An innovative model coupling TGO growth and crack propagation for the failure assessment of lamellar structured thermal barrier coatings

The failure of plasma-sprayed thermal barrier coating (TBC) is often caused by the coating spallation due to crack propagation. In this study, a new model with stacking lamellae is developed based on the cross-section micrograph to explore crack propagation behavior within the ceramic top coat (TC) during isothermal cycling. The dynamic growth process of thermally grown oxide (TGO) is simulated via material properties change step by step. The stress profiles in the lamellar model are first evaluated, and the pore and lamellar interface crack effects on the stress state are further explored. Then, the successive crack growth, linkage, and ultimate coating spallation process is simulated. The results show that the stress intensity in TC enhances with thermal cycling. Large stress concentration always occurs near the pore and lamellar interface crack, which can result in the incipient crack growth. Moreover, the lamellar interface crack also changes the stress distribution within the TC and at the TC/bond coat interface. The multiple crack propagation upon temperature cycling is explored, and the possible coalescence mechanism is proposed. The lamellar crack steadily propagates at the early stage. The crack length sharply increases before the occurrence of coating spallation. The simulated coat spalling path is in line with the experimental result. Therefore, the new lamellar model developed in this work is beneficial to further reveal coating failure mechanism and predict coating lifetime.     

Dynamic crack growth mechanism and lifetime assessment in plasma sprayed thermal barrier system upon temperature cycling

Failure of plasma-sprayed thermal barrier coatings (TBCs) is very complicated upon temperature cycling, therefore, to ascertain the crack propagation behavior is beneficial to understand the failure mechanism and life prediction of TBCs. In this paper, a finite element model is developed by coupling the dynamic growth of thermally grown oxide and dynamic crack propagation to explore the failure of TBCs induced by the instability of the interface between top coat (TC) and bond coat (BC). The thermal cyclic lifetime is deduced by obtaining the thermal cycles corresponding to the occurrence of complete delamination. The influence of the non-uniformity of the interface on thermal cyclic lifetime is quantitatively evaluated. Sensitivity studies including the effects of constituent properties and crack distance to the interface on the thermal cyclic lifetime are further examined. The results show that the incipient cracks usually nucleate above the valley due to the large tensile stress, and the shear stress near the peak plays a very crucial role. The crack growth involves three stages with different fracture dominated-mode. The crack propagation behavior obtained by simulation is in line with that observed by experiments. The TBCs system with a uniform interface exhibits a longer thermal cyclic lifetime compared to the non-uniform interface. Coating optimization methods proposed in this work may provide an alternative option for developing a TBCs system with longer service lifetime.     

Cracking behavior and delamination mechanism of lamellar structured TBC with localized mixed oxides

Mixed oxide (MO) with localized growth feature and high growth rate remarkably affects the lifetime of thermal barrier coatings (TBCs), which indicates that clarifying the ceramic cracking mechanism induced by MO is critical for developing new coatings with high durability. Two kinds of TBC models involving spherical and layered mixed oxides are created to explore the influence of MO growth on the local stress state and crack evolution during thermal cycle. The growth of α-Al₂O₃ is also included in the model. The undulating interface between ceramic coat and bond coat is approximated using a cosine curve. Dynamic ceramic cracking is realized by a surface-based cohesive interaction. The ceramic delamination by simulation agrees with the experimental observation. The effects of MO coverage ratio and growth rate on the TBC failure are also discussed. The results show that the MO growth causes the local ceramic coat to bear the normal tensile stress. The failure mode of coating is turned from α-Al₂O₃ thickness control to MO growth control. Once the mixed oxide appears, local ceramic cracking is easy to occur. When multiple cracks connect, ceramic delamination happens. Suppressing MO formation or decreasing MO growth can evidently improve the coating durability. These results in this work can provide important theoretical guidance for the development of anti-cracking TBCs.     

Preparation of plasma sprayed nanostructured GdPO4 thermal barrier coating and its hot corrosion behavior in molten salts

Nanostructured GdPO₄ coatings, designed as the outer layer of double-ceramic-layer thermal barrier coatings (DCL-TBCs), were produced by air plasma spraying (APS). The coatings have close chemical composition to that of the agglomerated particles used for thermal spray. Nanozones with porous structure are embedded in the coating microstructure, having a percentage of ~30%. Hot corrosion tests of the coatings were carried out in V₂O₅ and Na₂SO₄+V₂O₅ salts at 900 °C for 4 h. Results indicate that dense reaction layers, consisting of GdVO₄ and Gd₄(P₂O₇)₃, form on the coating surfaces, which could suppress further penetration of the molten salts. In the V₂O₅ molten salt, the reaction layer is thicker and less molten salt trace could be found beneath the layer.     

Comprehensive dynamic failure mechanism of thermal barrier coatings based on a novel crack propagation and TGO growth coupling model

Comprehensive understanding of failure mechanism of thermal barrier coatings (TBCs) is essential to develop the next generation advanced TBCs with longer lifetime. In this study, a novel numerical model coupling crack propagation and thermally grown oxide (TGO) growth is developed. The residual stresses induced in the top coat (TC) and in the TGO are calculated during thermal cycling. The stresses in the TC are used to calculate strain energy release rates (SERRs) for in-plane cracking above the valley of undulation. The overall dynamic failure process, including successive crack propagation, coalescence and spalling, is examined using extended finite element method (XFEM). The results show that the tensile stress in the TC increases continuously with an increase in an undulation amplitude. The SERRs for TC cracks accumulate with cycling, resulting in the propagation of crack toward the TC/TGO interface. The TGO cracks nucleate at the peak of the TGO/bond coat (BC) interface and propagate toward the flank region of the TC/TGO interface. Both TC cracks and TGO cracks successively propagate and finally linkup leading to coating spallation. The propagation and coalescence behavior of cracks predicted by this model are in accordance with the experiment observations. Therefore, this study proposed coating optimization methods towards advanced TBCs with prolonged thermal cyclic lifetime.     

Simulation of thermal barrier coating spallation induced by the initiation/growth/coalescence of internal crack and interfacial crack based on a real image model

In the furnace cycle test, the growth of oxide film leads to the propagation and coalescence of multiple cracks near the interface, which should be responsible for the spallation of thermal barrier coatings (TBCs). A TBC model with real interface morphology is created, and the near-interface large pore is retained. The purpose of this work is to clarify the mechanism of TBC spallation caused by successive initiation, propagation, and linkage of cracks near the interface during thermal cycle. The dynamic growth of thermally grown oxide (TGO) is carried out by applying a stress-free strain. The crack nucleation and arbitrary path propagation in YSZ and TGO are simulated by the extended finite element method (XFEM). The debonding along the YSZ/TGO/BC interface is evaluated using a surface-based cohesive behavior. The large-scale pore in YSZ near the interface can initiate a new crack. The ceramic crack can propagate to the YSZ/TGO interface, which will accelerate the interfacial damage and debonding. For the TGO/BC interface, the normal compressive stress and small shear stress at the valley hinder the further crack propagation. The growth of YSZ crack and the formation of through-TGO crack are the main causes of TBC delamination. The accelerated BC oxidation increases the lateral growth strain of TGO, which will promote crack propagation and coalescence. The optimization design proposed in this work can provide another option for developing TBC with high durability.     

Vertical crack distribution effect on the TBC delamination induced by crack growth from the ceramic surface and near the interface

The propagation of vertical crack on the surface of thermal barrier coatings (TBCs) may affect the interface cracking and local spallation. This research aims to establish a TBC model incorporating multiple cracks to comprehensively understand the effects of vertical crack distribution on the coating failure. The continuous TGO growth and ceramic sintering are together introduced in this model. The influence of the vertical crack spacing and non-uniform distribution on the stress state, crack driving force, and dynamic propagation is examined. Moreover, the influence of coating thickness on the crack growth driving is also explored. The results show that large spacing will lead to early crack propagation. The uniform distribution of vertical cracks can delay the spallation. When the spacing is less than 4 times ceramic coat thickness, the cracking driving force will come in a steady-state stage with the increase of vertical crack length. Prefabrication of vertical cracks with spacing less than 0.72 mm on the coating surface can greatly decrease the strain energy. The results in this study will contribute to the construction of an advanced TBC system with long lifetime.     

Stress states in plasma-sprayed thermal barrier coatings upon temperature cycling: Combined effects of creep,plastic deformation,and TGO growth

To ascertain material parameter effects on the stress states is beneficial to comprehend the crack growth behavior and delamination mechanism in thermal barrier coatings (TBCs). In this work, numerical models are established to explore the combined effects of material parameters including creep, plastic deformation, and thermally grown oxide (TGO) growth on the stress states upon temperature cycling. For all layers, thermal-physical properties reliant on temperature are incorporated into the model. The process of bond coat (BC) oxidation, namely TGO growth, is materialized by changing material properties with cycles. Based on the principle of a single variable, the residual stress states are explored using many different material combinations. The results indicate that the tensile stress in the ceramic top coat (TC) decreases with the increase in the TGO lateral strain distribution gradient. Increasing the BC yield strength or decreasing the TGO growth stress can reduce the tensile stress in TC if there is no creep in the model. When BC yield strength is relatively high (≥150 MPa), BC creep will strengthen the TC tensile stress. TGO creep can decrease the tensile stress in TC irrespective of TGO growth stress and BC creep. When TGO creep rate is higher than 10B^tgo, an exceedingly small tensile stress can always be achieved. This work could provide significant theory direction for material selection and composition control towards advanced TBCs with prolonged lifetime.     

Prolong the durability of La2Zr2O7/YSZ TBCs by decreasing the cracking driving force in ceramic coatings

Service lifetime and thermal insulation performance are both crucial for the application of thermal barrier coatings (TBCs). In this study, layered structure design under equivalent thermal insulation conception is introduced to lower the cracking driving force in TBCs, and with the goal of prolonging TBCs lifetime. Three groups of layered LZO/YSZ TBCs were designed with same thermal insulation of 500?μm YSZ, the LZO layers were deliberately designed with different initial elastic modulus. Virtual crack closure technique (VCCT) calculation result showed that the energy release rates at the crack tips are 28.2, 22, and 18.8?N/m corresponding to the initial elastic modulus of 70, 60, and 50?GPa. After gradient thermal cyclic tests with surface temperature of 1300?°C, TBCs with lowest initial elastic modulus showed the longest lifetime, and more than double of pure YSZ TBCs. This study provides a new option for the improvement of TBCs lifetime.     

Comprehensive understanding of horizontal and vertical crack effects on failure mechanism of lamellar structured thermal barrier coatings

The local spalling induced by the propagation and coalescence of cracks in the ceramic layer is the fundamental reason for the thermal barrier coatings (TBCs) failure. To clarify the effects of horizontal and vertical cracks on the coating failure, an integrated model combining dynamic TGO growth and ceramic sintering is developed. The effects of cracks on the normal and shear stress characteristics are analyzed. The driving force and propagation ability of cracks under different configurations are evaluated. The interaction between horizontal and vertical cracks is explored by analyzing the variation of the crack driving force. The results show that TGO growth causes the ratcheting increase of σ₂₂ tensile stress above the valley, and the σ₁₂ shear stress is on both sides of the peak. Ceramic sintering mainly contributes to the ratcheting increase of σ₁₁ tensile stress. There is minimum strain energy when the horizontal crack extends to the peak. The vertical cracks on the surface of the ceramic layer are easier to propagate through the coating than that of other locations. When the horizontal and vertical cracks simultaneously appear near the valley, they can promote the propagation of each other. The present results can offer theoretical support for the design of an advanced TBC system in the future.     

Thermal cycling and hot corrosion behavior of a novel LaPO4/YSZ double-ceramic-layer thermal barrier coating

LaPO₄ powders were produced by a chemical co-precipitation and calcination method. The ceramic exhibited a monazite structure, kept phase stability at 1400?°C for 100?h, and had low thermal conductivity (~ 1.41?W/m?K, 1000?°C). LaPO₄/Y₂O₃ partially stabilized ZrO₂ (LaPO₄/YSZ) double-ceramic-layer (DCL) thermal barrier coatings (TBCs) were fabricated by air plasma spray. The LaPO₄ coating contained many nanozones. Thermal cycling tests indicated that the spallation of LaPO₄/YSZ DCL TBCs initially occurred in the LaPO₄ coating. The failure mode was similar to those of many newly developed TBCs, probably due to the low toughness of the ceramics. LaPO₄/YSZ DCL TBCs were highly resistant to V₂O₅ corrosion. Exposed to V₂O₅ at 700–900?°C for 4?h, La(P,V)O₄ formed as the corrosion product, which had little detrimental effect on the coating microstructure. At 1000?°C for 4?h, a minor amount of LaVO₄ was generated.     

The sintering behavior of plasma-sprayed YSZ coating over the delamination crack in low temperature environment

The sintering behavior of plasma-sprayed yttria-stabilized zirconia (YSZ) coating over the delamination crack and its influence on YSZ cracking were investigated via gradient thermal cycling test and finite element model (FEM). The gradient thermal cycling test was performed at a peak surface temperature of 1150 °C with a duration of 240 s for each cycle. A three-dimensional model including delamination cracks with different lengths was employed to elaborate the temperature evolution characteristics in YSZ coating over the delamination cracks. The temperature over the delamination crack increases linearly with the crack propagation, which continuously promotes the sintering of YSZ coating in the region. As a result, the YSZ coating over the delamination crack sinters dramatically despite of the low temperature exposure. Meanwhile, the temperature distribution difference in YSZ coating induces an nonuniform sintering along both free surface and thickness of YSZ coating. Correspondingly, the maximum vertical crack driving force locates at the YSZ free surface over the delamination crack center, which makes the vertical cracks generate in this region and propagate to the interface of YSZ /bond coat with YSZ further sintering. The vertical crack promotes the delamination crack propagation via accelerating the oxidation velocity of the bond coat. The influence of temperature rise on delamination crack propagation can be divided into two stages: the little contribution stage and the promotion stage. For the actual engine exposure to low temperature, the study of phase transformation of YSZ over the delamination crack is indeed needed because of an extended remarkable temperature rise period.     

Phase structure and thermal conductivities of Er2O3 stabilized ZrO2 toughened Gd2Zr2O7 ceramics for thermal barrier coatings

3.5 mol% Er₂O₃ stabilized ZrO₂ (ErSZ) and Gd₂Zr₂O₇ powders were produced by a chemical co-precipitation and calcination method, and ErSZ was used to toughen Gd₂Zr₂O₇. The phase structure, toughness and thermal conductivities of ErSZ toughened Gd₂Zr₂O₇ ceramics were investigated. When the ErSZ content was below 15 mol%, the compound consisted of pyrochlore phase, the ordering degree of which decreased with the increase of the ErSZ content. High ErSZ doping led to the formation of metastable tetragonal (t′) phase in the compound. The addition of ErSZ in Gd₂Zr₂O₇ benefited its toughness, mainly attributable to the presence of t′ phase in the compound. With the increase of the ErSZ content in the compound, the thermal conductivity first decreased and then showed an upward tendency, and 10 mol% ErSZ toughened Gd₂Zr₂O₇ exhibited the lowest thermal conductivity.     

Experimental investigation of Al2O3/8YSZ and CeO2/8YSZ plasma sprayed thermal barrier coating on diesel engine

In this research work, aluminium oxide/yttria stabilized zirconia (20%Al₂O₃/80%8YSZ) and ceria/yttria stabilized zirconia (20%CeO₂/80%8YSZ) were coated through atmospheric plasma spray technique (APS) as thermal barrier coating (TBC) over CoNiCrAlY bond coat on aluminium alloy (Al-13%Si) substrate piston crown material and their thermal cycling behavior were studied experimentally. Thermal cycle test of both samples were conducted at 800?°C. Microstructural, phase and elemental analysis of the TBC coatings were experimentally investigated. The performance, combustion and emission characteristics of Al₂O₃/8YSZ, CeO₂/8YSZ TBC coated and uncoated standard diesel engine were experimentally investigated. The test results revealed that CeO₂/8YSZ based TBC has an excellent thermal cycling behavior in comparison to the Al₂O₃/8YSZ based TBC. The spallation of the Al₂O₃/8YSZ TBC occurred mainly due to the formation of thermally grown oxide (TGO), and growth of residual stresses at top coating and bond coating interface. The experimental results also revealed that the increase of brake thermal efficiency and reduction of specific fuel consumption for both TBC coated engine. Further reduction of HC, CO and smoke and increase of NOx emission were recorded for both TBC coated engine compared to the standard diesel engine.     

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.     

Analysis of crack initiation and propagation in Thermal Barrier Coatings using SEM-Based geometrical model with extended finite element method

Thermal Barrier Coatings (TBC) are widely used to protect the metallic components that operate at harsh conditions of elevated temperatures and oxidizing environments. Thermally grown oxide (TGO) causes cracks formation in the top coat (TC) that may lead to spallation failure of TBC. This work investigates effect of pores and TGO thickness on crack initiation and propagation due to thermal mismatch between TBC layers. Image processing is used to convert an SEM image, including pores, into a finite element (FE) model. An FE model using XFEM implemented in ABAQUS was developed to investigate crack initiation and propagation for various TGO thicknesses considering the effect of plastic deformation of BC, TGO and substrate. Results show that presence of pores changes the critical sites for crack initiation from the TC/TGO interface to be around the pores within the TC. Crack initiation temperatures and crack lengths were found to be affected with both TGO thickness and pores.     

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.     

Thermal shock resistance and mechanical properties of La2Ce2O7 thermal barrier coatings with segmented structure

La₂Ce₂O₇ (LCO) is a promising candidate material for thermal barrier coatings (TBCs) application because of its higher temperature capability and better thermal insulation property relative to yttria stabilized zirconia (YSZ). In this work, La₂Ce₂O₇ TBC with segmentation crack structure was produced by atmospheric plasma spray (APS). The mechanical properties of the sprayed coatings at room temperature including microhardness, Young's modulus, fracture toughness and tensile strength were evaluated. The Young's modulus and microhardness of the segmented coating were measured to be about 25 and 5 GPa, relatively higher than those of the non-segmented coating, respectively. The fracture toughness of the LCO coating is in a range of 1.3–1.5 MPa m^1/2, about 40% lower than that of the YSZ coating. The segmented TBC had a lifetime of more than 700 cycles, improving the lifetime by nearly two times as compared to the non-segmented TBC. The failure of the segmented coating occurred by chipping spallation and delamination cracking within the coating.     

Synthesis and electroluminescence properties of a novel poly(paraphenylene vinylene)‐based copolymer with tri(ethylene oxide) segments on the backbone

A novel light‐emitting copolymer [tri(ethylene oxide)–poly(paraphenylene vinylene) (TEO–PPV)] containing alternating rigid, conjugated distyrylbenzene [poly(paraphenylene vinylene) model oligomer] as light‐emitting units and flexible tri(ethylene oxide) as ionic conductive units was synthesized. The polymer was characterized with Fourier transform infrared, ¹H‐NMR, ultraviolet–visible spectroscopy, differential scanning calorimetry, and gel permeation chromatography. TEO–PPV has excellent solubility in conventional organic solvents such as tetrahydrofuran, chloroform, benzene, and toluene. The estimated lowest unoccupied molecular orbital, highest occupied molecular orbital, and band gap are 2.35, 5.29, and 2.94 eV, respectively. Single‐layer and double‐layer light‐emitting diodes with indium tin oxide anodes and calcium cathodes were fabricated, and the photoluminescence (PL) and electroluminescence (EL) properties were investigated. The maximum EL emissive peak (475 nm) of the devices is essentially the same as that of PL. Anomalous current–voltage characteristics were observed in both devices. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2195–2200, 2002