Oxidation behavior of γ-TiAl coated with zirconia thermal barriers

The applicability of the thermal barrier coating concept, which is an established concept for Ni-base alloys, was investigated for the first time for γ-TiAl. As potential bond coats, the following surface treatments were applied: Al-diffusion coating, Al-diffusion coating combined with short term pre-oxidation in air, short term pre-oxidation in oxygen of a rough surface finish γ-TiAl sample without aluminide coating. For the purpose of lowering the temperature of the γ-TiAl substrate surface, and thus, to prolong the life time, a zirconia thermal barrier coating (TBC) was applied on top of the above-mentioned modified TiAl surfaces. Oxidation resistance of the modified γ-TiAl alloys/TBC systems was evaluated by isothermal oxidation tests at 900 °C for 100 h in air. Whatever the pre-treatment conditions, the TBC was adherent to the oxide scale after 100 h oxidation, which was not the case for untreated γ-TiAl.     

预氧化处理对热障涂层热冲击性能及残余应力的影响

采用等离子喷涂工艺在镍基高温合金基体上制备了热障涂层(底层为MCrAlY,面层为ZrO2+ 8％ Y2O3),通过控制高真空烧结炉的氧分压对涂层进行预氧化处理,分析了预氧化处理对热障涂层热冲击性能和涂层应力状态的影响.结果表明,预氧化处理提高了粘接层的致密度,涂层组织变得均质化,降低了粘结层由于凸起尖角产生复杂应力的概率;有效干预热生长氧化物(TGO)的生长过程,降低了TGO的生长速度;热障涂层残余应力随热冲击次数的增加而增大,但经过预氧化处理的涂层应力增长幅度较缓慢,经过400次热冲击后的残余应力为492.5 MPa,未经过预氧化处理涂层热冲击350次后应力值为650.1 MPa.     

Thermal shock testing of burner cans coated with a thick thermal barrier coating

Thick (1.8 mm) thermal barrier coatings were air-plasma-sprayed onto two different substrate geometries, including small circular substrates and burner cans. Two different top-coating spray parameters were used, where the settings of the substrate temperature and the lamella thickness were varied. A segmentation crack network was found in the top coatings sprayed using a high substrate temperature and a high lamella thickness. The density of segmentation cracks was found to be independent of substrate geometry. No segmentation cracks were found in the top-coatings when a low substrate temperature and a low lamella thickness were used. In the segmented burner can, after 1000 thermal shock cycles, the segmentation crack network was still stable and no severe cracks had formed in the top coating. In the nonsegmented burner can, cracks were formed after only 35 thermal shock cycles. Among the crack types, horizontally oriented cracks were found in the top coating close to, and sometimes reaching, the bond coating. Cracks of this type are not tolerated in thermal barrier coatings because they can cause failure of the coating. Regarding the lifetime of the segmented burner can, it is believed the failure will be dependent on other mechanisms, such as bond-coating oxidation or top-coating decomposition.     

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。     

Isothermal Oxidation Behaviour of NiCoCrAlYTa Coatings Produced by HVOF Spraying and Tribomet™ Process

Protective NiCoCrAlYTa coatings are used on gas turbine single crystal superalloy blades to provide environmental resistance. They can be deposited by several processes. In this study, isothermal oxidation behaviour of NiCoCrAlYTa coatings produced by HVOF spraying and Tribomet? process and deposited on single crystal nickel-based superalloy CMSX-4 were compared between 950 and 1,150 °C for several exposure durations. Microstructure and chemical composition of both coatings were examined before and after oxidation testing and quite similar observations were made for both coating processes. The combination of phase and chemical analyses allowed the establishment of an occurrence diagram of phases for both coating processes, according to temperature and duration of exposure. The obtained diagrams seemed similar for both processes. Finally both processes appeared to be equivalent for the protection of CMSX-4 superalloy in isothermal oxidation conditions.     

Isothermal Oxidation Behavior of NiCoCrAlTaY Coating Deposited by High Velocity Air-Fuel Spraying

The performance of thermal barrier coatings is influenced by the high temperature oxidation behavior of the bond coat. In this paper, NiCoCrAlTaY bond coat was deposited by high velocity air-fuel (HVAF) spraying, and the microstructure and surface morphology of the bond coat before and after oxidation were examined to aim at developing high performance thermal barrier coatings. Results showed that the HVAF sprayed NiCoCrAlTaY coating presented a dense microstructure and some partially melted particles with a near spherical morphology were deposited on the coating surface. A uniform ??-Al₂O₃ scale was formed on the HVAF sprayed MCrAlY coating surface after the pre-oxidation treatment in an argon atmosphere. A small fraction of nodular-shaped mixed oxides was formed when the MCrAlY coating was oxidized for 100?h at 1000?°C. The amount of the mixed oxides increased less significantly after 200?h oxidation. A homogeneous ??-Al₂O₃ oxide scale was maintained over the large particles on the bond coat surface after 200?h oxidation at 1000?°C in air. A model is proposed to explain the formation of nodular-shaped mixed oxides.     

温度梯度热循环下纳米7YSZ陶瓷层结构演变

目的采用低温超音速等离子喷涂(LT-HVOF)在镍基高温合金基体(K417)上制备了NiCoCrAlYTa粘结层,使用大气等离子喷涂(APS)在粘结层上制备了纳米7%Y_2O_3-ZrO_2(7YSZ)陶瓷涂层,以获得温度梯度热循环下纳米陶瓷层的结构演变机制。方法通过燃气热冲击实验仪对热障涂层模拟真实服役条件下温度梯度热循环的工作环境,采用一维稳态热传导模型计算了热障涂层中各涂层界面的温度,探讨了在热驱动作用下等径晶粒和非等径晶粒的扩散长大机制。结果热循环次数为40次时,涂层近表面出现了烧结致密化现象,而陶瓷层底部涂层保持原来的结构。热循环次数增加到460次时,整个陶瓷层断面都发生了烧结致密化现象。结论温度是涂层烧结致密化的主导因素。涂层中当等大晶粒接触形成弯曲颈时,由于弯曲颈只受水平方向静压力作用,晶粒中原子扩散速率慢,导致晶粒长大速率较慢;而当非等大晶粒接触形成弯曲颈时,在晶粒接触弯曲颈处存在一偏大晶粒方向的剪切力,其导致晶粒向弯曲颈扩散速率增加,晶粒长大速率较快。     

Development of a Pre-Oxidation Treatment to Improve the Adhesion between Thermal Barrier Coatings and NiCoCrAlY Bond Coatings

High-temperature coating systems, consisting of a René N5 superalloy, a Ni–23Co–23Cr–19Al–0.2Y (at.%) bond coating (BC), and a yttria (7 wt%)-stabilized zirconia (YSZ) thermal barrier coating (TBC), were thermally cycled to failure for seven different controlled pre-oxidation treatments and one commonly employed industrial pre-oxidation treatment to establish the preferred microstructures of the thermally-grown oxide (TGO) on a NiCoCrAlY bond coating after pre-oxidation. It was found that the failure of the coating system occurred along the TGO/BC interface when the TGO attained a critical thickness, except if a NiAl₂O₄ spinel layer developed contiguous to the TBC/TGO interface. Then, the coating system failed at a smaller TGO thickness along the NiAl₂O₄/α-Al₂O₃ interface. The value for the TGO thickness at failure increased for a larger area fraction of Y-rich oxide pegs at the TGO/BC interface after pre-oxidation. A desired slow-growing oxide layer on the BC surface was promoted when the presence of the oxides NiAl₂O₄, θ-Al₂O₃, Y₃Al₅O₁₂ at the TGO surface after pre-oxidation was avoided. The α-Al₂O₃ layer, which developed adjacent to the BC upon thermal cycling, grew at a low rate if the initial oxide at the onset of oxidation consisted of θ-Al₂O₃ instead of α-Al₂O₃. Based on these results a pre-oxidation treatment is proposed for which the lifetime of the entire coating system during service is enhanced.     

Oxidation und Versagen von EB-PVD-ZrO2- Wärmedämmschichtsystemen für Gasturbinen unter Hochtemperaturbeanspruchung

Oxidation and failure of EB-PVD-ZrO₂- Thermal Barrier Coatings for turbine applications during high-temperature-load The damage behaviour of an EB-PVD (EB-PVD = electron beam physical vapour deposition) zirconia thermal barrier coating system was investigated during thermal and combined thermal and mechanical loading. The oxidation of the bond coating which causes the growth of a thin alumina layer at the interface bond coating/thermal barrier coating was investigated in annealing experiments. The kinetics of the diffusion controlled oxidation can be described by a power law. The growth of the alumina layer gives rise to a critical stress state at the interface bond coating/thermal barrier coating and leads to spallation of the ceramic layer, especially during long-term-operation. The determined crack densities and crack opening distributions in the ceramic coating after isothermal high-temperature creep experiments show a strong dependance on creep rate and temperature. Measurements of the porosity of the ceramic layer indicate aging by sintering effects during high temperature load. The sintering effects could also be observed by microscopic methods.     

Combined pre-annealing and pre-oxidation treatment for the processing of thermal barrier coatings on NiCoCrAlY bond coatings

A combined pre-annealing and pre-oxidation treatment was developed for the processing of partially yttria stabilized (PYSZ) thermal barrier coatings (TBC) on top of NiCoCrAlY bond coatings (BC). To develop this pre-treatment, the influence of the oxygen potential during pre-annealing and pre-oxidation on the life span and failure mechanisms of the entire high temperature coating system upon thermal cycling was investigated. The results of this study showed that the service life of the coating system depended strongly on the composition and microstructure of the thermally grown oxide (TGO) after pre-oxidation. The longer life spans were obtained if the TGO thickened very slowly during thermal cycling due to a large α-Al₂O₃ grain size. Such a slow-growing TGO corresponded with a pre-treatment for which θ-Al₂O₃ was formed during pre-oxidation and for which the yttrium was located within a high density of pegs along the TGO/BC interface after pre-oxidation. If the yttrium was present on top of the TGO after pre-oxidation, a thick mixed alumina-zirconia layer formed upon thermal cycling. This mixed oxide layer contributed significantly to the total oxide layer thickness, resulting in short life spans. The formation of NiAl₂O₄ spinel in between the TBC and the α-Al₂O₃ should be avoided, since this can lead to premature failure along the spinel/α-Al₂O₃ interface.     

热喷涂NiCoCrAlYTa+7YSZ热障涂层颗粒沉积行为

分别采用低压等离子喷涂和大气等离子喷涂在K4169基体上收集了NiCoCrAlYTa颗粒沉积物及涂层,并对颗粒沉积物的形貌及涂层性能进行了观察分析。结果表明:低压等离子喷涂收集到的单个NiCoCrAlYTa扁平颗粒主要呈圆盘状,涂层致密且氧含量低。而大气等离子喷涂收集到的扁平颗粒主要呈溅射状,涂层孔隙率和氧含量均较高。又在经镜面抛光的NiCoCrAlYTa涂层和K4169基体上分别收集了7YSZ颗粒沉积物,并对其沉积形貌进行了观察分析,结果表明:在K4169基体上收集到的7YSZ颗粒沉积物主要呈圆盘状,表面存在大量的网状微裂纹及宏观环状贯通裂纹。在镜面抛光的NiCoCrAlYTa涂层表面收集的7YSZ颗粒沉积物,周围有少量的指状溅射物,中心部存在一定数量的网状微裂纹,但宏观环状裂纹消失。     

Advanced burner-rig test for oxidation-corrosion resistance evaluation of MCrAlY/superalloys systems

Protective coatings are used on gas turbine components to enable them to survive in engine-operating conditions. This study presents a recently developed cyclic burner-rig test that is used to simulate helicopter engine conditions and to assess the oxidation and hot corrosion behaviour of MCrAlY coatings on nickel-base superalloys. A diluted sea-salt solution is atomised into the burner-rig to simulate hot-corrosion. Each cycle lasts 1 h with temperatures varying in the range of 900 °C to 1000 °C followed by 15 min cooling to room temperature. Specimens are tested up to 1000 such cycles. Three different NiCoCrAlYTa coating thicknesses are used to determine the influence of the Al reservoir on the lifetime of the coated MC2 superalloy. The evolving microstructural features are identified using high resolution scanning electron microscopy and energy dispersive spectroscopy and compared with isothermal testing in pure oxidising conditions. The NiCoCrAlYTa microstructure obtained after the burner-rig test has typical features of a Type 1 hot corrosion degradation, with internal oxidation and nitruration and a front of chromium and yttrium-rich sulphides. This type of advanced burner-rig test cycle is successful in reproducing the accelerated combined hot-corrosion/oxidation damage.     

CoCrAlY表面改性后热障涂层高温氧化及热震性能

采用大气等离子喷涂技术（APS）在镍基高温合金表面制备了CoCrAlY粘结层,利用电子束蒸发镀膜在CoCrAlY表面蒸镀纳米铝膜,并使用强流脉冲电子束熔敷纳米铝膜进行表面改性,最后使用APS在表面改性后的CoCrAlY表面沉积陶瓷层制备了热障涂层.在空气环境中对热障涂层进行高温氧化试验和热震试验.结果表明,CoCrAlY表面改性后热障涂层经1 050℃静态空气氧化后,界面处生成的热生长氧化物（TGO）具有较高的连续性和致密性,有效阻碍了氧化的进一步发展且避免尖角型氧化物的形成,提高了热障涂层的抗氧化能力;在1 050℃高温加热后10℃水淬热震条件下,脱落率仅为2%左右.     

Hot Corrosion Performance of AlO-CrO/NiCoCrAlYTa and AlO/NiCoCrAlYTa Coatings Deposited by Atmospheric Plasma Spraying

AlO-CrO/NiCoCrAlYTa and AlO/NiCoCrAlYTa coatings were deposited on 316L stainless steel substrate using atmospheric plasma spraying, respectively, in order to improve the oxidation and corrosion resistance. The hot corrosion performance of the coatings at 700 and 900 °C were studied, and the detailed microstructures and phase composition of the coatings were analyzed using x-ray diffraction, scanning electron microscope with energy dispersive spectrometer, and transmission electron microscope. The results show that both coatings are structurally featured by slatted layers, consisting of amorphous phase, Cr₂O₃, Ni₃Al, and Al₂O₃. The hot corrosion resistance of AlO-CrO/NiCoCrAlYTa coating is better than that of AlO/NiCoCrAlYTa coating. This improvement is attributed to lower porosity and more compact Cr₂O₃ in AlO-CrO/NiCoCrAlYTa coating which performs better than Al₂O₃ in blocking further inward progress of corrosion and oxidization.     

热障涂层的制备工艺及研究进展

采用激光熔覆和大气等离子喷涂技术在镍基高温合金（GH4169）上制备NiCoCrAlYTa涂层,研究2种涂层的微观组织和高温氧化性能。采用扫描电子显微镜、X射线衍射仪和能谱仪观察涂层的微观组织形态和物相分析。结果表明：激光熔覆涂层中形成胞状亚结构的等轴晶凝固组织,相对于等离子喷涂涂层结构更致密。在1100 ℃氧化100 h后,喷涂涂层的氧化产物主要为Cr₂O₃和尖晶石,抗氧化能力降低;而激光熔覆涂层较为致密、孔隙少,氧化产物为γ-matrix、NiO和少量尖晶石,其抗氧化性能明显优于等离子喷涂涂层。     

地面重型燃气轮机及其热障涂层的研究进展与发展趋势

国际公认的重型燃气轮机制造尖端技术之一—热障涂层技术,高温下通常面临CMAS(CaO-MgO-Al₂O₃-SiO₂)腐蚀、氧化、相变与烧结等问题,其抗CMAS腐蚀性等关键性能极大地影响涂层寿命,提高热障涂层的性能刻不容缓。对重型燃气轮机用热障涂层的研究进展与发展趋势进行全面总结与分析。首先介绍国内外重型燃气轮机的现状及发展趋势、热障涂层的系统结构、材料和几种典型的制备工艺,然后针对高温下燃气轮机热障涂层遇到的一些问题,对其隔热性、抗氧化性及抗热震性等关键性能的研究进展进行综述,最后分类详述热障涂层的CMAS腐蚀机理及其防护研究进展。综述热障涂层的几种关键性能,提出热障涂层的性能与其材料、结构及制备工艺密切相关,据此总结归纳提高热障涂层性能的方法,为热障涂层性能的提高提供参考依据,以弥补燃气轮机热障涂层领域目前缺乏这类综述文章的不足。     

粉体预氧化对NiAl激光熔覆涂层组织和性能的影响

目的 激光熔覆是集节能、环保、减排于一身的低碳技术，能够解决涂层存在的粗大枝晶、较大开裂敏感性及纳米增强颗粒昂贵等难题。方法 借助Al颗粒的易氧化特性，提出一种预氧化气固反应手段，原位制备铝粉表面附着氧化铝的复合型粉体，采用激光熔覆技术将复合粉末制备成冶金涂层，并考察预氧化方法对NiAl涂层组织和性能的改性规律。结果 通过预氧化方法获得了铝粉表面附着氧化铝的复合型粉体，且制备的涂层成形良好、无缺陷；预氧化涂层的枝晶更细小，XRD测试表明预氧化涂层中出现了Al₂O₃。由于预氧化方法带来的细晶强化和第二相强化作用，使得预氧化涂层的硬度在NiAl涂层的基础上提升了约20%，预氧化方法引入的氧促使摩擦界面形成了一层氧化物润滑膜，使得预氧化处理后涂层的摩擦因数降低了约23%，同时耐磨性得到显著提升。结论 采用预氧化方法以低成本原位合成了复合型粉体，通过预氧化方法使涂层实现了从组织结构到性能的良性转变，为推动绿色低碳技术发展，高性能新型粉体的研发，以及NiAl涂层的应用提供一些思路与方法。     

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...     

Influence of Manufacturing Route on the Oxidation Resistance of Platinum-Modified Aluminide Bond Coatings and Their Performance in Thermal Barrier Coatings Deposited on a Ni-Based Superalloy

The importance of manufacturing route of Pt-aluminide bond coatings in determining the life of thermal barrier coatings on Ni-based superalloys is demonstrated. It is shown that bond coatings aluminized by chemical vapor deposition exhibit higher resistance to oxidation in comparison with the pack cementation route, which results in about twofold increase in the life of the thermal barrier coating as determined under cycling oxidation conditions. This difference in behavior is correlated with the initial microstructures of the bond coatings and their effect on thermal stability and oxidation resistance. However, thermal barrier coatings utilizing the two types of bond coatings are found to fail by the same mechanism involving spallation of the top coating due to loss of adhesion between the thermally grown oxide and underlying bond coating. It is concluded that manufacturing by the CVD route with low Al activity decelerates the kinetics of the processes leading to degradation of the coating system in comparison with the pack cementation route with high Al activity.     

Influence of Heat Treatment on the Bond Coat Cyclic Oxidation Behaviour in an Air-plasma-sprayed Thermal Barrier Coating System

THE METALLIC BOND COAT is an importantconstituent in a TBC system.It enhances the adhesionof the ceramic thermal barrier layer(the topcoat)to thesubstrate and also provides oxidation protection to thesubstrate metal.The composition of the bond coat,generalized as M-Cr-Al-Y,where M represents Ni,Coand/or Fe,generally allows a layer of alumina(A12O3)to form during high temperature exposure.If acontinuous scale of A12O3forms along the interfacebetween the bond coat and the ceramic to…