Dense yttria-stabilized zirconia coatings fabricated by plasma spray-physical vapor deposition

Plasma spray-physical vapor deposition (PS-PVD) is a novel technique which can offer new opportunities to obtain advanced microstructures. In this study, dense yttria-stabilized zirconia (YSZ) coatings were deposited using PS-PVD with proper parameters. The dependencies of the microstructure of the as-sprayed coatings on axial spray distance and radial position were discussed. Four typical coatings were selected for the current work. The corresponding microstructures, phase compositions and mechanical properties were studied in detail. These as-sprayed coatings had dense lamellar or lamellar/columnar hybrid microstructures, the lowest porosity was 0.44%. Both monoclinic and tetragonal zirconia were detected in the as-sprayed coatings. The distribution of yttrium was not homogeneous, especially in the coatings deposited at shorter spray distance. Furthermore, oxygen got lost partly during the spraying process with decreasing spray distance. The hardness (H) and Young's modulus (E) of the coatings changed simultaneously with the different microstructures. The maximum values of H and E were 16.6±0.6 and 234.3±10.1 GPa respectively, which were found in the densest coatings. The dense PS-PVD ceramic coatings might be applicable in anti-corrosion fields (such as alkali corrosion, marine corrosion and hot corrosion).     

Microstructure evolution of Al-modified 7YSZ PS-PVD TBCs in thermal cycle

The PS-PVD method was used to prepare 7YSZ thermal barrier coatings (TBCs) and NiCrAlY bond coatings on a DZ40 M substrate. To prevent oxidation of the coating, magnetron sputtering was used to modify the surface of TBCs with an Al film. To explore the stability of TBCs during thermal cycling, water quenching was performed at 1100 °C, and ultralong air cooling for 16,000 cycles was performed. The results showed that before water quenching and air cooling, the top surface structure of the 7YSZ TBCs changed. After water quenching, the surface of the Al film was scoured and broken, the surface peeled off layer-by-layer, and cracks formed at the interface between the thermally grown oxide and NiCrAlY. During air cooling of the thermal cycle, the Al film reacted with O₂ in the air to form a dense Al₂O₃ top layer that coated the cauliflower-like 7YSZ surface and maintained the feather-like shape. At the same time, the TGO layer between 7YSZ and NiCrAlY grew and cracked. The two thermal cycles of water quenching and air cooling led to different failure mechanisms of TBCs. Water quenching failure was caused by layer-by-layer failure of the 7YSZ top coat, while air cooling failure occurred due to the internal cracking of the TGO layer at the 7YSZ/NiCrAlY interface and the failure of the TGO/NiCrAlY interface.     

Comprehensive study on corrosion protection properties of Al2O3, Cr2O3 and Al2O3–Cr2O3 ceramic coatings deposited by plasma spraying on carbon steel

In this study, individual Al₂O₃ and Cr₂O₃ coatings and Cr₂O₃-25, 50, 75 wt% Al₂O₃ composite coatings were applied on carbon steel by atmospheric plasma spraying method. Corrosion experiments were performed on as-sprayed and epoxy resin sealed coatings including potentiodynamic polarization, electrochemical impedance spectroscopy and long-term immersion in 3.5 wt% NaCl solution. Phase composition and microstructure of the coatings were investigated by x-ray diffraction, optical microscopy and scanning electron microscopy, before and after the corrosion experiment. The results showed that the Cr₂O₃ coating exhibited the best corrosion resistance, due to the densest microstructure and highest adhesion strength. The Cr₂O₃-25 wt% Al₂O₃ coating had the highest interconnected porosities and thus had the least corrosion resistance compared to other coatings. In general, the as-sprayed coatings induced a maximum increase of 3.93 times the polarization resistance (R_p) in the polarization experiment and a 3.5 times increase in the charge transfer resistance (R_ct) in the EIS experiment, which was not significant. Stresses caused by increased volume of corrosion products in the coating-substrate interface resulted in the spallation of Cr₂O₃-25, 50 wt% Al₂O₃ coatings from the substrate over long-term of immersion. The adhesion strength of the coatings was a determining criterion for the long-term durability of the coatings. The sealing treatment resulted in a significant increase in R_p and R_ct.     

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.     

Corrosion behavior of air plasma spraying zirconia-based thermal barrier coatings subject to Calcium–Magnesium–Aluminum-Silicate (CMAS) via burner rig test

Three different kinds of thermal barrier coatings (TBCs) — 8YSZ, 38YSZ and a dual-layered (DL) TBCs with pure Y₂O₃ on the top of 8YSZ were produced on nickel-based superalloy substrate by air plasma spraying (APS). The Calcium–Magnesium–Aluminum-Silicate (CMAS) corrosion resistance of these three kinds of coatings were researched via burner rig test at 1350 °C for different durations. The microstructures and phase compositions of the coatings were characterized by SEM, EDS and XRD. With the increase of Y content, TBCs exhibit better performance against CMAS corrosion. The corrosion resistance against CMAS of different TBCs in descending was 8YSZ + Y₂O₃, 38YSZ and 8YSZ, respectively. YSZ diffused from TBCs into the CMAS, and formed Y-lean ZrO₂ in TBCs because of the higher diffusion rate and solubility of Y³⁺ in CMAS than Zr⁴⁺. At the same time, 38YSZ/8YSZ + Y₂O₃ reacts with CAMS to form Ca₄Y₆(SiO₄)₆O/Y_4·67(SiO₄)₃O with dense structure, which can prevent further infiltration of CMAS. The failure of 8YSZ coatings occurred at the interface between the ceramic coating and the thermally grown oxide scale (TGO)/bond coating. During the burner rig test, the Y₂O₃ layer of the DL TBCs peeled off progressively and the 8YSZ layer exposed gradually. DL coatings keep roughly intact and did not meet the failure criteria after 3 h test. 38YSZ coating was partially ablated, the overall thickness of the coating is thinned simultaneously after 2 h. Therefore, 8YSZ + Y₂O₃ dual-layered coating is expected to be a CMAS corrosion-resistant TBC with practical properties.     

Isothermal oxidation and TGO growth behaviors of YAG/YSZ double-ceramic-layer thermal barrier coatings

In this study, yttrium aluminum garnet/yttria-stabilized zirconia (YAG/YSZ) double-ceramic-layer thermal barrier coatings (DCL TBC) and yttria-stabilized zirconia (YSZ) single-ceramic-layer thermal barrier coatings (SCL TBC) were deposited by atmosphere plasma spray (APS) on the Inconel 738 alloy substrate, and isothermal oxidation tests were performed to investigate the formation and growth behavior of thermally grown oxide (TGO). Results showed that the Al₂O₃ TGO thickness of both TBC groups increased by increasing the isothermal oxidation time，and then slowly decreased with the appearance and growth of the adverse multilayer structure comprising CoCr₂O₄, (Ni,Co)Al₂O₄, NiCr₂O₄, and NiO mixed oxides. However, since the significant inhibition effect of the YAG coating to oxygen ionic diffusion, the mixed oxides appearance time and TGO growth behaviors were delayed in the DCL TBC. As a result, the TGO thickness of the DCL TBC was always smaller than that of the SCL TBC in the entire oxidation process. And the Al₂O₃ layer thickness proportion in the total TGO of the DCL TBC was greater than or equal to that of the SCL TBC after oxidation for the same period. The results of weight gain showed that compared with the SCL TBC, the parabolic oxidation rate of the DCL TBC was decreased approximately 35%. Consequently, the DCL TBC has better high-temperature oxidation resistance than the SCL TBC.     

Solution precursor high-velocity oxy-fuel spray ceramic coatings

For the first time, the solution precursor high-velocity oxy-fuel spray process was used to deposit Al₂O₃–ZrO₂ ceramic coatings. X-ray diffraction analysis and transmission electron microscopy characterization show that the as-sprayed coating is composed of mixed nanocrystalline ZrO₂ and γ-Al₂O₃ as well as amorphous phases. The as-sprayed coating consists of ultrafine splats with diameters ranging from 2 to 5 μm. Few spherical particles, hollow-shell structures are also observed on the coating surface. Polished cross-section shows that the coating is quite dense with a thickness of 40 μm.     

Microstructure and mechanical properties of yttria stabilized zirconia coatings prepared by plasma spray physical vapor deposition

Plasma spray physical vapor deposition (PS-PVD) was used to deposit yttria stabilized zirconia (YSZ) coatings with different columnar morphologies by varying the spray distance. Although similar quasi-columnar structures were formed at the spray distances of 600 mm and 1400 mm, the formation mechanisms of particles in the coatings were different. Besides, an electron beam physical vapor deposition (EB-PVD) like columnar coating out of pure vapor was deposited at a spray distance of 1000 mm and the columnar consisted of elongated nano-sized secondary columns. The hardness and Young׳s modulus of the coatings were investigated. Compared to the other two quasi-columnar structures, the EB-PVD like columnar coating exhibited higher hardness (~9.0 GPa ) and Young׳s modulus (~110.9 GPa), mainly due to its low porosity and defect.     

Fabrication of corrosion-resistant Al2O3–CeO2 composite coating on AA7075 via plasma electrolytic oxidation coupled with electrophoretic deposition

Al₂O₃–CeO₂ composite coating was fabricated on AA7075 by combining plasma electrolytic oxidation (PEO) with electrophoretic deposition (EPD). CeO₂ nanoparticles are electrophoretically incorporated into the plasma electrolytic oxidized Al₂O₃ coatings by the synergetic effect of PEO and EPD processes. The passivation behavior of Al₂O₃ and inhibiting nature of CeO₂ have been studied by the electrochemical corrosion analysis in 3.5 wt% NaCl solution and salt spray corrosion test (SSCT) in 5 wt% NaCl as per ASTM standards. The results showed that the Al₂O₃–CeO₂ composite coating via PEO coupled EPD significantly improved the corrosion resistance (~10³ times higher R_p) compared to the plasma electrolytic oxidized Al₂O₃ coating.     

Preoxidation of bond coat in IN-738LC/NiCrAlY/LaMgAl11O19 thermal barrier coating system

The low thickness of thermally grown oxide (TGO) layer and presence of amorphous phase in the as-sprayed LaMgAl₁₁O₁₉ (LaMA) coating reduce the thermal cycling lifetime of thermal barrier coatings (TBCs). In the present study, the as-sprayed Ni-22Cr-10Al-1.0Y bond coat was preoxidized at 1060?°C to produce a continuous oxide scale prior to subsequent deposition of the ceramic top coat. The optimum time of peroxidation treatment and thickness of the continuous aluminum oxide layer were estimated 15?h and 2?µm respectively. The oxidized layer due to the preoxidation treatment of bond coating reduces the amorphous phase in as-sprayed LaMA coating and increases the microhardness of LaMA coating from approximately 600 to 900HV. Also, preoxidation of the NiCrAlY bond coating increases adhesion strength of the LaMA top coating, even slightly more than the adhesion strength of the as-spray 8YSZ coating. The LaMA coatings have a lower hardness in compared with the 8YSZ coating (~ 1010Hv), which results a better elastic behavior.     

Hot Corrosion of Stabilized Zirconia Thermal Barrier Coatings and the Role of Mg Inhibitor

The 3–4 mol% yttria‐stabilized zirconia (YSZ) is widely used as a material for thermal barrier coating; however, the corrosive constituents present in fuel typically result in mechanical disintegration of YSZ coatings. The 3–4 mol% YSZ coatings with respective porosity of ~3% and ~22% have been undertaken with the objective to compare the hot corrosion behavior in air and sulfur‐rich atmospheres. The coatings are kept in contact with V₂O₅ + MgO powder mixture at 750°C for different dwell times of 24 and 76 h. The samples kept in air have shown intact YSZ layer for both the coatings, whereas a delamination of YSZ layer is observed for high porosity sample kept in sulfur‐rich atmosphere. XRD patterns of all the samples treated in sulfur‐rich atmosphere have indicated a phase transformation in YSZ from tetragonal to monoclinic. However, no such phase transformation has been found for samples treated in air. The V₂O₅‐induced hot corrosion attack on YSZ coating in air has been successfully inhibited by MgO, which forms a thermally stable Mg₃V₂O₈ compound. However, in sulfur‐rich atmosphere, MgO is partially consumed to form sulfates, which allows certain fraction of V₂O₅ to react with Y₂O₃ causing the degradation of top coat.     

Comparison of corrosion behaviors and wettability of CMAS on Ta2O5-Y2O3 co-stabilized ZrO2 and YSZ thermal barrier coatings

High-temperature degradation of the plasma sprayed 16 mol% TaO_2.5 + 16 mol% YO_1.5 co-stabilized ZrO₂ (YTZ) and YSZ (7.6 wt% Y₂O₃-stabilized ZrO₂) coatings under calcium-magnesium-aluminon-silicate (CMAS) attack at 1200 °C and 1250 °C were comparatively investigated. Results indicated that the coatings were insensitive to the infiltration of CMAS after 10 h corrosion at 1200 °C. At 1250 °C, the entire YSZ cross-section completely failed and also underwent serious chemical corrosion after 3 h hot corrosion. Even after 10 h corrosion, the penetration depth of CMAS into the YTZ was only about 80 µm. For YTZ coating, the YTaO₄ stabilizer could not easily dissolve in CMAS and precipitated out of the YTZ crystal lattice owing to the strong chemical interaction between Ta⁵⁺ and Y³⁺. The wettability of CMAS on YTZ coating was worse than that on YSZ coating. Compared with YSZ coating, the YTZ coating showed better resistance to 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.     

Comparison of hot corrosion behaviors of plasma-sprayed nanostructured and conventional YSZ thermal barrier coatings exposure to molten vanadium pentoxide and sodium sulfate

The purpose of the current study was evaluation and comparison of hot corrosion behaviors of plasma-sprayed conventional and nanostructured yttria stabilized zirconia (YSZ) thermal barrier coatings (TBCs). Hot corrosion studies were performed on the surface of coatings in the presence of a molten mixture of V₂O₅+Na₂SO₄ at 1000 °C for 30 h. Results indicated that the hot corrosion mechanisms of conventional and nanostructured YSZ coatings were similar. The reaction between corrosive salt and Y₂O₃ produced YVO₄, leaching Y₂O₃ from YSZ and causing the detrimental phase transformation of zirconia from tetragonal to monoclinic. The nanostructured coating, as compared to its conventional counterpart, in spite of a further reaction with the corrosive salt, showed a higher degradation resistance during the hot corrosion test due to increased compliance capabilities resulting from the presence of an extra source of porosity associated with the nano-zones.     

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.     

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.     

Evolution of hot corrosion resistance of YSZ,Gd2Zr2O7, and Gd2Zr2O7 + YSZ composite thermal barrier coatings in Na2SO4 + V2O5 at 1050 °C

This paper compares the hot corrosion performance of yttria stabilized zirconia (YSZ), Gd₂Zr₂O₇, and YSZ + Gd₂Zr₂O₇ composite coatings in the presence of molten mixture of Na₂SO₄ + V₂O₅ at 1050 °C. These YSZ and rare earth zirconate coatings were prepared by atmospheric plasma spray (APS). Chemical interaction is found to be the major corrosive mechanism for the deterioration of these coatings. Characterizations using X-ray diffraction (XRD) and scanning electron microscope (SEM) indicate that in the case of YSZ, the reaction between NaVO₃ and Y₂O₃ produces YVO₄ and leads to the transformation of tetragonal ZrO₂ to monoclinic ZrO₂. For the Gd₂Zr₂O₇ + YSZ composite coating, by the formation of GdVO₄, the amount of YVO₄ formed on the YSZ + Gd₂Zr₂O₇ composite coating is significantly reduced. Molten salt also reacts with Gd₂Zr₂O₇ to form GdVO₄. Under a temperature of 1050 °C, Gd₂Zr₂O₇ based coatings are more stable, both thermally and chemically, than YSZ, and exhibit a better hot corrosion resistance.     

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.     

Constrained sintering and thermal ageing behaviour of electrophoretically deposited Yb2Si2O7 environmental barrier coating

The oxidation of SiC and the formation of a thermally grown oxide layer (TGO) limit the lifetime of environmental barrier coatings. Thus, this paper focuses on the deposition of denser Yb₂Si₂O₇ coatings using electrophoretic deposition to reduce the TGO growth rate. The findings showed densification for Yb₂Si₂O₇ can be achieved with an optimized sintering profile (heating/cooling rate, temperature, and time). However, the addition of 1.5 wt% of Al₂O₃ to Yb₂Si₂O₇ promoted densification and lowered the required sintering temperature, 1380 °C using 2 °C/min heating/cooling rate for 10 h provided efficient coating density. Moreover, adding Al₂O₃ reduced the TGO growth rate by more than 70 % compared to the Al₂O₃-free coatings, without cracking in TGO after 150 h of thermal ageing at 1350 °C. Results within this study suggest electrophoretic deposition with Al₂O₃ addition produces promising Yb₂Si₂O₇ environmental barrier coatings on SiC substrate with low oxidation rates and increased lifetime.     

Thermal conductivity of plasma sprayed Sm2Zr2O7 coatings

Rare-earth zirconates with a pyrochlore structure have been developed for potential application in thermal barrier coating systems to further improve the performance and durability of gas turbines. The Sm₂Zr₂O₇ (abbreviated as SZ) powder was synthesized by solid state reaction and then deposited by air plasma spraying. The phase stability, microstructure and thermal conductivity of SZ and 8 wt% Y₂O₃ stabilized zirconia (8YSZ) coatings were investigated. The X-ray diffraction results indicated that the crystal structure of the as-sprayed SZ coatings was defect-fluorite, and after heat treating at 1200 °C for 50 h, it started to transform to pyrochlore, and the content of pyrochlore increased with increase in temperature of the heat treatment. The thermal conductivities of SZ coatings were significantly lower than those of 8YSZ coatings before and after heat treatments, which increased considerably after heat treatments compared to the as-sprayed states for both coatings due to sintering effects.