热障涂层应力与失效机理若干关键问题的研究进展与评述

综述了热障涂层应力数值模拟类研究的现状。在此基础上,总结归纳了数值模拟类研究的三个关键性问题:热生长氧化物、材料非线性特性、涂层应力状态与失效机理的内在联系。分别探讨了热生长氧化物的生成对于涂层系统内部应力以及失效模式的影响;涂层蠕变特性对于涂层系统内应力的缓解机制;对比分析了APS/EB-PVD两种不同制备方法所制备的热障涂层的失效模式,总结归纳了涂层系统应力状态与其失效机理的内在联系。最后,探讨了当前传统8YSZ热障涂层的发展瓶颈,明确了未来热障涂层的发展将落在探索新型低热导率隔热材料、探索合理的热障涂层体系两个方面。着重介绍了新型双陶瓷层热障涂层,总结了双陶瓷层热障涂层几个重要的研究问题。对于研究新型热障涂层的应力状态及其失效行为、优化涂层结构,有限元数值模拟仍是一种重要的研究手段。     

铂铝黏结层体系EB-PVD热障涂层的热循环行为

在镍基单晶高温合金基体上采用化学气相沉积法制备铂铝金属黏结层,并采用电子束物理气相沉积制备氧化钇部分稳定化的氧化锆(YSZ)陶瓷面层。研究了黏结层相组成对热障涂层循环氧化行为的影响,借助扫描电子显微镜(SEM)、X射线能谱分析(EDS)和X-射线衍射分析(XRD)等方法分析涂层的相结构、显微组织和化学成分。结果表明：黏结层主要成分包括Ni、Al、Pt、Co和Cr元素并由β-(Ni,Pt)Al相和PtAl₂相组成;经热循环测试后,涂层在热生长氧化物(TGO)和黏结层内部及其界面可能出现剥离;随着热暴露时间的延长,TGO层处的残余应力总体上呈现出逐渐减小的演变趋势;控制铂铝黏结层前驱体活性、Pt/Al元素含量、抑制脆性PtAl₂相生成、改善TGO层/黏结层界面韧性和降低TGO层应力应变水平可有效延长铂铝黏结层体系热障涂层的热循环寿命。     

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.     

基体曲率对热障涂层结合强度影响的无损检测研究

 针对复杂型面航空发动机涡轮叶片表面热障涂层(TBCs)的失效问题,采用交流阻抗谱(IS)法和洛氏硬度(RH)压痕法对比研究了制备在平板基体和曲率基体上,热障涂层在热循环过程中微观结构和界面结合强度的演变规律。交流阻抗谱法的结果表明:两种涂层试样的热生长氧化(TGO)层厚度及陶瓷层内裂纹数量均随着热循环时间增加而增长,但曲率试样的微观结构恶化速度更快;洛氏硬度压痕法的结果验证了经热循环后,曲率基体上热障涂层界面结合强度低于平板样品。     

PS–PVD制备YSZ热障涂层的CMAS腐蚀行为研究

热障涂层（TBCs）广泛应用于先进航空发动机热端部件,有效延长了发动机热端部件的服役寿命,成为先进航空发动机必不可少的热防护材料。但在服役过程中一些大气沉积物CMAS加热后变为熔融体吸附在热障涂层表面,并沿着孔隙和裂纹等缺陷渗透至涂层内部,诱导涂层过早失效。采用等离子–物理气相沉积技术（PS–PVD）制备YSZ热障涂层,利用XRD、SEM等表征手段,对不同腐蚀时间的涂层物相成分、微观结构进行了表征。研究结果表明,YSZ涂层在1250℃下经过CMAS腐蚀后发生了相变;随着腐蚀时间的增加,CMAS沉积物会沿着热障涂层类柱状晶间隙渗透至内部,导致涂层结构出现疏松,并且在陶瓷层上部区域出现了类柱状晶断裂现象,涂层宏观表现为部分陶瓷层剥落;腐蚀8 h后陶瓷层部分区域出现了类柱状晶从粘结层上整体剥离;CMAS渗透深度随腐蚀时间的增加不断加大,在腐蚀3 h内其渗透速度相对较快,腐蚀3 h以后其渗透速度会相对变得缓慢。     

粘结层表面预处理对EB-PVD热障涂层循环氧化的影响

研究了在Ni3Al基高温合金基底上采用阴极电弧镀方法制备NiCoCrAlYHf粘结层、电子束物理气相沉积(EB PVD)方法制备Y2O3 ZrO2陶瓷层的热障涂层(TBCs)在1150～30℃之间的热循环氧化行为。通过对热循环过程中热障涂层界面韧性的测试和氧化行为的研究,分析了粘结层表面预处理工艺(喷丸和吹砂)对热障涂层使用寿命的影响。由于喷丸和吹砂会降低热障涂层的界面韧性,同时又促进了热生长氧化物(TGO)的生长,这些预处理工艺不利于提高热障涂层的寿命。     

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。     

稀土氧化物改性氧化锆/铂铝热障涂层的制备及其高温性能

针对我国某型航空发动机涡轮叶片用DZ125与DZ406高温合金,开展了稀土氧化物改性氧化锆/铂铝热障涂层体系的制备工艺及涂层高温性能研究。采用电镀Pt和气相渗铝的工艺制备了PtAl金属粘结层,研究了镀Pt前处理、不同镀Pt层厚度以及渗铝温度等关键工艺参数对涂层的微观结构和抗高温氧化性能的影响规律。采用优化后的涂层工艺制备的PtAl粘结层在1150℃时的抗氧化性能优异。采用电子束物理气相沉积（EB–PVD）在PtAl粘结层表面制备了稀土氧化物改性的氧化锆（GYb–YSZ）陶瓷涂层。由GYb–YSZ和Pt Al组成的热障涂层在1050℃热循环4320次（1050℃保温时间720 h）后,涂层表面状态完好,未发现明显剥落现象,表明该热障涂层体系具备良好的热循环性能。     

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.     

基于近场动力学理论的热障涂层热冲击开裂行为

为研究热障涂层热冲击后损伤行为,设计并完成了陶瓷基热障涂层(TBC)的热冲击试验,研究了热障涂层损伤规律,分析了热冲击温度对损伤的影响。基于近场动力学(PD)理论,推导了热障涂层的热力耦合计算列式,编程计算了热障涂层的温度响应和裂纹扩展过程,分析了冲击温度对热障涂层损伤的影响。结果表明：纵向裂纹从陶瓷层表面萌生,沿厚度方向扩展到陶瓷层/粘结层界面附近,部分裂纹出现分叉和转向的现象,形成了与界面平行的横向裂纹;随热冲击温度提高,涂层中纵向裂纹萌生时间提前且数量增加,纵向裂纹数量在0.50 s时达到峰值。近场动力学方法可较好地捕捉热障涂层内部纵向裂纹和横向裂纹的萌生与扩展现象,且裂纹位置、裂纹形式及不同参数对涂层损伤的影响规律与试验符合较好。     

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.     

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。     

长寿命热障涂层的剥落机理及抗剥落结构设计

涂覆于高温合金热端部件表面的热障涂层,具有隔热防护作用,属新一代燃气轮机的关键核心技术。等离子喷涂制备的热障涂层隔热性能好,但长时间高温服役后存在开裂剥落问题,引发基体烧蚀、造成巨大经济损失。因此,发展长寿命热障涂层是该技术领域的重大难题。本文从等离子喷涂热障涂层的独特层状结构特征入手,阐述涂层在高温服役中结构和性能的演变规律,揭示涂层剥落失效机理,总结长寿命热障涂层设计方法。研究表明,等离子喷涂热障涂层呈现以连通2D孔隙为主的层状多孔结构,具有优异的隔热功能和协调应变能力。然而,涂层在高温服役中发生烧结,2D孔隙大量消失,涂层显著刚化,使热障涂层开裂驱动力急剧增加,引发微观裂纹扩展并贯通形成大尺度裂纹,导致涂层最终剥落失效。据此,分别从降低开裂驱动力和增加开裂阻力两方面着手,总结抗开裂新结构涂层设计方法,为研发长寿命热障涂层指明了发展方向。在未来研究中,如何保证涂层高隔热和长寿命并同时兼顾经济性,是发展新一代高性能热障涂层的重点方向。     

Hot Corrosion Behavior of Double-ceramic-layer LaTi2 Al9O19/YSZ Thermal Barrier Coatings

LaTi 2 Al 9 O 19 (LTA) exhibits promising potential as a new kind of thermal barrier coating (TBC) material, due to its excellent high-temperature capability and low thermal conductivity. In this paper, LTA/yttria stabilized zirconia (YSZ) TBCs are produced by atmospheric plasma spraying. Hot corrosion behavior and the related failure mechanism of the coating are investigated. Decomposition of LTA does not occur even after 1 458 hot corrosion cycles at 1 373 K, revealing good chemical stability in molten salt of Na 2 SO 4 and NaCl. However, the molten salt infiltrates to the bond coat, causing dissolving of the thermally grown oxide (TGO) in the molten salt and hot corrosion of the bond coat. As a result, cracking of the TBC occurs within the oxide layer. In conclusion, the ceramic materials LTA and YSZ reveal good chemical stability in molten salts of Na 2 SO 4 and NaCl, and the bond coat plays a significant role in providing protection for the component against hot corrosion in the LTA/YSZ TBCs. LTA exhibits very promising potential as a novel TBC material.     

Effect of Sintering on Thermal Conductivity and Thermal Barrier Effects of Thermal Barrier Coatings

Thermal barrier coatings (TBCs) are mostly applied to hot components of advanced turbine engines to insulate the components from hot gas. The effect of sintering on thermal conductivity and thermal barrier effects of conventional plasma sprayed and nanostructured yttria stabilized zirconia (YSZ) thermal barrier coatings (TBCs) are investigated. Remarkable increase in thermal conductivity occurs to both typical coatings after heat treatment. The change of porosity is just the opposite. The grain size of the nanostructured zirconia coating increases more drastically with annealing time compared to that of the conventional plasma sprayed coating, which indicates that coating sintering makes more contributions to the thermal conductivity of the nanostructured coating than that of the conventional coating. Thermal barrier effect tests using temperature difference technique are performed on both coatings. The thermal barrier effects decrease with the increase of thermal conductivity after heat treatment and the decline seems more drastic in low thermal conductivity range. The decline in thermal barrier effects is about 80 °C for nanostructured coating after 100 h heat treatment, while the conventional coating reduces by less than 60 °C compared to the as-sprayed coating.     

热载荷下热障涂层表-界面裂纹间的相互影响

针对高温热载荷条件下APS制热障涂层裂纹失效问题,基于涂层系统热弹、热弹塑性本构关系,考虑陶瓷层/氧化层/粘结层界面凹凸形貌,依据表、界面裂纹位置、性质不同,分别运用断裂力学和损伤力学理论建立裂纹演化模型,结合围线积分和内聚力单元法,分析了热载荷下表、界面裂纹断裂参量及开裂状态,研究了陶瓷层表面裂纹与粘结层/氧化层界面裂纹间的相互影响,揭示了热、力、化多场耦合下的裂纹失效机理。结果表明,表面裂纹大幅改变界面微区域的应力分布状态,靠近界面时能使界面裂纹扩展程度整体增加20%,且相邻凸峰处开裂非均匀性可达81%,表面裂纹断裂参量主要受多层结构热失配及缺陷主导,界面裂纹对其影响相对较小,分析结果与试验结果一致。      

热障涂层的激光表面改性参数优化和结构设计

热障涂层是航空发动机涡轮叶片关键核心技术之一,但在服役条件下常受环境沉积物、熔盐等的腐蚀而过早失效。激光表面改性是一种提高涂层抗腐蚀性能的有效办法,但改性涂层的激光工艺优化和结构设计亟待研究。本文采用脉冲Nd：YAG激光系统对Y₂O₃部分稳定ZrO₂（YSZ）热障涂层进行表面改性,研究了激光功率、扫描速度以及光束长度对改性层厚度、微观结构的影响。结果表明,激光改性层呈致密的柱状晶结构,并有纵向裂纹贯穿其中。改性层的厚度与激光功率成正比,受扫描速度影响不大,与光束长度成反比。激光功率过高,则改性层裂纹增加明显;光束长度过大,则改性层与下方涂层的界面缺陷增多,不利于界面结合。优化的激光改性参数为：激光的功率为75~80 W,扫描速度8 mm/s,光束长度为160 mm。设计了双层激光改性层,每层中的纵向裂纹不连续,使得整个改性层中无贯穿的纵向裂纹,有助于抑制高温腐蚀熔体的内渗。     

激光重熔改性热障涂层抗CMAS腐蚀特性

采用激光对大气等离子喷涂7YSZ热障涂层进行表面重熔处理,探讨基体预热和Al₂O₃溶胶涂敷对激光重熔层裂纹愈合的影响,研究处理后热障涂层的耐CMAS熔盐腐蚀性能。结果表明:涂层经过激光重熔和基体预热后的激光重熔处理后,与未经重熔处理涂层的CMAS腐蚀厚度基本相同;而采用表面Al₂O₃溶胶涂敷加激光重熔的热障涂层的CMAS腐蚀厚度明显减小,表明Al₂O₃溶胶涂敷加激光重熔工艺可以有效地减轻CMAS熔盐侵蚀,其机理是表面形成的Al₂O₃薄膜溶于CMAS后生成了难熔晶体钙长石,降低了熔盐的流动性和腐蚀性。     

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.