Scale-progressive healing mechanism dominating the ultrafast initial sintering kinetics of plasma-sprayed thermal barrier coatings

The thermal insulating performance of plasma-sprayed thermal barrier coatings (PS-TBCs) depends dominantly on inter-splat pores, which would be inevitably healed during high temperature exposure. The sintering kinetics of TBCs appears to be highly stage-sensitive. However, the ultrafast sintering kinetics during the initial sintering stage is not yet well understood. In this study, the sintering behavior of PS-TBCs was investigated in a scale-progressive (from nano- to micro-scale) way. Moreover, a novel healing mechanism suitable for lamellar TBCs was proposed based on a combined-effect of material and pore structure. Regarding the changing behavior of material, nano-scale roughening can be found at the as-deposited smooth pore surface after thermal exposure. Regarding the 2D featured inter-splat pores, the roughening behavior facilitates multiple contacts between the counter-surfaces of inter-splat pores. As a result, micro-scale bridge-connection can be observed at the healed parts. This multiple contacts mechanism caused by scale-progressive healing behavior significantly accelerated the matter transfer, resulting in ultrafast sintering kinetics at the initial sintering stage.     

Stress-dependent sintering behavior of porous thermal barrier coatings

Thermal barrier coatings (TBCs) are subjected to high temperature and complex stress fields during service in gas turbines. In this process, densification and hardening take place as the result of sintering, which is sensitive to boundary condition/external load. The stress-dependent sintering behaviors of porous TBCs were investigated in this work using a customized four-point bending method. Furthermore, stress-dependent sintering model was developed and implemented in finite element analysis to elucidate sintering mechanisms. It was found that stress gradient induced nonlinear differential sintering behavior, due to the accelerating and retarding effects of compressive and tensile stresses, respectively. In addition, microstructure-mechanical property relation was determined following the exponential law and high-throughput method was proposed for the characterization of stress dependence. The in-depth understanding of stress-dependent sintering behavior could provide guidance to the design and failure analysis of TBCs applied on complex shaped components in the hot section of gas turbines.     

Modified thick thermal barrier coatings: microstructural characterization

Thick thermal barrier coatings were modified with laser glazing and phosphate based sealing treatments. Surface porosity of the sealed coatings decreased significantly in all cases. Structural analysis showed a strong preferred crystal orientation of the t′ZrO₂ phase in direction [002] in laser-glazed 25CeO₂–2.5Y₂O₃–ZrO₂ coating. In laser-glazed 22MgO–ZrO₂ coating the major phase was rhombohedral Mg₂Zr₅O₁₂. In phosphate sealed 8Y₂O₃–ZrO₂ coating the strengthening mechanism was identified as adhesive binding without chemical bonding. Coating microstructures were determined by scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy and optical microscopy. Coatings were also characterized by X-ray diffraction, microhardness and porosity.     

Combined effect of internal and external factors on sintering kinetics of plasma-sprayed thermal barrier coatings

Understanding the sintering kinetics of plasma-sprayed thermal barrier coatings (PS-TBCs) is crucial to retard their performance degradation. However, under real service condition, the sintering kinetics is often affected by multiple factors. This study investigated the sintering kinetics, in a novel scale-progressive view, under the combined-effect of internal and external factors. Results show that the sintering kinetics of PS-TBCs was highly associated with their unique sintering process from nanoscale to microscale. Firstly, sintering leads to nanoscopic roughening of the pore surface. Subsequently, multiple contacts are formed between counter-surfaces. As a result, microscopic healing of pores can be finally observed. In terms of external factors, the temperature further affects the level and rate of nanoscopic roughening. This is responsible for the differences of the microscopic healing ratios, as well as the macroscopic elastic modulus.     

A comprehensive mechanism for the sintering of plasma-sprayed nanostructured thermal barrier coatings

Nanostructured thermal barrier coatings (TBCs) are being widely researched for their superior thermal barrier effect and strain compliance. However, the sintering occurs inevitably in nanostructured TBCs that comprise both nanozones and lamellar zones, although the mechanism of sintering in such bimodal coatings is not yet clear. This study investigates the changes in microstructure and properties of nanostructured TBCs during thermal exposure with the aim to reveal the sintering mechanism operative in these coatings. Results show that the sintering process occurs in two stages. It was found that in the initial shorter stage (~0–10 h), the properties increased rapidly; moreover, this change was anisotropic. The main structural change was the significant healing of the intersplat pores through multiconnection. During the subsequent longer stage, the change in the properties was much smaller, where it was observed that the pores continued to heal, albeit at a much lower rate. Furthermore, the faster densification of the nanozones induced during sintering became significant, resulting in an opening at the interface between the nanozones and the lamellar zones. In brief, the pore healing at the lamellar zones affects the properties, especially in the initial stage. The presence of nanozones has a positive effect in that the performance degradation during the overall thermal exposure is slowed down. An understanding of this competing sintering mechanism would enable the structural tailoring of nanostructured TBCs in order to increase their thermal insulation and thermal cycling lifetime.     

Nondestructive measurements of residual stress in air plasma-sprayed thermal barrier coatings

Premature spallation of thermal barrier coatings (TBCs) is a critical issue during the service of gas turbines, and nondestructive evaluation is crucial to address this problem. Herein, a novel approach that indicates delamination by measuring the residual stress evolution of thermally grown oxide (TGO) for air plasma spraying (APS) TBCs is proposed and verified via the combination of photoluminescence piezo-spectroscopy (PLPS) and X-ray computed tomography. A mineral-oil-impregnating approach and a cold-mount low-shrinkage epoxy-mounting approach are used to alleviate the signal attenuation by pores and microcracks in APS TBCs, improving the detectable PLPS signal and X-ray transmission for stress measurement and delamination characterization, respectively. We have nondestructively measured the TGO residual stress mapping in APS TBCs and its evolution with oxidation. Furthermore, the evolution of TGO morphology and critical microcracks are obtained by X-ray computed tomography. The synchronous evolution of TGO residual stress, TGO thickness, and critical microcracks as a function of oxidation time is obtained and correlated. The transition point, as experimentally identified, at which the TGO stress starts to drop, agrees well with the critical moment of microcrack coalescence. This directly verifies that the TBC delamination can be effectively indicated by residual stress evolution of TGO in APS TBCs.     

Novel-structured plasma-sprayed thermal barrier coatings with low thermal conductivity,high sintering resistance and high durability

The microstructure of the ceramic topcoat has a great influence on the service performance of thermal barrier coatings (TBCs). In this study, conventional layered-structure TBCs, nanostructured TBCs, and novel-structured TBCs with a unique microstructure were fabricated by air plasma spraying. The relationship between the microstructure and properties of the three different TBCs was analysed. Their thermal insulation ability, sintering resistance, and durability were systematically evaluated. Additionally, their failure modes after being subjected to two kinds of thermal shock tests were analysed. The results revealed that the novel-structured TBCs had remarkably superior performances in all the examined aspects. The thermal conductivity of the novel-structured TBCs was significantly lower than those of the conventional and nanostructured TBCs both in the as-sprayed state and after thermal treatment for 500 h at 1100 °C. The macroscopic elastic modulus of the novel-structured TBCs after sintering at 1300 °C for 100 h was similar to those of the conventional and nanostructured TBCs in the as-sprayed state. During both a burner rig thermal shock test and a furnace cyclic oxidation test, the thermal shock lifetime of the novel-structured TBCs was much longer than those of the conventional and nanostructured TBCs. This study has demonstrated novel-structured plasma-sprayed TBCs with high thermal insulation ability and high durability.     

Electrophoretic fabrication of thermal barrier coatings

An electrochemical method of fabrication of (NiCoCrAlY)/MgO/yttria-stabilized zirconia (YSZ) multilayered coating was proposed. This multilayered coat is expected to work as a thermal barrier coating for nickel superalloy substrates. The (NiCoCrAlY) layer was deposited using the electrophoretic deposition technique, the MgO layer was deposited by the electrolytic deposition technique and the YSZ layer was electrophoretically deposited. The process of depositing (NiCoCrAlY) alloy particles revealed that the electrophoretic technique can be used for particles with submicron dimensions. The MgO intermediate layer was introduced to accommodate the difference in thermal expansion coefficient between the YSZ ceramic and the NiCoCrAlY metal layers.     

Comparative study on thermal shock behavior of thick thermal barrier coatings fabricated with nano-based YSZ suspension and agglomerated particles

Two kinds of segmentation-crack structured YSZ thick thermal barrier coatings (TTBCs) were deposited by suspension plasma spraying (SPS) and atmospheric plasma spraying (APS) with nano-based suspension and agglomerated particles, respectively. The phase composition, microstructure evolution and failure behavior of both TBCs before and after thermal shock tests were systematically investigated. Microstructure of the APS coating exhibits typical segmentation-crack structure in the through-thickness direction, similar with the SPS coating. The densities of segmentation-crack in APS and SPS coatings were about 3 cracks mm⁻¹ and 4 cracks mm⁻¹_, respectively. The microstructure observation also showed that the columnar and equiaxed grains existed in the SPS coating. As for the thermal shock test, the spallation life of the APS TTBCs was 146 cycles, close to that of the SPS TTBCs (166 cycles). Failure of the APS coating is due to the spallation of fringe segments and splats.     

Constrained sintering and cracking of air plasma sprayed thermal barrier coatings: Experimental observation and modeling

The development of vertical cracks in air plasma sprayed (APS) thermal barrier coatings (TBCs) during thermal cycling and constrained sintering under a temperature gradient is investigated. Microstructural analysis shows that the development of the vertical cracks is associated with multiple processes, including sintering during the hold period and cleavage during cooldown. Inspired by the experimental observations, an image-based sintering model is used to simulate the development of vertical cracks as the coating sinters while constrained by a substrate. The computational results show that microstructural imperfections can develop into vertical cracks, which then propagate toward the interface. A simple analytical model is presented for the threshold level of in-plane stress for the onset of propagation of a vertical crack during constrained sintering. By combining the results of these different modeling approaches, the cross-coupling of the material and geometric parameters, and how this determines the sintering response (microstructure evolution) and vertical crack formation is evaluated. In addition, the growth of vertical cracks by a cleavage mechanism during cooldown is examined and the coupling between sintering, cleavage crack growth, and TBC lifetime is explored.     

Atmospheric plasma sprayed 7%-YSZ thick thermal barrier coatings with controlled segmentation crack densities and its thermal cycling behavior

Yttria-stabilized zirconia (YSZ)-coatings are deposited on Ni-based superalloy IN738 by atmospheric plasma spraying (APS). For the first time, controlled segmentation crack densities are manually developed in the coatings, even after the APS deposition. This method allows to user to control segmentation densities as well as cracks depth, which could be designed as per coating thickness and required application. Thermal cycling test shows promising strain tolerance behavior for the segmented coatings, whereas coating without segmentation could not sustain even for its first thermal cycle period. Further, microstructural studies reveal that a very thin layer of TGO was formed and obvious no coating failure or spallation was observed after thermal cycling test at 1150 °C for 500 cycles.     

YAG thermal barrier coatings deposited by suspension and solution precursor thermal spray

Yttrium aluminium garnet (YAG) is a promising topcoat material for thermal barrier coatings due to its high temperature stability and better CMAS (calcium-magnesium-alumino-silicate) resistance. YAG topcoats were deposited by suspension and solution precursor high-velocity oxy-fuel (HVOF) thermal spray. The relationships between processing, microstructure and final properties were studied through a range of characterization techniques and thermal cycling tests. The microstructure of the as-sprayed YAG topcoat from stoichiometric solution precursor (SP-YAG) had distributed pores and inter-splat boundaries, while the as-sprayed topcoat produced from suspension (S-YAG) had vertical and branched micro cracks, pores, and inter-splat boundaries. Both as-sprayed coatings were composed of amorphous phase, hexagonal yttrium aluminium perovskite (YAP) and cubic YAG. In thermal cycling tests, 20% of SP-YAG failure was reached after the 10th cycle; whereas, S-YAG reached the failure criteria between the 60th and 70th cycle. The failure of both the SP-YAG and the S-YAG topcoats occurred due to thermal stresses during the thermal cycling.     

Outstanding durability of sol-gel thermal barrier coatings reinforced by YSZ-fibers

Thermal barrier coatings (TBC) were fabricated with commercial powders of yttria stabilized zirconia with spherical and fiber-like morphologies. The influence of fiber percentage and sintering temperature on the thermomechanical behavior was studied. TBCs with 60%–80% fibers content had the best lifetime in cyclic oxidation with less than 10% of coating spallation after 1000 cycles, with very good reproducibility. They reached lifetimes higher than industrial TBCs made by EB-PVD. The enhancement of durability is believed to be due to an increase in the thermomechanical constraints accommodation thanks to higher porosity and higher tenacity due to the presence of well anchored fibers, indeed deviation of the cracks were observed. Moreover, the morphology of the thermally grown oxide (TGO) layer is also favorable as it includes anchorage points of the TGO with fibers. This increased the adherence at the substrate interface and improved lifetime.     

CMAS corrosion of YSZ thermal barrier coatings obtained by different thermal spray processes

Degradation of yttria-stabilized zirconia (YSZ) layers by molten CaO-MgO-Al₂O₃-SiO₂ (CMAS)-based deposits is an important failure mode of thermal barrier coating (TBC) systems in modern gas turbines. The present work aimed to understand how the chemical purity and microstructure of plasma-sprayed YSZ layers affect their response to CMAS corrosion. To this end, isothermal corrosion tests (1 h at 1250 °C) were performed on four different kinds of YSZ coatings: atmospheric plasma-sprayed (APS) layers obtained from standard- and high-purity feedstock powders, a dense – vertically cracked (DVC) layer, and a suspension plasma sprayed (SPS) one. Characterization of corroded and non-corroded samples by FEG-SEM, EBSD and micro-Raman spectroscopy techniques reveals that, whilst all YSZ samples suffered grain-boundary corrosion by molten CMAS, its extent could vary considerably. High chemical purity limits the extent of grain-boundary dissolution by molten CMAS, whereas high porosity and/or fine crystalline grain structure lead to more severe degradation.     

Improve durability of plasma-splayed thermal barrier coatings by decreasing sintering-induced stiffening in ceramic coatings

In this study, a newly-tailored plasma-sprayed (PS) yttria-stabilized zirconia (YSZ) ceramic coating towards enhanced strain tolerance and sintering resistance was developed to improve the durability of TBCs. The thermal shock life was found to be markedly prolonged by more than four times. Failure mechanisms and sintering behavior of the newly-structured and conventional TBCs were systematically investigated through microstructural and mechanical analyses. Conventional TBCs suffered a premature spallation due to rapid sintering-induced stiffening of the ceramic top coat. In contrast, the new coating exhibits an enhanced sintering resistance whereby preserving a good strain tolerance over time. Specifically, its elastic modulus after thermal exposure remains comparable to the as-sprayed states. The effect of ceramic top coat stiffness on cracking behavior of TBCs was clarified by a corresponding cohesive zone finite element modeling. This study provides a new option for improving TBCs durability and the results could benefit the increased integrity of TBCs.     

Sintering‐induced delamination of thermal barrier coatings by gradient thermal cyclic test

Lifetime is crucial to the application of advanced thermal barrier coatings (TBCs), and proper lifetime evaluation methods should be developed to predict the service lifetime of TBCs precisely and efficiently. In this study, plasma‐sprayed YSZ TBCs were subjected to gradient thermal cyclic tests under different surface temperatures, with the aim of elucidating the correlation between the coating surface temperature and the thermal cyclic lifetime. Results showed that the thermal cyclic lifetime of TBCs decreased with the increasing of surface temperatures. However, the failure modes of these TBCs subjected to thermal cyclic tests were irrespective of different surface/BC temperatures, that is, sintering‐induced delamination of the top coat. The thickness of thermally grown oxide (TGO) was significantly less than the critical TGO thickness to result in the failure of TBCs through the delamination of top coat. There was no phase transformation of the top coat after failure. In contrast, in the case concerning the top coat surface of the failure specimens, the elastic modulus and microhardness increased to a comparable level due to sintering despite of the various thermal cyclic conditions. Consequently, it is conclusive that the failure of TBCs subjected to gradient thermal cyclic test was primarily induced by sintering during high‐temperature exposure. A delamination model with multilayer splats was developed to assist in understanding the failure mechanism of TBCs through sintering‐induced delamination of the top coat. Based on the above‐described results, this study should aid in facilitating the lifetime evaluation of the TBCs, which are on active service at relatively lower temperatures, by an accelerated thermal cyclic test at higher temperatures in laboratory conditions.     

Oxidation kinetics of atmospheric plasma sprayed environmental barrier coatings

Three different Si/Yb-silicate environmental barrier coating systems (EBCs) were atmospheric plasma sprayed using various spray currents (275, 325, 375 A) for Yb-silicate deposition. The EBCs were thermally cycled between room temperature and 1300 °C up to 1000 h in air. Additionally, bare Si coatings were tested under isothermal and thermal cycling conditions in the as-sprayed state and after polishing at 1300 °C in air. Parabolic oxidation kinetics were observed and oxidation protection provided by Yb-silicate was found to be influenced by the spray conditions, i.e. only at 325 A, Yb-silicate was effectively protecting the bond coat. The controlling mechanism was attributed to densification in the Yb-silicate layer during thermal cycling, which was quantified via image analysis. The surface finish of the Si coating was also found to be influencing the oxidation rate. The TGO was thinner and less cracked on polished APS Si coating in comparison with the as-sprayed Si coating surface.     

Research progress on hafnium-based thermal barrier coatings materials

Thermal barrier coatings (TBC) are important materials applied to hot part components of aero-engines in order to improve their service temperature. Increasing inlet temperature is an important factor to achieve elevated thrust-to-weight ratio and high heat engine efficiency. In recent years, traditional TBC materials have gradually reached their operating limits due to the increase in turbine operating temperature. Hafnium-based materials become promising new candidates for TBC because of the similar structure, higher temperature phase stability and lower thermal conductivity compared to traditional zirconium-based materials. In this review, recent progresses in the research and development for hafnium-based TBC materials are summarized. The phase stability, thermal and mechanical properties of rare-earth (RE)-doped HfO₂ and RE hafnate materials are introduced. RE-doped HfO₂ has good thermal properties and phase stability at high temperatures whereas relatively low fracture toughness. The RE hafnates possess the advantages of a higher phase transition temperature, lower thermal conductivity and superior fracture toughness than RE zirconates. However, the thermal expansion coefficients of most RE hafnates are quite different from the alloy matrix. Finally, further research directions for hafnium-based TBC materials are prospected in this study.     

Lanthanum cerate thermal barrier coatings generated from thermal plasma synthesized powders

Lanthanum cerate (La₂Ce₂O₇, LC) is one of the promising advanced thermal barrier coating (TBC) materials due to its high melting point, no phase transformation between room temperature and operating temperature, low thermal conductivity, comparable coefficient of thermal expansion (CTE) with metallic substrate. The present study investigates plasma transferred arc synthesis of LC powder, its subsequent spheroidization in a thermal plasma jet and plasma spray deposition. The PTA-synthesized LC powder, spheroidized as well as the plasma sprayed coatings was found to possess excellent phase stability; the single phase cubic fluorite structure of LC was found to be retained even after prolonged arc-melting, corroborating that the material was stable from room temperature up to its melting point. It was observed that PTA melting for longer duration resulted in small deviation from stoichiometry, although the phase structure of LC was retained. Spheroidization efficiency was found to increase with the input power of the torch. Very good adherent LC coatings could be deposited on nickel super alloy with reasonably good deposition efficiency.     

利用3ω法同时测量纳米流体热导率和热扩散系数

提出了应用基于谐波探测技术的3ω法进行液体导热性能测量的方法。设计了3ω测试系统，测试了不同浓度和不同温度下纳米流体的热导率和热扩散系数，与文献中的测试结果进行了对比。实验中测试的热波信号较好地满足频域内的导热方程，说明采用交流电流加热可使流体的微对流作用得到有效减弱。采用基于多颗粒布朗运动的微对流（MSBW）模型预测了纳米流体的热导率。浓度比较低时TiO₂+蒸馏水、Al₂ O₃+蒸馏水纳米颗粒流体的热导率随温度增加呈线性增大，并且与液体的Prandtl数有关，在测试温度为18～65℃范围内，水的热导率随温度升高以及纳米颗粒的布朗运动所引起周围基液的微对流作用是纳米流体强化传热的两个重要机理。