的抗氧化性能最好,氧化1000 h,质量增加0.20 mg/cm^2,约为Ti65基体氧化增重(1.13 mg/cm^2)的1/6。微观分析结果表明,两种磷酸盐涂层样品在650℃准等温氧化后,涂层与基体形成扩散层,生成TiAl3金属间化合物,涂层表面均保持完好,没有裂纹和孔隙,有效阻止了氧元素向Ti65基体的扩散,保护基体不受氧化。结论磷酸盐涂层能有效阻止650℃温度下氧向Ti65合金基体的扩散,具有优异的抗高温氧化性能。     

Al含量对Ti1-xAlxN涂层组织结构、力学性能和铣削性能的影响

目的研究不同Al含量对Ti_(1-x)Al_xN涂层的影响,以获得铣削铸铁材料性能最佳的Ti AlN涂层。方法采用阴极电弧蒸发沉积法在WC-Co硬质合金表面制备两种不同Al含量的Ti_(0.5)Al_(0.5)N和Ti_(0.33)Al_(0.67)N涂层,通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)和电子探针微区分析仪(EPMA)分析合金的微观组织和成分组成,通过CSM纳米硬度计和纳米划痕仪测定涂层的纳米硬度、弹性模量、抗塑性变形因子、显微硬度耗散系数MDP和划痕裂纹扩展阻力CPRs等性能指标,同时比较不同Al含量涂层刀片在铣削灰口铸铁HT250和球墨铸铁QT450时的性能和磨损机理。结果 Ti_(0.5)Al_(0.5)N和Ti_(0.33)Al_(0.67)N涂层主要物相均呈NaCl型面心立方结构,以(200)方向为择优取向,且高铝涂层的XRD衍射峰向高角度偏移量大于中铝涂层,说明高铝涂层具有更高的铝固溶量。与Ti_(0.5)Al_(0.5)N涂层相比,Ti_(0.33)Al_(0.67)N涂层的抗塑性变形因子较小,MDP和CPRs较大,表现出更优的塑性、韧性和膜基结合力。在铣削HT250和QT450时,Ti_(0.33)Al_(0.67)N涂层刀片的平均寿命分别为30、60 min,相比Ti_(0.5)Al_(0.5)N涂层,切削性能更好。结论对于Ti AlN涂层来说,提高Al的质量分数至67%可以获得更优的塑性、韧性和膜基结合力,在铣削HT250和QT450时,Ti_(0.33)Al_(0.67)N涂层刀片的切削性能较优。     

Induction Plasma Sprayed Nano Hydroxyapatite Coatings on Titanium for Orthopaedic and Dental Implants

This paper reports preparation of a highly crystalline nano hydroxyapatite (HA) coating on commercially pure titanium (Cp-Ti) using inductively coupled radio frequency (RF) plasma spray and their in vitro and in vivo biological response. HA coatings were prepared on Ti using normal and supersonic plasma nozzles at different plate powers and working distances. X-ray diffraction (XRD) and Fourier transformed infrared spectroscopic (FTIR) analysis show that the normal plasma nozzle lead to increased phase decomposition, high amorphous calcium phosphate (ACP) phase formation, and severe dehydroxylation of HA. In contrast, coatings prepared using supersonic nozzle retained the crystallinity and phase purity of HA due to relatively short exposure time of HA particles in the plasma. In addition, these coatings exhibited a microstructure that varied from porous and glassy structure at the coating-substrate interface to dense HA at the top surface. The microstructural analysis showed that the coating was made of multigrain HA particles of ~200 nm in size, which consisted of recrystallized HA grains in the size range of 15- 20 nm. Apart from the type of nozzle, working distance was also found to have a strong influence on the HA phase decomposition, while plate power had little influence. Depending on the plasma processing conditions, a coating thickness between 300 and 400 μm was achieved where the adhesive bond strengths were found to be between 4.8 MPa to 24 MPa. The cytotoxicity of HA coatings was examined by culturing human fetal osteoblast cells (hFOB) on coated surfaces. In vivo studies, using the cortical defect model in rat femur, evaluated the histological response of the HA coatings prepared with supersonic nozzle. After 2 weeks of implantation, osteoid formation was evident on the HA coated implant surface, which could indicate early implant- tissue integration in vivo.     

Surface preparation and thermal spray in a single step: The PROTAL process—Example of application for an aluminum-base substrate

Thermal spray techniques can fulfill numerous industrial applications. Coatings are thus applied to resist wear and corrosion or to modify the surface characteristics of the substrate (e.g., thermal conductivity/thermal insulation). However, many of these applications remain inhibited by some deposit characteristics, such as a limited coating adhesion or pores or by industrial costs because several nonsynchronized and sequential steps (that is, degreasing, sand blasting, and spraying) are needed to manufacture a deposit. The PROTAL process was designed to reduce the aforementioned difficulties by implementing simultaneously a Q-switched laser and a thermal spray torch. The laser irradiation is primarily aimed to eliminate the contamination films and oxide layers, to generate a surface state enhancing the deposit adhesion, and to limit the contamination of the deposited layers by condensed vapors. From PROTAL arises the possibility to reduce, indeed suppress, the preliminary steps of degreasing and grit blasting. In this study, the benefits of the PROTAL process were investigated, comparing adhesion of different atmospheric plasma spray coatings (e.g., metallic and ceramic coatings) on an aluminum-base substrate. Substrates were coated rough from the machine shop, for example, manipulated barehanded and without any prior surface preparation. Results obtained this way were compared with those obtained using a classical procedure; that is, degreasing and grit blasting prior to the coating deposition.     

Deposition of Electrically Conductive Coatings on Castable Polyurethane Elastomers by the Flame Spraying Process

Deposition of metallic coatings on elastomeric polymers is a challenging task due to the heat sensitivity and soft nature of these materials and the high temperatures in thermal spraying processes. In this study, a flame spraying process was employed to deposit conductive coatings of aluminum-12silicon on polyurethane elastomers. The effect of process parameters, i.e., stand-off distance and air added to the flame spray torch, on temperature distribution and corresponding effects on coating characteristics, including electrical resistivity, were investigated. An analytical model based on a Green’s function approach was employed to determine the temperature distribution within the substrate. It was found that the coating porosity and electrical resistance decreased by increasing the pressure of the air injected into the flame spray torch during deposition. The latter also allowed for a reduction of the stand-off distance of the flame spray torch. Dynamic mechanical analysis was performed to investigate the effect of the increase in temperature within the substrate on its dynamic mechanical properties. It was found that the spraying process did not significantly change the storage modulus of the polyurethane substrate material.     

Residual Stresses Distribution through Thick HVOF Sprayed Inconel 718 Coatings

Residual stress buildup in thick thermal spray coatings is a property of concern. The adhesion of these coatings to the substrate is influenced by residual stresses that are generated during the coating deposition process. In the HVOF spray process, significant peening stresses are generated during the impact of semimolten particles on the substrate. The combination of these peening stresses together with quenching and thermal mismatch stresses that arise after deposition can be of significant importance. Both numerical method, i.e., Finite Element Method (FEM), and experimental methods, i.e., the Modified Layer Removal Method (MLRM) and Neutron Diffraction, to calculate peening and quenching stresses have been utilized in this work. The investigation was performed on thick Inconel 718 coatings on Inconel 718 substrates. Combined, these numerical and experimental techniques yield a deeper understanding of residual stress formation in the HVOF process and thus a tool for process optimization. The relationship between the stress state and deposit/substrate thickness ratio is given particular interest.