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.     

Formation of titania composite coatings on carbon steel by plasma electrolytic oxidation

Titania composite coatings were prepared on carbon steel by plasma electrolytic oxidation in silicate electrolyte and aluminate electrolyte with titania powers doping in the electrolytes. The microstructure of the coatings was characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The properties of the coatings including bond strength, thickness, thermal shock resistance and corrosion resistance varying with the quantities of titania powers in the electrolytes were studied. Investigation results revealed that the coating obtained in silicate electrolyte was composed of anatase-TiO₂, rutile-TiO₂ crystal phases and some Fe, Si, P elements; coating obtained in aluminate electrolyte consisted of anatase-TiO₂, Al₂TiO₅ and some Fe, P elements. Coatings obtained in two types of electrolytes show porous and rough surface. With increasing the concentration of titania powers in the electrolytes, the coating surface first became more compact and less porous and then became more porous and coarse. The bond strength and thickness were not strongly affected by concentration of titania powers in electrolytes. The valves were 23 MPa and for 66 μm for coatings obtained in aluminate electrolyte, and 21 MPa and 35 μm for coatings obtained in silicate electrolyte. Coatings obtained in silicate electrolyte showed a little better thermal shock resistance than those obtained in aluminate electrolyte and the best coatings were obtained with middle concentration of titania powers in the electrolytes. All coated samples showed better corrosion resistance than the substrate in 3.5 wt% NaCl solution. The best coatings were also obtained with middle concentration of titania powers doping in both electrolytes whose corrosion current density was decreased by 2 orders of magnitude compared with the substrate.     

Effect of spraying power on microstructure and bonding strength of MoSi2-based coatings prepared by supersonic plasma spraying

MoSi₂-based oxidation protective coatings for SiC-coated carbon/carbon composites were prepared using a supersonic plasma spraying at the power of 40 kW, 45 kW, 50 kW and 55 kW, respectively. Effect of spraying power on the microstructure and bonding strength of MoSi₂-based coatings was studied. The results show that coatings become more and more compact and the bonding strength increases when the spraying power increases from 40 kW to 50 kW. At the power of 50 kW, the coatings were dense and the bonding strength reached a maximum value of 14.5 MPa. As the spraying power is of sufficient magnitude, many cracks and pores reappaer in coatings and the bonding strength between coating and substrate also decreases.     

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.     

Microstructure and corrosion resistance behavior of ceramic coatings on biomedical NiTi alloy prepared by micro-arc oxidation

In this paper, ceramic coatings were prepared on biomedical NiTi alloys by micro-arc oxidation (MAO) in constant voltage mode. The current density-time response was recorded during the MAO process. The microstructure, element distribution and phase composition of the coatings prepared at different MAO treatment times were investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), thin-film X-ray diffraction (TF-XRD) and X-ray photoelectron spectroscopy (XPS). The corrosion behavior of the coatings in 0.9% NaCl solution was evaluated by the potentiodynamic polarization test. It is found that the coatings become more compact with increasing the MAO treatment time, and the growth rate of coating decreases. The results of TF-XRD, EDS and XPS indicate that the coatings are composed of a large amount of γ-Al₂O₃ and a little α-Al₂O₃, TiO₂ and Ni₂O₃. The Ni content of the coatings is about 3 at.%, which is greatly lower than that of NiTi substrate. The bonding strength of coating-substrate is higher than 40 MPa for all the samples in this study. The corrosion resistance of the coatings is about two orders of magnitude higher than that of the uncoated NiTi alloy.     

In situ formation of low friction ceramic coatings on carbon steel by plasma electrolytic oxidation in two types of electrolytes

In situ formation of ceramic coatings on Q235 carbon steel was achieved by plasma electrolytic oxidation (PEO) in carbonate electrolyte and silicate electrolyte, respectively. The surface and cross-section morphology, phase and elemental composition of PEO coatings were examined by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS). The bond strength of the coating was determined using a direct pull-off test. The hardness as well as tribological properties of the ceramic coating was primarily studied. The results indicated that the coating obtained in carbonate electrolyte was Fe₃O₄, while the coating achieved from silicate electrolyte was proved to be amorphous. Both kinds of coatings showed coarse and porous surface. The Fe₃O₄ coatings obtained in carbonate electrolyte showed a high bonding strength to the substrate up to 20 ± 2 MPa and the value was 15 ± 2 MPa for the amorphous coatings obtained in carbonate electrolyte. The micro hardness of the amorphous coating and the Fe₃O₄ coating was 1001 Hv and 1413 Hv, respectively, which was more than two and three times as that of the Q235 alloy substrate (415 Hv). The friction coefficient exhibited by amorphous coating and Fe₃O₄ coating was 0.13 and 0.11, respectively, both lower than the uncoated Q235 substrate which ranged from 0.17 to 0.35.     

Excellent stability of plasma-sprayed bioactive Ca3ZrSi2O9 ceramic coating on Ti-6Al-4V

In this work, novel zirconium incorporated Ca-Si based ceramic powder Ca₃ZrSi₂O₉ was synthesized. The aim of this study was to fabricate Ca₃ZrSi₂O₉ coating onto Ti-6Al-4V substrate using atmospheric plasma-spraying technology and to evaluate its potential applications in the fields of orthopedics and dentistry. The phase composition, surface morphologies of the coating were examined by XRD and SEM, which revealed that the Ca₃ZrSi₂O₉ coating was composed of grains around 100 nm and amorphous phases. The bonding strength between the coating and the substrate was 28 ± 4 MPa, which is higher than that of traditional HA coating. The dissolution rate of the coating was assessed by monitoring the ions release and mass loss after immersion in the Tris-HCl buffer solution. The in vitro bioactivity of the coating was determined by observing the formation of apatite on its surface in simulated body fluids. It was found that the Ca₃ZrSi₂O₉ coating possessed both excellent chemical stability and good apatite-formation ability, suggesting its potential use as bone implants.     

Synthesis of Ti-Si-N nanocomposite coatings by a novel cathodic arc assisted middle-frequency magnetron sputtering

Ti-Si-N nanocomposite coatings were synthesized by using a cathodic arc assisted middle-frequency magnetron sputtering system in an industrial scale. X-ray photoelectron spectroscopy, X-ray diffraction, and transmission electron microscopy were employed to investigate the chemical bonding and microstructure of the coatings. Atomic force microscope and scanning electron microscope were used to characterize the surface and cross-sectional morphologies of the samples. The coating was found to be nc-TiN/a-Si₃N₄ structure and exhibit a high hardness of 40 GPa when the Si content was 6.3 at.%.     

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.     

Low infrared emissivity of polyurethane/Cu composite coatings

Polyurethane/Cu composite coatings with low infrared emissivity near to 0.10 at the wavelength of 8-14 μm were prepared by a simple and convenient process. The influences of the content of Cu powder, surface roughness, coating thickness and temperature on infrared emissivity of the coatings were systematically investigated. The results indicated that the emissivity decreases significantly with increasing content of Cu powder and coating thickness. The coatings with smooth surface exhibit lower emissivity values than those with rough coatings. Moreover, we found the relationship between the emissivity of coatings and temperature presents a “U” type, and the emissivity reaches to the minimum at about 380 K. The mechanisms of low emissivity were proposed by optical theories, which are found to be in a good agreement with the experimental results.     

Preparation and properties of titanium oxide film on NiTi alloy by micro-arc oxidation

Titanium oxide ceramic coatings were prepared by micro-arc oxidation (MAO) in galvanostatic regime on biomedical NiTi alloy in H₃PO₄ electrolyte using DC power supply. The surface of the coating exhibited a typical MAO porous and rough structure. The XPS analysis indicated that the coatings were mainly consisted of O, Ti, P, and a little amount of Ni, and the concentration of Ni was greatly reduced compared to that of the NiTi substrate. The TF-XRD analysis revealed that MAO coating was composed of amorphous titanium oxide. The coatings were tightly adhesive to the substrates with the bonding strength more than 45 MPa, which was suitable for medical applications. The curves of potentiodynamic porlarization indicated that the corrosion resistance of NiTi alloy was significantly improved due to titanium oxide formation on NiTi alloy by MAO.     

Characterization and corrosion behavior of hydroxyapatite/zirconia composite coating on NiTi fabricated by electrochemical deposition

NiTi alloy is used as biomaterial due to its unique properties, but the high content of Ni (about 50 at.%) in biomedical NiTi is concerned. Hydroxyapatite and hydroxyapatite/zirconia composite coatings were directly electrodeposited on NiTi alloy surface. The coated samples were characterized using X-ray diffraction, scanning electron microscopy, infrared spectroscopy, bonding strength test, polarization and EIS. Results showed that when ZrO₂ was added into the electrolyte, morphology of HAP was changed from thin flake-flower-like crystals to needle-flower-like crystals, and coating was denser. Besides, HAP crystal grains in the coating were preferentially arranged in the [0 0 1] direction. Addition of ZrO₂ could improve the bonding strength between the coating and the substrate. Corrosion resistance of NiTi in the simulated body fluid at 37 °C was significantly improved by almost 60 times by electrodeposition of the hydroxyapatite/zirconia composite coating.     

Microstructure and infrared emissivity property of coating containing TiO2 formed on titanium alloy by microarc oxidation

Ceramic coatings containing TiO₂ were formed on Ti6Al2Zr1Mo1V alloy surface by microarc oxidation (MAO) method. The microstructure, phase and chemical composition of the coatings were analyzed by SEM, XRD and EDS techniques. The coating mainly consists of rutile TiO₂ and a small amount of anatase TiO₂. The infrared emissivity values of coated and uncoated titanium samples when exposed to 700 °C were tested. It was found that the coating exhibits a higher infrared emissivity value (about 0.9) in the wavelength range of 8–14 μm than that of the uncoated titanium alloy, although which shows a slight increase from 0.1 to 0.3 with increasing exposure time at 700 °C. The relatively high infrared emissivity value of the MAO coating is possibly attributed to the photon emission from the as formed TiO₂ phase.     

Characteristic and biocompatibility of the TiO2-based coatings containing amorphous calcium phosphate before and after heat treatment

TiO₂-based coating containing amorphous calcium phosphate (CaP) was prepared on titanium alloy by microarc oxidation (MAO). The increase in the EDTA-2Na concentration was unfavorable for the crystallization of TiO₂. After heat treatment, the amorphous CaP was crystallized. The thickness of the MAO coatings did not change when heat-treated at 400, 600 and 700 °C; while it increased slightly after heat treatment at 800 °C due to the crystallization of amorphous CaP and growth of TiO₂. No apparent discontinuity between the coatings and substrates was observed at various heat-treatment temperatures, indicating the MAO coatings with good interfacial bonding to the substrate. The heat treatment did not alter the chemical composition of the MAO coating and the chemical states of Ti, Ca and P elements. However, it increased the roughness (Ra) of the MAO coating and improved the wetting ability of the MAO coating. In this work, preliminary investigation of the MG63 cell proliferation on the surface of the MAO and heat-treated MAO coatings was conducted. The MAO coating surface with about Ra = 220 nm may be suitable for the MG63 cell adhesion and proliferation. The increased roughness of the heat-treated MAO coatings may result in a decrease in the ability for cell adhesion and proliferation.     

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 wear resistance of pulse electrodeposited Ni-W/Al2O3 composite coatings

The aim of this work is to obtain the electroplating parameters for preparation of Ni-W/Al₂O₃ composite coating with high tungsten content, high micro-hardness and excellent wear resistance by pulse plating procedure. Our results showed that the duty cycle is a dominant parameter for the tungsten content in the coating and the tungsten content increases significantly with increasing duty cycle. The further analysis showed the great influence of tungsten content on micro-hardness of the coating. A maximum micro-hardness of about 859 Hv was obtained in pulse electrodeposited Ni-W/Al₂O₃ composite with tungsten content of 40 wt.% at a peak current density of 20 A/dm², a duty cycle of 80%, a pulse frequency of 1000 Hz and a particle loading of 10 g/L alumina in the plating bath. Although the hardness of Ni-W/Al₂O₃ composite coating was only slightly affected by the alumina content of the deposits prepared in present investigation, the alumina content effect on the tribological characteristic of Ni-W/Al₂O₃ composite coatings is significant. The friction coefficient was lowered to 0.25 and the wear loss was reduced to 1.05 mg by setting the control factors according to the values mentioned above for obtaining the coating with the highest micro-hardness.     

Effect of deposition temperature on boron-doped carbon coatings deposited from a BCl3-C3H6-H2 mixture using low pressure chemical vapor deposition

A mixture of propylene, hydrogen and boron trichloride was used to fabricate boron-doped carbon coatings by using low pressure chemical vapor deposition (LPCVD) technique. Effect of deposition temperature on deposition rate, morphologies, compositions and bonding states of boron-doped carbon coatings was investigated. Below 1273 K, the deposition rate is controlled by reaction dynamics. The deposition rate increases with increasing deposition temperature. The activation energy is 208.74 kJ/mol. Above 1273 K, the deposition rate decreases due to smaller critical radius r_c and higher nuclei formation rate J with increasing temperature. Scanning electron microscopy shows that the structure changes from glass-like to nano-laminates with increasing deposition temperature. The boron concentration decreases with increasing deposition temperature, corresponding with increasing carbon concentration. The five types of bonding states are B-C, B-sub-C, BC₂O, BCO₂ and B-O. B-sub-C and BC₂O are the main bonding states. The reactions are dominant at all temperatures, in which the B-sub-C and PyC are formed.     

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.     

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.     

Structure and infrared emissivity of collagen/SiO2 composite

Collagen/SiO₂ composites were prepared in aqueous suspensions. Adsorption behaviors of collagen onto the surfaces of SiO₂ spheres were studied. Structure and thermal properties were measured with FTIR, SEM, TEM, and TGA-DTA. The results showed that the self-aggregation of collagen macromolecules was taken place during the adsorption of collagen on SiO₂ sphere. The morphology of collagen evolved from line to microfibrils with the increase in the concentration of collagen along with the distortion of SiO₂. Interfacial interactions of electrostatic forces and hydrogen bonding between the collagen macromolecule and SiO₂ sphere had a vital effect on the adsorption of collagen. The amount of the collagen adsorption was increased with the increase of the collagen concentration, yet decreased in increased pH value of the solution. It was found that the composites exhibited lower infrared emissivity values in the wavelength ranged from 8 to 14 μm than not only pure collagen but also SiO₂ sphere, and the value of infrared emissivity was related to the adsorption amount of collagen in the composites.