Improvement of thermally grown oxide layer in thermal barrier coating systems with nano alumina as third layer

A thermally grown oxide (TGO) layer is formed at the interface of bond coat/top coat. The TGO growth during thermal exposure in air plays an important role in the spallation of the ceramic layer from the bond coat. High temperature oxidation resistance of four types of atmospheric plasma sprayed TBCs was investigated. These coatings were oxidized at 1000 °C for 24, 48 and 120 h in a normal electric furnace under air atmosphere. Microstructural characterization showed that the growth of the TGO layer in nano NiCrAlY/YSZ/nano Al₂O₃ coating is much lower than in other coatings. Moreover, EDS and XRD analyses revealed the formation of Ni(Cr,Al)₂O₄ mixed oxides (as spinel) and NiO onto the Al₂O₃ (TGO) layer. The formation of detrimental mixed oxides (spinels) on the Al₂O₃(TGO) layer of nano NiCrAlY/YSZ/nano Al₂O₃ coating is much lower compared to that of other coatings after 120 h of high temperature oxidation at 1000 °C.     

Novel thermal barrier coatings based on La2Ce2O7/8YSZ double-ceramic-layer systems deposited by electron beam physical vapor deposition

Novel thermal barrier coatings based on La₂Ce₂O₇/8YSZ double-ceramic-layer (DCL) systems, which were deposited by electron beam physical vapor deposition (EB-PVD), were found to have a longer lifetime compared to the single layer La₂Ce₂O₇ (LC) system, and even much longer than that of the single layer 8YSZ system under burner rig test. The DCL coating structure design can effectively alleviate the thermal expansion mismatch between LC coating and bond coat, as well as avoid the chemical reaction between LC and Al₂O₃ in thermally grown oxide (TGO), which occurs above 1000 °C as determined by differential scanning calorimetry (DSC) analysis. The failure mechanism of LC/8YSZ DCL coating is mainly due to the sintering of LC coating surface after long-term thermal cycling.     

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.     

Hot corrosion behaviour of plasma sprayed YSZ/Al2O3 dispersed NiCrAlY coatings on Inconel-718 superalloy

Oxide dispersed NiCrAlY bond coatings have been developed for enhancing thermal life cycles of thermal barrier coatings (TBCs). However, the role of dispersed oxides on high temperature corrosion, in particular hot corrosion, has not been sufficiently studied. Therefore, the present study aims to improve the understanding of the effect of YSZ dispersion on the hot corrosion behaviour of NiCrAlY bond coat. For this, NiCrAlY, NiCrAlY + 25 wt.% YSZ, NiCrAlY + 50 wt.% YSZ and NiCrAlY + 75 wt.% YSZ were deposited onto Inconel-718 using the air plasma spraying (APS) process. Hot corrosion studies were conducted at 800 °C on these coatings after covering them with a 1:1 weight ratio of Na₂SO₄ and V₂O₅ salt film. Hot corrosion kinetics were determined by measuring the weight gain of the specimens at regular intervals for a duration of 51 h. X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy techniques were used to determine the nature of phases formed, examine the surface attack and to carry out microanalysis of the hot corroded coatings respectively. The results show that YSZ dispersion causes enhanced hot corrosion of the NiCrAlY coating. Leaching of yttria leads not only to the formation of the YVO₄ phase but also the destabilization of the YSZ by hot corrosion. For the sake of comparison, the hot corrosion behaviour of a NiCrAlY + 25 wt.% Al₂O₃ coating was also examined. The study shows that the alumina dispersed NiCrAlY bond coat offers better hot corrosion resistance than the YSZ dispersed NiCrAlY bond coat, although it is also inferior compared to the plain NiCrAlY bond coat.     

Structure and durability evaluation of YSZ + Al2O3 composite TBCs with APS and HVOF bond coats under thermal cycling conditions

Plasma sprayed thermal barrier coatings (TBCs) are applied to gas turbine components for providing thermal insulation and oxidation resistance. The TBC systems currently in use on superalloy substates typically consists of a metallic MCrAlY based bond coat and an insulating Y₂O₃ partially stabilized ZrO₂ as a ceramic top coat (ZrO₂ 7–8 wt.% Y₂O₃). The oxidation of bond coat underlying yttria stabilized zirconia (YSZ) is a significant factor in controlling the failure of TBCs. The oxidation of bond coat induces to the formation of a thermally grown oxide (TGO) layer at the bond coat/YSZ interface. The thickening of the TGO layer increases the stresses and leads to the spallation of TBCs. If the TGO were composed of a continuous scale of Al₂O₃, it would act as a diffusion barrier to suppress the formation of other detrimental mixed oxides during the extended thermal exposure in service, thus helping to protect the substrate from further oxidation and improving the durability. The TBC layers are usually coated onto the superalloy substrate using the APS (Atmospheric plasma spray) process because of economic and practical considerations. As well as, HVOF (High velocity oxygen fuel) bond coat provides a good microstructure and better adhesion compared with the APS process. Therefore, there is a need to understand the cycling oxidation characteristic and failure mode in TBC systems having bond coat prepared using different processes. In the present investigation, the growth of TGO layers was studied to evaluate the cyclic oxidation behavior of YSZ/Al₂O₃ composite TBC systems with APS-NiCrAlY and HVOF-NiCrAlY bond coats. Interface morphology is significantly effective factor in occurrence of the oxide layer. Oxide layer thickening rate is slower in APS bond coated TBCs than HVOF bond coated systems under thermal cycle conditions at 1200 °C. The YSZ/Al₂O₃ particle composite systems with APS bond coat have a higher thermal cycle life time than with the HVOF bond coating.     

Cyclic oxidation behavior and thermal barrier effect of YSZ-(Al2O3/YAG) double-layer TBCs prepared by the composite sol-gel method

Novel YSZ (6 wt.% yttria partially stabilized zirconia)-(Al₂O₃/YAG) (alumina-yttrium aluminum garnet, Y₃Al₅O₁₂) double-layer ceramic coatings were fabricated using the composite sol-gel and pressure filtration microwave sintering (PFMS) technologies. The thin Al₂O₃/YAG layer had good adherence with substrate and thick YSZ top layer, which presented the structure of micro-sized YAG particles embedded in nano-sized α-Al₂O₃ film. Cyclic oxidation tests at 1000 °C indicated that they possessed superior properties to resist oxidation of alloy and improve the spallation resistance. The thermal insulation capability tests at 1000 °C and 1100 °C indicate that the 250 μm coating had better thermal barrier effect than that of the 150 μm coating at different cooling gas rates. These beneficial effects should be mainly attributed to that, the oxidation rate of thermal grown oxides (TGO) scale is decreased by the “sealing effect” of α-Al₂O₃, the “reactive element effect”, and the reduced thermal stresses by means of nano/micro composite structure. This double-layer coating can be considered as a promising TBC.     

NiCoCrAlY粘结层喷涂工艺对8YSZ热障涂层抗氧化性能的影响

目的 提高热障涂层粘结层的抗高温氧化性能。方法 分别采用爆炸喷涂和等离子喷涂工艺制备了不同结构的NiCoCrAlY粘结层,之后通过等离子喷涂制备8YSZ陶瓷层,分析了两种粘结层结构的热障涂层的抗高温氧化性能。利用XRD、SEM和EDS对涂层物相、微观结构和成分进行分析,并对其与基体结合状态、抗高温氧化性能进行研究。结果 爆炸喷涂粘结层内部组织致密,缺陷较少,与基体结合处孔隙少;而等离子喷涂粘结层内部的层状特征明显,孔隙较多,表面粗糙度较低。爆炸喷涂粘结层氧化5 h后,表面生成了一层富Al2O3的致密氧化物膜;而等离子喷涂粘结层表面形成了富NiO、CoO、Cr2O3和Ni(Cr,Al)2O4的氧化物层,并出现了许多微裂纹和片层状氧化物。爆炸喷涂制备的热障涂层试样在前5 h氧化增重速率高于等离子喷涂试样,随后变平缓,而等离子喷涂试样氧化速率依然较高。爆炸喷涂热障涂层的热生长氧化物层（Thermally grown oxide, TGO）经50 h氧化后,仍呈连续状,厚度均匀,粘结层内氧化物缺陷较少。结论 爆炸喷涂粘结层组织均匀、致密,喷涂时涂层的氧化以及热处理的内氧化较少,使得足够的Al较快速地在粘结层表面形成致密的氧化铝,表面一定厚度的氧化铝层抑制了氧和其他金属原子的相向扩散反应,提高了涂层的抗高温氧化性能。     

Synthesis and characterization of Y3Al5O12 and ZrO2-Y2O3 thermal barrier coatings by combustion spray pyrolysis

Y₃Al₅O₁₂ and ZrO₂-Y₂O₃ (8 mol% YSZ) coatings for potential application as thermal barrier coatings were prepared by combustion spray pyrolysis. Thermal cycling of as deposited coatings on stainless steel and FeCrAlY bond coat substrates was carried out at 1000 °C and 1200 °C to determine the thermal fatigue response. Structural and morphological studies on Y₃Al₅O₁₂ and 8 mol% YSZ coatings before and after thermal cycling have been carried out. It has been noted that the coatings on FeCrAlY substrates remain intact after 50 cycles between room temperature and 1200 °C, whereas the coatings on stainless steel show some minor damage such as peeling off near the periphery after 50 cycles at 1000 °C. Thermal diffusivity values of Y₃Al₅O₁₂ and 8 mol% YSZ films were measured by using photo thermal deflection spectroscopy and the values are lower than those of coatings produced by conventional techniques such as EBPVD and APS.     

Influence of TGO Composition on the Thermal Shock Lifetime of Thermal Barrier Coatings with Cold-sprayed MCrAlY Bond Coat

NiCoCrAlTaY bond coat was deposited by cold spraying to assemble thermal barrier coatings (TBCs). The microstructure of the cold-sprayed bond coat was examined using scanning electron microscopy. TBCs consisting of cold-sprayed bond coat and plasma-sprayed YSZ were pretreated at different conditions to form different thermally grown oxides (TGOs) before thermal cycling test. The influence of the TGO composition on the thermal cyclic lifetime was quantitatively examined through the measurement of the coverage ratio of the mixed oxides on the bond coat surface. The results showed that the bond coat exhibited a dense oxidation-free microstructure, and TGOs in different morphologies and constituents were present after thermal cyclic test. The formation of TGOs was significantly influenced by pretreatment conditions. Two kinds of TGO were detected on the surface of bond coat after the spallation of YSZ coatings. One is the α-Al₂O₃-based TGO and the other is the mixed oxide. It was found that the thermal cyclic lifetime is inversely proportional to the coverage ratio of the mixed oxides formed at the bond coat/YSZ interface. The high coverage ratio of the mixed oxide on the interface leads to the early spalling of YSZ coating.     

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。     

Thermo-physical and thermal cycling properties of plasma-sprayed BaLa2Ti3O10 coating as potential thermal barrier materials

Increased turbine inlet temperature in advanced turbines has promoted the development of thermal barrier coating (TBC) materials with high-temperature capability. In this paper, BaLa₂Ti₃O₁₀ (BLT) was produced by solid-state reaction of BaCO₃, TiO₂ and La₂O₃ at 1500 °C for 48 h. BLT showed phase stability between room temperature and 1400 °C. BLT revealed a linearly increasing thermal expansion coefficient with increasing temperature up to 1200 °C and the coefficients of thermal expansion (CTEs) are in the range of 1 × 10^− 5–12.5 × 10^− 6 K^− 1, which are comparable to those of 7YSZ. BLT coatings with stoichiometric composition were produced by atmospheric plasma spraying. The coating contained segmentation cracks and had a porosity of around 13%. The microhardness for the BLT coating is 3.9–4.5 GPa. The thermo-physical properties of the sprayed coating were investigated. The thermal conductivity at 1200 °C is about 0.7 W/mK, exhibiting a very promising potential in improving the thermal insulation property of TBC. Thermal cycling result showed that the BLT TBC had a lifetime of more than 1100 cycles of about 200 h at 1100 °C. The failure of the coating occurred by cracking at the thermally grown oxide (TGO) layer due to severe oxidation of bond coat. Based on the above merits, BLT could be considered as a promising material for TBC applications.     

多孔ZrO2-8 wt% Y2O3涂层的制备及性能

航空发动机的效率与转动叶片和机匣之间的间隙密切相关。为了控制转子和静子之间的间隙,需要在机匣表面制备可磨耗的封严涂层。在发动机的高温端,ZrO₂-8wt% Y₂O₃涂层是经常采用的封严涂层基体。涂层中的孔隙可以增加涂层的可磨耗性。本文利用聚苯酯(PHB)增加等离子喷涂的ZrO₂-8 wt% Y₂O₃涂层的孔隙率。为了避免聚苯酯在等离子喷涂过程中的烧损,利用溶胶-凝胶法在聚苯酯颗粒表面沉积一层TiO₂层。文中将讨论采用此方法制成的涂层的形态、孔隙率、硬度和可磨耗性。结果表明,在喷涂粉末中混合包覆型的聚苯酯后,涂层的孔隙率将会得到提升,涂层硬度将会下降。磨耗试验的结果表明涂层的磨耗深度随着涂层孔隙率的增加而增加。     

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.     

基于磁过滤技术的热障涂层表面Al2O3 覆盖层抗CMAS腐蚀性能

为了提高热障涂层（TBC）的抗沉积物（主要成分为CaO、MgO、Al₂O₃和SiO₂,简称CMAS）腐蚀性能,采用磁过滤阴极真空电弧（FCVA）技术在TBC表面上制备了致密的Al₂O₃覆盖层,比较和分析了Al₂O₃改性TBC和沉积态TBC的润湿行为和抗CMAS腐蚀性能。结果表明：使用FCVA技术制备Al₂O₃覆盖层的过程对7%（质量分数）氧化钇稳定的氧化锆（7YSZ）相的结构无明显影响,且经Al₂O₃改性的TBC综合性能均优于沉积态TBC。在1250 ℃、CMAS腐蚀条件下,Al₂O₃覆盖层有效地限制了熔融CMAS在TBC表面上的扩散行为。同时,Al₂O₃填充了7YSZ柱状晶之间的间隔并且阻碍了熔融CMAS的渗透,证明了FCVA可作为一种制备Al₂O₃涂层的新方法以提高TBC的抗CMAS腐蚀性能,且Al₂O₃涂层及其制备过程对TBC的热震性能均无消极影响。     

The Protectiveness of Thermally Grown Oxides on Cold Sprayed CoNiCrAlY Bond Coat in Thermal Barrier Coating

This paper presents the results of an oxidation behavior study for a thermal barrier coating (TBC) with air plasma sprayed yttria-stabilized zirconia top coat and CoNiCrAlY bond coat deposited using low pressure plasma spray (LPPS) and cold spray (CS). The TBC is subjected to isothermal oxidation and creep tests at 900?°C and evaluated using scanning electron microscopy, energy dispersive x-ray spectrometry transmission electron microscopy and electron backscatter diffraction. The thermally grown oxide (TGO) developed in the TBC with the LPPS bond coat was composed of only ??-Al₂O₃ and the TGO developed in the TBC with a CS bond coat is composed of ??-Al₂O₃ and ??-Al₂O₃. Despite the presence of this metastable ?? phase, the TGO in the CS specimens exhibits a dense microstructure and lower amounts of mixed oxides. The correlation between ??-Al₂O₃ and the formation of mixed oxides was investigated through the measurement of ??-Al₂O₃ thickness ratio and mixed oxides coverage ratio. It was found that the mixed oxides coverage ratio is inversely proportional to the ??-Al₂O₃ thickness ratio.     

Al2O3微粉添加量对镁合金微弧氧化膜特性影响研究

为了研究添加Al₂O₃微粉对AZ31A镁合金微弧氧化膜特性影响,在不同浓度Al₂O₃微粉电解液中对其进行了微弧氧化处理。利用扫描电镜(SEM)观察微弧氧化膜形貌,能谱仪(EDS)分析了膜层表面Ca、Mg、O、Al元素分布,X射线衍射仪(XRD)分析了相组成,测定了膜厚、硬度和氧化液中Al₂O₃表面电荷,讨论了掺杂改性机理。结果表明,加入Al₂O₃微粉后,氧化电压随Al₂O₃添加量增加先增加后降低;氧化膜表面孔洞数量和尺寸减小,膜层表面Ca元素分布逐渐减少,成膜效率降低,膜层致密度和表面疏松层硬度提高,氧化膜主要由MgO和MgO₄等相组成。     

The study of NiAl-TiB2 coatings prepared by electro-thermal explosion ultrahigh speed spraying technology

NiAl-TiB₂ composite coatings with 0, 10 and 20 wt.% TiB₂ were synthesized on the Ni-based superalloy substrate using electro-thermal explosion ultrahigh speed spraying technology. The microstructure analysis shows that the coatings consist of submicron grains. The bond between coatings and substrate is metallic cohesion. TiB₂ as a powerful reinforcement is doped in NiAl for increasing its hardness. The isothermal oxidation test is carried out for the composite coatings at 1100 °C in air. The result shows that the oxidation resistance of NiAl coating is higher than that of NiAl-10TiB₂ and NiAl-20TiB₂ coatings. The phases of oxides on the coatings during the process at high temperature have been analyzed by X-ray diffraction. The results show that Al₂O₃ and Cr₂O₃ coexistence on surface of NiAl coating, while Al₂O₃, Cr₂O₃, TiO₂ and a small amount of NiO form on surface of NiAl-10TiB₂ and NiAl-20TiB₂ coatings after oxidation for 4 h.     

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.     

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.     

Surface Modification of Thermal Barrier Coatings by Single-Shot Defocused Laser Treatments

Thermal barrier coatings (TBC) consisting of atmospheric plasma-sprayed ZrO₂-8 wt.% Y₂O₃ and a high velocity oxygen fuel-sprayed metallic bond coat were subjected to CO₂ continuous wave laser treatments. The effects of laser power on TBCs were investigated as was the thermally grown oxide (TGO) layer development of all as-sprayed and laser-treated coatings after thermal oxidation tests in air environment for 50, 100, and 200 h at 1100 °C. The effects of laser power on TBCs were investigated. TGO layer development was examined on all as-sprayed and laser-treated coatings after thermal oxidation tests in air environment for 50, 100, and 200 h at 1100 °C. Melted and heat-affected zone regions were observed in all the laser-treated samples. Oxidation tests showed a stable alumina layer and mixed spinel oxides in the TGO layers of the as-sprayed and laser-treated TBCs.