La2Ce2O7/YSZ热障涂层抗热震性能的陶瓷层厚度影响研究

采用实验和数值方法研究了陶瓷层厚度比对La2Ce2O7/YSZ(LC/YSZ)热障涂层热震性能的影响。实验结果表明,随着LC与YSZ厚度比的降低,涂层热震寿命显著提高,涂层失效区域逐渐向试样中心转移,剥离位置逐渐从两陶瓷层界面附近转移到LC内靠近上表面处。数值结果表明,界面边缘处较大的轴向应力与剪切应力易导致较大厚度比涂层边缘处剥落;LC表面中心区域较大的径向拉应力会导致垂直裂纹萌生,并伴随界面偏折,这是较小厚度比涂层自LC内部剥离的原因。     

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。     

等离子喷涂Mo/8YSZ功能梯度热障涂层结构优化与热力耦合模拟计算

目的研究不同结构参数对Mo/8YSZ热障涂层系统残余应力的影响因素。方法设计Mo/8YSZ功能梯度热障涂层,并利用ANSYS有限元软件建立了等离子喷涂Mo/8YSZ功能梯度热障涂层的数值模型,模型中考虑了材料热物理性能参数随温度变化,研究粘结层、过渡层及陶瓷层厚度对Mo/8YSZ功能梯度热障涂层残余应力的影响规律。结果随着径向距离的增大,粘结层与陶瓷层界面的残余应力逐渐由压应力变为拉应力,并且在涂层边缘位置,径向残余拉应力达到最大值。在0~12 mm路径范围内的同一位置,伴随着陶瓷层厚度的增加,粘结层与陶瓷层界面位置的轴向残余应力无明显变化,且轴向残余应力的数值几乎为0;在6~12.5 mm路径范围内的同一位置,伴随着陶瓷层厚度的增加,其剪切残余应力逐渐增大。在基体与粘结层界面边缘0.5 mm处存在着与其他位置相比更大的应力突变。粘结层与陶瓷层的厚度参数比控制在4∶10~4∶13时,涂层具有最低的热失配。过渡层与陶瓷层的厚度参数比控制在1∶4时,涂层具有最低的热失配。当功能梯度热障涂层的过渡层采用50%Mo与50%8YSZ复合而成时,将粘结层、过渡层及陶瓷层三者的厚度比值控制在16∶10∶40~16∶13∶52,涂层具有最低的热失配。结论通过设计功能梯度热障涂层,并合理调控热障涂层系统的结构参数,可进一步减小喷涂构件的残余应力和应力突变情况,提升基体与涂层的结合强度。     

表面陶瓷层厚度对Sm2Zr2O7/8YSZ热障涂层热冲击性能的影响

稀土锆酸盐与8YSZ所组成的双陶瓷层涂层是目前热障涂层领域研究的热点,而陶瓷层厚度对其热冲击性能有着显著影响。采用有限元软件ANSYS研究了表层厚度对Sm2Zr2O7/8YSZ热障涂层淬冲击热应力的影响,并与单一Sm2Zr2O7涂层进行了比较。结果表明,在Sm2Zr2O7/8YSZ涂层的表面处具有最大的径向热冲击应力,最大轴向应力则存在于陶瓷层/金属粘结层界面处,涂层各处剪应力基本相当。涂层表面及两陶瓷层界面处的径向热应力随表层厚度的增加而减小,陶瓷层/粘结层界面处径向应力则随表层厚度增加而增大。每个界面处的轴向应力随表层厚度增加而降低,而剪应力绝对值则随表层厚度增加而增大。与单一Sm2Zr2O7涂层相比,Sm2Zr2O7/8YSZ涂层的热应力明显偏小,说明增加涂层的层数有利益改善涂层的抗热冲击性能。     

Novel thermal barrier coatings based on La2(Zr0.7Ce0.3)2O7/8YSZ double-ceramic-layer systems deposited by electron beam physical vapor deposition

Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) and yttria stabilized zirconia (YSZ) were deposited by electron beam-physical vapor deposition (EB-PVD). The thermal cycling test at 1373 K in an air furnace indicates the DCL coating has a much longer lifetime than the single layer LZ7C3 coating, and even longer than that of the single layer YSZ coating. The superior sintering-resistance of LZ7C3 coating, the similar thermal expansion behaviors of YSZ interlayer with LZ7C3 coating and thermally grown oxide (TGO) layer, and the unique growth modes of columns within DCL coating are all very helpful to the prolongation of thermal cycling life of DCL coating. The failure of DCL coating is mainly a result of the reduction-oxidation of cerium oxide, the crack initiation, propagation and extension, the abnormal oxidation of bond coat, the degradation of t′-phase in YSZ coating and the outward diffusion of Cr alloying element into LZ7C3 coating.     

Sm2Ce2O7/YSZ功能梯度热障涂层的残余热应力

目的研究基体材质、厚度及半径对Sm_2Ce_2O_7/YSZ功能梯度热障涂层残余热应力的影响。方法采用ANSYS10.0软件中Plane13单元,通过直接耦合计算,系统分析了不同基体条件下,Sm_2Ce_2O_7/YSZ功能梯度热障涂层的残余热应力。结果在Sm_2Ce_2O_7/YSZ功能梯度热障涂层中存在较大的残余热应力。涂层残余热应力随时间的增加而逐渐降低,900 s后基本维持稳定。涂层径向热应力从中心处到试样边缘逐渐递减。2Cr13对应的涂层应力最小。金属基体厚度在2~10 mm范围内,径向热应力虽然增加,但变化幅度不大。当基体厚度为20 mm时,涂层径向热应力则显著增加。金属基体半径对涂层的最大剪切应力并不产生影响,轴向热应力随基体半径的增加而逐渐降低,径向热应力随半径增加到一定值后趋于稳定。结论 2Cr13钢基体对应的涂层具有最小热应力,基体厚度为10 mm时比较合适,基体半径对涂层轴向热应力的影响最明显。     

Non-destructive thermal property measurements of an APS TBC on an intact turbine blade

The ability to measure the properties of thermal barrier coatings (TBCs) applied to engine components is challenging due to the complex geometry of parts and the difficulty of preparing samples suitable for conventional techniques. As a result, there is a shortage of information related to the morphology and thermal properties of coatings on engine components. Phase of photothermal emission analysis (PopTea) is a relatively new non-destructive technique that is suitable for measuring the thermal properties of coatings on serviceable engine parts. To demonstrate this capability, measurements are performed on an intact turbine blade coated with air plasma sprayed (APS) 7 wt.% Y₂O₃-stabilized ZrO₂ (7YSZ). The average thermal diffusivity of the coating applied to the blade was ~ 0.5 mm²/s which is typical for thermal diffusivity previously measured on 7YSZ APS coatings made on test coupons with PopTea and laser flash. Furthermore, trends in thermal properties over the blade are studied and compared. It is discovered that variations in thermal properties are the result of differences in coating porosity.     

Impedance Analysis of 7YSZ Thermal Barrier Coatings During High-Temperature Oxidation

ZrO₂-7 wt.%Y₂O₃ (7YSZ) thermal barrier coatings (TBCs) were prepared by atmospheric plasma spraying. High-temperature oxidation of 7YSZ TBCs was accomplished at 950 °C and characterized by impedance spectroscopy and scanning electron microscopy with energy-dispersive spectrometry. The results indicated that the thermally grown oxide (TGO) mainly contained alumina. The increase of the thickness of the TGO layer appeared to follow a parabolic law. Impedance analysis demonstrated that the resistance of the TGO increased with increasing oxidation time, also following a parabolic law, and that characterization of the TGO thickness based on fitting an equivalent circuit to its measured resistance is feasible. The YSZ grain-boundary resistance increased due to increasing cracks within the coating for oxidation time less than 50 h. However, beyond 150 h, the YSZ grain-boundary resistance slightly decreased, mainly due to sintering of the coating during the oxidation process.     

Mo基体上锆酸镧热障涂层的研究

利用自行研制的La1.4Nd0.6Zr2O7(LNZ)喷涂粉末,采用大气等离子喷涂在Mo基体上制备LNZ热障涂层.测试粉末的各项热物理性能,考核涂层的抗热震性能和高温隔热性能,并与常规氧化钇稳定氧化锆(YSZ)涂层进行比较.结果表明,与YSZ相比,LNZ由于具有热膨胀系数小、导热系数低、烧结速率低等特点而更适合在Mo基体作为热障涂层使用.     

Reaction, transformation and delamination of samarium zirconate thermal barrier coatings

The rare earth zirconates have attracted interest for thermal barrier coatings (TBCs) because they have very low intrinsic thermal conductivities, are stable above 1200 °C and are more resistant to sintering than yttria-stabilized zirconia (YSZ). Samarium zirconate (SZO) has the lowest thermal conductivity of the rare earth zirconates and its pyrochore structure is stable to 2200 °C but little is known about its response to thermal cycling. Here, columnar morphology SZO coatings have been deposited on bond coated superalloy substrates using a directed vapor deposition method that facilitated the incorporation of pore volume fractions of 25 to 45%. The as-deposited coatings had a fluorite structure which transformed to the pyrochlore phase upon thermal cycling between 100 and 1100 °C. This cycling eventually led to delamination of the coatings, with failure occurring at the interface between the TGO and a “mixed zone” that formed between the thermally grown alumina oxide (TGO) and the SZO. While the delamination lifetime increased with coating porosity (reduction in coating modulus), it was significantly less than that of similar YSZ coatings applied to the same substrates. The reduced life resulted from a reaction between the rare earth zirconate and the alumina-rich bond coat TGO, leading to the formation of a mixed zone consisting of SZO and SmAlO₃. Thermal strain energy calculations show that the delamination driving force increases with TGO and mixed layer thicknesses and with coating modulus. The placement of a 10 μm thick YSZ layer between the TGO and SZO layers eliminated the mixed zone and restored the thermal cyclic life to that of YSZ structures.     

氧化物掺杂YSZ热障涂层的最新研究进展

随着先进航空发动机涡轮叶片热障涂层服役温度、服役寿命以及隔热性能的不断提升,研制温度高、使用寿命长和隔热性能优异的热障涂层材料,已成为国际高温防护涂层领域的研究热点。氧化物掺杂YSZ涂层因其良好的热学性能,成为最有可能替代YSZ涂层在航空发动机热端部件表面获得应用的热障涂层材料。综述了氧化物掺杂YSZ热障涂层研究取得的成果和存在的问题,重点阐述了不同氧化物掺杂对YSZ涂层性能的影响机理,并简述了目前国内外对该类涂层相关制备技术的研究进展。提出未来关于热障涂层的研究,应在进一步优化设计多元氧化物掺杂改性YSZ涂层的基础上,结合计算模拟,对多元氧化物掺杂的耦合作用机制进行深入剖析,同时结合新一代高温合金的性质,发展高温合金-粘结层-陶瓷层相匹配的新型热障涂层体系,从热力学-动力学两个方面考察其使役行为和失效机制,最终促进该类涂层的实际应用。     

Effects of Laser Remelting and Oxidation on NiCrAlY/8Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> Thermal Barrier Coatings

In this study, three groups of thermal barrier coatings (TBCs) samples were remelted by CO₂ laser with different laser energy densities (1, 5 and 10 J/mm²) to seal the surface of yttria-stabilized zirconia (YSZ) coatings. Microscopic observations showed that the cracks size and the remelted depth in YSZ coatings increased. A ~ 50-μm-thick dense layer was formed on the surface of YSZ coating in samples with 1 J/mm² energy density. Microindentation tests showed that the Vickers hardness of YSZ coatings increases with the increase in laser energy density. After isothermal oxidation at 1200 °C for 200 h, thinner thermally growth oxides were found in laser remelted YSZ samples under energy density of 1 J/mm² (6.32 ± 0.28 μm). Cyclic oxidation results showed that the weight gain per unit area of low energy density laser remelted TBCs was smaller than that of the high energy density laser remelted and as-sprayed TBCs.     

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.     

SiC/SiC–YAG–YSZ oxidation protective coatings for carbon/carbon composites

SiC/SiC–YAG–YSZ coatings were prepared by pack cementation, chemical vapor deposition and slurry painting on carbon/carbon (C/C) composites. The microstructures and oxidation behavior of coatings were investigated. The results show that the coatings displayed good oxidation and thermal shock resistance due to a dense glassy layer with silicates formed on the coating of SiC–YAG–YSZ. The weight gain rate of coated C/C composites was 1.77% after oxidation for 150 h at 1773 K. SiC in outer coating can promote the formation of oxygen diffusion barrier and lead to the optimum oxidation resistance for the coatings, compared with YSZ and YAG.     

Fabrication and Characteristics of YSZ�CYSZ/Al2O3 Double-Layer TBC

A novel YSZ?CYSZ/Al₂O₃ (YSZ means 6 wt% yttria partially stabilized zirconia) double-layer thermal barrier coating was fabricated using composite sol?Cgel and pressure filtration microwave sintering (PFMS) technologies. In this double-layer coating, the top layer was YSZ ceramics with a thickness of about 150 ??m and the bottom layer was composed of micro-sized YSZ particles packed by nano-sized ??-Al₂O₃ films and had a thickness of about 10 ??m. Cyclic oxidation tests indicated that this coating possessed superior properties to resist oxidation of alloy and spallation of coating. These beneficial effects could be mainly attributed to that, the alloy substrate could be sealed completely by ??-Al₂O₃ phase and the thermal stress could be decreased by means of better thermal matching and nano/micron structure in YSZ/Al₂O₃ layer. Moreover, thermal insulation capability tests indicated that the thermal barrier effect was improved due to the application of YSZ/Al₂O₃ layer. YSZ/Al₂O₃ layer could be considered as a promising bond coat in TBCs.     

Preparation of YSZ coatings by thermal pressure and filtration of sol-gel paint (TPFSP) for thermal barrier application

Thick YSZ ceramic coatings were prepared by thermal pressure and filtration of sol-gel paint (TPFSP), a modified sol-gel composite coating technique. SEM results show that the coatings were dense and crack-free by using paints of high mass ratios of YSZ powder to Zr-Y oxide in sol and high pressures. And the cross-sectional detail of coatings exhibited that the microstructure was consisted of micro/nano-size ceramic particles and micro-pores. The thermal insulation tests indicated that mass ratio of YSZ powder to Zr-Y oxide in sol was in inversely linear relationship with temperature drop per micron thickness. The coating showed good adherence with alloy substrate and maintained structural integrity when exposed at 1050 °C for 200 h. The cyclic oxidation test also indicated that both of oxidation resistance and spallation resistance for YSZ coated specimens were greatly improved. The TPFSP process could be a promising method to prepare TBCs for wide applications.     

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.     

Effect of Bond Coats on Thermal Shock Resistance of Thermal Barrier Coatings Deposited Onto Polymer Matrix Composites Via Air Plasma Spray Process

Thermal barrier coating systems with different bond coats were fabricated on polymer matrix composites via the air plasma spray process. During a thermal shock test at 400 °C, Zn and Al interlayers were helpful in improving the thermal shock resistance of coatings due to the low melting point. The coating system consisted of a soft zinc layer as a bond coat, and YSZ as a top coat exhibited the best thermal shock resistance, attributed to the lower residual stress and lower thermal stress in the Zn interlayer. The failure mechanism of the coating system was mainly ascribable to the residual stress derived from the deposition process, thermal stress, and further damage of the substrate.     

合金钢热障涂层等离子喷涂及高温力学特性研究

目的研究等离子喷涂热障涂层微观组织与高温力学性能,为热障涂层在合金钢的应用及其失效机制提供理论支撑。方法采用等离子喷涂技术在30Cr Mn Si A钢基体上制备Ni Co Cr Al Y/YSZ热障涂层,利用扫描电镜显微观察、物相分析、热震试验、拉伸试验等技术方法,考察涂层在高温条件下的失效行为。结果合金钢等离子喷涂热障涂层为典型双层层片状结构,YSZ涂层仅含有稳定四方相。800℃时,涂层试样拉伸试验后的断裂载荷与无涂层试样相比高10%。热障涂层的抗热震性良好,经900℃热震循环试验10次后,涂层完好;经1000℃热震循环6次后,涂层剥落失效,剥落面位于粘结层与基体之间。热震循环过程中,钢基体被氧化甚至腐蚀。涂层试样边缘产生应力集中,随着热震次数的增加,裂纹逐渐扩展,最终导致涂层成块剥落。温度由700℃升至900℃,Ni Co Cr Al Y涂层硬度下降幅度大于YSZ涂层和30Cr Mn Si基体。结论粘结层与钢合金基体的热膨胀不匹配是导致热震试验涂层剥落的主要原因。热障涂层的隔热作用使涂层试样的基体温度较低,导致其断裂载荷与无涂层试样相比较高。     

CMAS渗入对等离子喷涂YSZ热障涂层形貌的影响*

研究了等离子喷涂不同结构YSZ涂层在CMAS渗入作用下的形貌演变规律。对带有模拟CMAS沉积物的YSZ涂层进行高温热处理试验,并在低CMAS输送量条件下对YSZ涂层进行冲刷试验,试验后涂层均出现了严重的层间剥离失效。通过试验前后涂层的截面形貌及Raman光谱分析,结果表明:涂层的显微形貌变化主要表现在高温下熔融态CMAS沿涂层表面微裂纹和孔隙渗入内部,引起YSZ陶瓷层孔隙收缩、表层致密化,同时在涂层表面粘附的CMAS耦合作用下,YSZ涂层表层中产生大量横向微裂纹和明显分层;另外,YSZ涂层表层在CMAS中溶解并导致YSZ加速相变失稳也是影响涂层形貌变化和过快失效的因素之一。CMAS沉积层厚度增加时,同等条件下CMAS对涂层失效的影响会加剧。