高铬刚玉涂料及防粘砂机理研究

试验了醇基高铬刚玉粉涂料并在铸钢生产中应用,采用电子探针分析了高温钢液作用过的涂层断面结构,探讨了其防粘砂机理。结果表明,这种涂料有较好的防粘砂效果;发现了钢液表面的FeO和砂型中的水玻璃向涂层中渗透,涂层中耐火骨料颗粒表面熔融,烧结成彼此相连的大块状,骨料间隙填充硅酸铝、铁、钠玻璃相,形成一定厚度的致密隔离层,有效地防止了钢液的渗透。     

Optimizing thermally grown oxide for thermal barrier coatings on TiAl components via fluorine treatment

Titanium aluminides suffer from non-protective mixed-oxide scale formation during high-temperature exposure in oxidizing environments, so that they cannot be used at temperatures above approximately 800° C for longer times without additional treatment. A fluorine treatment on γ-TiAl alloys leads to the formation of a pure protective alumina scale and allows their use at service temperatures above 800°C. This thermally grown aluminum oxide layer can be used for bonding ceramic thermal barrier coatings to the TiAl substrate. Zirconia topcoats deposited by electron-beam physical vapor deposition were very adherent to F-treated TiA samples during cyclic oxidation tests at 900 to 1,000°C. A separate bond coat is not needed in this case.     

Oxidation-resistant coatings for ultra-high-temperature refractory Mo-based alloys

The synthesis of robust coatings that provide protection against environmental attack at ultra-high temperatures is a difficult challenge. In order to achieve this goal for Mo-based alloys the fundamental concepts of reactive diffusion pathway analysis and kinetic biasing are used to design a multilayer coating with a phase sequencing that provides for structural and thermodynamic compatibility and an underlying diffusion barrier to maintain coating integrity. The coating structure evolution during high-temperature exposure facilitates a prolonged lifetime as well as a self-healing capability. Both borosilicide and aluminide coatings that can be synthesized by a pack cementation process are demonstrated to yield superior environmental resistance on Mo-based systems at temperatures up to l,700°C and can be adapted to apply to other refractory metal systems.     

Corrosion of type 316L stainless steel in molten LiCl–KCl salt

Pyrochemical reprocessing in molten chloride salt medium has been considered as one of the best options for the reprocessing of spent metallic fuels. The AISI 316L stainless steel (SS) is envisaged as a candidate material for the fabrication of components for various unit operations like salt preparation vessel, electro‐refiner and cathode processor, on which ceramic coatings with metallic bond coat will be applied by the thermal plasma spraying. The unit operation like electro‐refining is carried out in the molten lithium chloride–potassium chloride (LiCl–KCl) eutectic salt at 773 K in argon atmosphere. The corrosion behaviour of the container vessel in molten chloride salts is therefore important, hence corrosion tests were carried out in a molten salt test assembly under argon gas atmosphere. The present paper discusses the corrosion behaviour of 316L SS in the molten LiCl–KCl eutectic salt at 873 K. The 316L SS samples were immersed in the molten LiCl–KCl eutectic for 25, 100 and 250 h, while 316L SS with yttria stabilized zirconia coating was exposed for 1000 h. The exposed samples were examined by optical and scanning electron microscope for corrosion attack. The X‐ray mappings of the cross‐section of the degraded layer onto the 316L SS indicated that the mechanism of corrosion corresponds to the selective diffusion of Cr to the surface with the formation of voids below, and the formation of chromium compounds at the surface. The results of the present study indicated that the yttria stabilized zirconia coating onto the 316L SS exhibits a better corrosion resistance in molten chloride salt than with uncoated 316L SS.     

定向凝固下Ti-48Al合金与不同氧化物铸型涂层界面反应的研究

通过SEM、EDS以及XRD等检测方法对Ti-48Al合金分别与Al2O3、Y2O3、ZrO2铸型涂层的界面反应处的微观组织、元素分布以及界面处的相组成等进行检测;同时结合对界面处的硬度测量,得到界面反应层厚度。结果表明,合金熔体与不同铸型涂层均发生了界面反应。铸型涂层材料不同,界面反应剧烈程度也不同。反应过程中在熔体和扩散元素的冲击下,物理侵蚀和化学反应同时存在形成了反应层,反应的强弱则与涂层材料有关。更值得注意的是,对钛铝合金与铸型涂层的热力学性质进行了计算。研究还表明,熔体在界面处的反应层主要由涂层材料的脱落扩散程度控制,涂层中的元素尤其是O元素的扩散是控制界面反应进程的重要因素。     

Sulphidation Behavior of a Non Harmful Water-Based Al and Al–Si Slurry Coating on CM247 Superalloy

Slurry aluminide coatings are widely applied to protect metallic surfaces from oxidation and corrosion. They are frequently used in gas turbine engine nozzles because of economical advantages and a straight-forward manufacturing route. A variety of commercial slurries are available to aluminize the surfaces of nickel-based superalloys, however, they have two main disadvantages. First, the phosphates and chromates or halides used as binders and to activate the diffusion species are environmentally harmful; second, the conventional systems have to be heat-treated in an inert atmosphere. As an outcome of the PARTICOAT project the variety of slurry derived coatings has been extended by tailoring the particle size of the metallic source. By doing that, environmentally friendly water-based slurries were developed to produce in a one-step process und atmospheric conditions, a thermal barrier system based on an aluminum diffusion layer and an alumina foam layer which serves as bond coat as well as top coat (TC). CM 247 nickel base superalloy was coated and heat-treated in air using newly developed Al and Al–Si slurries. The oxidation behavior was investigated at 1,000 °C and then compared to pack-cemented aluminide coatings. The sulphidation behavior was investigated at 1,000 °C in an atmosphere of 1.5 vol% SO₂ in synthetic air for Al and Al–Si slurry coated samples with and without the alumina foam TC layer. PARTICOAT Al-based slurries,, after the initial stabilization of the TC, showed similar oxidation kinetics as pack cemented aluminides when exposed to air. When the coatings were exposed to sulphide-containing atmospheres, their oxidation rates increased, producing typical type I corrosion damage. Coatings without TC produced more protective oxide scales. The weight gain and coating area affected by corrosion were slightly lower for the Al-based slurries after 1,000 h of exposure than for the Al–Si based ones. The new coating presented here offers unique advantages in comparison to state-of-the-art slurry and pack cemented coatings by opening a potential way to manufacture a complete thermal barrier coating system by a simple, inexpensive and environmentally safe deposition and heat-treatment in air.     

Effect of Annealing Temperature on Tribological Properties and Material Transfer Phenomena of CrN and CrAlN Coatings

This study evaluates the effects of annealing temperature and of the oxides produced during annealing processes on the tribological properties and material transfer behavior between the PVD CrN and CrAlN coatings and various counterface materials, i.e., ceramic alumina, steel, and aluminum. CrAlN coating has better thermal stability than CrN coating in terms of hardness degradation and oxidation resistance. When sliding against ceramic Al₂O₃ counterface, both CrN and CrAlN coatings present excellent wear resistance, even after annealing at 800 °C. The Cr-O compounds on the coating surface could serve as a lubricious layer and decrease the coefficient of friction of annealed coatings. When sliding against steel balls, severe material transfer and adhesive wear occurred on the CrN and CrAlN coatings annealed at 500 and 700 °C. However, for the CrAlN coating annealed at 800 °C, much less material sticking and only small amount of adhesive wear occurred, which is possibly due to the formation of a continuous Al-O layer on the coating outer layer. The sliding tests against aluminum balls indicate that both coatings are not suitable as the tool coatings for dry machining of aluminum alloys.     

热障涂层先进结构设计研究进展

随着航空航天技术的不断发展,不断提高的涡轮前进口温度及恶劣的使用环境对镍基高温合金的使用性能提出了更高的要求。热障涂层是一种应用于涡轮发动机热端部件的表面技术,通过沉积在镍基高温合金表面,降低合金表面的温度。概述了采用传统单层层状氧化钇部分稳定氧化锆热障涂层的优势,包括较低的制备成本、便捷的制备方式及较低的层间热膨胀失配应力。同时,归纳了单层层状热障涂层在高温环境下存在的问题,包括氧化锆相变与烧结造成的涂层失效,以及热膨胀系数和断裂韧性较差的新型陶瓷材料无法直接制备在黏结层表面。在此基础上重点综述了近年来热障涂层先进结构设计的研究进展,包括双层层状结构、柱状结构、垂直裂纹结构及复合结构热障涂层,其中复合结构包括激光表面改性结构、梯度涂层结构及粉末镶嵌结构热障涂层。针对各种先进结构热障涂层,分别从微观结构、热震寿命、涂层内部应力、耐腐蚀性能、抗氧化性能等方面进行了归纳,并总结了各先进结构热障涂层现阶段发展的不足之处。最后展望了热障涂层先进结构设计的发展方向。     

热障涂层中NiPtAl与MCrAlY粘结层表面氧化铝的生长差异研究

研究NiPtAl和MCrAlY作为粘结层的EB-PVD热障涂层不同温度循环氧化寿命差异,从涂层高温氧化角度理解氧化铝的生长差异对上述涂层不同寿命的影响原因。发现2种Pt浓度的NiPtAl涂层具有相似的氧化行为和涂层寿命,同时NiPtAl比MCrAlY作为粘结层的热障涂层表现出明显较长的循环氧化寿命。NiPtAl比MCrAlY具有较低的氧化铝生长速率和较大的临界失效厚度。NiPtAl氧化铝呈明显的等轴和柱状晶粒分布,涂层中的Pt和氧化铝晶界中Hf偏析物是影响氧化铝生长速率的重要因素。进一步证明铂能够提高氧化铝的粘结性能和热障涂层寿命,从而抵消铂的高成本进而促进NiPtAl涂层在涡轮机中的进一步广泛应用。     

Microstructural and Mechanical Property Evolutions of Plasma-Sprayed YSZ Coating During High-Temperature Exposure: Comparison Study Between 8YSZ and 20YSZ

Plasma-sprayed YSZ coatings, serving as the thermal insulating top coating for thermal barrier coatings, involve thermally activated microstructural evolution, which may change the physical and mechanical properties and thereby influence the thermal barrier performance and service lifetime. In this study, 8YSZ and 20YSZ coatings annealed at 1300 °C were comparatively investigated to understand the effects of phase structure on the sintering behavior. Results show that, compared with the 20YSZ coating consisting of mainly thermodynamically stable cubic phase, the as-sprayed 8YSZ coating presented a multiphase structure mainly composed of thermodynamically metastable tetragonal phase, and significant phase transformation occurred during high-temperature exposure. The lamellar bonding had significantly improved because of the healing of intersplat pores. Fracture toughness, microhardness, and elastic modulus increased with sintering duration. The 8YSZ coating exhibiting the thermodynamically metastable tetragonal phase structure experienced a slower sintering kinetics than the 20YSZ coatings consisting mainly of thermodynamically stable cubic phase.     

Comparative Study of Micro- and Nano-structured Coatings for High-Temperature Oxidation in Steam Atmospheres

For many high-temperature applications, coatings are applied in order to protect structural materials against a wide range of different environments: oxidation, metal dusting, sulphidation, molten salts, steam, etc. The resistance achieved by the use of different kind of coatings, such as functionally graded material coatings, has been optimized with the latest designs. In the case of supercritical steam turbines, many attempts have been made in terms of micro-structural coatings design, mainly based on aluminides, and other diffusion coating systems in order to consider alternatives, nano-structured coatings based on Cr and Al compositions and deposited by a physical vapor deposition technique, were assessed to high-temperature oxidation resistance in steam environments. The oxidation kinetics where analyzed for up to 2,000 h at 650 °C by means of gravimetric measurements. The evaporation behavior was also analyzed by thermogravimetric-mass spectrometry. Excellent results where observed for some of the nano-structured coatings tested. Those results where compared to results obtained for micro-structured coatings. Based on that comparison, it was deduced that the nano-structured coatings have a potential application as protective systems in high-temperature steam environments.     

Ni/AlN Composite Coating for Corrosion and Elements Interdiffusion Resistance in Molten Fluoride Salts System

The Ni/AlN composite coating was prepared for increasing corrosion and elements interdiffusion resistance of GH3535 alloy in molten fluoride salts,and the effect of mechanical interlocking on adhesion strength between AlN layer and nickel coating was also studied.Results indicated that the adhesion strength between AlN layer and nickel coating could be signifi-cantly enhanced through mechanical interlocking effect,which effectively prevented the nickel coating from flaking off at elevated temperature.Through an etching pre-treatment of AlN layer,the corrosion resistance of the Ni/AlN coated GH3535 alloy in molten FLiNaK salt was further improved,and elements interdiffusion between the substrate and nickel coating was completely suppressed.AlN layer as a diffusion barrier remained compact and continuous in Ni/GH3535 system after high-temperature molten salt corrosion.Moreover,a Ni-P layer consisting of Ni3P and Ni phases formed in the Ni coating after corrosion.     

Advanced microstructural characterization of plasma-sprayed zirconia coatings over extended length scales

Achieving control of the microstructure of plasma-sprayed thermal barrier coating (TBC) systems offers an opportunity to tailor coating properties to demanding applications. Accomplishing this requires a fundamental understanding of the correlations among processing, microstructure development, and related TBC properties. This article describes the quantitative characterization of the microstructure of plasma-sprayed partially stabilized zirconia (PSZ) coatings by means of x-ray and neutron-scattering imaging techniques. Small-angle neutron scattering, ultra-small-angle x-ray scattering, and x-ray microtomography were used to characterize and visualize the nature and structure of the features in these material systems. In addition, the influence of processing parameters on microstructure development is discussed along with thermal cycling effects on the pore morphology, and their resultant influence of the porosity on the thermal conductivity and elastic modulus of plasma-sprayed PSZ TBCs.     

Ceramic-lined compound copper pipe prepared by SHS process

Self-propagating high-temperature synthesis(SHS) is a new kind of material synthesis technique, and has characteristics with respect to low energy consumption, short synthetizing time, high production quantity, high product purity and no environmental pollution. When SHS combines with centrifugal casting, ceramic-lined compound copper pipe(CLCCP) can be produced, the inner surface of copper pipe can produce ceramic coatings having good wear and corrosion resistance. In order to increase the densification degree, combining strength and toughness of ceramic layer, the effects of additives such as SiO2, CrO3, Na2B4O7 and ZrO2 are researched, adding SiO2 and CrO3 in thermite, the densification degree of ceramic layer increases, adding Na2 B4 O7 in thermite can increase combining strength, adding ZrO2 in thermite can increase the toughness of ceramic layer. CLCCP is used in tubular billet crystallizer, having excellent service effects and decreasing the production cost of tubular billet.     

Degradation of Thermal Barrier Coatings by Fuel Impurities and CMAS: Thermochemical Interactions and Mitigation Approaches

Degradation of free-standing yttria-stabilized zirconia (YSZ) and CoNiCrAlY coatings (300 μm) due to V₂O₅ and a laboratory-synthesized CMAS was investigated at temperatures up to 1400 °C. Reactions, phase transformations, and microstructural development in coatings were examined by using x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The molten deposits destabilized the YSZ and reacted with the thermally grown oxide with various phase transformations and reaction product formation. A dense, continuous environmental barrier overlay, based on oxides, applied by electrophoretic deposition was effective in mitigating the molten deposit attack. Enriching CMAS composition with Al promoted the crystallization of anorthite platelets and MgAl₂O₄ spinel, and mitigated CMAS ingression. EPD MgO overlay was also effective in protection against V₂O₅ melt by formation of magnesium vanadates. EPD alumina overlay deposited on thermal barrier coatings with APS 8YSZ and bond-coated IN939 superalloy retained its adhesion and structural integrity after prolonged furnace thermal cycle test at 1100 °C.     

粘结层预处理对PS-PVD沉积7YSZ热障涂层氧化行为的影响

目的提高PS-PVD沉积7YSZ热障涂层的抗高温氧化性能。方法采用等离子喷涂-物理气相沉积(PS-PVD)分别在未预处理和预处理(抛光+预氧化)的粘结层表面制备了柱状结构7YSZ热障涂层,并在大气环境下测试了柱状结构7YSZ热障涂层的950℃静态高温氧化性能。利用扫描电子显微镜、X射线衍射仪、能谱仪对高温氧化过程中的陶瓷层/粘结层界面形貌、TGO层结构演变进行表征。结果粘结层的抛光处理能够降低表面几何受力不均匀部位,抑制陶瓷层/TGO/粘结层界面处微裂纹的产生,同时粘结层的预氧化处理形成的薄而连续的TGO层能有效降低TGO的生长速度,抑制陶瓷层-粘结层之间的元素互扩散。柱状结构7YSZ涂层的高温氧化动力学曲线符合Wagner抛物线规律,粘结层未预处理和预处理的7YSZ热障涂层的氧化速率常数分别为0.101×10~(-12) cm~2/s和0.115×10~(-13) cm~2/s。结论粘结层预处理能有效改善等离子物理气相沉积7YSZ热障涂层的抗氧化性能。     

Comparison of corrosion resistance between Al2O3 and YSZ coatings against high temperature LiCl-Li2O molten salt

In this study, the high-temperature corrosion resistance of plasma-sprayed ceramic oxide coatings has been evaluated in a LiCl-Li₂O molten salt under an oxidizing environment. Al₂O₃ and YSZ coatings were manufactured by atmospheric plasma spraying onto a Ni alloy substrate. Both the plasma-sprayed Al₂O₃ and YSZ coatings had a typical splat quenched microstructure which contained various types of defects, including incompletely filled pores, inter-splat pores and intra-splat microcracks. Corrosion resistance was evaluated by the thickness reduction of the coating as a function of the immersion time in the LiCl-Li₂O molten salt at a temperature of 650 °C. A linear corrosion kinetic was found for the Al₂O₃ coating, while no thickness variation with time occurred for the YSZ coating. The ceramic oxide coatings were reacted with LiCl-Li₂O molten salt to form a porous reaction layer of LiAl, Li₅AlO₄ and LiAl₅O₈ for the Al₂O₃ coating and a dense reaction layer of non-crystalline phase for the YSZ coating. The reaction products were also formed along the inside coating of the porous channel. The superior corrosion resistance of the YSZ coating was attributed to the formation of a dense protective oxide layer of non-crystalline reaction products on the surface and at the inter-splat pores of the coating.     

γ-TiAl合金定向凝固过程中与氧化钇陶瓷材料的界面反应

研究液态金属冷却定向凝固条件下,Ti-47%Al合金与Y2O3/Al2O3双层结构陶瓷管内层Y2O3的相互作用。分析熔体温度和相互作用时间对界面反应、合金组织和成分的影响。结果表明：虽然Y2O3层受到一定程度的侵蚀和溶解,但Y2O3层有效地阻隔化学稳定性较差的Al2O3外层与TiAl合金熔体接触,避免Al2O3与TiAl之间的化学反应。合金熔体受到一定程度的污染且含有少量夹杂物。在一定保温时间内,合金中的杂质含量（Y和O）和夹杂物（Y2O3）体积分数均随着过热温度的提高而增加,但随着保温时间的进一步延长,杂质含量和夹杂物体积分数趋于恒定值,不再显著变化。     

Oxidation behaviour of a Mo(Si,Al)2 based composite at 1500 °C

The oxidation of a Mo(Si,Al)₂ composite is investigated at 1500 °C in dry air using exposure times from 1 to 1000 h. Cross sections are examined with Scanning Electron Microscopy (SEM) and the phase composition is analyzed by X-ray diffraction (XRD). The material forms a continuous and protective alumina layer, the growth of the alumina layer following parabolic kinetics. Immediately below the scale Mo(Si,Al)₂ is replaced by a Mo₅(Si,Al)₃ layer due to the flux of aluminum to the scale. The Al concentration in the Mo(Si,Al)₂ phase in the underlying substrate decreases from 27% before exposure to 16–17% after 1000 h. The continuous alumina layer becomes covered by a top layer consisting of alumina grains embedded in a viscous melt with approximate composition 7 Na₂O–15 Al₂O₃–78 SiO₂. With time, sodium is volatilized from the melt and the top scale layer transforms to a mixture of alumina, mullite and silica melt.     

铝—硅涂层防护性能的研究

采用静态高温氧化、热腐蚀试验以及多种物理分析方法研究了镍基合金上的铝—硅涂层的防护性能。揭示了硅在涂层中的分布形式及其在高温曝置期间的变化情况。指出铝—硅涂层的防护性能明显优于渗铝涂层,而且在本试验范围内随硅含量的增加而提高。这是由于: (a) 铝—硅涂层减轻或防止涂层中“MC碳化物缺口”的出现; (b) 含硅的γ′-相具有优良的抗氧化性能; (c) 1100℃短时间曝置后在Al—Si涂层与基体界面处形成的连续的富硅M_6C“隔层”起扩散屏障的作用。