Effects of air annealing treatments on the microstructure,components, and mechanical properties of magnetron sputtered Al2O3–Cr2O3–ZrO2 composite coatings

To investigate the effects of air annealing on the microstructure, components, and mechanical properties of ceramic composite coatings, Al₂O₃–Cr₂O₃–ZrO₂ composite coatings were prepared on silicon substrate using radio frequency magnetron sputtering at room temperature, and then air-annealed in a temperature range of 450–850 °C for 30 min. The results indicated that the phase-structure and superficial characteristics, including morphology and surface roughness, were not visibly altered in the annealed coatings up to 600 °C; the elemental component distributions remained uniform. The improvement in the mechanical properties was attributed to the growth of oxide grains. There were no significant changes in the components of Al, Cr, Zr, and O in the annealed coatings. However, an increase in the Cr component and a decrease in the Zr component occurred on the coating surface; the overall structure of the composite coatings possessed a favorable heat resistance. Upon annealing at 750 °C, the thermally-driven formation of uniform and refined nanoparticles on the coating surface was responsible for the effective enhancement of the mechanical properties. Furthermore, annealing at 850 °C induced the enlargement of the precipitated Cr₂O₃ nanoparticles and the generation of micro-defects, resulting in a drastic morphological evolution, an evident increase in the surface roughness, and a significant decrease in the mechanical properties. This study provides new perspectives on designing novel thermal barrier coatings and understanding the role of high temperature air annealing on the microstructural transformation.     

Constrained sintering of YSZ/Al2O3 composite coatings on metal substrates produced from eletrophoretic deposition

Yttria stabilized zirconia/alumina (YSZ/Al₂O₃) composite coatings were prepared from electrophoretic deposition (EPD), followed by sintering. The constrained sintering of the coatings on metal substrates was characterized with microstructure examination using electron microscopy, mechanical properties examination using nanoindentation, and residual stress measurement using Cr³⁺ fluorescence spectroscopy. The microstructure close to the coating/substrate interface is more porous than that near the surface of the EPD coatings due to the deposition process and the constrained sintering of the coatings. The sintering of the YSZ/Al₂O₃ composite coating took up to 200 h at 1250 °C to achieve the highest density due to the constraint of the substrate. When the coating was sintered at 1000 °C after sintering at 1250 °C for less than 100 h, the compressive stress was generated due to thermal mismatch between the coating and metal substrate, leading to further densification at 1000 °C because of the ‘hot pressing’ effect. The relative densities estimated based on the residual stress measurements are close to the densities measured by the Archimedes method, which excludes an open porosity effect. The densities estimated from the hardness and the modulus measurements are lower than those from the residual stress measurement and the Archimedes method, because it takes account of the open porosity.     

Microstructure of HVOF-sprayed Ag–BaF2⋅CaF2–Cr3C2–NiCr coating and its tribological behavior in a wide temperature range (25 °C to 800 °C)

Ag–BaF₂?CaF₂–Cr₃C₂–NiCr composite powders were prepared by physically blending commercial BaF₂?CaF₂–Cr₃C₂–NiCr and Ag powders. Ag–BaF₂?CaF₂–Cr₃C₂–NiCr composite coatings were deposited on Inconel 718 alloy substrate by high velocity oxy-fuel (HVOF) spraying. The friction and wear behavior of the coatings under dry sliding against Si₃N₄ balls from 25 °C to 800 °C was evaluated with a ball-on-disk high temperature tribometer. The microstructure and composition of the samples were analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectrometer. Results showed that the composite coatings were mainly composed of hard phase of Cr₃C₂, binder phase of NiCr, high-temperature lubrication phase of fluorides and low-temperature lubrication phase of Ag. The fluorides existed in the forms of both crystal particles and amorphous state, while the silver featured as typical thermally sprayed splats. Due to the high flame temperature, some fluorides have been oxidized to chromates and around 30 wt% of Ag was lost during spraying. In addition, it was found that Ag content had an important influence on the composite coating, and an appropriate dosage of metallic silver could effectively improve the tribological performance of the coating. The generation of AgCrO₂ at moderate (500 °C and 650 °C) temperature and BaCrO₄ at high temperature (800 °C) could contribute to the decline in friction coefficients and wear rates of Ag–BaF₂?CaF₂–Cr₃C₂–NiCr coatings.     

Improving the tribological properties of plasma sprayed NiAl–Bi2O3–Ag–Cr2O3 composite coatings by hot isostatic pressing

In this study, the hot isostatic pressing (HIP) process was adopted to enhance the tribological response of plasma-sprayed NiAl–Bi₂O₃–Ag–Cr₂O₃ coatings under different temperature conditions. The HIP process was performed at a temperature of 800 °C, under a pressure of 100 MPa using argon gas. When compared with as-sprayed NiAl–Bi₂O₃–Ag–Cr₂O₃ composite coatings, the results revealed that the post-HIP process greatly reduced the porosity to a sufficiently low level of 2.7%, and led to a significant transformation from the splat lamellar to composition homogeneity across the entire coating. As highlighted in the hot isostatically pressed (HIPed) coating, more NiBi intermetallic compounds emerged. The mechanical hardness and adhesive strength increased considerably by 15.9% and 22.7%, respectively. The HIPed coating exhibited improved running stability in friction when exposed to different temperatures. In particular, the wear resistance increased significantly by one level of magnitude at the temperature range of room temperature (25 °C) to 400 °C, compared to the as-sprayed composite coating. This was attributed to the presence of the NiBi intermetallic compound and structural restoration after the HIP process. A protective tribo-layer was always present under alternating temperature conditions, and this allowed for continuous inhibition of wear. The mechanical evolution of the tribo-layer was further determined to clarify its effect on the resulting tribological behavior of the HIPed NiAl–Bi₂O₃–Ag–Cr₂O₃ coatings.     

Microstructure and mechanical properties of Al2O3/Cu joints brazed with Ag–Cu–Ti+Zn composite fillers

In this study, Al₂O₃ ceramic and Cu bars were brazed with newly designed Ag–Cu–Ti(ABA)+Zn composite fillers. Systematic analysis of the microstructure of the brazed joints indicated that the volatilization of Zn atoms during the brazing process could promote the spreading of liquid brazing fillers on the surface of the Al₂O₃ ceramic, resulting in a uniform dendritic interfacial structure. The typical interfacial structure was an Al₂O₃/TiO/(Cu, Al)₃Ti₃O+Ag(s, s)/Cu interface. Notably, the tensile strength was improved to 20.89 MPa for Al₂O₃/Cu joint brazed with ABA+Zn composite fillers at 900 °C for 20 min, approximately 67.6% higher than the sample brazed without Zn foil. In this case, the fracture model was straight and sharp-angled inside the Al₂O₃ ceramic. In addition, the joint strength decreased with increased brazing temperatures from 900 to 940 °C.     

Preparation of a thick NiAl/Al2O3 coating by embedding method and its corrosion resistance under supercritical water environment

One of the critical issues in the application of supercritical water oxidation technology is to improve the corrosion resistance of reactor materials. Use of Al₂O₃ coating is one of the most promising methods to address this issue. In this study, thick NiAl/Al₂O₃ coatings on Inconel 625 substrates were prepared by a consecutive pack embedding and in-situ thermal oxidation process. The effect of aluminizing and oxidation temperature on phase structure and coating thickness is studied. Results show the diffusion of Al from the exterior to the interior of the alloy matrix to form intermetallic compounds between Al and metal elements in the matrix (Ni, Cr, Mo, etc.). Moreover, the coating thickness can reach above 300 μm at the aluminizing temperature of 950 °C. Increasing the aluminizing temperature above 950 °C will not increase the coating thickness further. After high temperature oxidation subsequently, only phases of NiAl and Al₂O₃ were detected. The formation of Al₂O₃ layer can be ascribed to the surface oxidization of Al. And the NiAl between the alloy substrate and Al₂O₃ coating provides an interfacial layer that can alleviate the crack or exfoliation of ceramic coating due to the mismatching of thermal expand coefficient. The thick NiAl/Al₂O₃ coatings prepared by aluminizing 950 °C and oxidizing at 1100 °C exhibit satisfied corrosion resistance after supercritical water test. This work would provide a significant method to develop advanced ceramics coating for the corrosion resistance of alloys.     

Microstructure and mechanical properties of cold sintered porous alumina ceramics

New innovative approach to fabricate porous alumina ceramics by cold sintering process (CSP) is presented using NaCl as pore forming agent. The effects of CSP and post-annealing temperature on the microstructure and mechanical strength were investigated. Al₂O₃–NaCl composite with bulk density of 2.92 g/cm³ was compacted firstly using CSP and then a porous structure was formed using post-annealing at 1200°C–1500°C for 30 min. Brazilian test method and Vickers hardness test were used to determine the indirect tensile strength and hardness of the porous alumina, respectively. Meanwhile, the phases and the microstructure were respectively examined using X-ray diffractometer and scanning electron microscope (SEM) complemented by the 3D image analysis with X-ray tomography (XRT). SEM structural and XRT image analysis of cold sintered composite showed a dense structure with NaCl precipitated between Al₂O₃ particles. The NaCl volatization from the composite was observed during the annealing and then complete porous Al₂O₃ structure was formed. The porosity decreased from 48 vol% to 28 vol% with the annealing temperature increased from 1200 °C to 1500 °C, while hardness and mechanical strength increased from 14.3 to 115.4 HV and 18.29–132.82 MPa respectively. The BET analysis also showed a complex pore structure of micropores, mesopores and macropores with broad pore size distribution.     

Infrared radiative performance and anti-ablation behaviour of Sm2O3 modified ZrB2/SiC coatings

To improve the emissivity of ZrB₂/SiC coatings for serving in more serious environment, ZrB₂/SiC coatings with varying contents of high emissivity Sm₂O₃ were fabricated using atmospheric plasma spraying. The microstructure, infrared radiative performance and anti-ablation behaviour of the modified coatings were investigated. The results showed that as the content of Sm₂O₃ increased, the density of the coatings increased because of the low melting point of Sm₂O₃. When the content of Sm₂O₃ was 10 vol%, the coating had the highest emissivity in the 2.5–5 μm band at 1000 °C, up to 0.85, because of the oxygen vacancies promoting additional electronic transitions. Due to the high emissivity, the surface temperature of the coating modified with 10 vol% Sm₂O₃ decreased by 300 °C, which led to little volatilisation of the sealing phase. Further, the mass ablation ratio of the above coating was 3.19 × 10^?4 g/s, decreasing 31% compared to that of a ZrB₂/SiC coating. The formed dense surface structure of the coatings showed considerable oxygen obstructive effects. These findings indicate that the modified coatings show considerable anti-ablation performance, which provides effective anti-ablation protection for the C/C composite substrate.     

Reactive air brazing of 3YSZ ceramic to aluminized Crofer22H stainless steel using Ag–CuO fillers

In this work, an effective protected Al₂O₃ layer was fabricated first on the surface of Crofer22H by reactive air aluminization to suppress cathodic poisoning in solid oxide fuel cells. Then, the reactive air brazing of aluminized Crofer22H to 3YSZ ceramics was carried out by using Ag–CuO fillers. The effects of CuO content and brazing temperature on the interfacial microstructure and mechanical properties of the joints were studied in detail. The results indicated that maintaining a continuous Al₂O₃ layer was the prerequisite for achieving a reliable joint. And the interfacial reaction gradually became intense with the increase of CuO content, and the continuity of the Al₂O₃ layer was disrupted as it was increased to 6 mol%. The well-connected joints could be achieved when brazing at 970–1100°C with Ag–2CuO filler. The interfacial microstructure did not obviously change with increasing temperature, and the joint strength was stable at ∼35 MPa. While the interfacial reaction gradually weakened with increasing temperature as brazing with Ag–4CuO filler, the well-connected joints were obtained when brazing above 1000°C, and the maximum shear strength of ∼44.3 MPa was obtained when brazing at 1050°C for 30 min.     

Preparation of multilayered C–Si–Al2O3 coatings on continuous carbon fibers and C–Si–Al2O3-coated carbon-fiber-reinforced hydroxyapatite composites

Multilayered C–Si–Al coatings with various morphologies were deposited on carbon fibers (CFs) using magnetron sputtering. The thickness of the coatings was increased from 0.5 to 1.5 μm by magnetron sputtering between 90 and 120 min. C–Si–Al coatings of suitable thickness were heat-treated at 600 °C and transformed into C–Si–Al₂O₃ coatings by one-step anodic oxidation (AO). The oxidation time for the one/two-step anodic oxidation and the ratio of oxidation time for the two-step anodic oxidation significantly influenced the morphologies of the C–Si–Al₂O₃(AO) coatings. Al₂O₃ coatings with satisfactory morphologies and structures were prepared by two-step anodic oxidation with a total time of 30 min and a ratio of 1:1 between the initial and secondary oxidation times. The multilayered C–Si–Al₂O₃(AO) coatings were modified to C–Si–Al₂O₃ coatings by secondary heat treatment at 1050 °C. Subsequently, hot-press sintering was used to prepare CFs with multilayered C–Si–Al₂O₃ coating-reinforced hydroxyapatite (CF/C–Si–Al₂O₃/HA) composites. The multilayered C–Si–Al₂O₃-coated CFs demonstrated good resistance to oxidation and thermal shock. This could effectively protect CFs from oxidative damage and maintain its strengthening effect during sintering. The multilayered C, Si, and Al₂O₃ coatings effectively reduced the difference between the coefficient of thermal expansion of the CFs and HA matrixes. The interfacial gaps between the multilayered coatings and HA were reduced. This could enhance the mechanical performance of the composites. The CF/C–Si–Al₂O₃/HA composites exhibited improved mechanical properties with a bending strength of 83.94 ± 12.29 MPa, and fracture toughness of 2.45 ± 0.08 MPa m^1/2. This study can broaden the application of CF/C–Si–Al₂O₃/HA biocomposites as bone-repair materials and help obtain CF-reinforced composites with excellent mechanical properties that are fabricated or serviced at high temperatures.     

Preparation of Al2O3 coating on TiN coating by polymer-assisted deposition to improve oxidation resistance in coking inhibition applications

In order to inhibit the metal catalytic coking and improve oxidation resistance of single TiN coating, the TiN/Al₂O₃ double layer coatings were designed as a chemically inert coating for methylcyclohexane supercritical pyrolysis. Internal TiN coatings were prepared by atmospheric pressure chemical vapor deposition using TiCl₄–H₂–N₂ system. The external Al₂O₃ coatings with different thicknesses were prepared on the TiN surface by polymer-assisted deposition, and the coating with the most suitable thickness was further annealed at different temperatures of 600, 700, 800 and 900 °C. The morphology, elemental and phase composition of TiN/Al₂O₃ coatings were characterized by SEM, EDX and XRD respectively. The chemical state information of the coating elements was based on Ti 2p, Al 2p core level X-ray photoelectron spectroscopy (XPS) spectra. The results indicated that the external Al₂O₃ coating will partially peel off at 900 °C annealing temperature. The thermogravimetric analysis results indicated that all TiN/Al₂O₃ coatings show better oxidation resistance than single-layer TiN coating. The anti-coking test with methylcyclohexane supercritical pyrolysis showed that the TiN/Al₂O₃ coatings can effectively cover the metal catalytic sites and eliminate metal catalytic coking. However, the acid sites of external Al₂O₃ coating slightly promoted coking, so the anti-coking ratios of TiN/Al₂O₃ coatings were smaller than that of TiN. Thus, the addition of external Al₂O₃ coating can greatly improve the oxidation resistance of TiN coatings with little loss of coking resistance.     

Preparation of YSZ/Al2O3 micro-laminated coatings and their influence on the oxidation and spallation resistance of MCrAlY alloys

YSZ/Al₂O₃ micro-laminated coatings were successfully prepared on the surface of MCrAlY substrates by means of electrolytic deposition and microwave sintering. The as-prepared YSZ/Al₂O₃ coatings were characterized by high-resolution field emission SEM and XRD. Laminated structures of alternate YSZ and Al₂O₃ layers were observed in the coating with the phase composition of Y₂O₃ stabilized t-ZrO₂, α-Al₂O₃ and θ-Al₂O₃. High-temperature cyclic oxidation test at 1000 °C in air was also performed to investigate the oxidation and spallation resistance of such coatings on MCrAlY substrates. The results indicate that such coatings exhibit not only excellent oxidation resistance but also good spallation resistance under thermal cycling due to the structure of multi-sealed Al₂O₃ layers and the preferable high-temperature mechanical properties induced by the designed laminated composite structures, respectively.     

High temperature oxidation behavior of MoSi2–Al2O3 composite coating on TZM alloy

A novel MoSi₂–Al₂O₃ composite coating was prepared on Mo-based TZM alloy by slurry sintering method. The oxidation behavior of the coating was evaluated at 1600 °C in static air. Microstructure and phase composition of the as-prepared and oxidized coatings were characterized, and the antioxidant mechanism of the coating at high temperature was discussed. A three-layer structure was observed in the as-prepared coating, consisting of a ～2 μm thick Mo₅Si₃ diffusion layer, a ～65 μm thick MoSi₂ inner layer and a ～36 μm thick outer layer of mixture of MoSi₂ and Al₂O₃. After oxidation at 1600 °C for 5 h, all MoSi₂ phases were completely converted to intermediate silicide Mo₅Si₃ by solid-state diffusion, and the formed Mo₅Si₃ phase would be transformed into Mo₃Si phase with further extending the oxidation time. Furthermore, a dense oxide layer of SiO₂-mullite was formed on the specimen surface, which can effectively protect the material to further oxidation. The MoSi₂–Al₂O₃ coating could protect the substrate effectively at 1600 °C for 20 h without failure. The enhanced oxidation resistance of MoSi₂–Al₂O₃ coating is due to the formation of multi-layer structure containing a SiO₂-mullite composite oxide outer layer with high thermal stability and low oxygen permeability.     

Carbon nanotube/graphene oxide‐added CaO‐B2O3‐SiO2 glass/Al2O3 composite as substrate for chip‐type supercapacitor

A CaO‐B₂O₃‐SiO₂ (CBS) glass/40 wt% Al₂O₃ composite sintered at 900°C exhibited a dense microstructure with a low porosity of 0.21%. This composite contained Al₂O₃ and anorthite phases, but pure glass sintered at 900°C has small quantities of wollastonite and diopside phases. This composite was measured to have a high bending strength of 323 MPa and thermal conductivity of 3.75 W/(mK). The thermal conductivity increased when the composite was annealed at 850°C after sintering at 900°C, because of the increase in the amount of the anorthite phase. 0.25 wt% graphene oxide and 0.75 wt% multi‐wall carbon nanotubes were added to the CBS/40 wt% Al₂O₃ composite to further enhance the thermal conductivity and bending strength. The specimen sintered at 900°C and subsequently annealed at 850°C exhibited a large bending strength of 420 MPa and thermal conductivity of 5.51 W/(mK), indicating that it would be a highly effective substrate for a chip‐type supercapacitor.     

Mechanical properties of in situ synthesized mullite-based composite ceramics with three-dimensional network structure

Needle-like nanocrystalline mullite powders were prepared through the molten salt process at the temperature of 900°C using coal gangue as raw material. Then, mullite-based composite ceramics were prepared by a conventional solid-state reaction between in situ synthesized mullite and Al₂O₃ powders. Effects of Al₂O₃ content and sintering temperatures on phase compositions, microstructure, and mechanical properties of the mullite-based composite ceramics were also studied. The results show that mullite content productivity increase from 72% to 95%, as the sintering temperature increased from 1480°C to 1580°C, which led to the improvement in the bulk density and flexural strength of the samples. The three-dimensional interlocking structure for mullite-based composite ceramics was obtained by the in situ solid-state reaction process. The maximum bulk density, flexural strength, and fracture toughness for the sample with 15 wt% Al₂O₃ content are 2.48 g/cm³, 139.79 MPa, and 5.62 MPa··m^1/2, respectively, as it was sintered at the temperature of 1560°C for 3 h. The improved mechanical properties of mullite-based composite ceramics maybe ascribed to good densification and increased mullite phase content, as well as to the in situ three-dimensional network structure. Therefore, the results would provide new ideas for high-value utilization of coal gangue.     

Oxidation behavior of Al2O3 reinforced MoSi2 composite coatings fabricated by vacuum plasma spraying

MoSi₂, MoSi₂–10 vol.% Al₂O₃, MoSi₂–30 vol.% Al₂O₃ (denoted as MA0, MA1, MA3, respectively) coatings were fabricated by vacuum plasma spraying (VPS), and their oxidation behavior was examined at low temperature (500 °C) and high temperature (1500 °C). The test at 500 °C showed that the addition of Al₂O₃ effectively restrained the pest oxidation of MoSi₂. The MA1 coating had satisfactory fluid surface and presented good oxidation resistance at 1500 °C. However, the MA3 coating showed worse oxidation resistant behavior compared with the MA0 coating because of mullite formation.     

Microstructural evolution and enhanced mechanical properties of 95Al2O3–Yb/Mg/Si ceramics by optimizing sintering temperature

Designed component of 0.95Al₂O₃–0.015Yb₂O₃–0.01MgO–0.025SiO₂ (95Al₂O₃–Yb/Mg/Si) ceramics were prepared by the traditional mixed-oxide method in the sintering temperature range of 1450–1700 °C. The influence of sintering temperature on the crystal structure, densification, microstructure, mechanical, friction and wear properties of 95Al₂O₃-YbMgSi ceramics were systematically investigated. XRD and SEM analysis results revealed that the increase in sintering temperature was very beneficial to eliminate the pores, increase the density and grain size, which obeys the common grain growth law. Both the flexural strength and hardness of obtained samples were increased almost linearly when the sintering temperature increased from 1450 °C to 1700 °C. The ceramics sintered at 1650 °C showed the optimum properties: H_v = 1812.3, σ = 151.3 MPa, μ = 0.41, ρ = 3.72 g/cm³ and K_c = 8.06e^?5 mm³/N·m, respectively. Furthermore, the results of friction and wear experiments suggested that the 95Al₂O₃–Yb/Mg/Si ceramic prepared at the optimizing sintering process exhibited more stable friction state and lower wear degree under non-lubricated conditions. The enhanced mechanical properties could be attributed to their structure densification, pore elimination and gain growth with the increase of sintering temperature.     

Effect of MoS2 content on friction and wear properties of Mo and S co-doped CrN coatings at 25–600 °C

With increasingly harsh working environments for mechanical systems and the rapid development of various high-tech industries, requirements for the stable operation of mechanical systems are increasing in a wide temperature range. Mo and S co-doped CrN coatings with different MoS₂ contents were prepared via unbalanced magnetron sputtering to provide better friction properties to the coatings at high temperatures. Scanning electron microscopy and nanoindentation were adopted to analyze the microstructure and mechanical performance. The mechanical performance of the coatings was enhanced by increasing the MoS₂ content, however, excessive MoS₂ reduced the mechanical properties of the coatings. Besides, the adhesion of the coatings first increased and then decreased rapidly with the increase of the MoS₂ content. In addition, the residual stress of the coating first decreased and then increased upon increasing the MoS₂ content. The high-temperature tribological behavior of the coatings was measured from room temperature (25 °C) to 600 °C. The CrN/MoS₂-0.6A coating was found to exhibit low friction and wear coefficient at room temperature and relatively good comprehensive properties at high temperature. This study provides a feasible design for engineering applications and lays the foundations for the preparation of coatings with superior high-temperature friction properties.     

Comparative study of the corrosion resistance of thermally sprayed ceramic coatings and their bulk ceramic counterparts

A comparative study of the corrosion properties of thermally sprayed ceramic coatings (Al₂O₃, Al₂O₃–TiO₂ with different ratios, mullite, and ZrSiO₄) and their sintered bulk ceramic counterparts was performed. The coatings were deposited on corrosion-resistant steel substrates using atmospheric plasma spraying (APS) and high velocity oxy-fuel (HVOF) spraying processes. The corrosion properties were investigated in 1 N solutions of NaOH and H₂SO₄ at 85 °C, respectively. The coating microstructures and phase compositions, as well as the corrosive environment were shown to have a strong effect on the corrosion resistance of the coatings. Al₂O₃–coatings were more sensitive to these factors than Al₂O₃–TiO₂ coatings were.The corrosion resistance of the bulk ceramics was superior to that of the thermally sprayed coatings. This is mainly because the coatings exhibited specific microstructure and contained amorphous and/or metastable phases not appearing in the bulk ceramics.