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.     

Hot corrosion behavior of double ceramic layered CaZrO3/Yttria‐stabilized zirconia coatings

A novel double ceramic layered (DCL) CaZrO₃/Yttria‐stabilized zirconia (YSZ) thermal barrier coatings (TBCs) was designed for improved service life against sulfate vanadate hot corrosion as compared with that of YSZ single layered coating. The hot corrosion behavior of DCL CaZrO₃/YSZ coatings was studied at 950°C after dry spreading 50%Na₂SO₄+50%V₂O₅ mixture onto a coated surface. The CaZrO₃ as the topmost layer in DCL CaZrO₃/YSZ coatings, served as a sacrificial layer during sulfate vanadate hot corrosion protecting the underneath YSZ coating. The corrosion reactions in this case were sluggish due to the initial formation of low melting point meta‐calcium vanadate (CaV₂O₆) that isothermally transformed to higher melting point calcium vanadates having higher calcia (CaO) content. The corrosion reaction products sealed the top surface, impeding the oxygen movement and eventually retarded the thermally grown oxide (TGO) growth. The sulfate vanadate hot corrosion life of the DCL CaZrO₃/YSZ coatings was observed to be more than double as compared with single ceramic layered YSZ coatings.     

Thermal cycling behavior and bonding strength of single-ceramic-layer Sm2Zr2O7 and double-ceramic-layer Sm2Zr2O7/8YSZ thermal barrier coatings deposited by atmospheric plasma spraying

The single-ceramic-layer (SCL) Sm₂Zr₂O₇ (SZO) and double-ceramic-layer (DCL) Sm₂Zr₂O₇ (SZO)/8YSZ thermal barrier coatings (TBCs) were deposited by atmospheric plasma spraying on nickel-based superalloy substrates with NiCoCrAlY as the bond coat. The mechanical properties of the coatings were evaluated using bonding strength and thermal cycling lifetime tests. The microstructures and phase compositions of the coatings were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The results show that both coatings demonstrate a well compact state. The DCL SZO/8YSZ TBCs exhibits an average bonding strength approximately 1.5 times higher when compared to the SCL SZO TBCs. The thermal cycling lifetime of DCL SZO/8YSZ TBCs is 660 cycles, which is much longer than that of SCL 8YSZ TBCs (150 cycles). After 660 thermal cycling, only a little spot spallation appears on the surface of the DCL SZO/8YSZ coating. The excellent mechanical properties of the DCL LZ/8YSZ TBCs can be attributed to the underlying 8YSZ coating with the combinational structures, which contributes to improve the toughness and relieve the thermal mismatch between the ceramic layer and the metallic bond coat at high temperature.     

Enhanced properties of Al-modified EB-PVD 7YSZ thermal barrier coatings

7 wt% yttria-stabilized zirconia (7YSZ) thermal barrier coating (TBC) prepared by electron beam-physical vapor deposition (EB-PVD) has been used in gas turbine engines for many years, where the TBC must successfully withstands the damage caused by a variety of environmental and mechanical aspects. The primary failure modes for TBC are oxidation of bond coating, particle erosion and CMAS (calcium-magnesium-alumina-silicates) corrosion. The lifetime of TBC associated with above three failure factors will be reduced significantly. In order to prolong the operation time, an alternative approach depositing Al film on 7YSZ TBC surface by magnetron sputtering is proposed. An α-Al₂O₃ overlay was in-situ synthesized on each 7YSZ column through reaction of Al and ZrO₂ during vacuum heat treatment. And the results indicate that the Al-modified EB-PVD 7YSZ TBC shows better oxidation resistance, as well as lower particulate erosion and CMAS corrosion.     

Effect of CeO2 doping on high temperature oxidation resistance of YSZ TBCs

In the present work, YSZ TBCs and 10 wt% CeO₂-doped YSZ thermal barrier coatings (CeYSZ TBCs) were prepared via atmospheric plasma spraying(APS) respectively, whereupon high temperature oxidation experiment was carried out at 1100 °C to compare the high temperature oxidation behavior and mechanism of the two TBCs. The results showed that the doping of CeO₂ reduced the porosity of YSZ TBCs by 23%, resulting in smaller oxidation weight gain and lower TGO growth rates for CeYSZ TBCs. Besides, the TGO generated in CeYSZ TBCs was obviously thinner and there were fewer defects inside it. For YSZ TBCs, as the oxidation process proceeded, Al, Cr, Co and Ni elements in the bonding coating were oxidized successively to form loose and porous spinel type oxides (CS), which was apt to cause the spalling failure of TBCs. While, the Al₂O₃ layer of the TGO generated in CeYSZ TBCs ruptured later than that in YSZ TBCs, which delayed the oxidation of Cr, Co, and Ni elements and the formation of CS accordingly. Therefore, CeO₂ doping can effectively improve the high temperature oxidation resistance of YSZ TBCs.     

Evaluation of stress distribution and failure mechanism in lanthanum–titanium–aluminum oxides thermal barrier coatings

LaTi₂Al₉O₁₉ (LTA) is one of the most promising materials for new thermal barrier coatings (TBCs) to fulfill the demand of advanced gas turbines owing to its high temperature stability and low thermal conductivity. In the present study, a finite element (FE) based numerical study has been carried out to investigate the stress distribution in LTA single layered coating system in comparison with traditional yttria stabilized zirconia (YSZ) TBC. Stresses in YSZ/LTA double ceramic layer TBC system are also determined and presented for comparative analysis. The thermal cycling effect is simulated by sequent increment in TGO thickness in a series of FE simulations. In-plane stresses (σ_xx), out-of-plane stresses (σ_yy) and shear stresses (σ_xy) are determined for all systems, and peak stress values are presented for quantitative comparison. Elastic strain energy stored in TGO of all systems is calculated from FE results for TBC structural integrity assessment. It has been found that maximum in-plane and shear stresses are lower in the double ceramic layer coating system than in the single layer ceramic coating system. However, peak axial tensile and compressive stresses in the double ceramic layer coating are very close or higher than those in the single layer topcoat. Calculation of elastic store energy shows that double ceramic layer TBC system may exhibit better stability as compared to single layer systems. Results are presented to explain the failure mechanism in LTA coatings.     

Yb2Si2O7 Environmental barrier coatings with reduced bond coat oxidation rates via chemical modifications for long life

Spallation of environmental barrier coating (EBC) induced by thermally grown oxide (TGO) resulting from steam oxidation is a key EBC failure mode. A logical approach to improve EBC life, therefore, is to reduce TGO growth rates. A study was undertaken to investigate whether TGO growth rates can be reduced by adding modifier oxides. It was based on a hypothesis that modifier oxides dissolve in SiO₂ TGO and modify the SiO₂ structure, making the TGO less permeable to oxidants. Using a current state-of-the-art EBC (Si/Yb₂Si₂O₇) as the baseline, the Yb₂Si₂O₇ layer was modified by adding Al₂O₃ or Al₂O₃-containing oxide compounds, such as mullite and YAG (Y₃Al₅O₁₂), and TiO₂. EBCs were processed using air plasma spraying. Steam oxidation tests and post-oxidation test oxidation kinetics, chemistry, microstructure, and phase analysis were used to test the hypothesis. The best modified EBC reduced the TGO thickness by ~87% compared with that of the baseline EBC in 90% H₂O + 10% O₂ at 1316°C under thermal cycling. Correlations between oxidation kinetics, chemistry, and microstructure of EBC and TGO were used to explain the effect of modifier oxides on reducing TGO growth rates.     

Investigating the thermal,mechanical and thermal cyclic properties of plasma-sprayed Al2O3-7YSZ/7YSZ double ceramic layer TBCs

Double ceramic layer (DCL) TBCs consisting of a top 20 wt.% Al₂O₃-7YSZ layer and a bottom 7YSZ layer were desirably designed to achieve preferable performance while the thermal, mechanical and thermal cyclic properties were comprehensively investigated. Compared to the conventional 7YSZ TBCs, the thermal insulation properties of the DCL coating were significantly improved due to the increased oxygen vacancy concentration induced by Al₂O₃ addition while the thickness of the thermally grown oxides was diminished by the decreased oxygen diffusion rate. Furthermore, the improved fracture toughness of the DCL coating also prolonged the thermal cyclic life.     

Residual stress trend in thermal barrier coatings in through thickness direction measured by photoluminescence piezospectroscopy

Abstract

Photoluminescence piezospectroscopy (PLPS) has been used to determine residual stresses in sapphire, alumina in the yttria stablised zirconia (YSZ)/Al₂O₃ composite and alumina in thermal barrier coatings (TBCs). The TBC of YSZ containing 0·5?wt-% alumina has been produced using electron beam physical vapour deposition. The stress profile through the TBC thickness was measured using a depth sensing method. Reasonable residual stress profiles have been obtained using PLPS with the confocal system for all three material systems. Measurements of TBCs suggest that stress distribution in a TBC system is not uniform in general. However, uniform stress distribution has been found in some positions where damage in TBCs might occur.     

High-entropy thermal barrier coating of rare-earth zirconate: A case study on (La0.2Nd0.2Sm0.2Eu0.2Gd0.2)2Zr2O7 prepared by atmospheric plasma spraying

We report a double-ceramic-layer (DCL) thermal barrier coating (TBC) with high-entropy rare-earth zirconate (HE-REZ) as the top layer and yttria stabilized zirconia (YSZ) as the inner layer sprayed on Ni-based superalloy by atmospheric plasma spraying. La₂Zr₂O₇ (LZ) was selected as a reference for the HE-REZ. Thermal cycling test results demonstrate that the HE-REZ/YSZ DCL coating exhibited obviously improved thermal stability when compared to the LZ/YSZ DCL coating. The reasons for the improvement of the thermal shock resistance are considered to be the anti-sinterability of the HE-REZ ceramics during the thermal cycling test attributed to the sluggish diffusion effect and as well as the better match in the coefficient of thermal expansion of HE-REZ coating with the YSZ inner layer. In addition, the HE-REZ coating maintains fluorite structure after thermal cycling test. This study makes one step forward in the development and application of high-entropy rare-earth zirconate ceramic thermal barrier coatings.     

Studies on nanotribological and oxidation resistance properties of yttria stabilized zirconia (YSZ), alumina (Al2O3) based thin films developed by pulsed laser deposition

The present study aims at a detailed evaluation of mechanical, tribological, and high temperature oxidation resistance (at 1000 °C under isothermal condition) properties of YSZ, and Al₂O₃ based thin films developed by pulsed laser deposition technique. The mechanical and tribological properties of YSZ and Al₂O₃ thin films showed significant improvement with increasing the deposition temperature during pulsed laser deposition process. The kinetics of oxidation was reduced due to pulsed laser deposition and Al₂O₃ coating offered a superior oxidation resistance property as compared to YSZ coating. However, the deposition temperature has no significant effect in reducing the TGO growth rate of the pulsed laser deposited thin films.     

Thermal shock behavior of 8YSZ and double-ceramic-layer La2Zr2O7/8YSZ thermal barrier coatings fabricated by atmospheric plasma spraying

The single-ceramic-layer (SCL) 8YSZ (conventional and nanostructured 8YSZ) and double-ceramic-layer (DCL) La₂Zr₂O₇ (LZ)/8YSZ thermal barrier coatings (TBCs) were fabricated by plasma spraying on nickel-based superalloy substrates with NiCrAlY as the bond coat. The thermal shock behavior of the three as-sprayed TBCs at 1000 °C and 1200 °C was investigated. The results indicate that the thermal cycling lifetime of LZ/8YSZ TBCs is longer than that of SCL 8YSZ TBCs due to the fact that the DCL LZ/8YSZ TBCs further enhance the thermal insulation effect, improve the sintering resistance ability and relieve the thermal mismatch between the ceramic layer and the metallic layer at high temperature. The nanostructured 8YSZ has higher thermal shock resistance ability than that of the conventional 8YSZ TBC which is attributed to the lower tensile stress in plane and higher fracture toughness of the nanostructured 8YSZ layer. The pre-existed cracks in the surface propagate toward the interface vertically under the thermal activation. The nucleation and growth of the horizontal crack along the interface eventually lead to the failure of the coating. The crack propagation modes have been established, and the failure patterns of the three as-sprayed coatings during thermal shock have been discussed in detail.     

Finite element analysis of TGO thickness on stress distribution and evolution of 8YSZ thermal barrier coatings

According to the experimental research results of the thermally grown oxide (TGO) layered growth during the pre-oxidation process of 8 wt.% yttria-stabilized zirconia thermal barrier coating (TBC), a two-dimensional sinusoidal TC/bonding coat (BC) curve interface model of the longitudinal section of TBCs based on finite element simulation was constructed; the thickness and composition of the TGO layer relative to the TC/BC curve interfacial stress distribution and its evolution during the thermal cycling process were studied. The results show that when the TGO layer uses α-Al₂O₃ as the main oxide (black TGO), the thicker the black TGO layer, the more uniform the stress distribution of the TC/BC interface. When the TGO layer is dominated by spinel-structured Co and Cr oxides (gray TGO), the stress “band” of the TC/BC interface is destroyed; it shows the alternating phenomenon of tensile stress zone and compressive stress zone, and after the rapid random growth of TGO, the concentrated tensile stress increased by a large jump. Affected by the thickness of the prefabricated black TGO layer, there is a limit peak in the thickness of the black TGO layer, the normal stress at the TC/BC boundary is minimized, and the magnitude of the stress change is also minimized.     

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.     

Durability of YSZ coated Ti2AlC in 1300°C high velocity burner rig tests

A thermal barrier coating (TBC) system survived 500 hours in aggressive, 1300°C burner rig testing. The yttria-stabilized zirconia (7YSZ) TBC was plasma sprayed on an oxidation-resistant Ti₂AlC-type MAX phase and tested in a jet fuel burner at 100 m/s, using 5 hours cycles. No coating spallation or surface recession was observed; Al₂O₃-scale growth produced a slight 2.4 mg/cm² mass gain. The coating surface exhibited craze-cracked colonies of [111]_flourite textured columns, with no visible moisture attack. The 20 μm alumina scale remained intact under the YSZ face, about twice that producing failure for TBC/superalloy systems. TiO₂ nodules, initially formed on the uncoated backside, were removed, and Al₂O₃ was etched through volatile hydroxides formed in water vapor (~10%). Overall, the test indicated exceptional stability of the YSZ/Al₂O₃/Ti₂AlC system under turbine conditions due in large part to close thermal expansion matching.     

Effect of physical vapor deposited Al2O3 film on TGO growth in YSZ/CoNiCrAlY coatings

Thermal barrier coatings (TBCs) comprising of yttria stabilized zirconia (YSZ) ceramic top coat and CoNiCrAlY metallic bond coat have been widely used in gas turbines. However, the developed oxides layer in the interface of the top and bond coats during thermal exposure of the TBCs always results in the destruction of the system. In order to restrain the growth of oxides layer and improve the thermal shock resistance of TBCs, a thin Al₂O₃ film was pre-deposited on CoNiCrAlY bond coat by physical vapor deposition (PVD) technology. After thermal exposure, morphologies and phase compositions of the thermal growth oxides (TGO) layer in the conventional and pre-deposited Al₂O₃ film TBCs were examined by scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS). The residual stresses in the coatings were analyzed using micro-Raman spectroscopy (LabRam-1B). It was found that TGO layer formed in the conventional TBCs was mainly composed of Al₂O₃, (Cr,Al)₂O₃ + (Co,Ni)(Cr,Al)₂O₄ + NiO (CSN), and (Cr,Al)₂O₃ + (Co,Ni)(Cr,Al)₂O₄ (CS), while in the treated TBCs, the formed TGO layer appeared more uniform and compact. The CSN and CS clusters, which are normally considered as a weakness for TBCs, were greatly limited. The residual stresses in the TBCs after thermal shock were also reduced by the deposition of Al₂O₃ film.     

Solution combustion synthesis of calcia-magnesia-aluminosilicate powder and its interaction with yttria-stabilized zirconia and co-doped yttria-stabilized zirconia

Thermal Barrier Coatings (TBCs) play a significant role in improving the efficiency of gas turbines by increasing their operating temperatures. The TBCs in advanced turbine engines are prone to silicate particles attack while operating at high temperatures. The silicate particles impinge on the hot TBC surfaces and melt to form calcia-magnesia-aluminosilicate (CMAS) glass deposits leading to coating premature failure. Fine powder of CMAS with the composition matching the desert sand has been synthesized by solution combustion technique. The present study also demonstrates the preparation of flowable yttria-stabilized zirconia (YSZ) and cluster paired YSZ (YSZ-Ln₂O₃, Ln = Dy and Gd) powders by single-step solution combustion technique. The as-synthesized powders have been plasma sprayed and the interaction of the free standing TBCs with CMAS at high-temperatures (1200 °C, 1270 °C and 1340 °C for 24 h) has been investigated. X-ray diffraction analysis of CMAS attacked TBCs revealed a reduction in phase transformation of tetragonal to monoclinic zirconia for YSZ-Ln₂O₃ (m-ZrO₂: 44%) coatings than YSZ (m-ZrO₂: 67%). The field emission scanning electron microscopic images show improved CMAS resistance for YSZ-Ln₂O₃ coatings than YSZ coatings.     

Thermal shock behavior of a 8YSZ/CoCrAlYTaSi thermal sprayed barrier coating on GH202 superalloy

The thermal shock behavior of a thermal barrier coating (TBC) prepared by plasma spraying at 1100 °C was investigated. The TBC consisted of a double layer structure of 8YSZ/CoCrAlYTaSi. The morphology, microstructure, phases and the elemental distribution of the TBCs were characterized using scanning electron microscopy (SEM), transmission electron microscope (TEM), scanning transmission electron microscope (STEM), X-ray diffraction (XRD) and electron probe micro-analysis (EPMA). The characterization results showed that the film consisted primarily of metastable tetragonal phases (t′), and a large number of micro-cracks were present in the 8YSZ crystals. Following eighty-six thermal shock cycles of the specimens a large areal spallation was observed on the 8YSZ coating. The decreased concentration of yttrium at the coating interfaces weakened the inhibition of crystal growth and the phase transition of the Al₂O₃. The growth of TGO (Thermal growth oxide) and the diffusion into the 8YSZ coating produced deformation and stress in the ceramic coating. Tantalum appeared to absorb the oxygen that diffused into the coatings and delayed the growth of TGO in the interface between the CoCrAlYTaSi and substrate, which was beneficial to prolonging the life of the TBC.     

Porosity analysis and oxidation behavior of plasma sprayed YSZ and YSZ/LaPO4 abradable thermal barrier coatings

In this research, the high temperature oxidation behavior, porosity, and microstructure of four abradable thermal barrier coatings (ATBCs) consisting of micro- and nanostructured YSZ, YSZ-10%LaPO₄, and YSZ-20%LaPO₄ coatings produced by atmospheric (APS) method were evaluated. Results show that the volume percentage of porosity in the coatings containing LaPO₄ was higher than the monolithic YSZ sample. It was probably due to less thermal conductivity of LaPO₄ phases. Furthermore, the results showed that the amount of the remaining porosity in the composite coatings was higher than the monolithic YSZ at 1000 °C for 120 h. After 120 h isothermal oxidation, the thickness of thermally growth oxide (TGO) layer in composite coatings was higher than that of YSZ coating due to higher porosity and sintering resistance of composite coatings. Finally, the isothermal oxidation resistance of conventional YSZ and nanostructured YSZ coating was investigated.