热喷涂热障涂层的热生长氧化层的生长和演变

用大气等离子热喷涂工艺在镍基高温合金GH4169表面制备热障涂层的粘结层和陶瓷层。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和Cr~(3+)荧光光谱表征热障涂层的热生长氧化物(TGO)的物相、生长形貌与氧化铝相变的演化。研究表明,经1050℃高温氧化后,热障涂层的TGO生长服从幂指数函数规律。TGO的主要物相为Al_2O_3、Cr_2O_3和NiCr_2O_4;1050℃高温氧化300 h后,粘结层逐渐贫铝,导致Ni与已经形成的Al_2O_3反应生成尖晶石相,由于大量的Cr~(3+)参与了加速TGO相变的过程,导致Cr含量下降。     

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。     

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.     

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。     

TiAl合金表面EB-PVD制备热障涂层及高温抗氧化性能

利用EB-PVD技术在Ti Al合金表面制备了扩散铝/YSZ热障涂层。采用SEM、EDS和XRD分析了涂层原始及高温氧化后的微观组织及相组成,并测试了高温氧化性能。结果表明:涂层表面YSZ层为致密柱状晶结构,由非平衡四方相t′-ZrO_2组成。Ti Al合金沉积了扩散铝/YSZ热障涂层后高温氧化性能显著提高,氧化动力学曲线呈对数变化规律,900℃高温氧化时,氧化速率为2.2×10~(-5) mg/cm~2·h。1000℃高温氧化时,氧化速率为1.14×10~(-3) mg/cm~2·h。在高温氧化过程中,粘结层与基体之间发生元素扩散,膜基界面消失。在面层与中间粘结层之间形成了均匀连续的热生长氧化物层TGO。     

YAG/8YSZ双陶瓷热障涂层等温氧化性能研究

本文对比研究了YAG/8YSZ双陶瓷和8YSZ单陶瓷热障涂层体系的抗高温氧化性能。采用爆炸喷涂(D-GUN)在310S耐热不锈钢基体上制备粘结层(NiCoCrAlY),用大气等离子喷涂(APS)分别在粘结层试样上制备YAG/8YSZ双陶瓷和8YSZ单陶瓷热障涂层,利用SEM和XRD分析涂层氧化前后截面与表面特征,对比研究2种热障涂层体系在1100 ℃等温氧化不同时间后的氧化增重动力学、YAG陶瓷层微观结构与物相及TGO生长过程和生长动力学。结果表明,YAG陶瓷层在1100 ℃等温氧化200 h后无明显相结构转变,孔隙率稍有降低;YAG/8YSZ双陶瓷层体系较8YSZ单陶瓷层体系氧化增重速率降低1.7倍,TGO生长速率降低1.4倍,粘结层β-NiAl相消耗速度及岛状氧化物生长速度更低,表现出更好的抗高温氧化性能。     

铂含量对改性铝化物粘结层高温氧化和内应力的影响

研究镍基高温合金的热障涂层系统中不同铂含量的改性铝化物粘结层在1100℃空气中循环氧化和非连续氧化行为及生成的氧化铝层的内应力状态。发现在不同循环氧化条件下,铂铝粘结层表面都形成连续致密的α-Al2O3层,并且α-Al2O3具有相同的形态和相似的平均厚度。而在非连续氧化初期,Al2O3层热生长应力快速增大,在氧化至100h时内应力出现峰值。同时由于高含量铂促进Al元素的扩散从而改变了涂层力学性能,造成高含量铂涂层中表现较大的内应力,但铂含量不能影响Al2O3层中内应力曲线变化趋势。另外,低铂含量涂层γ′-Ni3Al多沿β-NiAl晶界生成,而高含量铂使涂层晶粒细化,导致γ′-Ni3Al相呈弥散分布生长,从而可以形成Al元素的"网"状快速扩散通道。     

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。     

铂改性铝化物涂层的热生长层内应力研究

研究了镍基高温合金热障涂层系统中铂改性铝化物粘结层在空气中非连续高温氧化生成的Al2O3层内应力状态及相应的粘结层微观结构。利用Raman光激发荧光谱技术,发现铂铝粘结层在900℃氧化初期生成了θ-和α-Al2O3,而在1100℃氧化时,表面则形成连续致密的α-Al2O3层。通过α-Al2O3的光激发荧光谱偏移量,计算得到了热障涂层中热生长层的内压应力略高于3.0GPa。铂改性铝化物涂层表面Al2O3"背脊"处的内应力相对较低,同时由于没有陶瓷层的压制,生成的Al2O3起伏较大,并发生局部的Al2O3脱落。随氧化时间延长,由于Al元素沿晶界扩散较快,导致更多的γ′-Ni3Al在粘结层晶界处形成,粘结层中基本相β-NiAl向γ′-Ni3Al转变,改变了粘结层本身的热膨胀系数,引起热生长层中内应力变化。     

交流阻抗谱法检测热障涂层中热致氧化层的厚度

采用交流阻抗谱法对1000℃高温氧化的热障涂层材料(TBCs)样品进行分析。结果显示,氧化时间100 h后,致密氧化物层形成,其厚度随氧化进程增加且成分也由氧化铝向混合氧化物转变。通过等效电路模拟对交流阻抗测试结果进行分析,得到了热致氧化层(TGO)电容与厚度倒数的正比例关系,实现了对TGO层厚度的检测。     

Characterization of a cyclic displacement instability for a thermally grown oxide in a thermal barrier system

The mechanism responsible for the performance of a commercial thermal barrier system upon thermal cycling has been investigated. It comprises an electron beam physical vapor deposited (EB–PVD) yttria-stabilized zirconia thermal barrier coating (TBC) on a (Ni,Pt)Al bond coat. At periodic interfacial sites, the thermally grown oxide (TGO) that forms between the TBC and the bond coat at high temperature displaces into the bond coat with each thermal cycle. These displacements induce strains in the superposed TBC that cause it to crack. The cracks extend laterally as the TGO displaces, until those from neighboring sites coalesce. Once this happens, the system fails by large scale buckling. The displacements are accommodated by visco-plastic flow of the bond coat and “vectored” by a lateral component of the growth strain in the TGO. They depend upon the initial morphology of the metal/oxide interface. The observed responses are compared with the predictions of a ratcheting model.     

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…     

On the interfacial degradation mechanisms of thermal barrier coating systems: Effects of bond coat composition

Thermal barrier coating (TBC) systems based on an electron beam physical vapour deposited, yttria-stabilized zirconia (YSZ) top coat and a substrate material of CMSX-4 superalloy were identically prepared to systematically study the behaviour of different bond coats. The three bond coat systems investigated included two β-structured Pt–Al types and a γ–γ′ type produced by Pt diffusion without aluminizing. Progressive evolution of stress in the thermally grown aluminium oxide (TGO) upon thermal cycling, and its relief by plastic deformation and fracture, were studied using luminescence spectroscopy. The TBCs with the LT Pt–Al bond coat failed by a rumpling mechanism that generated isolated cracks at the interface between the TGO and the YSZ. This reduced adhesion at this interface and the TBC delaminated when it could no longer resist the release of the stored elastic energy of the YSZ, which stiffened with time due to sintering. In contrast, the TBCs with Pt diffusion bond coats did not rumple, and the adhesion of interfaces in the coating did not obviously degrade. It is shown that the different failure mechanisms are strongly associated with differences in the high-temperature mechanical properties of the bond coats.     

A chromia forming thermal barrier coating system

Conventional thermal barrier coating (TBC) systems consist of an insulating ceramic topcoat, a bond coat for oxidation protection and the underlying superalloy designed to combat the oxidising conditions in aero‐ and land‐based gas turbines. Under high‐temperature oxidation, the use of an alumina forming bond coat is warranted, thus all current TBC systems are optimised for the early formation of a dense, protective thermally grown oxide (TGO) of alumina. This also offers protection against Type I hot corrosion but a chromia layer gives better protection against Type II corrosion and intermediate temperatures, the conditions found in land‐based gas turbines. In this paper the authors present the first known results for a chromia forming TBC system. Tests have been performed under oxidising conditions, up to 1000 h, at temperatures between 750 °C and 900 °C, and under Type I (900 °C) and Type II (700 °C) hot corrosion conditions up to 500 h. Under all these conditions no cracking, spallation or degradation was observed. Examination showed the formation of an adherent, dense chromia TGO at the bond coat / topcoat interface. These initial results are very encouraging and the TGO thicknesses agree well with comparable results reported in the literature.     

The role that bond coat depletion of aluminum has on the lifetime of APS‐TBC under oxidizing conditions

Bond coat oxidation as well as bond coat depletion of Al are still believed to be a major degradation mechanism with respect to the lifetime of thermal barrier coating (TBC) systems. In this study the top coat lifetime is described as being limited by both bond coat depletion of Al and mechanical failure of the top coat. The empirical results are introduced by considering three spallation cases, namely, Al depletion failure, thermal fatigue failure, and thermal aging failure. Al depletion failure occurs when the Al content within the bond coat reaches a critical value. In this paper bond coat depletion of Al is modeled by considering the diffusion of Al into both the thermally grown oxide (TGO) and substrate. The diffusion model results are compared to Al concentration profiles measured with an electron beam microprobe. These measured results are from oxidized air plasma sprayed TBC systems (APS‐TBC) with vacuum plasma sprayed (VPS) bond coats for exposures up to 5000 h in the temperature range of 950–1100 °C. This paper focuses on the Al depletion failure and how it relates to top coat spallation.     

Thermal cycling behavior of EBPVD TBC systems deposited on doped Pt-rich γ–γ′ bond coatings made by Spark Plasma Sintering (SPS)

In the last decade, an increasing interest was given to Pt-rich γ–γ′ alloys and coatings as they have shown good oxidation and corrosion properties. In our previous work, Spark Plasma Sintering (SPS) has been proved to be a fast and efficient tool to fabricate coatings on superalloys including entire thermal barrier coating systems (TBC). In the present study, this technique was used to fabricate doped Pt-rich γ–γ′ bond coatings on AM1® superalloy substrate. The doping elements were reactive elements such as Hf, Y or Zr, Si and metallic additions of Ag. These samples were then coated by electron beam physical vapour deposition (EBPVD) with an yttria partially stabilized zirconia (YPSZ) thermal barrier coating. Such TBC systems with SPS Pt rich γ–γ′ bond coatings were compared to conventional TBC system composed of a β-(Ni,Pt)Al bond coating. Thermal cycling tests were performed during 1000-1 h cycles at 1100 °C under laboratory air. Spalling areas were monitored during this oxidation test. Most of the Pt rich γ–γ′ samples exhibited a better adherence of the ceramic layer than the β-samples. After the whole cyclic oxidation test, cross sections were prepared to characterize the thickness and the composition of the oxide scales by using scanning-electron microscopy. In particular, the influence of the doping elements on the oxide scale formation, the metal/oxide roughness, the TBC adherence and the remaining Al and Pt under the oxide scale were monitored. It was shown that RE-doping did not improve the oxidation kinetics of the studied Pt rich γ–γ′ bond coatings, nevertheless most of the compositions were superior to “classic” β-(Ni,Pt)Al bond coatings in terms of ceramic top coat adherence, due to lower rumpling kinetics and better oxide scale adherence of the γ–γ′-based systems.     

Effects of vacuum treatment on the formation of TGO in YSZ-TBC on IN738LC — An interpretation of EDX line-scan data

This study examined the effects of vacuum heat-treatment on the growth of oxide (thermally grown oxide, TGO) between the ceramic top coat (yttria-stabilized zirconia, YSZ) and the metallic bond coat (NiCrAlY) of a thermal barrier coating (TBC). For the investigation, IN738LC coupons coated with a TBC were heat-treated in vacuum and/or isothermally oxidized at 1200 °C and then microscopically analyzed using SEM and EDX. The introduction of heat treatment in vacuum before isothermal oxidation resulted in a reduction of the TGO thickness and the number of interface cracks around the TGO layers. These TGO layers were further analyzed using EDX line scan data in terms of the dependence of the EDX Al intensity on the O intensity. The analysis showed that the TGO layers in the coupons only oxidized in air were divided into two sub-layers with respect to the gradient of the Al intensity on the O intensity. The pre-treatment in vacuum nullified this division and reduced cracks at the interfaces. The effects of the treatment in vacuum on the behavior of TGO and TBCs were analyzed and compared with the data obtained for a TBC-coated turbine blade serviced for a land-based heavy duty gas turbine.     

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.