高温合金热障涂层的氧化和失效研究

评述了热障涂层发展的现状，研究了电子束物理气相沉积（EB－PVD）热障涂层的恒温氧化和循环氧化行为。结果表明：热障涂层 1000℃氧化稳定后，基本遵循抛物线氧化规律。循环氧化过程中，微裂纹优先沿陶瓷层柱状晶界形成，并逐渐沿横向及纵向扩展。热障涂层热循环过程中产生的热应力、氧化物长大应力等引起金属氧化物（TGO）／粘结层分界面多处开裂，最终导致热障涂层失效于TGO中或TGO／粘结层的分界面。     

EB-PVD热障涂层的结构演变与表面拉曼光谱特性

热障涂层被广泛应用于航空发动机和燃气轮机等高温部件,其破坏机理和无损检测手段是研究中急需解决的问题。采用EB-PVD方法制备了陶瓷层厚度分别为180、120和90μm的3组热障涂层试样,经1 000℃高温氧化0、1、10、50和100h后,用HR800激光显微拉曼光谱仪测得试样表面的拉曼光谱特性,利用扫描电镜(SEM)观测了试样内部裂纹及氧化层(TGO)厚度的演变。研究表明,EB-PVD热障涂层裂纹主要发生在陶瓷层内部及陶瓷层与粘结层的界面处,粘结层和基体界面处产生裂纹的概率相对较小;同等条件下,增大陶瓷层的喷涂厚度,可以减缓氧化层的生长速度,但是会增大陶瓷层表面应力;热障涂层表面残余应力会随着热氧化时间的增加而增大,当表面残余应力减小时表明陶瓷层中有明显的裂纹或脱落产生。     

粘结层真空退火处理对热障涂层热循环寿命的影响研究

目的研究粘结层真空退火处理对热障涂层热循环条件下服役性能的影响。方法在某二代镍基单晶高温合金上涂覆铂铝粘结层,然后采用电子束物理气相沉积法沉积氧化钇稳定的氧化锆陶瓷层,构建热障涂层体系,在1100℃下可自动升降的循环氧化炉中进行热循环测试,通过高精度电子天平对涂层样品进行称量并绘制质量变化曲线,采用拍摄宏观照片的方式观察样品表面陶瓷层剥落情况,利用扫描电子显微镜观察沉积态及热循环后的样品截面微观组织结构形貌。结果与沉积态粘结层相比,在高真空中进行退火处理后,热障涂层的热循环寿命几乎增加一倍,且陶瓷层与热生长氧化膜结合良好。未经过真空处理的铂铝涂层表面陶瓷层发生明显剥落,且热生长氧化膜质量较差,出现了明显裂纹。结论真空退火处理可使铂铝涂层表面更加平整,在高温氧化过程中生成的低缺陷氧化膜有更好的质量,陶瓷层与粘结层的结合力更强,热障涂层体系的服役性能和寿命得到有效提升。     

四点弯曲条件下热障涂层断裂模式的声发射表征

采用声发射技术实时监测喷涂态8% Y₂O₃稳定的ZrO₂（8YSZ）在四点弯曲载荷下的损伤断裂行为。采用特征参数分析、聚类分析和小波包变换分析声发射信号结合涂层的微观形貌和应力状态,从而推测出热障涂层系统的失效形式。结果表明：内弯和外弯两种加载模式下,均各有4种失效行为。宏观断裂对应的剥落信号无明显频带,而基底变形、表面垂直裂纹、张开型界面裂纹和剪切型界面裂纹信号对应的主频带可清晰区分为：0~156.25 kHz、156.25~234.375 kHz、312.625~390.625 kHz和390.625~468.75 kHz。热障涂层在外弯载荷下,表面垂直裂纹不断出现,随后扩展到粘结层-陶瓷层界面处并转化为张开型界面裂纹;而在内弯载荷下,则在粘结层-陶瓷层界面附近产生剪切型界面裂纹,仅出现少量的表面垂直裂纹。两种界面裂纹均会引起热障涂层的宏观裂纹和剥落。     

等离子喷涂热障涂层高温 TGO 的形成与生长研究

目的研究热障涂层(TBC)和纯粘结层(BC)在1100℃下的氧化动力学,探讨热障涂层中热生长氧化物(TGO)组织结构的演化规律。方法运用大气等离子喷涂技术(APS)制备涂层,对比分析热障涂层和纯粘结层涂层在1100℃下等温氧化2,5,10,20,50,100,200,350 h后TGO的厚度变化,并对粘结层表面和热障涂层截面分别进行XRD和SEM分析。结果热障涂层和纯粘结层在1100℃下的氧化动力学均遵循抛物线规律,其氧化速率常数分别为0.344,0.354μm/h0.5。等温氧化5 h后,TGO的主要成分为α-Al2O3;随氧化时间的增加,生成Cr2O3、尖晶石、Co O和Ni O的混合氧化物;等温氧化100 h后,Co O消失,Ni O的含量减少,Cr2O3和尖晶石氧化物的含量增加;等温氧化350 h后,TGO中出现了裂纹,但涂层仍未剥落,TGO最终由顶层多孔的混合氧化物层和底层具有柱状晶结构的α-Al2O3层组成。结论顶层陶瓷层(TC)对热障涂层氧化速率常数的影响很小。TGO中α-Al2O3首先形成并以柱状结晶的方式生长,混合氧化物在α-Al2O3上形成,TGO生长速度逐渐变缓。     

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。     

热障涂层陶瓷层/TGO界面开裂行为的有限元模拟

目的更好地理解热障涂层在热循环条件下的失效行为。方法采用有限元方法引入了内聚力模型,研究热障涂层在多次热循环条件下的界面开裂行为,并且考虑了陶瓷层厚度和粘结层厚度对界面开裂行为的影响。结果涂层最先在陶瓷层/TGO层界面的波峰与波谷之间开裂,此外在界面波谷处也存在开裂现象。当陶瓷层厚度在300~500μm范围内,界面裂纹的平均长度随陶瓷层增厚而增长,裂纹密度也随之增加。粘结层厚度为50μm时,界面裂纹的平均长度为15μm;当厚度增加到100μm时,界面裂纹平均长度减少到10μm;而厚度为150μm时,界面裂纹平均长度又提高至12μm。当粘结层与陶瓷层厚度比在0.2~0.4的范围内时,陶瓷层/TGO层界面上的最大拉应力最小。结论陶瓷层厚度和粘结层厚度对热障涂层界面开裂行为的影响极大,小厚度陶瓷层以及当粘结层与陶瓷层厚度比在0.2~0.4的范围内时,热障涂层具有更好的抗界面开裂能力。粘结层厚度不宜过大,超过一定厚度时反而会降低涂层的抗界面开裂能力。计算结果与文献报道的结果相近,证明了模拟结果的准确性。     

等离子喷涂ZrO2-NiCoCrAlY梯度热障涂层的抗热震性及失效机理

研究了ZrO2-NiCoCrAlY热障涂层的抗热震性和热震失效机理.实验结果表明,梯度热障涂层能明显延缓热震裂纹的形成和扩展,具有较高的抗热震性.热震裂纹形成与扩展主要在粘结层与基体的界面处.随热循环次数的增加,热震裂纹可在表面陶瓷层内和陶瓷层与过渡层的界面处形成.实验表明热障涂层热震失效的过程主要是裂纹形成、扩展及涂层剥落,粘结层的氧化是导致涂层剥落失效的重要原因.     

粘结层成分对单晶合金热障涂层寿命影响研究

采用电子束物理气相沉积工艺(EB-PVD)制备了针对第二代单晶高温合金的热障涂层,用SEM观察分析了不同成分粘结层的热障涂层热循环试验后的结构和晶体形貌,在N2条件下对比了不同成分粘结层材料与第二代单晶高温合金的热膨胀系数,分析了热循环试验后粘结层与热生长氧化(TGO)层成分、厚度及完整性情况。结果表明:NiCoCrAlYHf与第二代单晶高温合金热膨胀系数更为接近,匹配性更好;采用EB-PVD工艺制备的热障涂层在热循环试验过程中会产生大量垂直裂纹使涂层具有良好的应变容限;粘结层中Al元素含量的提高以及Hf等元素的加入,使得热循环试验后涂层TGO层的Al2O3纯度较高、生长缓慢无块状物生成,并且极大地改善了粘结层和合金基体的内氧化,涂层1 100℃循环氧化寿命达到1 200 h以上。     

热生长下热障涂层残余应力及失效分析

针对典型热障涂层结构以界面开裂和涂层剥落为主要失效模式,考虑界面凹凸微观形貌特征,借助材料转换的方法实现氧化生长,利用粘弹塑性有限元法,研究了氧化层热生长和蠕变等因素对热障涂层残余应力的影响,并从应力应变循环演化的角度对热障涂层系统中微裂纹的萌生位置进行了预测。结果表明,随着氧化层厚度的增大,垂直于界面方向的残余应力迅速增大;材料蠕变对热障涂层系统应力释放作用显著;从残余应力和应变演化的角度进行评价,结构中的微裂纹会率先出现在粘接层凸峰以及陶瓷层/氧化层/黏结层界面的中间位置,仿真分析结果与试验结果一致。     

Intermetallic Al-, Fe-, Co- and Ni-Based Thermal Barrier Coatings Prepared by Cold Spray for Applications on Low Heat Rejection Diesel Engines

Conventional thermal barrier coating (TBC) systems consist of a duplex structure with a metallic bond coat and a ceramic heat insulating topcoat. They possess the desired low thermal conductivity, but at the same time they are very brittle and sensitive to thermal shock and thermal cycling due to the inherently low coefficient of thermal expansion. Recent research activities are focused on the developing of multilayer TBC structures obtained using cold spraying and following annealing. Aluminum intermetallics have demonstrated thermal and mechanical properties that allow them to be used as the alternative TBC materials, while the intermetallic layers can be additionally optimized to achieve superior thermal physical properties. One example is the six layer TBC structure in which cold sprayed Al-based intermetallics are synthesized by annealing in nitrogen atmosphere. These multilayer coating systems demonstrated an improved thermal fatigue capability as compared to conventional ceramic TBC. The microstructures and properties of the coatings were characterized by SEM, EDS and mechanical tests to define the TBC material properties and intermetallic formation mechanisms.     

Constitutive modeling of a directionally solidified nickel-based superalloy DZ125 subjected to thermal mechanical creep fatigue loadings

A transversely isotropic continuum elasto-viscoplasticity model,which was developed from Chaboche's unified constitutive model,was formulated to capture the thermal mechanical creep fatigue deformation behavior of a directionally solidified nickel-based superalloy.A fourthorder tensor was introduced to model material anisotropy.In order to model the tertiary creep behavior,the Kachanov damage evolution equation was coupled into the stress tensor.Based on the test results of uniaxial tensile,fatigue,and creep loadings at isothermal temperature conditions,the material parameters are obtained.Thermal mechanical fatigue(TMF) and creep-fatigue interaction test results were used to verify the robustness of the model.Additionally,strain-temperature-dependent stress-strain responses under TMF loadings were analyzed using the present model.Under strain-controlled conditions,both of the stress ranges and mean stresses are strongly influenced by the strain-temperature phases,a key parameter for TMF tests.     

Microstructure Evolution and Interface Stability of Thermal Barrier Coatings with Vertical Type Cracks in Cyclic Thermal Exposure

In this study, the effects of intrinsic feature of microstructure in thermal barrier coatings (TBCs) with and without vertical cracks on the microstructure and mechanical properties were investigated in cyclic thermal exposure. The hardness values of TBCs with vertical cracks were higher than those without vertical cracks, showing a good agreement with microstructure. The TBC prepared without vertical cracks using the 204-NS was delaminated after 250 cycles in the cyclic thermal exposure test. The TBCs with and without vertical cracks prepared with 204 C-NS and the TBC with vertical cracks prepared with 204 NS showed a sound condition without any cracking at the interface or spalling of top coat. After the thermal exposure of 381 cycles, the hardness values were increased in the survived TBC specimens, and the thicknesses of TGO layer for the TBCs with 204 C-NS and 204 NS were measured as in the ranges of 5-9 and 3-7 μm, respectively. In the thermal shock test, the advantage of vertical cracks for thermal durability of TBC could be well investigated, showing relatively longer sustained cycles in the TBCs with vertical cracks. The TBCs with vertical cracks are more efficient in improving thermal durability than those without vertical cracks in cyclic thermal exposure.     

On the thermo-mechanical loads and the resultant residual stresses in friction stir processing operations

In friction stir welding and processing both a thermal flux and a mechanical action are exerted on the material determining metallurgical evolutions, changes in the mechanical behaviour and a complex residual stress state. In the paper, the metallurgical changes are examined through numerical simulation and experiments to highlight and distinguish the effects of thermal and mechanical loadings. A particular focus is made on the residual stresses generated during the stir processing of AA7075-T6 aluminium blanks. The predictions of FE model are validated by experimental measurements. Lastly, this paper presents an in-process quenching of the processed blanks for improved mechanical properties and microstructure.     

Evaluation of interfacial strength by an instrumented indentation method and its application to an actual TBC vane

The thermal fatigue behaviour of an air plasma sprayed thermal barrier coating was investigated. And also the interfacial strengths of thermal barrier coated specimens subjected to thermal fatigue, as well as a retired TBC vane were also evaluated by means of an instrumented indentation machine. The results indicated that, (1) the TGO grew at the interface during thermal fatigue cycle as a function of the exposure time at elevated temperature; (2) the microcracks were initiated in the top coating and at the...     

Thermal Fatigue Behavior of Thick and Porous Thermal Barrier Coatings Systems

High-temperature thermal fatigue causes the failure of thermal barrier coating (TBC) systems. This paper addresses the development of thick TBCs, focusing on the microstructure and the porosity of the yttria partially stabilized zirconia (YPSZ) coating, regarding its resistance to thermal fatigue. Thick TBCs, with different porosity levels, were produced by means of a CoNiCrAlY bond coat and YPSZ top coat, both had been sprayed by air plasma spray. The thermal fatigue resistance of new TBC systems and the evolution of the coatings before and after thermal cycling was then evaluated. The limit of thermal fatigue resistance increases depending on the amount of porosity in the top coat. Raman analysis shows that the compressive in-plane stress increases in the TBC systems after thermal cycling, nevertheless the increasing rate has a trend which is contrary to the porosity level of top coat. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

Sol-gel thermal barrier coatings: Optimization of the manufacturing route and durability under cyclic oxidation

A new promising and versatile process based on the sol-gel transformation has been developed to deposit yttria-stabilised thermal barrier coatings. The non-oriented microstructure with randomly structured pore network, resulting from the soft chemical process, is expected to show satisfactory thermo-mechanical behaviour when the TBC is cyclically oxidized. First stage of the research consists of optimizing the processing route to generate homogeneous microstructure and controlled surface roughness. The objective is to reduce, as much as possible, the size and depth of the surface cracks network inherent to the process. Indeed, the durability of the TBC when cyclically oxidized strongly depends on the sharpness of those cracks that concentrate thermo-mechanical stresses and generate detrimental propagation resulting in spallation. Cyclic oxidation tests are performed using a cyclic oxidation rig instrumented with CCD cameras to monitor in a real time basis the mechanism of crack propagation and spallation. The impact of various parameters either directly related to the processing route, e.g. the intimate microstructure of the TBC and the TBC thickness, or to the thermal loading, e.g. the oxidation temperature and the cumulated hot time, on the durability of the TBC is investigated.     

Beneficial Effect of Pt and of Pre-Oxidation on the Oxidation Behaviour of an NiCoCrAlYTa Bond-Coating for Thermal Barrier Coating Systems

The oxidation behaviour of a thermal barrier coating (TBC) system is a major concern as the growth of the thermally grown oxide (TGO) layer on the bond-coating creates stresses that greatly favour the thermal barrier spallation. To delay the loss of the thermal protection provided, research has focused on the bond-coating composition and microstructure as well as on the parameters required for a suitable pre-oxidation treatment before the deposition of the ceramic top coat. Platinum is known to enhance the oxidation/corrosion resistance of MCrAlY coatings. The effect of Pt on the oxidation behaviour of a NiCoCrAlYTa coating was assessed in this study. In addition, pre-oxidation treatments were conducted to determine if the oxidation behaviour of the modified NiCoCrAlYTa coating could be further improved.     

Miniaturized bend tests on partially stabilized EB-PVD ZrO2 thermal barrier coatings

The elastic properties of thermal barrier coatings (TBCs) are important for modelling the lifetime of these coatings. A new test setup has been developed to measure the system modulus of electron-beam enhanced physical vapour deposited (EB-PVD) TBC coatings by miniaturized bend tests.Due to the brittleness, low stiffness and small thickness of the top coat and its complex microstructure, it is difficult to measure its Young's modulus by standard mechanical testing. For this reason, a special sample material has been prepared which consists of a 1 mm thick layer of EB-PVD TBC. This material was isothermally heat treated for different times at 950 °C, 1100 °C and 1200 °C and then tested in a specially developed miniaturized bend test. The bend test setup permits mechanical tests with a high resolution in stress and strain, where the strain is measured by digital image correlation. So the stiffness of the free-standing TBC samples could be measured with a high accuracy and the sintering behaviour of the EB-PVD TBC and the consequent rise of Young's modulus could be determined. The results show a significant increase of the system modulus with heat treatment time and temperature caused by sintering of the coating. An activation energy of 220 kJ/mol for the process has been determined.In addition, the material was tested by nanoindentation in order to measure Young's modulus on a local scale, and the porosity of the samples was determined by quantitative image analysis.     

A thermographic technique for the simultaneous estimation of in-plane and in-depth thermal diffusivities of TBCs

Absolute values and anisotropy of thermo-physical and mechanical properties of TBC are significantly affected by the microstructure. The thermal properties as a function of the specific microstructure along the different directions are therefore worth studying.In the present work a thermographic technique able to estimate in a single experiment both in-plane and in-depth thermal diffusivities of TBC has been described and the results obtained on three different freestanding APS TBC samples will be compared with the in-plane elastic modulus as measured by the three-point bending test. Depending on the microstructure and on the heat propagation direction, TBC thermal diffusivity in the range of 3-7 × 10^− 7 m² s^− 1 has been found. The technique allows measuring the thermal diffusivity along two orthogonal directions highlighting, when present, any anisotropic in-plane structure.An analytical model has been applied to semi-quantitatively estimate both in-depth and in-plane thermal diffusivities of the three samples starting from quantitative image analysis characterization of sample micrographs obtained by scanning electron microscopy. The agreement between model and experimental data resulted quite satisfactory. The model accounts for the anisotropy of thermal diffusivity observed in some samples.