Cycle oxidation behavior of nanostructured Ni60-TiB2 composite coating sprayed by HVOF technique

Cycle oxidation resistance at 800 °C in static air was investigated for a nanostructured Ni60-TiB₂ composite coating sprayed by high velocity oxy-fuel (HVOF). For comparison, a Ni60-TiB₂ conventional composite coating was also studied. The results indicate that, the oxidation processes of both composite coatings are controlled by diffusion mechanism, and the nanostructured composite coating has better cycle oxidation resistance than that of the conventional composite coating. The reasons for this improvement can be attributed to the formation of the intact SiO₂ and Cr₂O₃ protective layer, and the enhanced adhesion between oxide film and nanostructure coating.     

Surface properties of silicon oxide films deposited using low-pressure dielectric barrier discharge

The deposition of SiO_X films from low-pressure dielectric barrier discharge plasmas has been investigated using tetraethoxysilane (TEOS)/O₂ as the feed gas. Films were analyzed using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), AFM-based nanoindentation/nanowear techniques, and conductive AFM. Film deposition rates and hydrocarbon incorporation in the SiO_X film decrease with addition of O₂. High-quality SiO_X films with extremely low surface roughness are deposited at high oxidant concertrations. Addition of oxidant to the feed gas leads to a change in the SiO_X film structure from precursor-like to a dense SiO_X structure. The SiO_X films deposited with TEOS/O₂ plasmas were found to have soft surface layers, 0.5-1.5 nm thick, which contribute to an improvement of their field emission properties. The effect of gas phase compositions on the surface properties of the conductive surface layer was discussed.     

Preparation of PEO ceramic coating on Ti alloy and its high temperature oxidation resistance

Ceramic coatings were prepared in Na₂SiO₃–Na₂CO₃–NaOH system by pulsed bi-polar plasma electrolytic oxidation on Ti–6Al–4V alloy. The phase composition, structure and the elemental distribution of the coatings were studied by XRD, SEM and energy dispersive spectroscopy, respectively. The thermal shock resistance of the coated samples at 850 °C was evaluated by the thermal shock tests. The high temperature oxidation resistance of the coating samples at 500 °C was investigated. The results showed that the coating was mainly composed of rutile- and anatase TiO₂, Increasing the concentration of Na₂SiO₃, TiO₂ content decreased gradually while the thickness of the coating increased. There were a large amount of micro pores and sintered particles on the surface of the coatings. Increasing concentration of Na₂SiO₃, the sintered particles on the surface turned large, and the Si content increased while the Ti content decreased gradually. When the concentration of Na₂SiO₃ was 15 g/L, the thermal shock resistance of the coatings was better than that of the coatings that prepared under other Na₂SiO₃ concentrations. The coating samples prepared under the optimized technique process based on the thermal shock tests improved the high temperature oxidation resistance at 500 °C greatly, whether considering the isothermal oxidation or the cyclic oxidation.     

Oxidation behaviour of SiC coatings

Amorphous silicon carbide (SiC) films were deposited on silicon substrates by radio-frequency magnetron sputtering. The films were oxidized in air in the temperature range 400–900 °C and for times from 1 to 16 h. Neutron reflectivity measurements provided information on the thickness, density and roughness of the SiC and on the formed SiO₂ layers. Fourier transform infrared spectroscopy was used to determine the bond structure of the formed SiO₂ and changes in the bonding of SiC after exposure at the oxidation temperature. The surface morphology of the oxidized films was characterized by atomic force microscopy measurements. The oxidation kinetics is initially fast and as the SiO₂ layer is formed it slows down. The SiC consumption varies linearly with time at all oxidation temperatures. Exposure of the SiC at the oxidation temperature affects its density and to some degree its bond structure, while the formed SiO₂ has density and bond structure as that formed by oxidation of Si under the same conditions. PACS  66.30.Ny; 68.47.Gh; 68.55.J-     

Effect of SiO2 protective layer on the femtosecond laser-induced damage of HfO2/SiO2 multilayer high-reflective coatings

Two kinds of HfO₂/SiO₂ 800 nm high-reflective (HR) coatings, with and without SiO₂ protective layer were deposited by electron beam evaporation. Laser-induced damage thresholds (LIDT) were measured for all samples with femtosecond laser pulses. The surface morphologies and the depth information of all samples were observed by Leica optical microscopy and WYKO surface profiler, respectively. It is found that SiO₂ protective layer had no positive effect on improving the LIDT of HR coating. A simple model including the conduction band electron production via multiphoton ionization and impact ionization is used to explain this phenomenon. Theoretical calculations show that the damage occurs first in the SiO₂ protective layer for HfO₂/SiO₂ HR coating with SiO₂ protective layer. The relation of LIDT for two kinds of HfO₂/SiO₂ HR coatings in calculation agrees with the experiment result.     

Interfacial reactions and oxidation behavior of Al2O3 and Al2O3/Al coatings on an orthorhombic Ti2AlNb alloy

The uniform and dense Al₂O₃ and Al₂O₃/Al coatings were deposited on an orthorhombic Ti₂AlNb alloy by filtered arc ion plating. The interfacial reactions of the Al₂O₃/Ti₂AlNb and Al₂O₃/Al/Ti₂AlNb specimens after vacuum annealing at 750 °C were studied. In the Al₂O₃/Ti₂AlNb specimens, the Al₂O₃ coating decomposed significantly due to reaction between the Al₂O₃ coating and the O-Ti₂AlNb substrate. In the Al₂O₃/Al/Ti₂AlNb specimens, a γ-TiAl layer and an Nb-rich zone came into being by interdiffusion between the Al layer and the O-Ti₂AlNb substrate. The γ-TiAl layer is chemically compatible with Al₂O₃, with no decomposition of Al₂O₃ being detected. No internal oxidation or oxygen and nitrogen dissolution zone was observed in the O-Ti₂AlNb alloy. The Al₂O₃/Al/Ti₂AlNb specimens exhibited excellent oxidation resistance at 750 °C.     

Influence of FeSO4 concentration on thermal emissivity of coatings formed on titanium alloy by micro-arc oxidation

Ceramic coatings with high emission were fabricated on Ti6Al4V alloy by microarc oxidation (MAO) with additive FeSO₄ into the electrolyte. The microstructure, chemical composition and chemical state of the coatings were determined by SEM, XRD, EDS and XPS, respectively. The bonding strength between the coating and substrate was studied by tensile strength test, together with the thermal shock resistance of the coating. The results showed that Fe content in the coating layer significantly affect its thermal emissivity. The relative content of Fe in the coatings surface increased at first and then decreased with increasing the concentration of FeSO₄ in electrolytes, so does the emissivity of the coatings. The bonding strength became weaker with increasing the concentration of FeSO₄. In addition, the coating remains stable over 40 cycles of thermal shocking. The coating formed at 3 g/L FeSO₄ demonstrates the highest an average spectral emissivity value around of 0.87, and bonding strength higher than 33 MPa.     

Preparation and properties of composite ceramic coating containing Al2O3–ZrO2–Y2O3 on AZ91D magnesium alloy by plasma electrolytic oxidation

A composite ceramic coating containing Al₂O₃–ZrO₂–Y₂O₃ was successfully prepared on AZ91D magnesium alloy by plasma electrolytic oxidation (PEO) technique in an alkaline aluminate electrolyte. The morphology, elemental and phase composition, corrosion behavior and thermal stability of the uncoated and coated samples were studied by environmental scanning electron microscopy (ESEM), energy dispersive X-ray spectrometer (EDS), X-ray diffractometer (XRD), electrochemical corrosion test, high temperature oxidation test and thermal shock test. The results showed that the composite ceramic coating was composed of Al₂O₃, c-ZrO₂, t-ZrO₂, Y₂O₃ and some magnesium compounds, such as MgO, MgF₂ and MgAl₂O₄. After PEO treatment, the corrosion potential of AZ91D alloy was increased and the corrosion current density was significantly reduced. Besides, the coated magnesium alloys also showed excellent high temperature oxidation resistance and thermal shock resistance at 500 °C environment.     

Microstructure development and properties of the AlCuFe quasicrystalline coating on near-α titanium alloy

A protective quasicrystalline AlFeCu coating was deposited on TIMETAL 834 substrate by nonreactive magnetron sputtering in order to improve resistance of the alloy to oxidation. Microstructure characterisation of the substrate and the coating was performed by analytical scanning- and transmission electron microscopy as well as X-ray diffractometry. Depending on annealing temperature and time, the deposited coating (2.7 μm thick) has a different microstructure. The coating in Specimen 1 (annealed 600 °C/4 h in vacuum) consisted of two zones: outer, composed of Al₅Fe₂ and Al₂Cu₃ phases and inner, in which only quasicrystalline ψ phase was present. The coating in Specimen 2 (annealed 600 °C/4 h + 700 °C/2 h in vacuum) was fully quasicrystalline and consisted of icosahedral ψ phase.Both coatings exhibit higher microhardness than the substrate material. It was established that the applied surface treatment essentially improves oxidation resistance of the alloy tested at 750 °C during 250 h in static air. Sample weight gain was 60% lower than in the case of uncoated sample. Oxide scale spallation occurred for uncoated alloy while the coated one did not show any spallation. It was found that the very brittle scale formed during oxidation on the uncoated alloy was consisting of TiO₂, while that on the coated one consisted mainly of α-Al₂O₃.     

Influence of Co(CH3COO)2 concentration on thermal emissivity of coatings formed on titanium alloy by micro-arc oxidation

Ceramic thermal protection coatings on Ti6Al4V alloy were achieved by micro-arc oxidation (MAO) in the presence of Co(CH₃COO)₂. The morphology, crystallographic structure and chemical composition of the coating were characterized by various techniques. The thermal emission of the coating was measured by Fourier transform spectrometer apparatus. The bonding strength between the coating and substrate was studied, together with the thermal shock resistance of the coating. The results indicate that the content of Co in the coating layer significantly affects its thermal emissivity. Higher concentration of Co(CH₃COO)₂ in electrolytes leads to more Co ions into the coating, which enhances the emissivity of the coating. All the coatings show bonding strength higher than 10 MPa. In addition, the coating remains stable over 40 cycles of thermal shocking. The coating formed at 4 g/L Co(CH₃COO)₂ displays an average spectral emissivity value more than 0.9 and bonding strength about 10.4 MPa.     

水含量对溶胶-凝胶SiO2增透膜结构和性能的影响

利用正硅酸乙脂(TEOS)的碱催化,溶胶-凝胶法制备多孔SiO₂增透膜.较详细地研究了工艺参量H₂O/TEOS摩尔比对薄膜结构和性能的影响.结果表明,随H₂O/TEOS摩尔比的增大,薄膜厚度、折射率和致密度减小;而薄膜透射率增大.     

Effect of surface roughness on the development of protective Al2O3 on Fe-10Al (at.%) alloys containing 0-10 at.% Cr

The effect of alloy surface roughness, achieved by different degrees of surface polishing, on the development of protective alumina layer on Fe-10 at.% Al alloys containing 0, 5, and 10 at.% Cr was investigated during oxidation at 1000 °C in 0.1 MPa oxygen. For alloys that are not strong Al₂O₃ formers (Fe-10Al and Fe-5Cr-10Al), the rougher surfaces increased Fe incorporation into the overall surface layer. On the Fe-10Al, more iron oxides were formed in a uniform layer of mixed aluminum- and iron-oxides since the layer was thicker. On the Fe-5Cr-10Al, more iron-rich nodules developed on an otherwise thin Al₂O₃ surface layer. These nodules nucleated preferentially along surface scratch marks but not on alloy grain boundaries. For the strong Al₂O₃-forming Fe-10Cr-10Al alloy, protective alumina surface layers were observed regardless of the surface roughness. These results indicate that the formation of a protective Al₂O₃ layer on Fe-Cr-Al surfaces is not dictated by Al diffusion to the surface. More cold-worked surfaces caused an enhanced Fe diffusion, hence produced more Fe-rich oxides during the early stage of oxidation.     

Characterization and oxidation behavior of NiCoCrAlY coating fabricated by electrophoretic deposition and vacuum heat treatment

Electrophoretic deposition (EPD) was showed to be a feasible and convenient method to fabricate NiCoCrAlY coatings on nickel based supperalloys. The microstructure and composition of the NiCoCrAlY coatings after vacuum heat treatment were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive X-ray analysis (EDAX). Isothermal-oxidation test was performed at 1100 °C in static air for 100 h. The results show that the major phases in electrophoretic deposited and vacuum heat treated NiCoCrAlY coating are γ-Ni and γ′-Ni₃Al phases, also there is an extremely small quantity of Al₂O₃ in the coating. Composition fluctuations occur in the coating and a certain amount of titanium diffuse from the superalloy substrate to the top of the coating during vacuum heat treatment. The oxidation test results exhibit that the oxidation kinetics of this coating has two typical stages. The protective oxide layer is mainly formed in the initial linear growth stage and then the oxide layer hinders further oxidation of the coating in the subsequent parabolic growth stage. The coating can effectively protect the superalloy substrate from oxidation. A certain amount of rutile TiO₂ is formed in the coating during oxidation and it is adverse to the oxidation resistance of the coating.     

SiC/SiO2 coating for improving the oxidation resistive property of carbon nanofiber

The SiC/SiO₂ deposition was performed to improve the oxidation resistive properties of carbon nanofiber (CNF) from electrospinning at elevated temperatures through sol-gel process. The stabilized polyacrylonitrile (PAN) fibers were coated with SiO₂ followed by heat treatment up to 1000 and 1400 °C in an inert argon atmosphere. The chemical compositions of the CNFs surface heat-treated were characterized as C, Si and O existing as SiC and SiO₂ compounds on the surface. The uniform and continuous coating improved the oxidation resistance of the carbon nanofibers. The residual weight of the composite was 70-80% and mixture of SiC, SiO₂ and some residual carbon after exposure to air at 1000 °C.     

Improvement in the properties of plasma-sprayed metallic, alloy and ceramic coatings using dry-ice blasting

Dry-ice blasting, as an environmental-friendly method, was introduced into atmospheric plasma spraying for improving properties of metallic, alloy and ceramic coatings. The deposited coatings were then compared with coatings plasma-sprayed using conventional air cooling in terms of microstructure, temperature, oxidation, porosity, residual stress and adhesion. It was found that a denser steel or CoNiCrAlY alloy coating with a lower content of oxide can be achieved with the application of dry-ice blasting during the plasma spraying. In addition, the adhesive strength of Al₂O₃ coating deposited with dry-ice blasting exceeded 60 MPa, which was nearly increased by 30% compared with that of the coating deposited with conventional air cooling. The improvement in properties of plasma-sprayed metallic, alloy and ceramic coatings caused by dry-ice blasting was attributed to the decrease of annulus-ringed disk like splats, the better cooling efficiency of dry-ice pellets and even the mechanical effect of dry-ice impact.     

Ultrasound-assisted fast encapsulation of metal microparticles in SiO2 via an interface-confined sol-gel method

Although the traditional Stoˇber process-based methods are widely used for encapsulation of metal nanoparticles in SiO₂, these time-consuming methods are not effective for coating metal microparticles with a uniform SiO₂ layer of desired thickness. Herein, an ultrasound-assisted, interface-confined sol–gel method is proposed for fast encapsulation of metal microparticles in SiO₂, and the encapsulation of Sn microparticles is chosen as an example to illustrate its feasibility. The proposed method involves covering metal microparticles with liquid films that contain water, alcohol, surfactant (Span-80) and catalyst (NH₄F) and then ultrasonically dispersing these particles into cyclohexane, where tetraethylorthosilicate (TEOS) is added. To ensure the hydrolysis-condensation reactions of TEOS occurring at the particle-cyclohexane interface so that the formed SiO₂ is coated on the particles, the microparticles should be well dispersed into cyclohexane with the liquid films being not broken away from their surfaces. It is found that the assistance of probe sonication and the addition of surfactant are crucial to achievement of a good dispersion of metal microparticles in cyclohexane. And using high-viscosity alcohol (namely glycerol), controlling the volume ratio of water to alcohol and the amount of water, and choosing a suitable ultrasonic power are essential for preventing the formation of free SiO₂ (namely SiO₂ that is not coated on the particles), which is a result that the liquid films escape from the particle surfaces under ultrasonic cavitation. Our results have also revealed that the thickness of SiO₂ layer can be adjusted by changing the reaction time or the total amount of water. In particular, the thickness of SiO₂ layer can be easily raised by simply repeating the encapsulation procedure. Compared with the traditional Stoˇber process-based methods, the proposed method is time-saving (reaction time: about 30 min vs. more than 12 h) and extremely effective for coating microparticles with a continuous, uniform SiO₂ layer of desired thickness.     

Double layer oxidation resistant coating for carbon fiber reinforced silicon carbide matrix composites

Double layer coatings, with celsian-Y₂SiO₅ as inner layer and Y₂Si₂O₇ as outer layer, were prepared by microwave sintering on the surface of carbon fiber reinforced silicon carbide matrix composite. Both celsian, Y₂SiO₅ and Y₂Si₂O₇ were synthesized by in situ method using BAS glass, Y₂O₃ and SiO₂ as staring materials. The sintering temperature was 1500 °C, and little damage was induced to the composite. The composition and micrograph of the fired coating were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The oxidation and thermal shock resistance of samples with doubled-layered coating were characterized at 1400 °C in air. After 150 min oxidation and thermal cycling between 1400 °C and room temperature for 15 times, the weight loss of double layer-coated sample was 1.22% and there were no cracks in the coating.     

Synthesis and properties of silicon dioxide films prepared by pulsed laser deposition using ceramic SiO2 target

Silicon dioxide (SiO₂) thin films were deposited on BK7 substrates by pulsed laser deposition (PLD) method using ceramic SiO₂ targets (C-SiO₂-Ts), which was sintered by solid state sintering. The reason for using C-SiO₂-T instead of the silicon target is to reduce the oxygen-deficiency phenomenon in deposited SiO₂ thin films. The influence of substrate-temperatures, oxygen-pressures and oxygen-plasma-assistance on the properties of synthesized films was studied. X-ray diffraction, atomic force microscopy, ultraviolet–visible–near-infrared scanning spectrophotometry were used to characterize the crystallinity, morphology and optical properties of deposited films. Results show that the root-mean-square roughness of films increased with the increase of oxygen-pressure, substrate-temperature and with the employment of oxygen-plasma. The transmittance of films increased with the increase of oxygen-pressure and decreased with the increase of substrate-temperature and with the employment of oxygen-plasma. Stoichiometric SiO₂ thin film with high optical quality was synthesized at room-temperature and 20 Pa oxygen-pressure using C-SiO₂-T.     

Tribological behavior of microarc oxidation coatings formed on titanium alloys against steel in dry and solid lubrication sliding

The coatings mainly composed of nanostructured TiO₂ were deposited on Ti6Al4V alloy by microarc oxidation (MAO). The duplex coatings of microarc oxidation combined with spraying graphite process were fabricated for the antifriction purpose. The tribological properties of unpolished, polished and duplex coating against steel under dry friction conditions were examined. It is found that antifriction property of the polished microarc oxidation coating is superior to that of the unpolished one. The improvement is attributed to the low surface roughness and the nanocrystalline structure of coatings. The duplex coating exhibits best antifriction property, registering a lower and steady friction coefficient of ≈0.12 than that of the polished microarc oxidation coating sliding in the similar condition. The good tribological property is attributed to the specially designed duplex structure, the coating adhering strongly to the substrate and serving as the load-supporting underlayer and the graphite layer on top of it working as solid lubricant.     

Influence of preparation technology on the microstructure and anti-oxidation property of SiC-Al2O3-mullite multi-coatings for carbon/carbon composites

Oxidation protective SiC-Al₂O₃-mullite multi-coatings for carbon/carbon (C/C) composites were prepared with a two-step pack cementation process. The influence of preparation temperature and SiO₂/Al₂O₃ ratio of the pack powder on the phase, microstructure and oxidation resistance of the multi-coatings were investigated. It showed that the multi-coatings that contained mullite could be produced at 1700-1800 °C. A denser coating surface was acquired with the decrease of SiO₂/Al₂O₃ ratio in the pack chemistries while a little damnification to the interface of the coating and C/C substrate. The as-prepared coating could effectively protect C/C composites from oxidation at 1600 °C for 81 h.