Corrosion protection of aluminium pretreated by vinyltriethoxysilane in sodium chloride solution

The corrosion protection of vinyltriethoxysilane (VTES) films on aluminium during exposure to 3% NaCl was investigated using electrochemical impedance spectroscopy (EIS), potential-time measurements and optical microscopy coupled with image analysis. Composition and thickness of films were analyzed using Auger electron spectroscopy (AES) combined with depth profiling. It was shown that films deposited from 5% solution were significantly thicker and exhibited lower porosity and better corrosion stability, as compared to films deposited from 2 vol.% solution. VTES films deposited from 5 vol.% solutions and cured for 30 min exhibited better protection properties than other investigated films.     

Fabrication and characterization of ITO thin films on heat-resistant transparent flexible clay films

Transparent conductive indium tin oxide (ITO) thin films were deposited on transparent flexible clay films with heat resistant and high gas barrier properties by rf magnetron sputtering. The electrical, structural, and optical properties of these films were examined as a function of deposition temperature. A lowest resistivity of 4.2 × 10^− 4 Ωcm and an average transmittance more than 90% in the visible region were obtained for the ITO thin films fabricated at deposition temperatures more than 300 °C. It was found that ITO thin films with low resistivity and high transparency can be achieved on transparent flexible clay film using conventional rf magnetron sputtering at high temperature, those characteristics are comparable to those of ITO thin films deposited on a glass substrate.     

Corrosion Protection of In Situ Al-Based Composite by Cerium Conversion Treatment

Cerium conversion films were deposited on the surface of in situ aluminum-based composite in solutions containing different cerium chloride (CeCl₃) and hydrogen peroxide (H₂O₂) concentrations at 30 °C. The morphology and composition of conversion films deposited in various solutions were investigated using scanning electron microscopy, energy dispersive x-ray analysis, and x-ray photoelectron spectroscopy (XPS). SEM observations revealed that only patches of film can be deposited on the composite surface when immersed in solutions with low CeCl₃ and H₂O₂ concentrations. However, entire composite surface was covered with a compact film when immersed in a solution containing 10 g/L CeCl₃ and 100 mL/L H₂O₂. XPS results indicated that cerium was incorporated as Ce⁴⁺ species in the hydrated oxide film. The formation of such hydrated conversion film on the composite resulted in low anodic current density and more noble pitting potential when exposed to 3.5% NaCl solution.     

Fabricating TiO2 Photocatalysts by rf Reactive Magnetron Sputtering at Varied Oxygen Partial Pressures

Titanium dioxide (TiO₂) thin films were fabricated onto non-alkali glass substrates by rf reactive magnetron sputtering at room temperature using Ti-metal target at varied oxygen partial pressure [O₂/(Ar + O₂)]. The sputtering deposition was performed under an rf power of 200 W. The target to substrate distance was kept at 80 mm, and the total gas pressure was 10 mTorr after 2 h of deposition. It was found that the crystalline structure, surface morphology, and photocatalytic activities of the TiO₂ thin films were affected by the oxygen partial pressure during deposition. The XRD patterns exhibited a broad-hump shape indicating the amorphous structure of TiO₂ thin films. The thin films deposited at a relatively high value of oxygen partial pressure (70%) had a good photo-induced decomposition of methylene blue (MB), photo-induced hydrophilicity, and had a small grain size.     

Characteristics of copper oxide films deposited by PBII&D

Copper oxide films were deposited by plasma based ion implantation and deposition using a copper antenna as rf sputtering ion source. A gas mixture of Ar + O₂ was used as working gas. During the process, copper that was sputtered from the rf antenna reacted with oxygen and was deposited on a silicon substrate. The composition and the chemical state of the deposited films were analyzed by XPS. The structure of the films was detected by XRD. It is observed that Cu₂O film has been prepared on the Si substrate. It is found that the microstructure of the deposited film is amorphous for the applied voltage of − 5 kV. The surface layer of the deposited films is CuO. This is because the surface layer absorbs the oxygen from ambient air after the treated sample was removed from the vacuum chamber. An appropriate applied voltage, 2 kV under the present conditions, brings the lowest resistance. It is also seen that the maximum absorbance of the deposited films moves to a lower wavelength with increased applied voltage.     

Formation and breakdown of surface films on magnesium and its alloys in aqueous solutions

The influences of surface films formed by open-circuit exposure to neutral solutions on the corrosion and electrochemical behaviour of pure Mg and Mg alloys have been examined by in situ ellipsometric analysis and electrochemical measurements. Surface films mainly composed of Mg(OH)₂ grew rapidly during open-circuit exposure to 0.1 M NaCl and 0.1 M Na₂SO₄ solutions. These films had protective ability to passivate Mg in the solutions. However, they suffered local breakdown under anodic polarisation. The passive current density decreased and the breakdown potential increased with increasing immersion time and film thickness. Influences of purity and alloying elements on the passivity and its breakdown of Mg have been discussed.     

Corrosion protection of magnesium alloy AZ31 sheets by spin coating process with poly(ether imide) [PEI]

In the present study, the potential of poly(ether imide) as corrosion protective coating for magnesium alloys was evaluated using the spin coating technique. The influence of different parameters on the coating properties was evaluated and the corrosion behaviour of the coatings was investigated using electrochemical impedance spectroscopy. The best corrosion protection was obtained preparing the coatings under N₂ atmosphere, using 15 wt.% solution in N′N′-dimethylacetamide (DMAc) which resulted in a coating of approximately 2 μm thickness, with an initial impedance of 10⁹ Ω cm² and of 10⁵ Ω cm² after 240 h of exposure to a 3.5% NaCl solution.     

Surface characterization of Mo oxynitride films obtained by RF sputtering at various N2 ratios

Molybdenum oxynitride (MoN_xO_y) thin films were deposited on p-type Si(100) wafer by rf magnetron sputtering method at various nitrogen gas ratios. The surface characteristics of deposited thin films were investigated using scanning electron microscopy, atomic force microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The thickness of films decreased down to 70 from 1000 nm and the roughness was varied with increasing N₂ gas ratio. The formation of MoN_xO_y was confirmed by existence of Mo species between Mo^δ+ and Mo⁵⁺ oxidation state and ON bond in XP spectra. At 0% of N₂ gas ratio, metallic simple cubic Mo structure was observed. As the N₂ gas ratio increased, Mo nitrate and Mo silicate phases were appeared.     

Constitution, microstructure, and battery performance of magnetron sputtered Li-Co-O thin film cathodes for lithium-ion batteries as a function of the working gas pressure

Li-Co-O thin film cathodes have been deposited onto Si and stainless steel substrates by RF magnetron sputtering from a ceramic LiCoO₂ target at various working gas pressures from 0.15 to 25 Pa. Composition, crystal structure and thin film morphology were examined and properties such as intrinsic stress, conductivity and film density were determined. As-deposited films at 0.15 Pa as well as in the range between 5 Pa and 10 Pa working gas pressure showed a nanocrystalline metastable rocksalt structure with disordered cation arrangement and were nearly stoichiometric. To induce a cation ordering the films were annealed in a furnace at temperatures between 100 and 600 °C for 3 h in argon/oxygen atmosphere (Ar:O₂ = 4.5:5) of 10 Pa. This cation ordering process was observed by XRD and Raman spectroscopy. For the films deposited at 10 Pa gas pressure an annealing temperature of 600 °C leads to the formation of the high temperature phase HT-LiCoO₂ with a layered structure. The Raman spectrum of the films deposited at 0.15 Pa and annealed at 400 °C indicates the formation of the low temperature phase LT-LiCoO₂ with a cubic spinel-related structure, which is assumed to be stabilized due to high compressive stress in the film. The electrochemical characterisation of annealed thin film cathodes revealed that the discharge capacity strongly depends on the crystal structure. Thin Li-Co-O films with a perfect layered HT-LiCoO₂ structure showed the highest discharge capacities.     

Effect of plasma surface treatment and heat treatment ambience on mechanical and corrosion protection properties of hybrid sol-gel coatings on aluminum

Hybrid sol-gel coatings derived from a base catalyzed hydrolysis of tetraethylorthosilicate and methyltriethoxysilane were deposited on aluminum substrates by a dip coating technique. Some of the coatings were deposited on substrates whose surfaces were pre-treated using atmospheric-air plasma prior to coating in order to study the effect of surface activation by plasma pre-treatment. The coated substrates were heat treated in different ambiences like air, flowing N₂ and vacuum to see the effect of heat treatment ambience on the properties of the coatings. Characterization of the coatings after heat treatment was carried out with respect to coating thickness, pencil scratch hardness, adhesion, water contact angle and their microstructure. Corrosion testing for all the coatings was carried out by electrochemical polarization measurements as well as electrochemical impedance spectroscopy in 3.5% NaCl solution for 1 h exposure time to investigate on their corrosion resistance. Coating thicknesses ranging from 1 μm-5 μm were obtained by varying the withdrawal speeds. Heat treatment in a controlled atmosphere with low oxygen content was seen to improve the hydrophobicity of coated surface, as measured by water contact angles (20^o — air; 71^o — N₂; 95^o — vacuum), thereby improving the corrosion resistance. Surface pre-treatment using open-air plasma was seen to improve the adhesion of the sol-gel coatings thus making it possible to obtain adherent and thick coatings in a single dip coating process. Both the methods of processing the coatings reduced the corrosion rate of aluminum from 1.95 mpy to 0.004 mpy in case of coatings densified in nitrogen and to 0.00068 mpy for coatings deposited on a plasma treated substrate and densified in air.     

Study of bactericidal efficiency of magnetron sputtered TiO2 films deposited at varying oxygen partial pressure

TiO₂ thin films have been deposited at different Ar:O₂ gas ratios (20:80,70:30,50:50,and 40:60 in sccm) by rf reactive magnetron sputtering at a constant power of 200 W. The formation of TiO₂ was confirmed by X-ray photoelectron spectroscopy (XPS). The oxygen percentage in the films was found to increase with an increase in oxygen partial pressure during deposition. The oxygen content in the film was estimated from XPS measurement. Band gap of the films was calculated from the UV-Visible transmittance spectra. Increase in oxygen content in the films showed substantial increase in optical band gap from 2.8 eV to 3.78 eV. The Ar:O₂ gas ratio was found to affect the particle size of the films determined by a transmission electron microscope (TEM). The particle size was found to be varying between 10 and 25 nm. The bactericidal efficiency of the deposited films was investigated using Escherichia coli (E. coli) cells under 1 h UV irradiation. The growth of E. coli cells was estimated through the Optical Density measurement by UV-Visible absorbance spectra. The qualitative analysis of the bactericidal efficiency of the deposited films after UV irradiation was observed through SEM. A correlation between the optical band gap, particle size and bactericidal efficiency of the TiO₂ films at different argon:oxygen gas ratio has been studied.     

Comparison of electrochemical corrosion behaviour of MgO and ZrO2 coatings on AM50 magnesium alloy formed by plasma electrolytic oxidation

Two types of PEO coatings were produced on AM50 magnesium alloy using pulsed DC plasma electrolytic oxidation process in an alkaline phosphate and acidic fluozirconate electrolytes, respectively. The phase composition and microstructure of these PEO coatings were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The corrosion behaviour of the coated samples was evaluated by open circuit potential (OCP) measurements, potentiodynamic polarization tests, and electrochemical impedance spectroscopy (EIS) in neutral 0.1 M NaCl solution. The results showed that PEO coating prepared from alkaline phosphate electrolyte consisted of only MgO and on the other hand the one formed in acidic fluozirconate solution was mainly composed of ZrO₂, MgF₂. Electrochemical corrosion tests indicated that the phase composition of PEO coating has a significant effect on the deterioration process of coated magnesium alloy in this corrosive environment. The PEO coating that was composed of only MgO suffered from localized corrosion in the 50 h exposure studies, whereas the PEO coating with ZrO₂ compounds showed a much superior stability during the corrosion tests and provided an efficient corrosion protection. The results showed that the preparation of PEO coating with higher chemical stability compounds offers an opportunity to produce layers that could provide better corrosion protection to magnesium alloys.     

The Corrosion Behaviour of Electrochemical Zn Coated with Conversion Chromate and Phosphate Films in Concrete

The corrosion behaviour of electrochemical Zn coatings with and without chromate (VI, III) and phosphate (amorphous and crystalline) films in aerated 0.1 M NaOH + 0.1 M NaCl solution and concrete, immersed into water has been studied. The estimated corrosion rate in 0.1 M NaOH + 0.1 M NaCl solution is minimal cf. Zn chromatised in Cr³⁺ solution. The value of j_cor of Zn chromatised in Cr⁶⁺ solution is 1.5 times as high as that in Cr³⁺. The experiments carried out in concrete immersed into water (pH 12.5) have shown that all the chromate films studied do not extend the operating time of the sample. The best corrosion protection is provided by crystalline phosphate film.     

High-repetition rate pulsed laser deposition of ZrC thin films

ZrC thin films were grown on (100) Si substrates by the pulsed laser deposition (PLD) technique using a high-repetition rate excimer laser working at 40 Hz. The substrate temperature during depositions was set at 300 °C and the cooling rate was 5 °C/min. X-ray diffraction investigations showed that the films were crystalline. Films deposited under residual vacuum or 2 × 10^− 3 Pa of CH₄ atmosphere exhibited a (200)-axis texture, while those deposited under 2 × 10^− 2 Pa of CH₄ atmosphere were found to be equiaxed. The surface elemental composition of as-deposited films, analyzed by Auger electron spectroscopy (AES), showed the usual high oxygen contamination of carbides. Once the topmost − 3-5 nm region was removed, the oxygen concentration rapidly decreased, being around 3-4% only in bulk. Scanning electron microscopy (SEM) investigations showed a smooth, featureless surface morphology, corroborating the roughness values below 1 nm (rms) obtained from simulations of the X-ray reflectivity (XRR) curves. From the same simulations we also estimated films mass density values of around 6.32-6.57 g/cm³ and thicknesses that correspond to a deposition rate of around 8.25 nm/min. Nanoindentation results showed a hardness of 27.6 GPa and a reduced modulus of 228 GPa for the best quality ZrC films deposited under an atmosphere of 2 × 10^− 3 Pa CH₄.     

Effects of growth temperature on μc-Si:H films prepared by plasma assistant magnetron sputtering

Hydrogenated microcrystalline silicon thin films (μc-Si:H) were deposited by plasma assistant magnetron sputtering in Ar-H2 gas mixture. The effects of growth temperature from 150 to 450 ℃ on properties of deposited Si films were investigated at two different hydrogen diluted gases with [H2]/([Ar]+[H2]) of 10％and 50％at 3 Pa. The crystallinity of Si films examined by Raman scattering exhibited higher degradation by lowering growth temperature from 250 to 150 ℃ in low hydrogen diluted gas of 10％ than that in high hydrogen diluted gas of 50％. The IR absorption band around 845 and 890 cm-1 as well as calculated concentration of bonded hydrogen showed more obvious decrease of samples deposited in low hydrogen diluted gas of 10％ than that in high hydrogen diluted gas of 50％. The optical band gasps of both groups of samples measured by ultraviolet-visible optical absorption were decreased with increasing temperature in both gas conditions.     

Dealloying behaviour of Cu-20Zr alloy in hydrochloric acid solution

The dealloying of the duplex-phase Cu-20Zr cast alloys and corresponding sputtered Cu-20Zr films (wt.%) in hydrochloric acid solution was investigated using electrochemical, chemical and surface analysis techniques. Results show that the dissolution mechanisms for the cast alloy and the films were strongly depended on the electrochemical activities of Zr and Cu in each phase in 0.1 mol/l HCl solution. When the potential was between the redox potentials of Cu/Cl⁻/CuCl_s and Zr/Zr⁴⁺, the dissolution is attributed to the selective removal of Zr atoms in the cast alloy and the sputtered films; when the potential was higher than the redox potential of Cu/Cl⁻/CuCl_s, Cu and Zr atoms in the samples dissolved simultaneously. In duplex-phase cast alloy, of Zr in the different phases in the alloy, Zr in the zirconium-rich phase was in preference to dissolve owing to its high electrochemical activities. Namely the selective phase attach firstly happens in the cast alloy. The study of the corrosion characteristic of sputtered films showed that Cu atoms reacted with Cl⁻ ions in the solution and formed the corrosion product of Cu(I) and Cu(II) complex ions, which restrained the dissolution of Cu atoms.     

Magnetic Properties,Microwave Characteristics,and Thermal Stability of the FeCoAlN Films

FeCoAlN films were prepared by reactive radio frequency magnetron co-sputtering technique in an argon and nitrogen mixture atmosphere. The soft magnetic properties, GHz dynamic properties, and magnetic thermal stability of the FeCoAlN films were investigated. The FeCoAlN films deposited at N₂/(Ar + N₂) gas flux percentages larger than 8% have amorphous structure. The (Fe_64.8Co_35.2)_96.3Al_3.7N film as-deposited at the N₂/(Ar + N₂) gas flux percentage of 9% has good magnetic softness and uniaxial in-plane anisotropy, as demonstrated by the typical hysteresis loops along easy and hard axis. The magnetic thermal stability of the FeCoN films can be obviously improved by introduction of a high Al content. The (Fe_64.8Co_35.2)_86.5Al_13.5N films annealed at 400 °C for 1 h exhibit good magnetic softness and GHz dynamic properties with a saturation magnetization (μ₀ M _s) of 1.21 T, an easy axis coercive field (H _ce) of 8.5 Oe, an anisotropy field (H _k) of 35 Oe, a ferromagnetic resonance frequency (f _r) of 1.89 GHz, and a real part of permeability (μ′) of 380. The dynamic characteristics can be described by the theoretical model based on Landau-Lifshitz-Gilbert (L-L-G) equation and eddy current dynamics.     

High deposition rates of uniform films in tetramethylsilane-based plasmas generated by elementary microwave sources in matrix configuration

Plasma scaling up can be achieved by distributing elementary microwave plasma sources on planar rectangular networks. These so-called matrix plasmas can generate uniform sheets of plasma over a wide argon pressure range, from 7.5 to 750 Pa, with densities between 10¹² and 10¹³ cm^− 3. In order to estimate the capabilities of matrix plasmas for PACVD processing in terms of deposition rate and uniformity, SiOCH and SiNCH films were deposited using TMS (tetramethylsilane), as the organic gas precursor of silicon, mixed with oxygen or nitrogen flows. Plasmas of O₂ / TMS and N₂ / TMS gas mixtures can be sustained between 5 and 25 Pa. Variations in the deposition rate as a function of microwave power and nitrogen partial pressure are reported. Thickness uniformity of SiOCH and SiNCH films was measured across a silicon wafer. The obtained deposition rates exceed 1.3 μm/min and the films present a uniformity better than 5% on 75 mm diameter silicon wafers. Composition of the films has also been analyzed by XPS as a function of process parameters: microwave input power, composition of gas mixture, and N₂ partial pressure. In particular, these analyses have shown a very low yield of nitrogen incorporation when using N₂ gas as nitrogen precursor and high Si and Si-Si bonding contents in the films, probably due to a strong fragmentation of the TMS precursor in the high density plasma.     

X-ray diffraction study of the effect of annealing temperature on the phase and structural states of Fe79Zr10N11 films produced by magnetron sputtering

Fe₇₉Zr₁₀N₁₁ films 0.7 μm thick deposited on glass substrates have been produced by rf reactive magnetron sputtering. The films are a soft magnetic material, which can exhibit a combination of a high saturation inductance and a low coercive force and, therefore, shows promise as magnetic recording cores for the high-density magnetic recording. The results of X-ray diffraction studies of the phase and structural states of the films and the effect of annealing on these states are considered.     

Synthesis of layered birnessite-type manganese oxide thin films on plastic substrates by chemical bath deposition for flexible transparent supercapacitors

Layered birnessite-type manganese oxide thin films are successfully fabricated on indium tin oxide coated polyethylene terephthalate substrates for flexible transparent supercapacitors by a facile, effective and inexpensive chemical bath deposition technology from an alkaline KMnO₄ aqueous solution at room temperature. The effects of deposition conditions, including KMnO₄ concentration, initial molar ratio of NH₃·H₂O and KMnO₄, bath temperature, and reaction time, on the electrochemical properties of MnO₂ thin films are investigated. Layered birnessite-type MnO₂ thin films deposited under optimum conditions display three-dimensional porous morphology, high hydrophilicity, and a transmittance of 77.4% at 550 nm. A special capacitance of 229.2 F g⁻¹ and a capacitance retention ratio of 83% are obtained from the films after 1000 cycles at 10 mV s⁻¹ in 1 M Na₂SO₄. Compressive and tensile bending tests show that as-prepared MnO₂ thin film electrodes possess excellent mechanical flexibility and electrochemical stability.