电子束物理气相沉积LaZrCeO热障涂层微结构与热循环性能

热障涂层(thermal barrier coatings,TBCs)是一种由金属黏结层、热生长氧化物层和陶瓷面层组成的金属-陶瓷复合系统,在先进的航空发动机领域上引起了广泛的关注,但目前先进热障涂层的热循环寿命提升和失效行为研究仍然是一个难点。本研究采用电子束物理气相沉积技术(electron beam physical vapour deposition,EB-PVD)制备LaZrCeO/YSZ双陶瓷层热障涂层,研究热障涂层的相结构、显微组织和失效行为。结果表明:LaZrCeO/YSZ涂层为烧绿石与萤石结构组成的复合涂层材料,LaZrCeO/YSZ涂层的微观结构由羽毛状纳米结构和柱内孔隙组成;在1100℃热循环条件下,LaZrCeO/YSZ双陶瓷层热障涂层展现了良好的热循环寿命;热循环实验后,由于应力累积的作用裂纹在热生长氧化层(TGO)中萌生并扩展,包括水平裂纹和垂直裂纹两大类,进而引起整个涂层体系的不稳定,最终导致涂层失效。     

等离子喷涂纳米结构8%Y2O3-ZrO2热障涂层研究

研究了纳米结构8%Y2O3-ZrO2(YSZ)热障涂层(TBCs)的等离子喷涂工艺及其组织性能.使用大颗粒纳米结构8%Y2O3-ZrO2粉末,在一定的等离子热喷涂条件下制备出纳米结构TBCs,然后分别进行1 000℃、1 100℃和1 200℃至室温(约20℃自来水)的热震试验,通过光学金相、扫描电镜、透射电镜等分析手段,对涂层进行了形貌、微观结构分析.结果表明,同传统的微米粉体制备的传统TBCs比较,纳米结构TBCs热震寿命更高.     

等离子喷涂纳米陶瓷热障涂层组织与性能

采用纳米陶瓷粒子团聚体粉末等离子喷涂制备纳米陶瓷热障涂层,研究了纳米陶瓷热障涂层的组织和性能.试验表明,采用纳米结构的陶瓷涂层有利于增加热障涂层的高温使用寿命.     

梯度热障涂层的设计

 采用电子束物理气相沉积方法 (EB PVD)制备了梯度热障涂层,其结构设计为NiCoCrAlY粘结层 /Al₂O₃ YSZ过渡层 /YSZ陶瓷层。YSZ陶瓷层的结构为柱状晶结构,Al₂O₃ YSZ梯度过渡层为梯度微孔结构。采用有限元方法对梯度热障涂层进行热应力分析,优化了Al₂O₃ YSZ梯度过渡层的组成。计算结果表明,梯度涂层的内应力显著降低,而且界面及其附近应力和应变变化较平缓。过渡层厚度的增加有利于降低涂层内应力和缓和涂层界面处的应力集中。     

双陶瓷层热障涂层3.5％Y2O3-La2(Zr0.7Ce0.3)2O7/YSZ研究

采用EB-PVD沉积了3.5％Y2O3-La2(Zr0.7Ce0.3)2O7(3.5Y-LZ7C3)/YSZ双陶瓷热障涂层,分析了涂层的成分、相结构、组织形貌和热循环氧化性能.研究表明:La2(Zr0.7Ce0.3)2O7(LZ7C3)材料中掺杂Y2O3能有效地降低涂层中La2O3/ZrO2/CeO2的成分偏差;双陶瓷涂层在1050℃下氧化增重动力学为M=0.1219t1/3,相比抛物线型YSZ涂层的氧化增重曲线,较大减缓了氧化速度;沉积态双陶瓷涂层表面结构(即3.5Y-LZ7C3涂层结构)为烧绿石结构,经过热循环后逐渐分解,出现了萤石结构以及La2O3的衍射峰;在1050℃双陶瓷层热循环氧化寿命达768h.     

激光重熔等离子喷涂纳米氧化锆热障涂层组织与性能

采用等离子喷涂纳米氧化锆(ZrO_2-8%Y_2O_3)团聚粉末制备了纳米氧化锆热障涂层,利用连续CO_2激光对其进行重熔处理.以常规热障涂层作为比较对象,研究了纳米氧化锆热障涂层和激光重熔涂层的组织结构、硬度、抗热冲击性能.结果表明:纳米氧化锆热障涂层组织结构为独特的纳米-微米复合结构,主要有柱状晶和未熔融或部分熔融纳米颗粒组成;激光重熔热障涂层的组织结构为表面等轴晶+断面柱状晶.硬度试验和抗热冲击性能试验综合比较结果显示:相对于常规氧化锆热障涂层,纳米氧化锆热障涂层和激光重熔热障涂层拥有更好的性能.因此将纳米技术和激光重熔表面处理技术与等离子喷涂技术结合起来制备热障涂层是提高热障涂层性能的非常有前景的工艺方法.     

ZrO2陶瓷热障涂层显微结构及隔热性能研究

用电子束物理气相沉积法(EB-PVD)在DZ125高温合金上制备Y2O3部分稳定化的ZrO2(YSZ)陶瓷热障涂层,并用扫描电镜(SEM)观察涂层显微结构.采用激光脉冲法对EB-PVD热障涂层的热扩散系数进行测试.为防止热扩散系数测试时激光穿透ZrO2陶瓷层,在试样表面制备不同材料的遮挡层.结果表明,EB-PVD热障涂层呈明显的柱状晶结构,柱状晶垂直于涂层/基体界面.基体的热扩散系数随温度的升高而急剧增加,陶瓷热障涂层的热扩散系数随温度的升高呈下降趋势,但变化幅度不大.室温下陶瓷层的热扩散系数小于基体的1/3,1200℃时约为基体的1/67.试样的激光遮挡层很好解决了激光脉冲法测试涂层热扩散系数时的不稳定性和激光穿透问题.在满足遮挡要求的条件下,遮挡层材料种类对热扩散系数测试无明显影响.     

钛合金基体EB-PVD热障涂层的制备与初步研究

在TC11钛合金上制备两种以NiCoCrAlY为粘结层,8wt%Y2O3-ZrO2(YSZ)为陶瓷层的热障涂层,粘结层制备技术分别为电子束物理气相沉积(EB-PVD)和超音速火焰喷涂(HVOF),陶瓷层由EB-PVD同炉沉积.两种热障涂层的微结构、显微硬度及热循环测试表明,EB-PVD制备的粘结层均匀致密,上层YSZ组织细密,硬度较高,而HVOF获得的粘结层疏松不均,上层YSZ晶粒粗大,硬度较低;前者有较好的抗热冲击性能,裂纹较分散,防护性能较好,而后者易开裂剥落,裂纹密集,防护性能较差.     

电子束物理气相沉积Nd2O3和Yb2O3共掺杂的YSZ热障涂层研究

采用固相烧结的方法制备了10 mol% Nd2O3和Yb2O3共掺杂的YSZ(3.5 mol% Y2O3部分稳定的ZrO2)材料.掺杂材料为t/t'相,而8YSZ则为t/t'与m的混合相.测试结果表明:1 100 ℃时掺杂材料的热扩散系数为4.10×10-7 m2/s,而8YSZ(8 wt.% Y2O3部分稳定的ZrO2)的则为6.41×10-7 m2/s.在200～1 300 ℃温度范围内,掺杂材料的比热容均大大低于8YSZ.电子束物理气相沉积的掺杂材料的热障涂层陶瓷层为树枝晶结构.1 100 ℃下,掺杂材料的热障涂层热循环寿命为350～500 h,而同等条件下8YSZ涂层仅为160～200 h.     

电子束物理气相沉积YSZ热障涂层热循环性能

考察了YSZ热障涂层的抗热循环性能;分别利用SEM、XRD分析了热循环前后涂层的显微结构和相组成。经分析可知,YSZ热障涂层具有典型的柱状晶结构,沉积态时YSZ涂层为t/t′相,经过600次热循环后,YSZ涂层未发现脱落。     

Effects of Shot Peening Process on Thermal Cycling Lifetime of TBCs Prepared by EB-PVD

Conventional two-layered thermal barrier coatings (TBCs) are prepared by electron beam physical vapor deposition (EB-PVD) with ZrO2-8 wt% Y2O3 (8YSZ) as top coat and CoCrAlY as bond coat on disk-shaped Ni based super-alloy. In this paper, three kinds of shot peening process with different lengths of operating time were adopted for bond coating. As a result, changes took place in its sur- face roughness and the surface micro-hardness. A thermal cycling test at 1 273 K×55 min and another at room temperature for 5 min were performed to study the effects of shot peening process on the thermal cycling lifetime of TBCs. It is found that a moderate shot peening process will be able to prolong the life time. The oxidation dynamic of the as-processed TBCs basically accords with the para- bolic rule, and the oxidation test also attests to the spallation between YSZ and thermal growth oxide (TGO) responsible mainly for the failure of TBCs.     

7YSZ coating prepared by PS-PVD based on heterogeneous nucleation

Plasma spray-physical vapor deposition (PS-PVD) as a novel coating process based on low-pressure plasma spray (LPPS) has been significantly used for thermal barrier coatings (TBCs). A coating can be deposited from liquid splats, nano-sized clusters, and the vapor phase forming different structured coatings, which shows obvious advantages in contrast to conventional technologies like atmospheric plasma spray (APS) and electron beam-physical vapor deposition (EB-PVD). In addition, it can be used to produce thin, dense, and porous ceramic coatings for special applications because of its special characteristics, such as high power, very low pressure, etc. These provide new opportunities to obtain different advanced microstructures, thus to meet the growing requirements of modern functional coatings. In this work, focusing on exploiting the potential of gas-phase deposition from PS-PVD, a series of 7YSZ coating experiments with various process conditions was performed in order to better understand the deposition process in PS-PVD, where coatings were deposited on different substrates including graphite and zirconia. Meanwhile, various substrate temperatures were investigated for the same substrate. As a result, a deposition mechanism of heterogeneous nucleation has been presented showing that surface energy is an important influencing factor for coating structures. Besides, undercooling of the interface between substrate and vapor phase plays an important role in coating structures.     

High-temperature oxidation behavior and analysis of impedance spectroscopy of 7YSZ thermal barrier coating prepared by plasma spray-physical vapor deposition

Quasi-columnar structure 7YSZ(yttria stabilized zirconia) thermal barrier coatings(TBCs) are prepared by plasma spray-physical vapor deposition(PS-PVD) onto pretreated and un-pretreated bond coating, respectively. An isothermal oxidation experiment of 7YSZ TBCs is carried out in the atmosphere of 950 °C in order to simulate the high-temperature oxidation process of engine blades. The isothermal oxidation process of 7YSZ thermal barrier coatings is investigated systematically by impedance spectroscopy. The electrochemical physical model and equivalent circuit of columnar 7YSZ coatings are established. Results show that the isothermal oxidation kinetic curve of columnar 7YSZ thermal barrier coatings appears to follow the parabolic law. A pretreatment of bond coating can reduce the growth rate of the thermally grown oxide(TGO) layer, restraining the initiation and propagation of microcracks between YSZ and TGO layers. The oxidation rate constants of 7YSZ coatings with pretreated and un-pretreated bond coating are 0.101×10~(-12) cm~2·s~(-1) and 0.115 × 10~(-13) cm~2 ·s~(-1), respectively. Impedance analysis shows that the content of oxygen vacancies decreases and the density increases after the TGO layer is oxidized for 150 h. In addition, shrinkage microcracks formed by sintering during the oxidation process is the main reason for an increase of the capacitance and a decrease of the resistance in the grain boundary of YSZ.     

电子束物理气相沉积La2Zr2O7热障涂层研究

为克服传统热障涂层材料YSZ耐温性能和隔热性能的不足,以ZrO2和La2O3为原料,采用无压烧结法合成了烧绿石结构化合物La2Zr2O7,用电子束物理气相沉积(EB-PVD)法在高温合金基体上制备了La2Zr2O7涂层,分析了涂层的成分,并对其显微结构、热物理性能与传统YSZ热障涂层进行了对比研究.结果表明,La2Zr2O7涂层成分处于P结构范围内,呈典型的柱状晶结构,柱状晶头部呈明显的金字塔形状.与传统YSZ柱状晶相比,La2Zr2O7涂层的柱状晶紊乱度更大,尺寸更加细小,并且柱状晶上的树枝状亚晶更多.在25～1200℃范围内,La2Zr2O7涂层的热导率最大为0.985W/(m·K),最小为0.796 W/(m·K),大大低于同条件下的YSZ涂层.低本征热导率、小柱状晶直径、大紊乱度、密度轻及高孔隙率是造成La2.Zr2O7涂层低热导率的主要因素.     

Failure of EB-PVD Thermal Barrier Coatings Subjected to Thermo-Mechanical Loading

Thermal barrier coatings (TBCs) were developed to protect metallic blades and vanes working in turbo-engines. The two-layered structure TBCs, consisting of NiCoCrAlY bond coat and yttria stabilized zirconia (YSZ), were deposited on a cylinder of superalloy substrate by the electron beam-physical vapor deposition (EB-PVD). The failure mechanism of the TBCs was investigated with a thermo-mechanical fatigue testing system under the service condition similar to that for turbine blades. Non-destructive evaluation of the coated specimens was conducted through the impedance spectroscopy. It is found that the crack initiation mainly takes place on the top coat at the edge of the heated zones.     

等离子喷涂工艺参数对GdPO4热障涂层组织结构和结合强度的影响

随着航空发动机涡轮进口温度提升,目前最广泛使用的Y₂O₃部分稳定ZrO₂(YSZ)热障涂层(TBCs)已难以满足需求,亟须发展新一代超高温TBCs。GdPO₄是一种极具应用前景的TBCs材料。本工作采用等离子喷涂方法制备GdPO₄/YSZ双陶瓷层结构TBCs,研究喷涂工艺参数特别是喷涂功率对GdPO₄陶瓷涂层相组成、表面形貌、微观结构以及结合强度的影响。结果表明:等离子喷涂GdPO₄过程中会有元素P损耗,得到的涂层除了GdPO₄外,还有一些Gd₃PO₇相;随着喷涂功率降低,Gd₃PO₇相含量减少;GdPO₄陶瓷涂层的主体结构由充分熔融的喷涂粒子堆垛构成,其中镶嵌有未熔化粒子构成的微区;随着喷涂功率降低,未熔化微区增多,涂层厚度降低;GdPO₄/YSZ TBCs的结合强度随喷涂功率降低而减小,主要是由于未熔化微区增多降低了涂层的内聚力;因此,低喷涂功率不利于涂层的结合强度。     

航空发动机热障涂层材料体系的研究

介绍了热障涂层的结构、陶瓷表层材料和中间粘结层的材料发展趋势。热障涂层的结构已由经典的双层结构向成分、结构连续变化的梯度结构发展,涂层的寿命有明显的提高。制备方法中电子束物理气相沉积技术具有明显优势。热障涂层表层材料的最佳成分是(质量百分数6%～8%)Y2O3部分稳定的ZrO2陶瓷材料。粘结层体系发展的一个重要趋势是能同时保证力学性能和抗氧化性能的低Al含量NiCoCrAlY。     

Influence of Gd2O3 and Yb2O3 Co-doping on Phase Stability,Thermo-physical Properties and Sintering of 8YSZ

The role of multicomponent rare earth oxides in phase stability, thermophysical properties and sintering for ZrO2-based thermal barrier coatings (TBCs) materials is investigated. 8YSZ codoped with 3 mol% Gd2O3 and 3 mol% Yb2O3 (GYb-YSZ) powders are synthesized by solid state reaction for 24 h at various temperatures. As temperature increases, stabilizers are dissolved into zirconia matrix gradually. Synthesized at 1 500 °C, GYb-YSZ is basically composed of cubic phase. GYb-YSZ exhibits excellent phase stability and sinters lower than 8YSZ by nearly three times. The thermal conductivity of GYb-YSZ is much lower than that of 8YSZ, and the thermal expansion coefficient of GYb-YSZ is comparable to that of 8YSZ. The influence of Gd2O3 and Yb2O3 co-doping on phase stability, thermal conductivity and sintering of 8YSZ is discussed.