等离子喷涂热障涂层热震失效过程及残余应力分析

采用等离子喷涂技术在高温合金上制备了热障涂层(粘接层为NiCoCrAlY,陶瓷层为ZrO2-8%Y2O3),利用扫描电镜(SEM)、拉曼光谱(RFS)等试验手段研究了热障涂层热震失效的过程及残余应力大小和分布状态。结果表明:150次热循环后,陶瓷层和热生长氧化物(TGO)生成裂纹,其中陶瓷层的裂纹已扩展至TGO;350次热循环后,出现贯通陶瓷层与金属过渡层的纵向裂纹,涂层局部出现剥离,剥离位置位于TGO与陶瓷层界面;拉曼光谱(RFS)分析结果显示TGO内应力水平分布不均,局部厚大区和凸凹处残余应力较大,是裂纹萌生、扩展的主要部位。     

On TGO creep and the initiation of a class of fatigue cracks in thermal barrier coatings

The initiation of a class of fatigue cracks observed in thermal barrier coatings (TBCs) subjected to thermal gradient mechanical fatigue testing is investigated. The coating system is based on a NiCoCrAlY bond coat and a partially yttria stabilized zirconia top coat. To explain the development of the cracks of interest, the thermo-mechanical response of the bond coat and the thermally grown oxide (TGO) is examined and quantified through finite element analyses. The models include non-linear and time-dependent behavior such as creep, TGO growth stress, and thermo-mechanical cyclic loading. The simulations suggest that stress-redistribution due to creep can lead to tensile stresses in the TGO during TGMF testing that are large enough to initiate the cracks investigated.     

Through-thickness determination of phase composition and residual stresses in thermal barrier coatings using high-energy X-rays

High-energy X-rays were used to determine the local phase composition and residual stresses through the thickness of as-sprayed and heat-treated plasma-sprayed thermal barrier coatings consisting of a NiCoCrAlY bond coat and an yttria-stabilized zirconia (YSZ) topcoat produced with through-thickness segmentation cracks. The as-sprayed residual stresses reflected the combined influence of quenching stresses from the plasma spray process, thermal expansion mismatch between the topcoat, bond coat and substrate, and stress relief from the segmentation cracks. Heat treatments led to the formation of a thermally grown oxide (TGO) which was in compression in the plane, as well as relief of quenching stresses and development of a stress gradient in the YSZ topcoat. The high-energy X-ray technique used in this study revealed the effects that TGO and segmentation cracks have on the in-plane stress state of the entire coating.     

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。     

The influence of coating compliance on the delamination of thermal barrier coatings

Low relative density yttria stabilized zirconia (YSZ) thermal barrier coatings have been deposited on NiCoCrAlY over-lay bond-coated Hastelloy-X substrates by an electron beam-directed vapor deposition (EB-DVD) method. The coatings have been applied to both roughened and smooth bond coat surfaces. During thermal cycling, those deposited on roughened surfaces spalled by delamination with the failure located in the YSZ layer close to the thermally-grown oxide (TGO). The cracks were initiated at “corn kernel” defects in the YSZ layer by a bond coat rumpling mechanism. Coatings applied to smooth bond coat surfaces had much longer (factor of two) spallation lifetimes and delamination occurred at the bond coat/TGO interface by the nucleation and coalescence of interfacial voids. In both cases, the delamination lifetime decreased with coating density and significantly exceeded the lifetimes of higher density coatings made by conventional electron beam deposition methods. The enhanced life of the more porous coatings is consistent with an increased compliance. This reduces the YSZ layers stored strain energy contribution to the driving force for interface delamination.     

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.     

高温拉压环境下DZ125高温合金的热障涂层失效

采用电子束物理气相沉积法（EB-PVD）在定向凝固Ni基高温合金DZ125基体上制备了NiCoCrAlY粘结层和YSZ陶瓷层，研究了高温拉压环境下热障涂层的失效模式，并对其进行了有限元分析。实验结果表明，热障涂层的失效与仅受热载荷作用下的有很大不同，仅有热载荷作用下的热障涂层裂纹多萌生于热氧化层（TGO）内部，进而扩展引起热障涂层的失效。而高温拉压试验后热障涂层体系存在两种裂纹，分别萌生于TGO／粘结层界面和粘结层／扩散层界面附近。有限元模拟结果显示TGO／陶瓷层和TGO／粘结层处存在应力状态的转变和应力值的突变，径向应力的突变导致了界面分离现象的产生，而轴向应力的突变加速了垂直于界面裂纹的扩展，并导致了试样的最终断裂。     

Spinel formation in thermal barrier systems with a Pt-enriched γ-Ni + γ′-Ni3Al bond coat

The oxidation of electron beam physical vapour deposited thermal barrier coatings with a Pt-enriched γ-Ni + γ′-Ni₃Al bond coat was investigated. Due to the growth of the thermally grown oxide (TGO), γ-Ni formed underneath the TGO as a result of Al depletion. Phase characterisation by X-ray diffraction, as well as microstructural observations, indicated that a NiAl₂O₄ spinel phase formed at the TGO/bond coat interface after prolonged oxidation. It is proposed that the formation of spinel occurs when local cracks present at the interface and the underlying bond coat is Al-depleted. The cracks provide a direct path for oxygen and nickel oxide forms at the bond coat surface. With further oxidation, the spinel forms at the interface through solid state reaction between the TGO and nickel oxide.     

EB-PVD热障涂层热循环过程中粘结层的氧化和相结构

采用磁控溅射方法在镍基单晶高温合金基体上沉积Ni-30Cr-12Al-0.3Y（质量分数，％）粘结层，采用电子束物理气相沉积方法（EB－VPD）沉积7％Y2O3（质量分数）－ZrO2陶瓷顶层，结果表明，在热循环过程中，非平衡相t′-ZrO2中的Y2O3含量逐渐减少，t′－ZrO2相逐渐分解成平衡相t-ZrO2（冷却时变转变成斜相）和立方组ZrO2,1050℃循环200次，粘结层氧化物（Al2O3)厚度约为3μm，表明Ni-Cr-Al-Y达宜作粘结层，继续热循环，陶瓷层中出现单斜阳，粘结层中Al贫化，氧化层中出现NiO及尖晶石等，引起应力集中，导致涂层失效。     

Reaction, transformation and delamination of samarium zirconate thermal barrier coatings

The rare earth zirconates have attracted interest for thermal barrier coatings (TBCs) because they have very low intrinsic thermal conductivities, are stable above 1200 °C and are more resistant to sintering than yttria-stabilized zirconia (YSZ). Samarium zirconate (SZO) has the lowest thermal conductivity of the rare earth zirconates and its pyrochore structure is stable to 2200 °C but little is known about its response to thermal cycling. Here, columnar morphology SZO coatings have been deposited on bond coated superalloy substrates using a directed vapor deposition method that facilitated the incorporation of pore volume fractions of 25 to 45%. The as-deposited coatings had a fluorite structure which transformed to the pyrochlore phase upon thermal cycling between 100 and 1100 °C. This cycling eventually led to delamination of the coatings, with failure occurring at the interface between the TGO and a “mixed zone” that formed between the thermally grown alumina oxide (TGO) and the SZO. While the delamination lifetime increased with coating porosity (reduction in coating modulus), it was significantly less than that of similar YSZ coatings applied to the same substrates. The reduced life resulted from a reaction between the rare earth zirconate and the alumina-rich bond coat TGO, leading to the formation of a mixed zone consisting of SZO and SmAlO₃. Thermal strain energy calculations show that the delamination driving force increases with TGO and mixed layer thicknesses and with coating modulus. The placement of a 10 μm thick YSZ layer between the TGO and SZO layers eliminated the mixed zone and restored the thermal cyclic life to that of YSZ structures.     

Thermally grown oxide growth behavior and spallation lives of solution precursor plasma spray thermal barrier coatings

The effects of thermally grown oxide (TGO) growth rate and bond coat oxidation behavior on the spallation lives of thermal barrier coatings (TBCs) have been investigated. Yttria partially stabilized zirconia (7YSZ) coatings have been applied to various bond coat/superalloy substrate combinations using the Solution Precursor Plasma Spray (SPPS) process. The coatings have been furnace thermal cycled at 1121 °C, using one hour cycles. A large variation in the spallation lives, from 125 to 1230 cycles, has been observed and are attributed to (a) the spatially averaged TGO growth rate, (b) the maximum localized TGO thickness, (c) the formation of non-alumina oxides with weak interfaces, and (d) the formation of yttrium aluminate stringers in low pressure plasma spray (LPPS) processed bond coat. Of these four factors, the average TGO thickness is the most important. Surprisingly vacuum plasma sprayed bond coated samples consistently had shorter cyclic live compared to air plasma sprayed bond coated samples.     

Effects of breakaway oxidation on local stresses in thermal barrier coatings

It is known that fast-growing non-alumina scales in thermal barrier coating (TBC) systems tend to form at features where aluminium depletion is enhanced due to a high surface-area to volume ratio, a phenomenon known as breakaway oxidation. In this work, the influence of breakaway oxidation around protuberances in an MCrAlY bond coat in a TBC system during isothermal oxidation and after cooling is quantified numerically. A finite element approach is used which incorporates elastic, plastic and creep deformation of the bond coat and thermally grown oxide (TGO) and, importantly, the volumetric strains associated with oxide formation during the isothermal exposure. It is shown how volumetric strains which develop during breakaway oxidation can result in the formation of significant (>0.5 GPa) out-of-plane tensile stresses within the yttria-stabilized zirconia top coat at the oxidation temperature. These stresses are located along the flanks of the bond coat protuberances in locations where sub-critical cracks have previously been reported. The magnitude of the stresses increases with bond coat surface roughness, after the initiation of breakaway oxidation and after cooling. Results are also presented for the normal tractions across both TGO interfaces, and the influence of breakaway oxidation on these is discussed.     

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。     

Thermal Failure of Nanostructured Thermal Barrier Coatings with Cold-Sprayed Nanostructured NiCrAlY Bond Coat

Nanostructured thermal barrier coatings (TBCs) were deposited by plasma spraying using agglomerated nanostructured YSZ powder on Inconel 738 substrate with cold-sprayed nanostructured NiCrAlY powder as bond coat. The isothermal oxidation and thermal cycling tests were applied to examine failure modes of plasma-sprayed nanostructured TBCs. For comparison, the TBC consisting of conventional microstructure YSZ and conventional NiCrAlY bond coat was also deposited and subjected to the thermal shock test. The results showed that nanostructured YSZ coating contained two kinds of microstructures; nanosized zirconia particles embedded in the matrix and microcolumnar grain structures of zirconia similar to those of conventional YSZ. Although, after thermal cyclic test, a continuous, uniform thermally grown oxide (TGO) was formed, cracks were observed at the interface between TGO/BC or TGO/YSZ after thermal cyclic test. However, the failure of nanostructured and conventional TBCs mainly occurred through spalling of YSZ. Compared with conventional TBCs, nanostructured TBCs exhibited better thermal shock resistance.     

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。     

A numerical assessment of the durability of thermal barrier systems that fail by ratcheting of the thermally grown oxide

Interactions between cracks induced in thermal barrier coatings (TBCs) upon thermal cycling have been calculated. The interactions are motivated by displacement instability in the thermally grown oxide (TGO). The results indicate that the energy release rate G cycles as the temperature changes, with the largest value arising at ambient temperature. It increases on a cycle-by-cycle basis. Cracks that converge from neighboring imperfections exhibit a minimum energy release rate prior to coalescence. Equating this minimum to the toughness of the TBC provides a criterion for coalescence and failure. Imposing this criterion allows the change in crack length upon cycling and the number of cycles to failure to be ascertained.This simulation capability is used to explore various influences on durability. The roles of the heating/cooling rate and the high temperature hold time are assessed, demonstrating substantial variation in durability, especially when the bond coat is relatively soft. The trends from these simulations are compared with experimental results for furnace cycle and burner rig tests. Improvements in the durability upon increasing the high temperature strength of the bond coat and upon decreasing the growth stress in the TGO are established, as well as the influence of the geometric imperfections in the bond coat. Some effects of the thermal expansion misfit between the bond coat and the substrate are explored.     

Performance of Dy2Zr2O7 Thermal Barrier Coating in Thermal-Shock Test

通过北气等离子喷涂(APS)制备了一种基于锆酸镝(Dy2Zr2O7)的新型热障涂层,该涂层具有更低的热导率及与镍基高温合金更匹配的热膨胀系数。对涂层的结构、相组成以及抗热震性能进行了研究。此外,对涂层在热震循冲过程中的失效过程进行了讨论。结果表明,在6~8次热震循冲后,涂层从基体表面脱落。陶瓷层中的微裂纹在热震过程中生长并导致粘结层界面附近的陶瓷层被压碎,从而最终导致陶瓷层的脱落。     

Surface geometry and strain energy effects in the failure of a (Ni, Pt)Al/EB-PVD thermal barrier coating

Thermal cycling tests were conducted on a commercial yttria-stabilized zirconia electron beam-physical vapor deposited thermal barrier coating (TBC) on a platinum aluminide (β-(Ni, Pt)Al) bond coat. Surprisingly, the longest life sample lasted 10 times longer than the shortest life sample. Two distinct mechanisms have been found responsible for the observed damage initiation and progression at the thermally grown oxide (TGO)/bond coat interface. The first mechanism leads to localized debonding at the TGO/bond coat interface due to increasing out-of-plane tensile stresses at ridges that form along bond coat grain boundaries. The second mechanism is driven by cyclic plasticity of the bond coat that leads to cavity formation at the TGO/bond coat interface. The primary finding of this work is that the first mechanism, involving tensile stress at ridge tops, is life limiting. Based on this mechanism, it is demonstrated that the variation in bond coat ridge aspect ratio can explain the unusual 10× variation in observed sample life. It is proposed that ridge top spallation leads to debonds of sufficient size to result in unstable fracture driven by the strain energy stored in the TGO. The criticality of the flaw created by local debonding is supported by experimental determination of the strain energy available in the TGO through measurement of TGO stress and thickness combined with published fracture mechanics solutions of the relevant flaw geometry.     

粘结层表面处理对热障涂层残余应力及热冲击寿命的影响

采用真空电弧离子镀技术在二代单晶高温合金DD32表面制备NiCoCrAlYHf（HY5）金属粘结层,通过振动光饰、吹砂及振动光饰和吹砂3种不同的表面处理方法改变粘结层表面状态,利用电子束物理气相沉积（EB-PVD）技术制备氧化钇部分稳定氧化锆（7~8YSZ）陶瓷层。借助扫描电子显微镜（SEM）、电子探针（EPMA）、光激发荧光压电光谱（PLPS）等分析手段,研究1100 ℃热冲击过程中热障涂层界面结构、成分及残余应力的演变。结果表明:表面处理能够改善粘结层表面形貌,其对TGO层残余应力大小及热冲击寿命存在影响;未处理试样应力水平高于经过表面处理的热障涂层试样,并且随着热冲击次数的增加未处理试样残余应力涨幅更大;经过表面处理后试样热冲击寿命提高,其中经过振动光饰处理的试样提升最为显著;粘结层表面吹砂处理会造成砂粒进入粘结层表层某些部位,TGO层局部过度生长,造成应力集中,从而涂层寿命低于振动光饰处理试样。     

Microstructural analysis of YSZ and YSZ/Al2O3 plasma sprayed thermal barrier coatings after high temperature oxidation

Air plasma sprayed TBCs usually include lamellar structure with high interconnected porosities which transfer oxygen from YSZ layer towards bond coat and cause TGO growth and internal oxidation of bond coat.The growth of thermally grown oxide (TGO) at the interface of bond coat and ceramic layer and internal oxidation of bond coat are considered as the main destructive factors in thermal barrier coatings.Oxidation phenomena of two types of plasma sprayed TBC were evaluated: (a) usual YSZ (yttria stabilized zirconia), (b) layer composite of (YSZ/Al₂O₃) which Al₂O₃ is as a top coat over YSZ coating. Oxidation tests were carried out on these coatings at 1100°C for 22, 42 and 100h. Microstructure studies by SEM demonstrated the growth of TGO underneath usual YSZ coating is higher than for YSZ/Al₂O₃ coating. Also cracking was observed in usual YSZ coating at the YSZ/bond coat interface. In addition severe internal oxidation of the bond coat occurred for usual YSZ coating and micro-XRD analysis revealed the formation of the oxides such as NiCr₂O₄, NiCrO₃ and NiCrO₄ which are accompanied with rapid volume increase, but internal oxidation of the bond coat for YSZ/Al₂O₃ coating was lower and the mentioned oxides were not detected.