热障涂层失效机理、改进方法及未来发展方向

热障涂层(Thermal Barrier Coatings,TBCs)是用于航空发动机及燃气轮机的一种高效功能性隔热涂层,常用材料为氧化钇(质量分数6％～8％)部分稳定氧化锆(YSZ).首先,从TGO生长、高温烧结、CMAS腐蚀、盐雾腐蚀和热膨胀失配等方面介绍了YSZ的失效机理,以上因素会从不同程度上造成涂层分层、开裂乃至失效.其次,介绍了通过控制界面反应速度和元素扩散速度,改变涂层化学成分及结构等方法,改善YSZ性能.为适应下一代超高温热障涂层的发展要求,近年来,国内外针对制备工艺的改善和新材料性能进行了研究.通过调控等离子物理气相沉积的喷距,能得到不同微观结构的热障涂层,运用纳米粉体再造粒技术,能制备出抗热震性能、耐磨抗腐蚀性、韧性以及可加工性更为优异的纳米结构涂层.ABO3型钙钛矿结构钡盐、钽酸盐、石榴石结构稀土铝酸盐、磁铅石结构稀土铝酸盐、独居石结构稀土磷酸盐等新型陶瓷层材料的研究是一大热点.与传统YSZ相比,新陶瓷层材料有优异的高温相稳定性、高热膨胀系数、高热导率等性能,但存在断裂韧性低、组分复杂等缺点.最后,为热障涂层未来研究指出了方向,并展望了其面临的挑战.     

热喷涂制备固体氧化物燃料电池电解质层的研究进展

分析了固体氧化物燃料电池(SOFC)的发展趋势以及电解质的制备和特性对SOFC的工作温度及导电性的影响,并对SOFC电解质材料的研究现状进行了详细阐述。介绍了热喷涂技术在SOFC电解质材料制备中的技术优势,综述了热喷涂技术在SOFC电解质层材料制备中的应用,并对其进行了总结和展望。通过分析相关研究成果,认为降低工作温度必然成为未来SOFC研究的主要方向之一,而开发更多在中、低温下具有高电导率的电解质材料是未来研究工作的关键。应用最广泛的高温SOFC电解质材料是萤石结构的氧化钇稳定氧化锆,而钙钛矿结构的掺杂镁和锶的镓酸镧是最有前景的中、低温SOFC电解质材料。热喷涂技术具有基体材料不受限制、沉积速度快、灵活、成本低等一系列优点,在SOFC电解质涂层的制备中得到了广泛应用。对于高温SOFC电解质涂层可采用等离子喷涂辅助后处理工艺或直接优化其工艺,从而获得高致密、高电导率的电解质涂层,而中、低温电解质层的热喷涂制备方面的研究还有较大的拓展空间。     

超音速火焰喷涂纳米结构涂层研究进展

超音速火焰(High Velocity Oxy -Fuel,简称HVOF)喷涂具有高速和相对较低的温度两个重要特征,能够获得比普通火焰喷涂或等离子喷涂(Plasma Spray,简称PS)结合强度更高的致密涂层.纳米材料具有独特的表面效应、体积效应及量子尺寸效应,其电学、力学、磁学、光学和热学等性能产生了惊人的变化.随着材料科学技术的深入发展, 在实际生产和生活中运用性能优良的纳米材料倍受人们关注,其中,采用热喷涂技术制备纳米结构涂层是构筑纳米结构材料的最具前途的方法之一.从目前国内外的情况来看,HVOF喷涂纳米结构涂层技术的研究取得了较大的进展.综合国内外文献,总结了HVOF喷涂制备纳米结构涂层的研究现状,着重阐述了热喷涂纳米涂层的基本过程和结合机理,指出了利用HVOF喷涂纳米结构涂层存在的问题,并对热喷涂纳米结构涂层的发展前景作了展望.     

Elastic modulus measurements via laser-ultrasonic and knoop indentation techniques in thermally sprayed coatings

Nondestructive techniques for evaluating and characterizing coatings were extensively demanded by the thermal spray community; nonetheless, few results have been produced in practice due to difficulties in analyzing the complex structure of thermal spray coatings. Of particular interest is knowledge of the elastic modulus values and Poisson’s ratios, which are very important when seeking to understand and/or model the mechanical behavior or to develop life prediction models of thermal spray coatings used in various applications (e.g., wear, fatigue, and high temperatures). In the current study, two techniques, laser-ultrasonics and Knoop indentation, were used to determine the elastic modulus of thermal spray coatings. Laser-ultrasonics is a noncontact and nondestructive evaluation method that uses lasers to generate and detect ultrasound. Ultrasonic velocities in a material are directly related to its elastic modulus value. The Knoop indentation technique, which has been widely used as a method for determining elastic modulus values, was used to compare and validate the measurements of the laser-ultrasonic technique. The determination of elastic modulus values via the Knoop indentation technique is based on the measurement of elastic recovery of the dimensions of the Knoop indentation impression. The approach used in the current study was to focus on evaluating the elastic modulus of very uniform, dense, and near-isotropic titania and WC-Co thermal spray coatings using these two techniques. Four different coatings were evaluated: two titania coatings produced by air plasma spray (APS) and high-velocity oxyfuel (HVOF) and two types of WC-Co coatings, conventional and multimodal (nanostructured and microsized particles), deposited by HVOF. 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), 5–8 May, 2003, Basil R. Marple and Christian Moreau, Eds., ASM International, 2003.     

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.     

Using Thermal Spray and Laser Micromachining to Fabricate Sensors

The use of thermal spray to fabricate sensors directly onto engineering components is an emerging technology. The capabilities for sensor fabrication are considerably enhanced with the use of laser micromachining, in which feature sizes as small as 15-20 μm can be achieved. Such feature sizes are required for a variety of sensors, including strain and heat flux sensors, thermopiles and microheaters. Ultrafast lasers—lasers with pulse durations ≲1 ps—are particularly well suited for the multimaterial/multilayer processing required to fabricate sensors from materials deposited using thermal spray. In this work, the key issues associated with laser micromachining of thermal spray coatings for sensor applications are presented. Both resistive strain gages and microheaters are discussed in detail as representative sensor designs that require the fine feature and linewidth capability that laser micromachining provides, including details of their fabrication and practical design restrictions. This article summarizes with recommendations for future work.     

The Sensitivity of Abradable Coating Residual Stresses to Varying Material Properties

This paper reports recent research on abradable materials employed for aero-engine applications. Such thermal spray coatings are used extensively within the gas turbine, applied to the inner surface of compressor and turbine shroud sections, coating the periphery of the blade rotation path. The function of an abradable seal is to wear preferentially when rotating blades come into contact with it, while minimizing over-tip clearance and improving the efficiency of the engine. Thermal spraying of an abradable coating onto a substrate imparts two components of residual stress; rapid quenching stresses as the spray material cools on impact and stresses arising from differential thermal contraction. In-service thermal stresses are superimposed by the differential expansion of these bonded layers. The combination of the production and operation history will lead to thermal-mechanical fatigue damage within the abradable coating. The present paper will describe the numerical modeling and sensitivity analysis of the thermal spray process. The sensitivity of residual stresses (with varying material properties, coating/substrate thickness, Poisson’s ratio, and substrate temperature) predicted by the Tsui and Clyne progressive deposition model enabled identification of performance drivers to coating integrity. Selecting material properties that minimize in-service stresses is a crucial stage in advancing future abradable performance.     

Thermal Spray Coatings on Orthopedic Devices: When and How the FDA Reviews Your Coatings

Thermal spray coatings have been commonly applied on medical devices for various reasons, e.g., surface roughening, biological fixation, and similarity of chemical composition to bone minerals. Generally, to introduce a thermal spray-coated device to the US market, a premarket review of the coated device is necessary by the US Food and Drug Administration (FDA). This article aims to improve understanding regarding FDA review of thermal spray coatings in orthopedic medical device marketing applications and expectations for information to be submitted as part of this process. While different thermal spray technologies and materials have been used for coatings on medical devices, thermal spray coatings often seen by the FDA on orthopedic devices include plasma-sprayed titanium (Ti) coatings and hydroxyapatite (HA) coatings as well as Ti/HA dual coatings. The coated devices are mostly metals (e.g., Ti alloy, cobalt-chromium alloy, stainless steel alloys) and some polymers (e.g., polyetheretherketone). The FDA does not clear or approve individual coatings or materials; rather, coatings and materials are evaluated as part of the final, finished medical device in the context of the specific device technological characteristics and intended use. The FDA has two current guidance documents for orthopedic implants with modified metallic surfaces and hydroxyapatite coatings, which outline the FDA’s recommendations for full characterization and testing of these two types of coatings, respectively. Additionally, the standards organizations (e.g., ISO and ASTM) have developed many materials and testing standards for these coatings, some of which are recognized by the FDA. It is helpful that the coating companies reference these standards for appropriate material/coating specifications, testing methods, and acceptance criteria. Depending on the intended use of the coated device, it is important that coating properties also address some items specific to that device type. Additionally, the impact of cleaning, sterilization, and packaging/shelf-life processes on the coating properties is also considered to ensure that the coated device is safe for its intended use.     

Influence of substrate properties on the impact resistance of WC cermet coatings

This research delivers a generic understanding of the design and integrated performance of the coating-substrate systems under impact loading, and comprehends the understanding of underpinning failure mechanisms. Repeated severe impacts to the coatings often result in poor performance by cracking and delamination from the coating-substrate interface. The durability of coatings thus depends on the choice of coating and substrate materials, coating deposition process, and service conditions. The design of thermal spray coatings thus requires an optimization of these parameters. This investigation provides insight into the role of coating and substrate properties on the impact resistance of coated materials, and maps the relationship between the impact resistance of WC cermet coatings on a variety of substrates. Results indicate that the delamination resistance of the coating during impact loading not only depends upon the hardness and roughness of the substrate material, but, more importantly, substrates with a higher work-hardening coefficient indicate a higher delamination resistance. The original version of this paper was published as part of the DVS Proceedings: “Thermal Spray Solutions: Advances in Technology and Application,” International Thermal Spray Conference, Osaka, Japan, 10–12 May 2004, CD-Rom, DVS-Verlag GmbH, Düsseldorf, Germany.     

On the Role of Spraying Process on Microstructural, Mechanical, and Thermal Response of Alumina Coatings

Thermal spraying is a widely used technology for industrial applications to provide coatings that improve the surface characteristics. According to the specificities of processes (APS, VPS, flame, electric arc), any kind of material can be sprayed. Among materials, ceramic coatings present several interesting aspects such as wear resistance, corrosion protection as well as thermal or electrical insulation; particularly alumina coatings which appear as the most commonly used. From all spraying processes, atmospheric plasma spraying (APS) is a rather well-established process but some others can also be used with a lower economical impact such as the flame technology. The aim of this study was to analyze the alumina coating properties according to the technology employed such as APS or wire flame spraying using the Rokide™ and the Master Jet^? guns. After micrographic analyses by SEM, physical and mechanical properties were measured considering the thermal conductivity and the hardness. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

The effect of a simple annealing heat treatment on the mechanical properties of cold-sprayed aluminum

Cold spray, a new member of the thermal spray process family, can be used to prepare dense, thick metal coatings. It has tremendous potential as a spray-forming process. However, it is well known that significant cold work occurs during the cold spray deposition process. This cold work results in hard coatings but relatively brittle bulk deposits. This work investigates the mechanical properties of cold-sprayed aluminum and the effect of annealing on those properties. Cold spray coatings approximately 1 cm thick were prepared using three different feedstock powders: Valimet H-10: Valimet H-20: and Brodmann Flomaster. ASTM E8 tensile specimens were machined from these coatings and tested using standard tensile testing procedures. Each material was tested in two conditions: as-sprayed; and after a 300°C, 22h air anneal. The as-sprayed material showed high ultimate strength and low ductility, with <1% elongation. The annealed samples showed a reduction in ultimate strength but a dramatic increase in ductility, with up to 10% elongation. The annealed samples exhibited mechanical properties that were similar to those of wrought 1100 H14 aluminum. Microstructural examination and fractography clearly showed a change in fracture mechanism between the as-sprayed and annealed materials. These results indicate good potential for cold spray as a bulkforming process. The original version of this paper was published in the CD ROM Thermal Spray Connects: Explore Its Surfacing Potential, International Thermal Spray Conference, sponsored by DVS, ASM International, and HW International Institute of Welding, Basel, Switzerland, May 2–4, 2005, DVS-Verlag GmbH, Düsseldorf, Germany.     

A new approach to online thickness measurement of thermal spray coatings

In the past 10 years, significant progress has been made in the field of advanced sensors for particle and spray plume characterization. However, there are very few commercially available technologies for the online characterization of the as-deposited coatings. In particular, coating thickness is one of the most important parameters to monitor and control. Current methods such as destructive tests or direct mechanical measurements can cause significant production downtime. This article presents a novel approach that enables online, real-time, and noncontact measurement of individual spray pass thickness during deposition. Micron-level resolution was achieved on various coatings and substrate materials. The precision has been shown to be independent of surface roughness or thermal expansion. Results obtained on typical high-velocity oxyfuel and plasma-sprayed coatings are presented. Finally, current fields of application, technical limitations, and future developments are discussed. This article was originally published inBuilding on 100 Years of Success: Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

热喷涂汽车发动机气缸内壁涂层的研究进展

为了达到越来越苛刻的内燃机排放标准,减轻车身重量以降低燃油消耗是近年来车辆行业的重要发展方向之一。采用热喷涂方法在铝合金或铸铁气缸内壁喷涂减摩、耐磨并耐腐蚀的涂层代替传统铸铁缸套具有广阔的应用前景。首先介绍制备气缸内壁涂层的工艺流程,主要阐述现有制备气缸涂层的超音速火焰喷涂、电弧喷涂、大气等离子喷涂和等离子转移弧线材喷涂等工艺的原理,对不同热喷涂工艺特点进行了总结,阐明不同热喷涂方法获得的涂层结构特点。通过列举国内外车辆制造商先进热喷涂涂层的应用实例,进一步分析各类涂层的优缺点。最后提出优化喷涂参数、开发新型喷涂材料、控制涂层内应力和应对未来生物燃料是汽车气缸涂层的下一步研究方向。     

航空发动机涡轮叶片热障涂层研究现状

热障涂层是一种可以有效保障航空发动机涡轮叶片正常工作，同时显著提高其工作效率和服役时间的表面防护技术。热障涂层的性能在很大程度上影响叶片的承温和抗腐蚀能力，进而间接影响航空发动机的服役性能。涂层性能主要受其结构和材料2个方面的影响。介绍了涂层结构的优缺点和研究进展，当前常见的结构形式有双层结构、多层结构和梯度结构；介绍了粘结层材料的研究进展；对陶瓷层材料的研究进展进行了详述，如YSZ的掺杂改性、A₂B₂O₇型化合物、钙钛矿结构材料以及近年来兴起的几种高熵陶瓷材料，其中高熵陶瓷材料包括：高熵稀土钽酸盐、铝酸盐、锆/铪酸盐、磷酸盐、硅酸盐以及高熵稀土氧化物，分别从热导率、热膨胀系数、断裂韧性、热循环寿命和抗腐蚀能力等方面对其进行介绍；概述了热障涂层常见的几种失效形式如：TGO失效、CMAS腐蚀以及高温烧结，并且对其发生机理进行简要的介绍；展望了热障涂层未来的发展趋势和方向。     

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.     

Plasma Spray-CVD: A New Thermal Spray Process to Produce Thin Films from Liquid or Gaseous Precursors

New dedicated coating processes which are based on the well-known LPPS™ technology but operating at lower work pressure (100 Pa) are being actively developed. These hybrid technologies contribute to improve the efficiencies in the turbine industry such as aero-engines and land-based gas turbines. They also have a great potential in the domain of new energy concepts in applications like Solid Oxide Fuel Cells, membranes, and photovoltaic with the adoption of new ways of producing coatings by thermal spray. Such processes include Plasma Spray-Thin Film (PS-TF) which gives the possibility to coat thin and dense layers from splats through a classical thermal spray approach but at high velocities (400-800 m/s) and enthalpy (8000-15000 kJ/kg). Plasma Spray-PVD (PS-PVD) which allows producing thick columnar-structured Thermal Barrier Coatings (100-300 μm) from the vapor phase with the employment of the high enthalpy gun and specific powder feedstock material. On the other hand, the Plasma Spray-CVD (PS-CVD) process uses modified conventional thermal spray components operated below 100 Pa which allows producing CVD-like coatings (<1-10 μm) at higher deposition rates using liquid or gaseous precursors as feedstock material. The advantages of such thermal spray-enhanced CVD processes are the high ionization degree and high throughput for the deposition of thin layers. In this article, we present an overview of the possibilities and limitations encountered while producing thin film coatings using liquid and gaseous precursors with this new type of low pressure plasma spray equipment and point out the challenges faced to obtain efficient injection and mixing of the precursors in the plasma jet. In particular, SiO _x thin films from Hexamethyldisiloxane (HMDSO or C₆H₁₈OSi₂) can be deposited on wafers at deposition rates of up to 35 nm/s at an efficiency of about 50%. The process was also used for producing metal oxide coatings (Al₂O₃, ZnO, and SnO₂) by evaporating different metals in combination with an oxygen gas flow. The effect of process parameters on the deposition rate, coating build up, uniformity, and quality of the coatings are discussed. An overview of different potential applications of this new technology will be also presented.     

Harmful risks for workers in thermal spraying: A review completed by a survey in a French company

Thermal spray technologies are implemented in spray booths either manually or automatically. In both cases, workers can be exposed to several potential and real risks. The major risks are to workers’ respiratory systems and result from harmful feedstock materials. To the authors’ knowledge, very few specific studies have been conducted to assess the significance of these risks. This study describes the major risks encountered and reviews the results of a survey conducted in a French company that uses thermal spray technology on a large scale.     

Grinding of nanostructured ceramic coatings: surface observations and material removal mechanisms

Surface grinding of thermally sprayed nanostructured WC/12Co and Al₂O₃/13TiO₂ (n-WC/12Co and n-Al₂O₃/13TiO₂) coatings has been undertaken with diamond wheels and under various grinding conditions. This paper investigates the effects of the grinding parameters such as depth of cut, feedrate, wheel grit size and bond materials on grinding forces, surface finish and surface topography. Different from their consolidated counterparts, the coatings have large quantities of defects inherited from thermal spray process, which greatly influence the grinding process and ground coatings. The competing phenomenon between the effects on surface finish from both the thermal spray process and the grinding process is studied. Different surface topographies are observed and their relationship with grinding conditions and material properties is investigated. Furthermore, the material removal mechanisms in grinding are explored. The effects of grinding parameters, material properties and the defects from thermal spray process on material removal mechanisms are discussed.     

Planning robotic trajectories for thermal spray shape deposition

Thermal spray shape deposition is a new process for fabricating net-shape parts by incremental material buildup of cross-sectional layers. This article presents an approach for spraying thin, flat layers using a robotic thermal spray system. Asymmetries of the spray distribution are first corrected by tilting the spray torch based on a computer model of the measured spray distribution. The path of the torch is then found using heuristics that are based on the estimated standard deviation of the corrected distribution. For example, thick arc-sprayed coatings of approximately 4.0 mm thickness have been deposited using this method, with the resulting standard deviation from the mean thickness ranging from 20.0 to 30.0 μm. To demonstrate the shape deposition process, a prototype turbine blade shape was built using these optimized trajectories.