Electrodeposition and properties of Zn-nanosized TiO2 composite coatings

Nanosized TiO₂ particles were prepared by sol-gel method. The TiO₂ particles were co-deposited with zinc from a sulphate bath at pH 4.5 using electrodeposition technique. The corrosion behavior of the coatings was assessed by electrochemical polarization, impedance, weight-loss and salt spray tests. Wear resistance and microhardness of the composite coating was measured. The smaller grain size of the composite coatings was observed in the presence of TiO₂ and it was confirmed by the images of scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques.     

A new approach to optimizing pigmented coatings considering both thermal and aesthetic effects

Pigmented coatings with high reflectivity against solar irradiation can be used to control unwanted thermal heating that occurs as materials absorb sunlight such as heat in buildings that increases cooling loads. However, these surfaces produce glare that is unpleasant to the eye, and the coatings themselves can damage the appearance of the coated object. We introduce a new optimization method that embraces both thermal and aesthetic requirements. Our proposed coatings maximize the reflectivity of the near infrared (NIR) region to reduce thermal heating, while for aesthetic appeal they also minimize the visible (VIS) reflected energy received by human eyes, especially at wavelengths where eye sensitivity is high. The optimization parameter is defined as the ratio of the total reflected energy in the NIR region to that in the VIS region weighted by human eye sensitivity. Titanium dioxide is used as the pigment, and databases of its radiative properties are constructed using the Mie theory. To compute reflectivity, nongray radiative heat transfer in an anisotropic scattering monosized pigmented layer, with independent scattering, including direct and diffuse solar irradiations, is analyzed using radiation element method by ray emission model (REM²). Colors are calculated and optimization parameter is evaluated by using spectral reflectivity. Finally, the optimum values of particle size, volume fraction of pigment, and coating thickness are obtained.     

Diffuse reflectance of TiO2 pigmented paints: Spectral dependence of the average pathlength parameter and the forward scattering ratio

Diffuse reflectance spectra of paint coatings with different pigment concentrations, normally illuminated with unpolarized radiation, have been measured. A four-flux radiative transfer approach is used to model the diffuse reflectance of TiO₂ (rutile) pigmented coatings through the solar spectral range. The spectral dependence of the average pathlength parameter and of the forward scattering ratio for diffuse radiation, are explicitly incorporated into this four-flux model from two novel approximations. The size distribution of the pigments has been taken into account to obtain the averages of the four-flux parameters: scattering and absorption cross sections, forward scattering ratios for collimated and isotropic diffuse radiation, and coefficients involved in the expansion of the single particle phase function in terms of Legendre polynomials.     

Influences of laser remelting on microstructure of nanostructured Al2O3-13 wt.% TiO2 coatings fabricated by plasma spraying

The effects of laser remelting on microstructure of nanostructured Al₂O₃-13 wt.% TiO₂ ceramic coatings prepared by plasma spraying with agglomerated powders were studied. The microstructure of the feedstock, as-sprayed and laser-remelted coatings were investigated by using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffractometry (XRD). The results indicate that the plasma-sprayed ceramic coating consists of both fully melted regions and partially melted regions. The totally ceramic coating, especially the fully melted regions, has a typical plasma-sprayed lamellar-like structure as the conventional coating, and has some pores. According to the difference of microstructures, the partially melted regions can be divided into liquid-phase sintered regions (a three-dimensional net or skeleton-like structure: Al₂O₃-rich submicron particles embedded in the TiO₂-rich matrix) and solid-phase sintered regions (remained nanoparticles). The lamellar defect of the as-sprayed coating is erased, and the compactness of the coating is improved significantly after laser remelting. The laser-remelted region composed of fine equiaxed grains, which are different from the conventional column-like crystals along the direction of the heat current. Due to the rapid solidification of laser remelting process, there are still some nanoparticles in the remelted region because of an insufficient time for grains growth.     

The effects of activated carbon supports on the structure and properties of TiO2 nanoparticles prepared by a sol-gel method

TiO₂-coated activated carbon (TiO₂/AC) composites and pure TiO₂ powders were prepared by a sol-gel method using tetrabutylorthotitanate as a precursor. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), differential thermal analysis (DTA), X-ray photoelectron spectrum (XPS) and nitrogen absorption. The photoactivity of samples was evaluated by methylene blue (MB) degradation. The analysis results show that compared with pure TiO₂ powders, the spherical-shaped TiO₂ particles are well-dispersed in the AC matrix and the size of the resulting TiO₂ crystallites decreases to below 40 nm with increasing phase transformation temperature. The AC matrix creates anti-calcination effects and shows interfacial energy effects that control the growth of the TiO₂ particles, baffle the anatase to rutile phase transition, and cumber the TiO₂ particles to agglomerate. Compared with the surface areas of TiO₂ powders, the combination of TiO₂ and AC forms composites with high surface areas which are slightly affected by calcination temperature. By AC support, the photoactivity of TiO₂ is increased in MB photocatalytic course, possible because active carbon increases photocatalytic activity of TiO₂ particles by producing high concentration of organic compound near TiO₂, and small-size TiO₂ particles are well-dispersed on the surface of AC.     

Effects of coating parameters on the morphology of SiO2-coated TiO2 and the pigmentary properties

SiO₂-coated TiO₂ powders were prepared by the chemical deposition method starting from rutile TiO₂ and Na₂SiO₃. The SiO₂-coated TiO₂ powders were characterized by X-ray photoelectron spectroscopy, Zeta-potential analysis, Fourier transform infrared spectroscopy, and transmission electron microscopy. The evolution of island-like and uniform coating layers was found to depend upon the ratio of Na₂SiO₃ to TiO₂, reaction temperature, and pH. The whiteness and brightness of the SiO₂-coated TiO₂ powders increased in response to an increase in the SiO₂ loading, but there was a maximum value among the light scattering indexes. The SiO₂-coated TiO₂ powders possessed more negative Zeta potentials than the naked TiO₂. The dispersibility of the SiO₂-coated TiO₂ powders with the continuous and uniform SiO₂ coating layers was higher than that of the naked TiO₂ and the SiO₂-coated TiO₂ powders with the island-like SiO₂ coating layers.     

Comparison between aesthetic and thermal performances of copper oxide and titanium dioxide nano-particulate coatings

Nano-particulate coatings with high reflectance against solar irradiation can control undesirable thermal heating by sunlight absorption. It can reduce the energy consumption for air conditioning of houses and cars. For the objects covered by these coatings and subjected to human sight, e.g. roofing surfaces, high dazzle of reflected visible light can offend the human eyes and spoil the fine view of covered objects. The authors introduced a new optimization method in designing pigmented coatings which considers both thermal and aesthetic effects in previous studies. The optimization is possible by controlling the material, size and concentration of pigment particles. The proposed coatings maximize the reflectance of near infrared (NIR) region to care the thermal effects and minimize the visible (VIS) reflected energy to keep the dark tone because of aesthetic appeal. Two different types of copper oxide pigment particles namely cupric oxide (CuO) and cuprous oxide (Cu₂O) were considered in this study. The optimum characteristics and performances are obtained and compared with titanium dioxide (TiO₂) particle as a typical cool pigment. The results show that cupric oxide has much better performance for our objective.     

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

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

Synthesis of TiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>-based ceramics by plasma spraying

Structure of ceramics obtained by the plasma spray deposition of spherical TiO₂ powders has been investigated. An electron microscopy study of the surfaces and cross sections of particles in the initial powder and of the deposited ceramic coatings was performed. X-ray diffraction and Raman scattering data proved that the coatings were mainly structured as rutile. In addition, Raman and X-ray diffraction data have revealed an amorphous phase, an anatase phase, and non-stoichiometric phases Ti₈O₁₅, Ti₁₀O₁₉, Ti₇O₁₃, etc. being present in the coatings. The observed suppression of (011) and (111) XRD peaks and an increased intensity of (110) peak are indicative of a predominant orientation of grains in the synthesized ceramics. Mechanisms of formation of the complex coating structure are discussed.     

Evolution of TiO2 coating layers on lamellar sericite in the presence of La and the pigmentary properties

TiO₂-coated sericite powders were prepared by the chemical deposition method starting from lamellar sericite and TiCl₄ in the presence or absence of La³⁺ cations. After calcination at 900 °C for 1 h, the resultant TiO₂ nanoparticles on the sericite surfaces existed in anatase phase. The light scattering indexes of the TiO₂-coated lamellar sericite powders were dozens of times higher than that of the naked lamellar sericite powders. The presence of La³⁺ in the deposition solution was beneficial to the formation of the small-sized anatase TiO₂ nanoparticles, resulting in the formation of the dense and uniform island-like TiO₂ coating layers in a large range of the weight ratios of TiO₂ to sericite from 5% to 20%. The TiO₂-coated lamellar sericite powders prepared in the presence of La³⁺ had higher light scattering index than that prepared in the absence of La³⁺. XPS analysis shows that when La³⁺ cations were absent in the reaction solution, TiO₂ coating layers anchored at the sericite surface via the Ti-O-Si and Ti-O-Al bonds. The presence of La³⁺ cations caused the formation of Si-O-La and Al-O-La bonds at the sericite surface and Ti-O-La bond at the surface of TiO₂ coating layers. After coating TiO₂ on the sericite surface, the yellowness of the TiO₂-coated sericite powders obviously increased and the brightness slightly decreased.     

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.     

Morphological, mechanical, corrosion and hydrogen permeation characteristics of Ni-nano-TiO2 composite coating compared to Ni electrodeposited on low carbon steel

Ni and Ni-nano-TiO₂ composite coatings with various amounts of TiO₂ in electrolyte, on low carbon steel, have been prepared from Watts-bath using electrodeposition process. The morphological, mechanical, corrosion and hydrogen permeation characteristics of Ni and Ni-nano-TiO₂ coatings were studied and compared with each other. The results revealed that, existence of nano-TiO₂ particles in Ni matrix improved the microstructure as well as microhardness, whereas increasing particle incorporation from 4.33 to 7.62 vol % concluded to microhardness enhancement. The corrosion behavior of Ni and Ni-nano-TiO₂ composite coatings with various amount of particle content was studied by the anodic polarization curves in 5% H₂SO₄ solution at room temperature. It was seen Ni-nano-TiO₂ composite coatings exhibited higher corrosion resistances comparing to pure Ni coating and corrosion protection improved with increasing nano-TiO₂ in coatings. In addition to the corrosion and engineering properties, comparison of hydrogen permeation characteristics of the Ni coating was made with Ni-nano-TiO₂ composite coating through Devanthan-Stachurski hydrogen permeation test. From the resulting data analysis, Ni-nano-TiO₂ composite coating was seen not only to provide longer life under corroding media, but also reduces greatly the risk of the substrate being exposed to hydrogen permeation when compared to electrodeposited Ni coating.     

Evolution mechanism of alumina coating layer on rutile TiO2 powders and the pigmentary properties

The evolution of alumina coating layers on rutile TiO₂ particle surfaces was investigated starting from aluminum sulfate by a chemical liquid deposition method. The morphology of the alumina coating layers was determined by transmission electron microscopy. The chemical structure and the evolution mechanism of the alumina coating layers on TiO₂ surfaces were investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and powder X-ray diffraction techniques. The dispersibility of the alumina-coated TiO₂ powders was determined by dynamic laser scattering (DLS) mode. The alumina coating layers existed in boehmite phase, AlOOH, and anchored at the surfaces of TiO₂ via Ti-O-Al bond. The formation of alumina coating layers on TiO₂ surfaces depended on the pH value of the deposition solution and the alumina loading. After coated by alumina layer, the dispersibility, whiteness, brightness, and light scattering index of the resultant samples were promoted.     

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

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

Ni-Co-TiO2 nanocomposite coating prepared by pulse and pulse reversal methods using acetate bath

Ni-Co/nano TiO₂ (Ni-Co-TiO₂) composite coatings were prepared under pulse current and pulse reverse current methods using acetate bath. The microstructure and corrosion resistance of the coatings were characterized by means of XRD, SEM and EIS. Both the Ni-Co alloy and composite coatings exhibited single phase of Ni matrix with face centered cubic (fcc) crystal structure. The crystal orientation of the Ni-Co-TiO₂ composite coating was transformed from crystal face (2 0 0) to (1 1 1) compared with Ni-Co alloy coatings. The results showed that the microstructure and performances of the coatings were greatly affected by TiO₂ content on the deposits prepared by PC and PRC methods. The microhardness and corrosion resistance were enhanced in the optimum percentage of TiO₂ composite coatings. The PRC composite coatings were exhibited from compact surface, higher microhardness and good corrosion resistance compared with that of the PC composite coating.     

Comparison of self-cleaning properties of three titania coatings on float glass

This work compares the self-cleaning properties of experimental TiO₂ and TiO₂-Ag coatings on float glass with a commercial self-cleaning glass. In the experimental surfaces, TiO₂ coating was applied to float glass via the sol-gel route, while TiO₂-Ag coating was applied by the liquid flame spray method, which deposits TiO₂-Ag composite nanoparticles on the surface. The effect of the coatings on the surface wettability and the activation time for achieving hydrophilicity was studied through water contact angle as a function of exposure time to UV light. The surface morphology was investigated by using scanning electron microscopy (SEM) and confocal optical microscopy. The photocatalytic activity of the coatings was examined with methylene blue and stearic acid degradation tests. Finally, the soil attachment to the surfaces was tested with a sebum-based model soil. The sol-gel TiO₂ coating became superhydrophilic within a few hours, while the activation time needed for the commercial titania coated glass was several days. The surface with the TiO₂-Ag nanoparticles did not show any marked changes in the water contact angle. The commercial titania coated and the sol-gel TiO₂ surfaces showed self-cleaning properties and clearly lower attachment of soil than the uncoated and TiO₂-Ag coated surfaces. The difference in the interaction of the surfaces with the organic contaminants was assumed to depend mainly on differences in the thickness of the coatings.     

Surface modification of pure titanium by hydroxyapatite-containing composite coatings

Micro-arc oxidation (MAO) is commonly applied to modify the surface of titanium (Ti)-based medical implants with a bioactive and porous Ti oxide (TiO₂) coating. The study reports a new method of incorporating hydroxyapatite (HA) within the TiO₂ coating by MAO and alkali heat treatment (AHT) in the solution containing Ca ion and P ion. The morphology, composition and phase composition of the coatings were analyzed with scanning electron microscopy with energy-dispersive X-ray spectrometer and X-ray diffraction. Surface topography and roughness of the coatings were investigated by atomic force microscopy operated in the tapping mode. The results showed that TiO₂-based coatings were obtained on pure Ti by MAO with an electrolyte containing Ca ion and P ion; the prepared MAO coatings were mainly composed of Ca, P, O and Ti. AHT transformed Ca and P to HA crystals. In conclusion, the TiO₂/HA composite coatings can be obtained on the surface of pure Ti by MAO and AHT, and the addition of Ca ion and P ion to the AHT solution contributed to the formation of HA.     

Formation of Heterogeneous Powder Coatings with a Two-Level Micro-and Nanocomposite Structure under Gas-Dynamic Spraying Conditions

Heterogeneous coatings have been deposited by the cold gas-dynamic spraying of mechanically synthesized AMg2/graphite + Al₂O₃ powders. A specific feature of the coatings formed is the existence of a two-level micro-and nanocomposite structure. It has been established that an increase in the content of microsized Al₂O₃ particles in the mixture from 10 to 30 wt % produces a twofold increase in the thickness of the coating deposited for the same time period from 140 to 310 μm. A further growth in the content of microsized Al₂O₃ particles in the mixture up to 50 wt % leads to a decrease in the thickness of the coating formed to 40 μm. The manufactured coatings have a high microhardness ranging from 1.7 to 3.2 GPa depending on their composition. The high microhardness of these coatings is caused by an increase in the hardness of the matrix material due to the creation of a nanocomposite structure, which strengthens the immobilization of microsized Al₂O₃ particles in it, thus improving the properties of the heterogeneous coating as a whole.     

Mechanical performance of apatite/TiO2 composite coatings formed on Ti and NiTi shape memory alloy

To make metals bioactive for orthopaedic applications, apatite/TiO₂ composite coatings were formed on Ti and NiTi shape memory alloy (SMA) using a H₂O₂-oxidation and hot water aging technique and the subsequent accelerated biomimetic process. In the current investigation, nanoindentation, scratch testing and frictional testing were employed to assess mechanical properties and the adhesion of apatite/TiO₂ composite coatings formed on Ti and NiTi SMA. Nanoindentation testing conducted on cross-sections of composite coatings indicated that there was no significant difference in nanohardness and elastic modulus between apatite/TiO₂ composite coatings formed on Ti and NiTi SMA samples. The enhancement of the adhesion between the apatite layer and the metal substrates arose from the TiO₂ intermediate layer in the composite coating. The highest values of coating adhesion strength for Ti and NiTi SMA samples, as measured by scratch tests, were 22.58 N and 19.07 N, respectively. However, compared to corresponding Ti samples, NiTi SMA samples had better tribological properties.     

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.