Finite element simulation of stress distribution and development in 8YSZ and double-ceramic-layer La2Zr2O7/8YSZ thermal barrier coatings during thermal shock

In this paper, the thermal stress of the double-ceramic-layer (DCL) La₂Zr₂O₇/8YSZ thermal barrier coatings (TBCs) fabricated by atmospheric plasma spraying (APS) during thermal shock has been calculated. The residual stress of the coating after being sprayed has been regarded as the initial condition of the first thermal cycle. The characteristic of the stress development during the thermal cycle has been discussed, and the influence of the defects on the failure mode during the thermal cycle has also been discussed systematically. Finite element simulation results show that there exist higher radial thermal shock stresses on the ceramic layer surface of these two coatings. There also exist higher thermal stress gradient at the interface between the ceramic layer and the metallic layer. Higher thermal stress in 8YSZ/NiCoCrAlY coating lead to the decrease of thermal shock property as compared to that of LZ/8YSZ/NiCoCrAlY coating. The addition of LZ ceramic layer can increase the insulation temperature, impede the oxygen transferring to the bond coating and can also reduce the thermal stress. Considering from the aspects of thermal insulation ability and the thermal shock resistance ability, DCL type LZ/8YSZ TBCs is a more promising coating material compared with the single-ceramic-layer (SCL) type 8YSZ TBCs for the application.     

Effect of Young's modulus evolution on residual stress measurement of thermal barrier coatings by X-ray diffraction

Subjected to thermal cycling, the apparent Young's modulus of air plasma-sprayed (APS) 8 wt.% Y₂O₃-stabilized ZrO₂ (8YSZ) thermal barrier coatings (TBCs) was measured by nanoindentation. Owing to the effects of sintering and porous microstructure, the apparent Young's modulus follows a Weibull distribution and changes from 50 to 93 GPa with an increase of thermal cycling. The evolution of residual stresses in the top coating of an 8YSZ TBC system was determined by X-ray diffraction (XRD). The residual stresses derived from the XRD data are well consistent with that obtained by the Vickers indention. It is shown that the evolution of Young's modulus plays an important role in improving the measurement precision of residual stresses in TBCs by XRD.     

High performance nanostructured ZrO2 based thermal barrier coatings deposited by high efficiency supersonic plasma spraying

In this paper, the nanostructured zirconia (ZrO₂) based thermal barrier coatings (TBCs) deposited by high efficiency supersonic atmospheric plasma spraying (SAPS), were described. The phase composition, microstructure, thermal conductivity and thermal shock resistance of as-sprayed coating were studied. The results revealed that the as-sprayed coating was composed of tetragonal zirconia and consisted of some unmelted nanoparticles (30-50 nm) and nanograins (60-110 nm), and the latter was the main microstructure of the coating. The nanograins and homogeneously distributed micro-cracks of coating resulted in not only low thermal conductivity, but also high thermal cycling lives. Besides, the failure process of coating during thermal cycles was also investigated in the present work.     

Double-ceramic-layer thermal barrier coatings based on La2(Zr0.7Ce0.3)2O7/La2Ce2O7 deposited by electron beam-physical vapor deposition

Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) and La₂Ce₂O₇ (LC) were deposited by electron beam-physical vapor deposition (EB-PVD). The composition, interdiffusion, surface and cross-sectional morphologies, cyclic oxidation behavior of DCL coating were studied. Energy dispersive spectroscopy and X-ray diffraction analyses indicate that both LZ7C3 and LC coatings are effectively fabricated by a single LZ7C3 ingot with properly controlling the deposition energy. The chemical compatibility of LC coating and thermally grown oxide (TGO) layer is unstable. LaAlO₃ is formed due to the chemical reaction between LC and Al₂O₃ which is the main composition of TGO layer. Additionally, the thermal cycling behavior of DCL coating is influenced by the interdiffusion of Zr and Ce between LZ7C3 and LC coatings. The failure of DCL coating is a result of the sintering of LZ7C3 coating surface, the chemical incompatibility of LC coating and TGO layer and the abnormal oxidation of bond coat. Since no single material that has been studied so far satisfies all the requirements for high temperature applications, DCL coating is an important development direction of TBCs.     

Preparation and characterization of nickel nano-Al2O3 composite coatings by sediment co-deposition

Ni-Al₂O₃ composite coatings were prepared by using sediment co-deposition (SCD) technique and conventional electroplating (CEP) technique from Watt's type electrolyte without any additives. The microstructure, hardness, and wear resistance of resulting composites were investigated. The results show that the incorporation of nano-Al₂O₃ particles changes the surface morphology of nickel matrix. The preferential orientation is modified from (2 0 0) plane to (1 1 1) plane. The microhardness of Ni-Al₂O₃ composite coatings in the SCD technique are higher than that of the CEP technique and pure Ni coating and increase with the increasing of the nano-Al₂O₃ particles concentration in plating solution. The wear rate of the Ni-Al₂O₃ composite coating fabricated via SCD technique with 10 g/l nano-Al₂O₃ particles in plating bath is approximately one order of magnitude lower than that of pure Ni coating. Wear resistance for SCD obtained composite coatings is superior to that obtained by the CEP technique. The wear mechanism of pure Ni and nickel nano-Al₂O₃ composite coatings are adhesive wear and abrasive wear, respectively.     

Effect of NaAlO2 concentrations on microstructure and corrosion resistance of Al2O3/ZrO2 coatings formed on zirconium by micro-arc oxidation

In this study, Al₂O₃/ZrO₂ composite coatings were prepared on Zr substrates by micro-arc oxidation (MAO) in the NaAlO₂-containing electrolytes, and the effect of NaAlO₂ concentration on the microstructure, bond strength, microhardness and corrosion resistance of coatings was systematically investigated. The study reveals that the adequate NaAlO₂ in the electrolyte (>0.2 M) is essential to the formation of needle-like α-Al₂O₃ in the coatings, and the amount of α-Al₂O₃ rises with the increase of the NaAlO₂ concentration. m-ZrO₂ and t-ZrO₂ are present in all of the coatings, but their relative amount largely depends on the amount of Al₂O₃. It is also found that as the NaAlO₂ concentration increases from 0.2 to 0.3 M, the coating becomes denser and thicker, and its bond strength, maximum microhardness and corrosion resistance increases as well. The coating formed at 0.3 M NaAlO₂ demonstrates the highest bond strength of 52 MPa, the maximum microhardness of 1600 Hv_0.2N and the superior corrosion resistance. However, the overhigh concentration of NaAlO₂ (0.35 M) is found harmful to the coating's microstructure and properties.     

Microstructure and properties of Ni-Co/nano-Al2O3 composite coatings by pulse reversal current electrodeposition

Ni-Co/nano-Al₂O₃ (Ni-Co/Al₂O₃) composite coatings were prepared under pulse reversal current (PRC) and direct current (dc) methods respectively. The microstructure of coatings was characterized by means of XRD, SEM and TEM. Both the Ni-Co alloy and composite coatings exhibit single phase of Ni matrix with face-centered cubic (fcc) crystal structure, and the crystal orientation of the Ni-Co/Al₂O₃ composite coating was transformed from crystal face (2 0 0) to (1 1 1) compared with alloy coatings. The hardness, anti-wear property and macro-residual stress were also investigated. The results showed that the microstructure and performance of the coatings were greatly affected by Al₂O₃ content and the electrodeposition methods. With the increasing of Al₂O₃ content, the hardness and wear resistance of the composite coatings enhanced. The PRC composite coatings exhibited compact surface, high hardness, better wear resistance and lower macro-residual stress compared with that of the dc composite coatings.     

Preparation and high-temperature properties of Au nano-particles doped α-Al2O3 composite coating on TiAl-based alloy

Au nano-particles doped α-Al₂O₃ composite coatings were successfully prepared on TiAl-based alloy by electrodeposition, using the Al₂O₃ sols with minor addition of HAuCl₄ solution. The even distribution of Au nano-particles (<2.0 wt.%) in the α-Al₂O₃ matrix has been observed. Isothermal oxidation tests of the samples coated with the as-prepared novel coatings at 900 °C in static air for 200 h shown that the oxygen inward diffusion can be effectively suppressed to a low level. The results of high-temperature cyclic oxidation test at 900 °C in air revealed that the oxidation and spallation resistance of TiAl-based alloy were improved significantly under thermal cycling. In the as-prepared coatings, cracks were shielded by means of crack bridging and the fracture resistance of the formed scales can be improved by toughening effects of the composite structure. Surface scratching tests after the cyclic oxidation exhibited that the adhesion of the formed composite scale on TiAl-based alloy was remarkably improved by the Au nano-particles doped α-Al₂O₃ composite coating.     

Active oxidation of Cu3Au(1 1 0) using hyperthermal O2 molecular beam

Oxidation of Cu₃Au(1 1 0) using a hyperthermal O₂ molecular beam (HOMB) was investigated by X-ray photoemission spectroscopy in conjunction with a synchrotron light source. From the incident energy dependence of the O-uptake curve, the precursor-mediated dissociative adsorption occurs, where the trapped O₂ molecule can migrate and dissociate at the lower activation-barrier sites, dominantly at thermal O₂ exposures. Dissociative adsorption of O₂ on Cu₃Au(1 1 0) is as effective at the thermal O₂ exposure as on Cu(1 1 0). On the other hand, at the incident energies of HOMB where the direct dissociative adsorption is dominant, it was determined that the dissociative adsorption of O₂ implies a higher activation barrier and therefore less reactivity due to the Au alloying in comparison with the HOMB oxidation of Cu(1 1 0). The dissociative adsorption progresses with the Cu segregation on Cu₃Au(1 1 0) similarly as on Cu₃Au(1 0 0). The growth of Cu₂O for 2 eV HOMB suggests that the diffusion of Cu atoms also contribute to the oxidation process through the open face, which makes the difference from Cu₃Au(1 0 0).     

Investigation of the characteristics and corrosion resistance of Al2O3/TiN coatings

Al₂O₃ /TiN double and Al₂O₃/Cr/TiN triple coatings were produced on stainless steel substrates using plasma-detonation techniques. Investigation of the microstructure and characteristics of the coatings after the preparation was performed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and Auger electron spectroscopy (AES). The corrosion resistance of the coatings was studied in several electrolytic solutions (0.5 M H₂SO₄, 1 M HCl, 0.75 M NaCl) using electrochemical techniques (open circuit potential, cyclovoltammetry and potentiodynamic polarization). The obtained results showed, in most of the cases, an improvement of the corrosion resistance, except in NaCl solutions. The effect of the controlled thickness of TiN and Cr layers as well as the additional treatment with a high-current electron beam was also investigated. Nuclear reaction analysis (NRA), Rutherford backscattering spectroscopy (RBS) and scanning electron microscopy (SEM) were applied for the characterization of the samples before and after the corrosion experiments.     

Electrodeposition and characterization of Ni-Y2O3 composite

Nano-sized Y₂O₃ particles were codeposited with nickel by electrolytic plating from a nickel sulfate bath. The effects of the incorporated Y₂O₃ on the structure, morphology and mechanical properties (including microhardness, friction coefficient and wear resistant) of Ni-Y₂O₃ composite coatings were studied. It is observed that the addition of nano-sized Y₂O₃ particles shows apparent influence on the reduction potential and pH of the electrolyte. The incorporated Y₂O₃ increases from 1.56 wt.% to 4.4 wt.% by increasing the Y₂O₃ concentration in the plating bath from 20 to 80 g/l. XRD results reveal that the incorporated Y₂O₃ particles favour the crystal faces (2 0 0) and (2 2 0). SEM and AFM images demonstrate that the addition of Y₂O₃ particles causes a smooth and compact surface. The present study also shows that the codeposited Y₂O₃ particles in deposits decrease the friction coefficient and simultaneously reduce the wear weight loss. Ni-Y₂O₃ composite coatings reach their best microhardness and tribological properties at Y₂O₃ content 4.4 wt.% under the experiment conditions.     

Characterization of single-crystalline In2O3 films deposited on Y-stabilized ZrO2 (1 0 0) substrates by MOCVD

Epitaxial In₂O₃ films have been deposited on Y-stabilized ZrO₂ (YSZ) (1 0 0) substrates by metalorganic chemical vapor deposition (MOCVD). The films were deposited at different substrate temperatures (450-750 °C). The film deposited at 650 °C has the best crystalline quality, and observation of the interface area shows a clear cube-on-cube epitaxial relationship of In₂O₃(1 0 0)||YSZ(1 0 0) with In₂O₃[0 0 1]||YSZ[0 0 1]. The Hall mobility of the single-crystalline In₂O₃ film deposited at 650 °C is as high as 66.5 cm² V⁻¹ s⁻¹ with carrier concentration of 1.5 × 10¹⁹ cm⁻³ and resistivity of 6.3 × 10⁻³ Ω cm. The absolute average transmittance of the obtained films in the visible range exceeds 95%.     

Large room temperature magnetoresistance in YSZ doped La0.67Ba0.33MnO3 composite

The temperature dependence of the resistivity for composite samples of (1−x)La_0.67Ba_0.33MnO₃+xYSZ(LBMO/YSZ) with different YSZ doping level of x has been investigated in a magnetic field range of 0-7000 Oe, where the YSZ represents yttria-stabilized zirconia (8 mol% Y₂O₃+92 mol% ZrO₂). With increasing YSZ doping level, the range of 0-10%, the metal-insulator transition temperature (T_P) decreases. However, the resistivity, specially the low temperature resistivity, increases. Results also show that the YSZ doping level has an important effect on a low field magnetoresistance (LFMR). In the magnetic field of 7000 Oe, a room temperature magnetoresistance value of 20% was observed for the composite with a YSZ doping level of 2%, which is encouraging for potential application of CMR materials at room temperature and low field.     

Microstructure and properties of TiB2-containing coatings prepared by arc spraying

Low cost arc spraying and cored wires were used to deposit composite coatings consisting of TiB₂ and TiB₂/Al₂O₃ hard particles in a Ni(Cr) and stainless steel 304L matrix. Four coatings were prepared namely Ni(Cr)-TiB₂, Ni(Cr)-TiB₂/Al₂O₃, 304L-TiB₂ and 304L-TiB₂/Al₂O₃. The microstructural characteristics of powders and coatings were observed by scanning electron microscopy (SEM). Phase compositions of powders were analyzed by X-ray diffraction (XRD). Although all the analyzed coatings exhibited similar lamella structure, remarkable differences not only in the morphology of hard phase and matrix but also in the size and distribution of hard phases were observed from one coating to another. Tribological behavior of the coatings was analyzed in room temperature dry sliding wear tests (block-on-ring configuration), under 75 N at low velocity (0.5 m/s). The coatings showed far high wear resistance than low carbon steel substrate under same conditions examined. Wear loss of 304L-TiB₂ and Ni(Cr)-TiB₂ coatings were lower nearly 15 times than that of steel substrate. TiB₂ hard phases in coatings bonded well with metal matrix contributed to high wear resistance.     

Preparation and characterization of the electrodeposited Cr-Al2O3/SiC composite coating

To increase the SiC content in Cr-based coatings, Cr-Al₂O₃/SiC composite coatings were plated in Cr(VI) baths which contained Al₂O₃-coated SiC powders. The Al₂O₃-coated SiC composite particles were synthesized by calcining the precursor prepared by heterogeneous deposition method. The transmission electron microscopy analysis of the particles showed that the nano-SiC particle was packaged by alumina. The zeta potential of the particles collected from the bath was up to +23 mV, a favorable condition for the co-deposition of the particles and chromium. Pulse current was used during the electrodeposition. Scanning Electron Microscopy (SEM) indicated that the coating was compact and combined well with the substrate. Energy dispersive X-ray analysis of Cr-Al₂O₃/SiC coatings demonstrated that the concentration of SiC in the coating reached about 2.5 wt.%. The corrosion behavior of the composite coating was studied by potentiodynamic polarization and electrochemical impedance spectroscopy techniques. The data obtained suggested that the Al₂O₃/SiC particles significantly enhanced the corrosion resistance of the composite coating in 0.05 M HCl solution.     

Preparation and annealing study of TaNx coatings on WC-Co substrates

To prevent Co diffusion from cemented carbides at high temperatures, we fabricated TaN_x coatings by reactive direct current (d.c.) magnetron sputtering onto 6 wt.% cobalt cemented carbide substrates, to form diffusion barrier layers. Varying the nitrogen flow ratio, N₂/(Ar + N₂), from 0.05 to 0.4 during the sputtering process had a significant effect on coating structure and content. Deposition rate reduced as the nitrogen flow ratio increased. The effects of nitrogen flow ratio on the crystalline characteristics of the TaN_x coatings were examined by X-ray diffraction. The TaN_x coatings annealing conditions were 500, 600, 700, and 800 °C for 4 h in air. We evaluated the performance of the diffusion barrier using both Auger electron spectroscopy depth-profiles and X-ray diffraction techniques. We also investigated oxidation resistance of the TaN_x coatings annealed in air, and under a 50 ppm O₂-N₂ atmosphere, to evaluate the fabricated layers effectiveness as a protective coating for glass molding dies.     

Influence of treating frequency on microstructure and properties of Al2O3 coating on 304 stainless steel by cathodic plasma electrolytic deposition

Alumina ceramic coatings were fabricated on 304 stainless steel by cathodic plasma electrolytic deposition (CPED). Influence of treating frequency of the power supply on the microstructure and properties of the coatings were studied. The results indicated that coatings obtained at various frequencies on 304 stainless steels were all composed of α-Al₂O₃ and γ-Al₂O₃, and α-Al₂O₃ was the dominant phase. The contents of α-Al₂O₃ decreased gradually in a very small rate with increasing the frequency and γ-Al₂O₃ gradually increased. The surface of alumina ceramic coating was porous. With increasing the frequency, the coating surface gradually became less rough and more compact, resulting in low surface roughness. The bonding strength of Al₂O₃ coating was higher than 22 MPa and was not strongly affected by treating frequency. With increasing the frequency, the alumina coated steels showed better and gradually increasing corrosion resistance than the uncoated one in 3.5% NaCl solution. The coating steel with desirable corrosion resistance was obtained at 800 Hz whose corrosion current potential and corrosion density were −0.237 V and 7.367 × 10⁻⁸ A/cm², respectively.     

Influence of C3H8O3 in the electrolyte on characteristics and corrosion resistance of the microarc oxidation coatings formed on AZ91D magnesium alloy surface

Ceramic coatings were fabricated on AZ91D Mg-alloy substrate by microarc oxidation in Na₂SiO₃-NaOH-Na₂EDTA electrolytes with and without C₃H₈O₃ addition. The effects of different concentrations of C₃H₈O₃ contained in the electrolyte on coatings thickness were investigated. The surface morphologies, RMS roughness, phase compositions and corrosion resistance property of the ceramic coatings were analyzed by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), and electrochemical corrosion test respectively. It is found that the addition of C₃H₈O₃ into silicate electrolyte leads to increase of the unit-area adsorptive capacity of the negative ions at anode-electrolyte interface and thus improves the compactness and corrosion resistance of the MAO coating. The coating thickness decreases gradually with the increase of concentrations of C₃H₈O₃ in the electrolyte. The oxide coating formed in base electrolyte containing 4 mL/L C₃H₈O₃ exhibits the best surface appearance, the lowest surface RMS roughness (174 nm) and highest corrosion resistance. In addition, both ceramic coatings treated in base electrolyte with and without C₃H₈O₃ are mainly composed of periclase MgO and forsterite Mg₂SiO₄ phase, but no diffraction peak of Mg phase is found in the patterns.     

Microstructure, bonding strength and thermal shock resistance of ceramic coatings on steels prepared by plasma electrolytic oxidation

Ceramic coatings were successfully prepared on steel by plasma electrolytic oxidation (PEO) in aluminate electrolyte and silicate electrolyte, respectively. The microstructure of the coatings including surface morphology, phase and element composition were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The bonding strength between the ceramic coating and the substrate was tested using different methods including tensile tests and shearing tests. The thermal shock resistance of the coatings was also evaluated. The results indicated that coatings obtained in both electrolytes were porous and coarse. The average diameters of the pores were below 10 μm. PEO coatings obtained in aluminate electrolyte were composed of Fe₃O₄ and FeAl₂O₄, while those obtained in silicate electrolyte were in a noncrystal state. PEO coatings obtained in aluminate electrolyte showed similar change trend of tensile strength and shearing strength with increasing treating time, namely, a relatively high values with middle time treating and low value with short and long time treating. The best coating was the samples treated with 30 min, whose tensile strength was 20.6 MPa and shearing strength was 16 MPa. The tensile strength and shearing strength of coatings obtained in silicate electrolyte were not strongly influenced by the treating time, the values of which were range in 14 ± 2 MPa and 11 ± 2 MPa, respectively. Coatings obtained in both electrolytes showed the best thermal shock resistance with middle time treating. Coatings obtained in silicate electrolyte show a little better thermal shock resistance than those obtained in aluminate electrolyte.     

A Ni/YSZ composite containing Ce0.9Ca0.1O2−δ particles as an anode for SOFCs

A composite material (hereafter referred to as NYC) containing Ni, Y₂O₃-stabilized ZrO₂ (YSZ) and Ce_0.9Ca_0.1O_2−δ (CC10) particles was prepared and used as the anode of solid oxide fuel cells (SOFCs). The performance of NYC was better than that of conventional Ni/YSZ anodes in terms of anodic overpotential and interface impedance. The additional CC10 particles improved the anode properties. XRD results suggest that a solid solution of YSZ and CC10 was produced. From impedance measurements, it is concluded that the solid solution exhibits substantial electronic conduction. Ni/YSZ/15 wt% Ce_0.9Ca_0.1O_2−δ anodes exhibited the best properties over the experimental temperature range. A SOFC with an anode of Ni/YSZ/15 wt% Ce_0.9Ca_0.1O_2−δ provided the maximum power density and current density. Addition of CC10 with an average particle size of 0.3 μm was more advantageous than that with an average size of 3 μm.