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。     

Performance of thermal barrier coatings on γ‐TiAl

The current development of new generation gamma titanium aluminides is expected to result in alloy chemistries and microstructures capable of operating at temperatures in excess of 850 °C. Under these conditions, environmental and thermal protection becomes a concern since oxidation might eventually limit the maximum service temperatures achievable. Therefore protective coatings are necessary to exploit the full potential of gamma titanium aluminides at moderately elevated temperatures; however, as yet no coating system tested has proven sufficient performance for long‐term use in automotive and aerospace applications. Thermal barrier coatings (TBCs), typically applied to nickel‐based alloys, offer the potential to increase the service temperature of components by lowering the metal surface temperature in combination with cooling systems. The paper is focussed on development of thermal barrier coatings for gamma titanium aluminides. Different coatings were used for oxidation protection and bond coat application. Substrate specimens were either pre‐oxidized or coated with PVD‐Al₂O₃, TiAlCrYN, or diffusion aluminides. Yttria‐stabilized zirconia TBCs were deposited applying electron‐beam physical vapour deposition. Cyclic and quasi‐isothermal oxidation tests were carried out at 900 °C in air. Post‐oxidation analysis of the coating systems was performed using scanning electron microscopy with energy‐dispersive X‐ray spectroscopy. Zirconia top coats offer a promising thermal protection concept to be applied on γ‐TiAl components. However, high oxidation resistance has to be supplied by protective coatings. Diffusion layers of the TiAl₃ aluminide provided excellent environmental protection because of the formation of a continuous alumina scale. No spallation of the thermal barrier coatings was observed on aluminized specimens during 1000 1‐h cycles and 3000 h of cyclic and isothermal oxidation testing, respectively.     

Thermal stability and oxidation resistance of TiCrAlYO coatings on SS430 for solid oxide fuel cell interconnect applications

Chromia-forming ferritic stainless steels are being considered for interconnect applications in planar solid oxide fuel cell (SOFC) stacks because of their low cost and physical properties. At high temperatures, ferritic steels lack environmental stability in the SOFC operating environment, and gradually degrade the cell stack performance. In this study, an effective, dense and well adherent TiCrAlYO coating was deposited on an SS430 alloy using the filtered arc deposition technique. High-energy ion backscattering was used to characterize the composition and the thermal stability of the coatings. The chromium volatility of the coated steel plates at 800 °C was also measured using ion beam analysis. Significant reductions in oxidation rates as well as reduced Cr volatility were observed for the coated alloys.     

基板温度对EB-PVD ZrO2涂层微观组织及残余应力的影响

采用电子束物理气相沉积(EB-PVD)技术在不锈钢基板上沉积ZrO2涂层.研究基板温度对涂层微观组织和残余应力的影响.结果表明:沉积的涂层均为t-ZrO2结构,涂层表面平整致密;随着基板温度的升高,涂层表面颗粒逐渐长大,表面粗糙度增大;涂层残余应力也随着基板温度的升高而增加,当基板温度为1000 ℃时,涂层残余应力的增量最大,ZrO2涂层的残余应力主要是由于涂层与基板热膨胀系数差别而产生的热应力引起.     

Atmospheric Plasma Spraying Low-Temperature Cathode Materials for Solid Oxide Fuel Cells

Atmospheric plasma spraying (APS) is attractive for manufacturing solid oxide fuel cells (SOFCs) because it allows functional layers to be built rapidly with controlled microstructures. The technique allows SOFCs that operate at low temperatures (500-700 °C) to be fabricated by spraying directly onto robust and inexpensive metallic supports. However, standard cathode materials used in commercial SOFCs exhibit high polarization resistances at low operating temperatures. Therefore, alternative cathode materials with high performance at low temperatures are essential to facilitate the use of metallic supports. Coatings of lanthanum strontium cobalt ferrite (LSCF) were fabricated on steel substrates using axial-injection APS. The thickness and microstructure of the coating layers were evaluated, and x-ray diffraction analysis was performed on the coatings to detect material decomposition and the formation of undesired phases in the plasma. These results determined the envelope of plasma spray parameters in which coatings of LSCF can be manufactured, and the range of conditions in which composite cathode coatings could potentially be manufactured.     

Development and characterization of vacuum plasma sprayed thin film solid oxide fuel cells

The vacuum plasma spraying (VPS) process allows the production of thin solid oxide fuel cells (SOFCs) with low internal resistances. This enables the reduction of the cell operating temperature without a significant decrease in power density. Consequently, the long-term stability of the cells can be improved and low-cost materials can be used. Different material combinations and spray parameter variations were applied to develop thin-film SOFCs, which were plasma sprayed in a consecutive deposition process onto different porous metallic substrates. The use of Laval nozzles, which were developed at the German Aerospace Center (DLR), and the use of conical F4V standard nozzles enable the fabrication of thin gas tight yttria- and scandia-stabilized ZrO₂ (YSZ and ScSZ) electrolyte layers and of porous electrode layers with high material deposition rates. The optimization of the VPS parameters has been supported by laser doppler anemometry (LDA) investigations. The development of the plasma-sprayed cells with a total thickness of approximately 100 μm requires an overall electrical and electrochemical characterization process of the single layers and of the completely plasma-sprayed cell assembly. The plasma-sprayed cell layers reveal high electrical conductivities. The plasma-sprayed cells show very good electrochemical performance and low internal resistances. Power densities of 300 to 400 mW/cm² at low operating temperatures of 750 to 800 °C were achieved. These cells can be assembled to high performance SOFC stacks with active cell areas up to 400 cm², which can be operated at reduced temperatures and good long-term stability.     

The Structure and Properties of Plasma Sprayed Iron Oxide Doped Manganese Cobalt Oxide Spinel Coatings for SOFC Metallic Interconnectors

Manganese cobalt oxide spinel doped with Fe₂O₃ was studied as a protective coating on ferritic stainless steel interconnects. Chromium alloying causes problems at high operation temperatures in such oxidizing conditions where chromium compounds evaporate and poison the cathode active area, causing the degradation of the solid oxide fuel cell. In order to prevent chromium evaporation, these interconnectors need a protective coating to block the chromium evaporation and to maintain an adequate electrical conductivity. Thermal spraying is regarded as a promising way to produce dense and protective layers. In the present work, the ceramic Mn-Co-Fe oxide spinel coatings were produced by using the atmospheric plasma spray process. Coatings with low thickness and low amount of porosity were produced by optimizing deposition conditions. The original spinel structure decomposed because of the fast transformation of solid-liquid-solid states but was partially restored by using post-annealing treatment.     

Post-treatment of thermal spray coatings on magnesium

Magnesium alloys have a beneficial combination of high strength to weight ratio, good machinability and high recycling potential. Despite this, the application of magnesium still is behind that of other constructive materials mainly due to low wear and corrosion resistance. For more demanding applications, a large amount of surface treatment methods are developed to overcome this problem. Thermal spraying is an efficient and flexible method of coating deposition and is widely used for protection of different materials against corrosion and wear. Nevertheless, the bonding of thermal spray coatings on magnesium alloys is not sufficient, so the following post-treatment processes are needed. One of such possibilities is high energy beam treatment of thermally sprayed coatings. During the heat treatment of magnesium substrates with coating the remelting of coating and a thin surface layer of substrate occurs. Depending on the combination of applied coating system and treatment method, different processes can be realised in modified layers: the alloying of magnesium substrate with other elements to improve corrosion properties, redistribution of hard particles from composite coating and new phases formation during the processing to improve the wear resistance of magnesium alloys. In the present work some examples concerning the laser and electron beam treatment of aluminium based composite coatings as well as infra red irradiation of zinc based coatings are described. Coatings are deposited on magnesium substrates (AM20, AZ31, AZ91) by arc spraying with Zn, ZnAl4 and ZnAl15 solid wires and cored wires in aluminium core with powder filling containing different hard particles, such as boron, silicon and tungsten carbide or titanium oxide. Remelting of thermal spray coatings is carried out by means of continuous irradiation of СО₂-laser in nitrogen or argon atmosphere, electron beam in vacuum and focused tungsten halogen lamp line heater in atmosphere. Microstructure of sprayed coatings as well as that of modified surface layers is investigated by metallographic methods. Corrosion properties are estimated by electrochemical measurements. Abrasion wear resistance of the modified layers is determined by scratch test, corundum grinding disk test and Rubber wheel test. It is shown that all methods applied for processing of thermal spray coatings lead to formation of modified surface layers in magnesium substrate with improved wear and corrosion properties. Different mechanisms of microstructure formation such as redistribution of chemical composition of composite coating components, partial remelting of hard phase particles, and new phases formation are discussed. Electrochemical behaviour of modified surface layers is mostly improved due to alloying, homogenization of element distribution and strong decrease of as-sprayed coating porosity. Abrasion wear resistance of processed magnesium substrates strongly depends on the microstructure and usually is 5 to 20 times higher compared with base material.     

The influence of coating compliance on the delamination of thermal barrier coatings

Low relative density yttria stabilized zirconia (YSZ) thermal barrier coatings have been deposited on NiCoCrAlY over-lay bond-coated Hastelloy-X substrates by an electron beam-directed vapor deposition (EB-DVD) method. The coatings have been applied to both roughened and smooth bond coat surfaces. During thermal cycling, those deposited on roughened surfaces spalled by delamination with the failure located in the YSZ layer close to the thermally-grown oxide (TGO). The cracks were initiated at “corn kernel” defects in the YSZ layer by a bond coat rumpling mechanism. Coatings applied to smooth bond coat surfaces had much longer (factor of two) spallation lifetimes and delamination occurred at the bond coat/TGO interface by the nucleation and coalescence of interfacial voids. In both cases, the delamination lifetime decreased with coating density and significantly exceeded the lifetimes of higher density coatings made by conventional electron beam deposition methods. The enhanced life of the more porous coatings is consistent with an increased compliance. This reduces the YSZ layers stored strain energy contribution to the driving force for interface delamination.     

Oxidation resistant coatings in combination with thermal barrier coatings on γ-TiAl alloys for high temperature applications

Titanium aluminide alloys based on γ-TiAl are considered of growing interest for high temperature applications due to their attractive properties. To extend the service temperatures above 750 °C, the oxidation behaviour has to be improved predominantly by protective layers. In the present study environmental and thermal protection coatings on gamma titanium aluminides were investigated. Nitride and metallic overlay coatings based on Ti-Al-Cr-Y-N and Ti-Al-Cr, respectively, were produced by magnetron sputtering techniques. Thermal barrier coatings (TBCs) of partially yttria stabilized zirconia were deposited onto Ti-45Al-8Nb, either pre-oxidized or coated with protective layers, applying electron beam physical vapour deposition (EB-PVD).Cyclic oxidation tests were performed at 900 °C and 950 °C in air. The nitride coating exhibited poor oxidation resistance when exposed at 900 °C providing no protection for γ-TiAl. The oxidation behaviour of the Ti-Al-Cr coating was reasonable at both exposure temperatures. During prolonged exposure the coating was depleted in chromium, resulting in the breakdown of the protective alumina scale. EB-PVD zirconia coatings deposited on γ-TiAl exhibited promising lifetime, particularly when specimens were coated with Ti-Al-Cr. The adherence of the TBC on the thermally grown oxide scales was excellent; failure observed was associated with spallation of the oxide scale. At 950 °C, TBCs on specimens coated with Ti-Al-Cr spalled after less than 200 thermal cycles caused by severe oxidation of γ-TiAl and reactions between the zirconia coatings and the thermally grown oxides.     

Evaluation of aluminide diffusion coatings for thermal cyclic oxidation protection of a nickel‐base superalloy

Active element modified aluminide diffusion coatings on IN738 substrates were produced by a new route using continuously cast, aluminum alloy wires consisting of Al‐Y, Al‐Ce, Al‐La and Al‐Si‐Y. The cast wires were used as evaporation sources for ion‐vapour deposition followed by diffusion heat treatments to form nickel aluminide coatings. In order to examine the oxidation resistance of these coatings at elevated temperatures, thermal cyclic oxidation experiments were carried out in air at 1050°C. While all coatings were found to provide significant protection, the Al‐La modified coatings provided the greatest resistance to cyclic oxidation. On the other hand, with coatings based on Al‐Si‐Y alloys, while silicon has a strong ability to reduce the outward diffusion of aluminum, the adverse effect of silicon on mechanical properties of the coating, together with the formation of volatile silicon monoxide, led to catastrophic localized oxidation of the protective coatings.     

Microstructural Analysis and Transport Properties of Thermally Sprayed Multiple-Layer Ceramic Coatings

Multilayer, graded ceramic/metal coatings were prepared by an air plasma spray method on Ti-6Al-4V, 4140 steel and graphite substrates. The coatings were designed to provide thermal barriers for diesel engine pistons to operate at higher temperatures with improved thermal efficiency and cleaner emissions. A systematic, progressive variation in the mixture of yttria-stabilized zirconia and bondcoat alloys (NiCoCrAlYHfSi) was designed to provide better thermal expansion match with the substrate and to improve thermal shock resistance and cycle life. Heat transfer through the layers was evaluated by a flash diffusivity technique based on a model of one-dimensional heat flow. The aging effect of the as-sprayed coatings was captured during diffusivity measurements, which included one heating and cooling cycle. The hysteresis of thermal diffusivity due to aging was not observed after 100-h annealing at 800 °C. The measurements of coatings on substrate and freestanding coatings allowed the influence of interface resistance to be evaluated. The microstructure of the multilayer coating was examined using scanning electron microscope and electron probe microanalysis.     

An efficient protection of stainless steel against corrosion: Combination of a conversion layer and titanium dioxide deposit

In the present work, a novel process has been developed to improve the corrosion properties of ferritic stainless steels. Titanium oxide coatings have been deposited onto stainless steel by sol-gel process after a pre-functionalization of the substrate in a conversion bath. Gel titania was prepared by hydrolysis of a titanium butoxide through a sol-gel process. Duplex systems “conversion layer/uniform TiO₂ coating” have been prepared on stainless steels using a dipping technique and thermal post-treatments at 450 °C. The preparation of sol-gel coatings with specific chemical functions offers tailoring of their structure, texture and thickness and allows the fabrication of large coatings. The morphology and structure of the coatings were analysed using scanning electron microscopy with field effect gun (SEM-FEG), Mass spectroscopy of secondary ions (SIMS) and X-ray diffraction (XRD). The anticorrosion performances and the ageing effects of the coatings have been evaluated in neutral and aggressive media by using several normalized tests.The results show that the conversion layer was not sufficient to protect steel but sol-gel TiO₂ coatings, anchored on the metal substrate via the conversion layer, show good adhesion with the substrate and act as a very efficient protective barrier against corrosion. So, duplex layers with TiO₂ nanoparticle coatings on steels exhibit an excellent corrosion resistance due to a ceramic protective barrier on metal surface. Analysis of the data indicates that the films act as geometric blocking layers against exposure to the corrosive media and increase drastically the lifetime of the substrate.     

Development and Application of HVOF Sprayed Spinel Protective Coating for SOFC Interconnects

Protective coatings are needed for metallic interconnects used in solid oxide fuel cell (SOFC) stacks to prevent excessive high-temperature oxidation and evaporation of chromium species. These phenomena affect the lifetime of the stacks by increasing the area-specific resistance (ASR) and poisoning of the cathode. Protective MnCo₂O₄ and MnCo_1.8Fe_0.2O₄ coatings were applied on ferritic steel interconnect material (Crofer 22 APU) by high velocity oxy fuel spraying. The substrate-coating systems were tested in long-term exposure tests to investigate their high-temperature oxidation behavior. Additionally, the ASRs were measured at 700 °C for 1000 h. Finally, a real coated interconnect was used in a SOFC single-cell stack for 6000 h. Post-mortem analysis was carried out with scanning electron microscopy. The deposited coatings reduced significantly the oxidation of the metal, exhibited low and stable ASR and reduced effectively the migration of chromium.     

Thermal fatigue of hot working steel after hybrid surface treatment

Abstract

The application of surface treatment methods like ion nitriding, physical vapour deposition (PVD) coatings and their combination in duplex treatments effectively reduces the occurrence of oxidation, corrosion, erosion and wear processes. However, it is still uncertain whether nitriding and duplex treatment have any real effect on the decrease in the nucleation and growth of thermal fatigue cracks on the surface. This paper presents the results of thermal fatigue investigations of a nitrided layer and different composite layers ‘nitrided layer/PVD coating’ (TiN, CrN and TiAlN) obtained on the EN X40CrMoV5·1 hot working steel. The ion nitrided only and three different duplex treated substrates were compared, based on the intensity of the thermal fatigue cracks observed after testing. The nitrided layer and composite layers investigated were obtained with the use of the hybrid surface treatment technology consisting of ion nitriding followed by arc evaporation coating deposition. Apparatus based on high frequency induction heating and water spray cooling was used for thermal fatigue tests under the following conditions: maximum temperature 600°C, minimum temperature 80°C and two different rates of thermal cycling: 500 and 1000. The thermal fatigue intensities of the nitrided layer and the three different composite layers were measured according to the surface crack density and crack length (i.e. penetration into the testpiece) after different numbers of thermal cycles. Finally, based on the results obtained, the influence of different PVD coatings in the composite layer on the increase in thermal fatigue resistance of hot working steel was discussed.     

The Influence of Process Equipment on the Properties of Suspension Plasma Sprayed Yttria-Stabilized Zirconia Coatings

Suspension plasma-sprayed YSZ coatings were deposited at lab-scale and production-type facilities to investigate the effect of process equipment on coating properties. The target application for these coatings is solid oxide fuel cell (SOFC) electrolytes; hence, dense microstructures with low permeability values were preferred. Both facilities had the same torch but different suspension feeding systems, torch robots, and substrate holders. The lab-scale facility had higher torch-substrate relative speeds compared with the production-type facility. On porous stainless steel substrates, permeabilities and microstructures were comparable for coatings from both facilities, and no segmentation cracks were observed. Coating permeability was further reduced by increasing substrate temperatures during deposition or reducing suspension feed rates. On SOFC cathode substrates, coatings made in the production-type facility had higher permeabilities and more segmentation cracks compared with coatings made in the lab-scale facility. Increased cracking in coatings from the production-type facility was likely caused mainly by its lower torch-substrate relative speed.     

CMAS对热障涂层界面裂纹和残余应力的影响

随着航空发动机涡轮叶片工作温度的提升,使得一种主要由CaO,MgO,Al₂O₃和SiO₂组成的玻璃态物质(CMAS)对热障涂层的危害越来越严重,从而对热障涂层的性能和耐久性有了更高的要求。本文以电子束物理气相沉积热障涂层为研究对象,利用有限元方法研究了CMAS的渗入对界面裂纹扩展及CMAS对陶瓷层(TC)内部残余应力的影响规律。采用波长固定、振幅变化的正弦曲线表示不同粗糙度的涂层界面,同时考虑了CMAS的弹性模量变化的影响及不同界面形貌与CMAS之间的相互作用。结果表明：CMAS弹性模量的增加对界面裂纹具有抑制作用,并且TGO幅值和厚度越小,抑制作用越明显。CMAS弹性模量对TC层最大残余应力S₂₂的影响存在临界点,在临界点之前,CMAS弹性模量的变化对TC层最大残余应力的影响较大,随着CMAS弹性模量的增加,TC层最大残余应力大幅度减小;在临界点之后,TC层最大残余应力基本不受CMAS弹性模量变化的影响。这些结果对电子束物理气相沉积喷涂的热障涂层失效机理的研究具有重要意义,可以为热障涂层界面的优化提供指导。     

Electrodeposition of hydroxyapatite–silver–chitosan nanocomposite coatings

Hydroxyapatite (HA)–Ag–chitosan nanocomposite coatings were electrochemically deposited on various conductive substrates and studied using X-ray diffraction analysis, thermogravimetric and differential thermal analysis, energy dispersive X-ray spectroscopy, scanning and transmission electron microscopy. It was shown that the coating composition can be varied by the variation of AgNO₃ or HA concentration in the solutions used for electrodeposition. Nanocomposite coatings were deposited as HA–Ag–chitosan monolayers or multilayers containing individual HA–chitosan and Ag–chitosan layers. The coating thickness was varied in the range of 0−20 µm by the variation of deposition time for individual layers and by the variation of the number of different layers. Inductively coupled plasma optical emission spectroscopy studies showed that the Ag⁺ release rate from the Ag–chitosan layer can be reduced in the layered structure using a HA–chitosan layer. The obtained results can be used for the development of biocompatible antimicrobial coatings with controlled Ag⁺ release rate. Electrochemical impedance spectroscopy and potentiodynamic polarization studies showed that the multilayer coatings provide corrosion protection of the stainless steel substrates in Ringer's physiological solutions.     

等离子-物理气相沉积（PS-PVD）及其射流非接触检测方法

等离子-物理气相沉积(PS-PVD)是制备高温防护涂层和功能涂层的一种新方法,既可涵盖等离子喷涂和电子束物理气相沉积工艺,还可实现涂层宏观/介观/微观等跨尺度结构的定制化设计与制备,在热障涂层(TBCs)、环境障涂层(EBCs)、环境热障涂层(TEBCs)、透氧薄膜、燃料电池和太阳电池电极薄膜等领域具有广泛应用前景,尤其在航空发动机和燃气轮机防护涂层领域被视为高性能TBCs/EBCs制备技术发展的新方向。比较分析了PS-PVD等离子射流膨胀流动、材料快速加热气化离化和长距离多模式输运沉积的全流程过程,介绍了PS-PVD原理与设备系统,面向等离子射流参数快速无损检测分析的目标,建立了基于光学发射光谱学(OES)的等离子射流和材料特性非接触式检测与诊断装备系统,发展了射流和材料特性参数的定量表征和精确诊断方法。依据电子数密度等检测结果,进一步计算分析等离子温度分布规律。基于射流与材料检测结果,研究了粉末材料在等离子射流中的多相态转变行为,归纳了调控沉积单元多相态转变的工艺控制参数集。这些硬件平台和表征检测方法的建立,为构建PS-PVD理论和研制新型高性能热防护涂层提供了坚实的理论基础和必要的条件支撑。     

Relationship Between Particle and Plasma Properties and Coating Characteristics of Samaria-Doped Ceria Prepared by Atmospheric Plasma Spraying for Use in Solid Oxide Fuel Cells

Samaria-doped ceria (SDC) has become a promising material for the fabrication of high-performance, intermediate-temperature solid oxide fuel cells (SOFCs). In this study, the in-flight characteristics, such as particle velocity and surface temperature, of spray-dried SDC agglomerates were measured and correlated to the resulting microstructures of SDC coatings fabricated using atmospheric plasma spraying, a manufacturing technique with the capability of producing full cells in minutes. Plasmas containing argon, nitrogen and hydrogen led to particle surface temperatures higher than those in plasmas containing only argon and nitrogen. A threshold temperature for the successful deposition of SDC on porous stainless steel substrates was calculated to be 2570?°C. Coating porosity was found to be linked to average particle temperature, suggesting that plasma conditions leading to lower particle temperatures may be most suitable for fabricating porous SOFC electrode layers.