TiO2–ZnO/Ni–5wt.%Al composite coatings on GH4169 superalloys by atmospheric plasma spray techniques and theirs elevated-temperature tribological behavior

Ni–based composite coatings with different amounts of TiO₂–ZnO were fabricated by atmospheric plasma spraying (APS) to protect GH4169 superalloy substrates against excess wear and friction at elevated temperatures. In addition, the influence of the simultaneous addition of the oxides on the microstructure, microhardness, and wear behaviour was investigated. According to the results, the simultaneous addition of TiO₂/ZnO provides anti-friction and wear inhibition over 600 °C. In particular at 800 °C, the TiO₂–ZnO/Ni–5wt.%Al composite coating (10 wt% TiO₂ and 10 wt% ZnO were incorporated within Ni–5wt.%Al matrix) exhibits a superior lubricity and wear resistance compared to the Ni–5wt.%Al based coatings. The XRD, Raman, and TEM characterisations reveal the formation of a glaze oxide layer consisting of NiO, TiO₂, ZnO and the in-situ production of ternary oxide (Zn₂TiO₄), which was primarily responsible for the tribological performance of the sliding wear contacts at the specific temperature.     

TiO2/ZnO double-layer broadband antireflective and down-shifting coatings for solar applications

Making full use of sunlight in solar cells requires reducing the reflection of light and minimizing spectral mismatch. Here, a TiO₂/ZnO double-layer coating with both wider band antireflection and down-shifting performance was prepared. TiO₂ sols and ZnO nanoparticles were synthesized via the sol-gel method and then successively coated on the surface of the Si substrate by dip-coating. Computational simulations were used to obtain the optimal refractive index and thickness of the coatings. In the experiments, the thicknesses of the TiO₂ and ZnO coatings were adjusted by changing the lifting speed, and the refractive index of the TiO₂ and ZnO coatings were adjusted by adding the porosity inducing agent and varying the concentration of the solution. The TiO₂/ZnO coating reduces the reflectivity of the silicon substrate by 24.97% in the 400–1100 nm band, and the ZnO nanoparticles can convert light at approximately 345 nm–527 nm, reducing the spectral mismatch of the solar cell. The photocurrent of solar cells coated with TiO₂/ZnO coatings was markedly improved, with an increase of 29% in the average photocurrent at 300–800 nm. Herein, TiO₂/ZnO coatings have the potential to benefit the development of multifunctional coatings that are important for improving the efficiency of solar cells.     

Microstructural Properties of Air Plasma Sprayed Coating Consisting of Tungsten Carbide and Yttria‐Stabilized Zirconia

Thermal Spraying technologies are proven to be capable of producing composite materials and structures. In the present work, an innovative composite coating was produced to achieve high wear and thermal resistant properties in a single‐step process using air plasma spraying (APS) technique. Tungsten carbide has shown high wear resistance and zirconia coatings exhibited excellent tribological and insulation properties. It is speculated that a composite material consisting of zirconia and tungsten carbide exhibits excellent thermomechanical properties. A powder mixture of 50wt% WC‐10wt% Ni (WC‐Ni) and 50wt% ZrO₂‐8wt% Y₂O₃ (YPSZ) was deposited on a low carbon steel substrate using APS technique. Important microstructural properties of WC‐Ni/YPSZ coating such as splat boundaries, pore and grain morphology, microcracks, phase composition, elemental distribution of coatings, and lattice parameters of the crystals were investigated using optical microscopy, scanning electron microscopy (SEM), energy dispersive X‐ray (EDS), and X‐ray diffractometry (XRD). A good adhesion was observed between different phases in tungsten carbide mixed with zirconia coatings. Decarburization process which occurred during APS process resulted in formation of tungsten hemi‐carbide (W₂C) phase in plasma sprayed samples. The calculated crystal size for APS‐deposited coating was smaller than those of feedstock powder.     

Microstructural,mechanical and tribological properties of carbon nanotubes reinforced plasma sprayed molybdenum disulphide composite coatings

The development of 1-Dimensional (1D) and 2-Dimensional (2D) materials have gained considerable attention towards achieving solid-state lubricity. Herein, we present the effect of carbon nanotubes (1D) reinforcement into the molybdenum disulphide (2D) coatings. Plasma sprayed MoS₂ coatings reinforced with 2-4 wt% CNTs were fabricated using shroud plasma spraying over steel substrates. The shroud attachment envelops the plasma plume and cut down its exposure to surroundings, which minimizes the oxidation of MoS₂ powder during spraying. The microstructural analysis revealed the presence of MoS₂ and CNTs in the composite coating. The mechanical hardness and elastic modulus of MoS₂ coating improved by 2–3 folds in the composite coating. In tribological performance, the coefficient of friction (COF) decreased from 0.13 to 0.07 in M2C coating. The wear weight loss was estimated as 0.89 ± 0.07 mg, 0.18 ± 0.02 mg and 0.39 ± 0.03 mg for M, M2C and M4C coatings respectively. It can be attributed that tubular CNTs acted as bearing on MoS₂ layers. This work opens an impressive stepping for the synergistic mixture of 1D (CNTs) and 2D (MoS₂) material to obtain high-quality wear-resistant coatings.     

Effect of Y2O3 addition on tribological properties of plasma sprayed Al2O3-13% TiO2 coating

The effect of Y₂O₃ addition on structure, mechanical properties and tribological properties of Al₂O₃-13 wt% TiO₂ coating was investigated. The addition of 20 wt% Y₂O₃ resulted in better densification, stabilization of alpha (α) alumina phase and improvement in fracture toughness of Al₂O₃-13 wt% TiO₂ coating. Abrasive wear tests were performed over a range of loads and sliding speeds. The stabilization of α alumina phase further increased with an increase in severity of wear test conditions, as noted from X-Ray Diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS) analysis of worn coatings. Al₂O₃-13 wt% TiO₂-20 wt% Y₂O₃ coating displayed lower friction coefficient and lower abrasive wear rate than Al₂O₃-13 wt% TiO₂ coating, which was due to synergistic effect of α alumina phase and formation of magneli phase oxide of titanium; Ti₂O₃. Friction energy map was used to rationalize observed wear rates, to identify different regimes of wear and degradation modes of coatings.     

Photocatalytic decomposition of benzene with plasma sprayed TiO2-based coatings on foamed aluminum

Plasma spraying technique was used to deposit thin TiO₂-based photocatalytic coatings on foamed aluminum. Before plasma spraying, the composites of nano-TiO₂ powder (P25) and nano-ZnO/CeO₂/SnO₂ powders were agglomerated into microsized powders by spray-drying process. X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and photocatalytic activity evaluation by the decomposition of gas-phase benzene (C₆H₆) were applied to characterize the starting powders and the coatings, respectively. The results showed that all the three plasma sprayed TiO₂-based coatings were the mixture phases of anatase and rutile. On the splats’ surfaces of the as-sprayed coatings, fine nano-crystalline particles were observed. However, grain growth occurred on the surface of plasma sprayed 90%TiO₂–10%ZnO coating. The XPS spectra revealed that the Ti, Zn, Ce and Sn elements existed on the surfaces of plasma sprayed TiO₂-based coatings as the chemical states of Ti⁴⁺, Zn²⁺, Ce⁴⁺ and Sn⁴⁺, respectively, whilst, the oxygen element was composed of three kinds of chemical states, i.e. crystal lattice oxygen, hydroxyl oxygen and physical-adsorbed oxygen. It was found that plasma sprayed 90%TiO₂–10%CeO₂ coating and 90%TiO₂–10%SnO₂ coating exhibited similar photocatalytic activity, which was higher than that of plasma sprayed 90%TiO₂–10%ZnO coating. The photocatalytic activity is not only dependent on the anatase content but also on the surface morphology and the hydroxyl content formed on the surface of plasma sprayed TiO₂-based coatings as well as the additive character.     

Microstructure and fracture toughness of in-situ nanocomposite coating by thermal spraying of Ti3AlC2/Cu powder

The low fracture toughness of ceramic coatings has always hindered their wide application. In this study, an in-situ nanocomposite coating was prepared by the atmospheric plasma spraying of a 50 wt% Ti₃AlC₂-50 wt% Cu mixed powder. The in-situ nanocomposite coating was found to have an unusual microstructure with a nano-micrometre phase synergistic enhancement, which consisted of submicrometre-thick layers of Cu and nanoparticles of Cu(Al), Ti₄O₅, TiO₂, and Al₂TiO₅. Thus, in the spraying process, Al was delinked out of Ti₃AlC₂, forming a large amount of plastic Cu(Al) with Cu. The delinked channel provided a path for Cu to diffuse into Ti₃AlC₂, which a spatial Cu network structure was formed in the coating. The in-situ nanocomposite coating has high fracture toughness and crack growth resistance by a three-point bending test. This paper reports a new method to prepare a high-fracture-toughness composite ceramic coating.     

Effect of silane modified nano ZnO on UV degradation of polyurethane coatings

Nanosized ZnO modified by 2-aminoethyl-3-aminopropyltrimethoxysilane (APS) was prepared using the precipitation method. Modified nano ZnO by silane (ZnO-APS) was characterized by XRD, SEM, TEM and UV–vis measurements. The degradation of the polyurethane coating, the polyurethane coatings containing 0.1 wt% nano ZnO and the polyurethane coatings containing nano ZnO-APS at two concentrations (0.1 and 0.5 wt%) during QUV test was evaluated by gloss measurement and electrochemical impedance spectroscopy. The coating surface after QUV test was observed with SEM. The results show that nano ZnO-APS has spherical structure with particle size around 10–15 nm. Nano ZnO improved the UV resistance of the PU coating and surface treatment by APS enhanced the effect of nano ZnO. The presence of nano ZnO-APS at 0.1 wt% concentration significantly improved the UV resistance of polyurethane coating.     

Protective properties of Al2O3 + TiO2 coating produced by the electrostatic spray deposition method

Mechanical resistance of Al₂O₃ + TiO₂ nanocomposite ceramic coating deposited by electrostatic spray deposition method onto X10CrAlSi18 steel to thermal and slurry tests was investigated. The coating was produced from colloidal suspension of TiO₂ nanoparticles dispersed in 3 wt% solution of Al₂(NO₃)₃, as Al₂O₃ precursor, in ethanol. TiO₂ nanoparticles of two sizes, 15 nm and 32 nm, were used in the experiments. After deposition, coatings were annealed at various temperatures, 300, 1000 and 1200 °C, and next exposed to cyclic thermal and slurry tests. Regardless of annealing temperature and the size of TiO₂ nanoparticles, the outer layer of all coatings was porous. The first five thermal cycles caused a rapid increase of aluminum content of the surface layer to 30–37 wt%, but further increase in the number of thermal cycles did not affect the aluminum content. The oxidation rate of coating-substrate system was lower during the thermal tests than during annealing. The oxidation rate was also lower for smaller TiO₂ particles (15 nm) forming the coating than for the larger ones (32 nm). The protective properties of Al₂O₃ + TiO₂ coating against intense oxidation of substrate were lost at 1200 °C. Slurry tests showed that coatings annealed at 1000 °C had the best slurry resistance, but thermal tests had weakened this slurry resistance, mainly due to decreasing adhesion of the coating.     

Effects of modification of hBN by nickel plating on coating structure and properties of supersonic plasma spraying NiCr-Cr3C2-hBN@Ni coatings

Hexagonal boron nitride (hBN) with excellent self-lubrication performance is expected to relieve the friction resistance and wear of NiCr–Cr₃C₂ coatings. However, the poor wettability of hBN with most materials makes it difficult to fabricate NiCr–Cr₃C₂-hBN composite coating with good cohesion strength. In this study, hBN was firstly pretreated through magnetron-sputtering aided Ni plating to form hBN@Ni particles. Then, NiCr–Cr₃C₂-hBN@Ni powder was prepared by spray granulation. Next, corresponding coatings were prepared through supersonic atmosphere plasma spraying. It was found that in comparison with NiCr–Cr₃C₂-hBN coating, the NiCr–Cr₃C₂-hBN@Ni coating exhibited a decreased porosity (from 3.6% to 0.3%), elevated cohesion (from 52.78 N to 62.11 N), and the wear rate decreased by an order of magnitude. It was concluded that hBN@Ni can effectively improve the component interface inside powder, enhance the cohesion of molten in-flight particles, and make the internal structure of the coating denser.     

Effects of plasma gas composition on bond strength of hydroxyapatite/titanium composite coatings prepared by rf-plasma spraying

The effects of plasma gas composition on the bond-strength of HA/Ti composite coatings were investigated. HA/Ti composite coatings were deposited on titanium substrates by a radio-frequency (rf) thermal plasma spraying method with input powers of 10–30 kW. The ratio of the HA and Ti powders supplied into the plasma was precisely controlled by two microfeeders so as to change the coating's composition from Ti-rich at the bottom to HA-rich at its upper layer. The bond (tensile) strength of the obtained HA/Ti composite coatings was 40–65 MPa when sprayed with plasma gas containing N₂ (i.e., Ar–N₂). On the other hand, HA/Ti composite coatings prepared with plasma gas containing O₂ (i.e., Ar–O₂) had significantly lower bond strength (under 30 MPa). XRD patterns of Ti coatings without HA showed that titanium nitride and titanium dioxide formed, respectively, on titanium deposits sprayed with Ar–N₂ and Ar–O₂ plasma. Scanning electron microscopic (SEM) observation showed an acicular texture on the Ti deposits prepared with Ar–N₂ plasma. SEM observations implied that, when sprayed with Ar–O₂ plasma, a thin TiO₂ layer formed at the interfaces between the Ti splats in the deposits.     

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.     

Fabrication of graphene oxide reinforced plasma sprayed Al2O3 coatings

Graphene oxide (GO) reinforced Al₂O₃ ceramic coatings were prepared on the surface of medium carbon steel by plasma spraying. The microstructure of the raw materials and coatings were characterized and analyzed by XPS, XRD, Raman and SEM. The bonding strength of the coatings was studied using a scratch method. The wear resistance of the coatings was assessed by the sliding test. The results showed that, after adding GO, the porosity of the coating reduced by about 31%, the hardness increased by approximately 10%, the bonding strength improved by 250%, and the wear rate reduced by 81% (Load: 30 N) and 84% (Load: 60 N), respectively.     

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.     

Photocatalytic performance of plasma sprayed Pt-modified TiO2 coatings under visible light irradiation

Plasma sprayed Pt/TiO₂ coatings were prepared by Atmospheric Plasma Spraying process. As-sprayed coatings were characterized by TEM, XRD and XPS. The photocatalytic performance was evaluated through the photo mineralization of methylene blue. All the Pt modified titanium dioxide coatings show significant absorption in the visible light range, while the pure titania coating reflects almost all the visible light. The photocatalytic efficiencies of as-sprayed pure TiO₂ coating and Pt/TiO₂ coatings are almost same under the irradiation of visible light. However, the efficiencies of all Pt/TiO₂ coating are greatly improved comparing with that of pure TiO₂ coating by applying 15 V external bias under the irradiation of visible light.     

Influence of original powders on the microstructure and properties of thermal barrier coatings deposited by supersonic atmospheric plasma spraying,Part I: Microstructure

In this work, two types of yttria-stabilised zirconia (YSZ) powders, a microsized powder and a reconstituted nanostructured powder, were used as the original feedstock for depositing thermal barrier coatings (TBCs) using a high-efficiency supersonic atmospheric plasma spraying (SAPS) system. The effect of the original powder on the coating microstructure was studied by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The results indicated that the microsized powder was fully melted in the plasma jet and that the as-sprayed conventional coating (named MC) was composed of regular-shaped tetragonal ZrO₂ with grain size of 200–500 nm. However, the cross-section morphology of the water-quenched powders revealed that the reconstituted nanostructured powder was partially melted during plasma spraying and that the as-sprayed nanostructured coating (named NC) exhibited a multi-modal microstructure that mainly consisted of unmelted nanoparticles (30–50 nm) and nanograins (60–110 nm), with the latter being the main microstructure of the coating. One visible polycrystalline region consisting of 10 nm grains was also found in NC. In addition, due to the full melting of the microsized powder in the plasma jet, MC exhibited a lower porosity and higher microhardness and Weibull modulus compared with those of NC. In the following paper (Part II), the thermo-mechanical properties, such as thermal shock resistance, oxidation resistance and thermal insulation performance, of the above two coating types will be further studied.     

Role of phase content on the photocatalytic performance of TiO2 coatings deposited by suspension plasma spray

In this work, suspension plasma spraying (SPS) with different hydrogen (H₂) flow rates was employed to produce TiO₂ coatings with various phase contents, oxygen contents, and roughnesses. To eliminate the role of the morphology and oxygen content on the photocatalytic activity, all coatings were polished to reach the same roughness followed by heat-treatment at 550 °C in air for 48 h. Then coatings were analyzed by X-ray diffractometer (XRD), confocal laser microscope, scanning electron microscope (SEM), UV–visible spectrometer, Raman microscope, and thermogravimetric analyzer. The XRD data indicated that the percentage of anatase decreased as function of H₂ flow rates, and almost 46% of anatase transformed to rutile during SPS process at the highest H₂ flow rate. Moreover, the photocatalytic performance was evaluated by monitoring the degradation of methylene blue under visible light irradiation, and the results indicated that anatase phase positively enhances the photocatalytic activity of TiO₂ coatings.     

Suspension high velocity oxy-fuel spraying of a rutile TiO2 feedstock: Microstructure,phase evolution and photocatalytic behaviour

Nano-structured TiO₂ coatings were produced by suspension high velocity oxy fuel (SHVOF) thermal spraying using water-based suspensions containing 30 wt% of submicron rutile powders (~180 nm). By changing the flame heat powers from 40 kW to 101 kW, TiO₂ coatings were obtained with distinctive microstructures, phases and photocatalytic behaviour. Spraying with low power (40 kW) resulted in a more porous microstructure with the presence of un-melted nano-particles and a lower content of the anatase phase; meanwhile, high powers (72/101 kW) resulted in denser coatings and rougher surfaces with distinctive humps but not necessarily with a higher content of anatase. Linear sweep voltammetry (LSV) was used to evaluate the photocatalytic performance. Surprisingly, coatings with the lowest anatase content (~20%) using 40 kW showed the best photocatalytic behaviour with the highest photo-conversion efficiency. It was suggested that this was partially owing to the increased specific surface area of the un-melted nano-particles. More importantly, the structural arrangement of the similarly sized TiO₂ nano-crystallites between rutile and antase phases also created catalytic “hot spots” at the rutile−anatase interface and greatly improved the photo-activity.     

Preparation of high solids content nano-titania suspensions to obtain spray-dried nanostructured powders for atmospheric plasma spraying

Nanosized TiO₂ powder with an average primary size of ∼20 nm and surface area of ∼50 m²/g (Aeroxide^® P25, Degussa-Evonik, Germany) was used as starting material. A colloidal titania suspension from the same supplier was also used (W740X). The dispersing conditions were studied as a function of pH, dispersant content, and solids loading. Well-dispersed TiO₂ nanosuspensions with solids contents up to 30 vol.% (62 wt%) were obtained by dispersing the powder with 4 wt% PAA. Suspensions with solids contents as high as 35 vol.% were prepared by adding the TiO₂ nanoparticles to the TiO₂ colloidal suspension under optimised dispersing conditions.TiO₂ powder reconstitution was performed by spray drying both types of nanosuspensions to obtain free-flowing micrometre-sized nanostructured granules. The spray-dried nanostructured TiO₂ granules were deposited on austenitic stainless steel coupons using atmospheric plasma spraying. Coating microstructure and phase composition were characterised using scanning electron microscopy and X-ray diffraction techniques.     

Preparation and antibacterial activity of Ag/TiO2-functionalized ceramic tiles

An Ag/TiO₂ coating was deposited onto glazed ceramic tiles by a sol-gel and spraying method at high temperatures. The coating was characterized by X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The results showed that silver was present in rutile-TiO₂, and the temperature did not change the phase composition of the samples. The Ag/TiO₂ coating had a higher roughness than the TiO₂ coating. The tape test (D 3359–08) showed that the coatings prepared at 950 °C and 1000 °C had good adhesion to the ceramic tile substrate. The antibacterial activity of the coating was tested by photocatalytic sterilization experiments. The results showed that the Ag/TiO₂ coating had a higher antibacterial activity than the TiO₂ coating, and the sterilization efficiency of Escherichia coli, Staphylococcus aureus, Shigella, and Salmonella exceeded 99.655% under 2 h of visible light irradiation. This research provides a method to create Ag/TiO₂ coatings with good thermal resistance, adhesion, and antibacterial activity. This improves the low photocatalytic activity caused by the anatase-to-rutile transformation of TiO₂ at high temperatures and the poor adhesion at low temperatures.