Silane solution stability and film morphology of water-based bis-1,2-(triethoxysilyl)ethane for thin-film deposition on aluminium

Thin-film silane coating (<1 μm) has been introduced as a chromium free multi-metal surface pre-treatment for corrosion protection, adhesion promotion and surface passivation of metals such as aluminium, steel, zinc, magnesium and others. Bis-1,2-(triethoxysilyl)ethane (BTSE) has received much attention as it is, after hydrolysis, highly reactive towards (covalent) metal/film bonding and cross-link formation for the creation of barrier properties. Much of the past work on BTSE was performed on methanol-based laboratory solutions due to the low solubility of BTSE in water. For industrial applications these solutions are not considered suitable anymore because of the high process cost as well as ecological and health issues associated with methanol and the high monomer content of such solutions. For industrial practice water-based silane solutions are being considered. In the present work water-based BTSE solution is compared to a reference methanol-based solution. The silane solution is analysed using ²⁹Si NMR spectroscopy, and the deposited silane films are morphologically characterised using infra-red spectroscopic ellipsometry and field-emission gun-scanning electron microscopy.     

Adhesion aspects of hydrophobic silane zeolite coatings for corrosion protection of aluminium substrate

The adhesive properties of an anti-corrosion silane–zeolite coatings on aluminium substrates have been evaluated in this work. The coated samples were obtained by dip-coating sol–gel solution. Four different composite coatings at increasing zeolite amount (60–90 wt% of zeolite) have been investigated.     

Rapid growth of particles by coagulation between particles in silane plasma reactor

The changes of particle size distribution were investigated during the rapid growth of particles in the silane plasma reactor by the discrete-sectional model. The particle size distribution becomes bimodal in the plasma reactor and most of the large sized particles are charged negatively, but some fractions of small sized particles are in a neutral state or even charged positively. As the mass generation rate of monomers increases or as the monomer diameter decreases, the large sized particles grow more quickly and the particle size distribution becomes bimodal earlier. As the mass generation rate of monomers decreases, the electron concentration in the plasmas increases and the fraction of particles charged negatively increases. With the decrease in monomer diameter, the electron concentration decreases in the beginning of plasma discharge but later increases.     

Structure of copolymer films created by plasma enhanced chemical vapor deposition

The interface structure in copolymer films made using plasma enhanced chemical vapor deposition (PECVD) has been probed for the first time using X-ray reflectivity. Copolymer films made from comonomers benzene (B), octafluorocyclobutane (OFCB), and hexamethyldisiloxane (HMDS) show extremely sharp interfaces and scattering length density depth profiles that are uniform with depth, making them useful for optical applications. The polymer/air interface has an rms roughness (∼5 Å) that is only slightly larger than that of the supporting substrate (∼3 Å). Addition of either benzene or HMDS as a comonomer in the deposition of OFCB alters a transient deposition behavior at the silicon oxide interface that occurs when using only OFCB. For the B-OFCB copolymer films, a facile control of refractive index with monomer feed composition is achieved. A nonlinear variation in the X-ray scattering length density with composition for the HMDS-OFCB copolymer films is consistent with the nonlinear visible light refractive index (632.8 nm) variation reported earlier.     

Ethylene/ ammonia plasma polymer deposition for controlled adhesion of graphite fibers to PEEK

Plasma polymerization of ethylene and ammonia gas mixtures is used to obtain uniform polymer coatings on the surface of AS4 graphite fibers. The polymer deposition rates were determined for processing parameters such as composition of the monomer mix, monomer flow rate, chamber pressure, and power input of the radio frequency field. Plasma formed polymers were characterized using Fourier Transform Infrared (FTIR) and X-ray Photoelectron Spectroscopy (XPS). XPS spectra were collected at 75° and 30° takeoff angles to obtain elemental composition and functional group populations at different sampling depths. Plasma deposition rate was the smallest for 100% ethylene and increased by three to four fold when ammonia was added to the monomer mixture. The polymer coatings were of uniform thickness and exhibited a complex crosslinked structure. The 100% ethylene plasma polymer was strongly hydrocarbon in nature but had some oxygen and nitrogen containing groups. Plasma polymers from ethylene/ammonia mixture were much more polar and contained reactive and polar group constituents, including carbonyl, ether, primary and secondary amines, and hydroxyl groups. The presence of oxygen and nitrogen functionalities is presumed to arise primarily from the reaction of trapped radicals with oxygen and nitrogen when exposed to air. Small amounts of silicon were also detected in the plasma formed films.     

Microstructures of La2Ce2O7 coatings produced by plasma spray-physical vapor deposition

La₂Ce₂O₇ (LC) coatings were produced by plasma spray-physical vapor deposition (PS-PVD). To achieve the quasi-columnar microstructure, three spray parameters with different net power, spray distance, and carrier gas flow rate were applied. The relationships between the spray parameters and the microstructures were investigated. It was found that the coatings’ microstructure is more sensitive to the net power and carrier gas flow rate rather than the spray distance. The corresponding phase and chemical compositions of coatings were studied by X-ray diffraction (XRD) and energy dispersive spectrometer (EDS), respectively. The results indicate that the lattice parameters of LC phases have positive correlations with average atomic La/Ce ratios of the coatings. The regional characteristics of the optimized coating were investigated by transmission electron microscope (TEM). Super-lattice diffraction patterns of TEM revealed that the coating is pyrochlore phase. “Particle-interruption” mechanisms in the quasi-columnar coating were proposed and discussed.     

Characterization of composite titanium nitride coatings prepared by reactive plasma spraying

Reactive plasma spraying (RPS) technology has been used to produce high thickness (>100 μm) films of composite Ti-TiN-Ti_xN_y coatings. Reactively sprayed coatings obtained from SP700 (Ti-4.5Al-3V-2Mo-2Fe) and Ti6242 (Ti-6Al-2Sn-4Zr-2Mo) powders, deposited onto flat substrates of Ti-6Al-4V, have been investigated. X-ray diffraction (XRD) and micro-hardness measurements have been used to characterize the crystallographic features and differences between the hardness of cross-section and surface. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) techniques have been used to determine the morphology and surface chemical composition of the coatings. Back-scattered electron imaging has revealed the distribution of Ti and TiN in the composite material. Obtained results evidenced a sharp interface between the coating and substrate in terms of the profile of chemical composition. The presence of unmelted Ti particles as well as the formation of nitrides was observed.     

Incorporation of zirconia nanoparticles into coatings formed on aluminium by AC plasma electrolytic oxidation

Composite ceramic coatings were formed on aluminium by AC plasma electrolytic oxidation (PEO) using Na₆P₆O₁₈ or Na₂SiO₃ · 5H₂O/KOH electrolytes with monoclinic zirconia nanoparticles in suspension. The coatings grown in Na₂SiO₃ · 5H₂O/KOH electrolyte revealed γ-Al₂O₃ and amorphous phase; α-Al₂O₃ and AlPO₄ were additionally produced with the Na₆P₆O₁₈ electrolyte. Higher temperature zirconia phases, possibly tetragonal and orthorhombic, in addition to the monoclinic phase, were indicative of elevated temperatures at sites of microdischarges. Further, local melting resulted in zirconium-rich dendrites in the coating formed in silicate electrolyte. Zirconium was mainly located in the relatively compact, outer layer of the coating, constituting ∼70–90% of the coating thickness. Nanoparticles appeared to be incorporated at the coating surface and following transport to the interface regions between the inner and outer layers along short-circuit paths through the outer 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.     

Interactions of BTESPT silane and maleic anhydride grafted polypropylene with epoxy and application to improve adhesive durability between epoxy and aluminium sheet

For improvement of adhesive strength and durability of adhesion between epoxy and aluminium sheet bis-(triethoxysilylpropyl)tetrasulfide (BTESPT) silane and maleic anhydride grafted polypropylene (PP-g-MAH) are chosen for surface pretreatment of the aluminium sheet respectively. Fourier transform infrared (FTIR) spectroscopy was used for characterization of the structure and the interactions in the systems. It is shown that BTESPT silane and the anhydride on PP-g-MAH take part in the curing reactions of the epoxy/polyamide system. The adhesive shear strength of the samples, prepared under different curing temperatures, and after immersion in boiling water and 3.5% NaCl water solution respectively, was tested. The features of the shear fractured surfaces were examined by scanning electron microscope (SEM). For the aluminium sheet pretreated by BTESPT silane, the maximum adhesive shear strength is 22.2 MPa, which is higher than that of 17.5 MPa for aluminium sheet without pretreatment by the silane. After immersion in boiling water for 80 h and in NaCl water solution at 50 °C for 180 h the adhesive shear strengths are 13.39 MPa and 18.4 MPa respectively, which are higher than these (below 6 MPa) for aluminium sheet without pretreatment by the silane. As for the aluminium sheet pretreated by PP-g-MAH, the maximum adhesive shear strength is 13.17 MPa. After immersion in boiling water for 80 h and in NaCl water solution at 50 °C for 180 h the adhesive shear strengths decline to 10.67 MPa and 8.1 MPa respectively.     

Microstructure and mechanical properties of yttria stabilized zirconia coatings prepared by plasma spray physical vapor deposition

Plasma spray physical vapor deposition (PS-PVD) was used to deposit yttria stabilized zirconia (YSZ) coatings with different columnar morphologies by varying the spray distance. Although similar quasi-columnar structures were formed at the spray distances of 600 mm and 1400 mm, the formation mechanisms of particles in the coatings were different. Besides, an electron beam physical vapor deposition (EB-PVD) like columnar coating out of pure vapor was deposited at a spray distance of 1000 mm and the columnar consisted of elongated nano-sized secondary columns. The hardness and Young׳s modulus of the coatings were investigated. Compared to the other two quasi-columnar structures, the EB-PVD like columnar coating exhibited higher hardness (~9.0 GPa ) and Young׳s modulus (~110.9 GPa), mainly due to its low porosity and defect.     

Photocatalytic functional coatings of TiO2 thin films on polymer substrate by plasma enhanced atomic layer deposition

We prepared photocatalytic TiO₂ thin films which exhibited relatively high growth rate and low impurity on polymer substrate by plasma enhanced atomic layer deposition (PE-ALD) from Ti(NMe₂)₄ [tetrakis (dimethylamido) Ti, TDMAT] and O₂ plasma to show the self-cleaning effect. The TiO₂ thin films with anatase phase and bandgap energy about 3.3 eV were deposited at growth temperature of 250 °C and the photocatalytic effects were compared with commercial Activ glass. From contact angles measurement of water droplet and photo-induced degradation test of organic liquid, TiO₂ thin films with anatase phases showed superhydrophilic phenomena and decomposed organic liquid after UV irradiation. The anatase TiO₂ thin film on polymer substrate showed highest photocatalytic efficiency after 5 h UV irradiation. We attribute the highest photocatalytic efficiency of TiO₂ thin film with anatase structure to the formation of suitable crystalline phase and large surface area.     

Design of novel plasma reactor for diamond film deposition

Development of microwave plasma reactors is a key factor for improving microwave plasma chemical vapor deposition (MPCVD) techniques for producing high quality diamond films. In this paper, a new microwave plasma reactor operated at 2.45 GHz was proposed on the basis of numerical simulation. The Finite Element Method (FEM) was used to optimize the geometry, and the Finite Difference Time Domain (FDTD) method was employed to calculate the electric field and the plasma density. The proposed reactor works mainly at the TM₀₂₁ mode, and it has an excellent power handing capability. Preliminary experiment showed that high density hemispherical plasma could be ignited inside the reactor, and uniform diamond film could be deposited on substrates at high input microwave power.     

Investigation of the growth processes of coatings formed by AC plasma electrolytic oxidation of aluminium

The formation of alumina-based coatings on aluminium by AC plasma electrolytic oxidation (PEO) has been investigated using a silicate electrolyte with selective additions of fine zirconia particles. The coatings comprised an amorphous barrier layer, a relatively dense intermediate layer and a more porous outer layer that contained silicon species. Zirconia was incorporated non-uniformly into the outer layer and, to a limited extent, the intermediate layer, as both particles and a component of cellular microstructures. Following treatments firstly in zirconia-containing electrolyte and secondly in zirconia-free electrolyte, the zirconia did not extend beyond about the middle of the intermediate layer, indicating its limited inward mass transfer during microdischarges. The coating efficiency decreased at oxidation times in excess of 40 min due to dissolution of either the substrate or the coating, or physical loss of coating material. The oxidation of aluminium consumed on average ∼29% of the anodic charge; the remainder was used mainly in generation of oxygen gas.     

Microstructure and plasma corrosion behavior of yttria coatings prepared by the aerosol deposition method

Particle contamination arising from inner ceramic components of the plasma etching equipment has become a serious issue. Yttria (Y₂O₃) coatings prepared via aerosol deposition (AD) have demonstrated superior plasma resistance in the reduction of particle contamination. The superior particle contamination performance of Y₂O₃ coatings prepared by AD has been speculatively attributed to its unique microstructure; however, the relationship between the coatings’ microstructure and plasma corrosion behavior has been insufficiently clarified. Herein, we investigated the relationship between the microstructure and plasma corrosion behavior of Y₂O₃ coatings prepared by the AD method and compared the results with those for coatings prepared by other coating methods. When internal pores are present, these internal pores were selectively plasma corroded; plasma corrosion marks reflecting their pore shape were formed, and the surface roughness increased with increasing plasma exposure time. However, when no internal pores were present, as in the case of the AD coating, the surfaces were homogeneously corroded and maintained their initial surface. As the risk of particle contamination caused by the corrosion of the plasma-resistant coatings is greatly increased with surface roughness, we concluded that the Y₂O₃ coating prepared via AD will contribute greatly to reducing particle contamination.     

Variations in cross-link density with deposition pressure in ultrathin plasma polymerized benzene and octafluorocyclobutane films

Neutron reflectometry (NR) measurements of ultrathin films from octafluorocyclobutane (OFCB) and benzene (B) precursors deposited using Plasma Enhanced Chemical Vapor Deposition (PECVD) at two pressures (0.6 and 0.05 torr) reveal that under both deposition conditions there are a 7 nm-thick surface layer and an approximately 1 nm-thick transition layer next to the substrate which have structures different than those in the middle of the film. NR measurements of films swollen with solvent reveal that the density of cross-linking next to the substrate is lower than that in the middle of the film or the region adjacent to the surface of the film for both precursors. Variations in the cross-link density with processing pressure are much stronger for PP-B films than for PP-OFCB films.     

Impact of cathode loss on plasma characteristics,microstructures and properties of 7YSZ coatings in PS-PVD

The slight changes in geometry and mass of the cathode of O3CP plasma torch during service life caused the variety of arc motion between the cathode and anode. The voltage appeared to rise first and then fall. In this experiment, the impact of cathode loss on plasma characteristics, microstructures and properties of 7YSZ coatings was investigated. Optical emission spectroscopy (OES) was used to characterize the plasma jet characteristics such as plasma temperature and electron number density. It is found that vapor deposition is the main deposition mechanism, and the microstructures of the coatings are mainly affected by the supersaturation and subcooling of the vapor phase, which determine the nucleation and growth of crystals. At the middle of cathode service life, the plasma temperature and electron number density are the highest and the powder is completely evaporated. High crystal growth rates and surface diffusion lead to large columnar crystals with large grain size. The best thermal shock resistance. The thermal shock resistance is the best in this case. When the cathode is in the beginning and end of service life, there are columnar grains with small size produced and many solid particles in the gaps due to diffusion difficulties generated by low temperature. Shadowing enhances to manufacture fine grains and few branches. The presence of solid particles prevents the release of thermal stress and reduces thermal shock resistance of coatings. Fine grains prevent cracks propagation to improve the bonding strength of coatings.     

Onion-like carbon deposition by plasma spraying of nanodiamonds

A deposit of carbon nanoparticles based on an onion-like structure was fabricated from detonation nanodiamond powders by a novel plasma spraying process, electromagnetically accelerated plasma spraying (EMAPS). EMAPS was able to transform nanodiamonds to onion-like structured carbon within 300 μs through a thermal graphitization process in which the temperature of the particles would be in the range of 2700-4500 K. Synthesized onion-like carbon nanoparticles were spherical or polyhedral. The G-band in the UV-Raman spectra of the produced deposits was found to be a superposition of a characteristic band of well-formed carbon onions at 1571 cm⁻¹ and the G-band of defective carbon onions at 1592 cm⁻¹. The availability of a plasma spraying process for developing solid lubricant coatings incorporating nanodiamond and onion-like carbon was demonstrated.     

Deposition mechanisms of columnar structured La2Ce2O7 coatings via plasma spray-PVD

Recently, a columnar structured La₂Ce₂O₇ (LC) coating was successfully produced via plasma spray-physical vapor deposition (PS-PVD) but in a relatively narrow processing window. In this paper, spray distances were adjusted in suitable regions of columnar structures based on our previous work attempting to precisely control coating microstructures. The columnar coatings were investigated to be regularly distributed along the axial (spraying) and radial directions of the plasma jet, and can be divided into three types including PVD-like, Closely-packed and Particle-concomitant, respectively. The PVD-like coatings deposited mainly from vapor phase distribute at relatively short spray and radial distances, while the Closely-packed ones distribute at long radial distances (periphery of the samples). In addition, the Particle-concomitant ones distribute at long spray distances. The related deposition mechanisms are discussed and a deposition model is built to provide an additional understanding of PS-PVD.