Dependence of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> coating thickness and annealing conditions on microstructural and electrochemical properties of LiCoO<Subscript>2</Subscript> film

We studied the dependence of Al₂O₃ coating thickness and annealing conditions on the surface morphology and electrochemical properties of Al₂O₃ coated LiCoO₂ films. The optimum coating thickness allowing for the highest capacity retention was about 24 nm. A sample consisting of Al₂O₃ coated on annealed LiCoO₂ film with additional annealing at 400 °C had a uniform coating layer between the coating materials and cathode films. This sample showed the best capacity retention of ∼91 % with a charge-cut off of 4.5 V after 30 cycles, while the bare cathode film showed a capacity retention of ∼32 % under the same conditions. The formation of second phases such as Co-Al-O was observed in the coating films by X-ray photoelectron spectroscopy (XPS). The Co-Al-O containing samples showed a higher initial capacity because of their smaller grain size, but less capacity retention than the Al₂O₃ containing samples.     

Effects of the FeCl<Subscript>3</Subscript> concentration on the polymerization of conductive poly(3,4-ethylenedioxythiophene) thin films on (3-aminopropyl) trimethoxysilane monolayer-coated SiO<Subscript>2</Subscript> surfaces

This study examined the effects of the FeCl₃ (oxidant) concentration on the vapor phase polymerization (VPP) of conducting poly (3,4-ethylenedioxythiophene) (PEDOT) thin films on (3-aminopropyl)trimethoxysilane (APS)-coated SiO₂ surfaces, in which the interaction between Fe(III) and the -NH₂ groups of APS enabled a uniform distribution of FeCl₃ on the surface. The FeCl₃ concentration has a strong impact on the thickness, surface morphology, and conductivity of the PEDOT films deposited by VPP on an APS monolayer. The thickness of the PEDOT thin films increased linearly as the FeCl₃ concentration increased, as predicted by a model of spun films from a FeCl₃ solution. However, the rate of the increase in PEDOT thin film thickness per unit of FeCl₃ in wt.% was lower than the predicted value. This suggests that the consumption of FeCl₃ not participating in polymerization to produce Fe₂O₃ or FeCl₃ aggregates increased as the FeCl₃ concentration increased. In addition, the surface morphology improved as the FeCl₃ concentration increased from 1 wt.% to 3 wt.% and the conductivity increased to approximately 400 S/cm. However, further increases in the FeCl₃ concentration to 5 wt.% and 7 wt.% significantly degraded the morphology by creating holes in the PEDOT film, which reduced the conductivity.     

Microstructure and Electron Energy-Loss Spectroscopy Analysis of Interface Between Cu Substrate and Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Film Formed by Aerosol Deposition Method

Aerosol deposition method is a technique to form dense films by impacting solid particles on a substrate at room temperature. To clarify the bonding mechanism between AD films and substrates, TEM observation and electron energy-loss spectroscopy (EELS) analysis of the interface between Al₂O₃ AD films and Cu substrates were conducted. The Al₂O₃ film was directly adhered to the Cu substrate without any void or crack. The film was composed of randomly oriented α-Al₂O₃ crystal grains of about 10-20 nm large. At the Al₂O₃/Cu interface, the lattice fringes of the film were recognized, and no interfacial layer with nanometer-order thickness could be found. EELS spectra near O-K edge obtained at the interface had the pre-peak feature at around 528 eV. According to previously reported experiments and theoretical calculations, this suggests interactions between Cu and O in Al₂O₃ at the interface. It is inferred that not only the anchoring effect but also the ionic bonding and covalent bonding that originates from the Cu-O interactions contribute to the bonding between Al₂O₃ AD films and Cu substrates.     

Flame-Sprayed Y<Subscript>2</Subscript>O<Subscript>3</Subscript> Films with Metal-EDTA Complex Using Various Cooling Agents

In this study, yttrium oxide (Y₂O₃) films were synthesized from a metal-ethylenediaminetetraacetic (metal-EDTA) complex by employing a H₂-O₂ combustion flame. A rotation apparatus and various cooling agents (compressed air, liquid nitrogen, and atomized purified water) were used during the synthesis to control the thermal history during film deposition. An EDTA·Y·H complex was prepared and used as the staring material for the synthesis of Y₂O₃ films with a flame-spraying apparatus. Although thermally extreme environments were employed during the synthesis, all of the obtained Y₂O₃ films showed only a few cracks and minor peeling in their microstructures. For instance, the Y₂O₃ film synthesized using the rotation apparatus with water atomization units exhibited a porosity of 22.8%. The maximum film’s temperature after deposition was 453 °C owing to the high heat of evaporation of water. Cooling effects of substrate by various cooling units for solidification was dominated to heat of vaporization, not to unit’s temperatures.     

Dielectric properties of Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> thin films deposited onto Ti and TiO<Subscript>2</Subscript> layer

The present study describes the dielectric properties of RF sputtered Ta₂O₅ thin films as a function of the buffer layer and annealing condition. The buffer layers were Ti or TiO₂. And the thin film was annealed in various conditions. The X-ray pattern results showed that the phase of the RF sputtered Ta₂O₅ thin films was amorphous and this state was kept stable to RTA (rapid thermal annealing) even at 700°C. Measurements of the electrical and dielectric properties of the reactive sputtered Ta₂O₅ fabricated in two simple metal insulator semiconductor (MIS) structures, (Cu/Ta₂O₅/Ti/Si/Cu and Cu/Ta₂O₅/TiO₂/Si/Cu) indicated that the amorphous Ta₂O₅ grown on Ti possesses a high dielectric constant (30–70) and high leakage current (10⁻¹–10⁻⁴ A/cm²), whereas a relatively low dielectric constant (−10) and low leakage current (−10⁻¹⁰ A/cm²) were observed in the amorphous Ta₂O₅ deposited on the TiO₂ buffer layer. In addition, the leakage current mechanisms of the two amorphous Ta₂O₅ thin films were investigated by plotting the relation of current density (J) vs. applied electric field (E). The Ta₂O₅/Ti film exhibited three dominant conduction mechanism regimes contributed by the Ohmic emission at low electrical field, by the Schottky emission at intermediate field and by the Poole-Frenkel emission at high field. In the case of Ta₂O₅/TiO₂ film, the two conduction mechanisms, the Ohmic and Schottky emissions, governed the leakage current density behavior. The conduction mechanisms at various electric fields applied were related to the diffusion of Ta, Ti and O, followed by the creation of vacancies, in the rapid thermal treated capacitors.     

Corrosion and time dependent passivation of Al 5052 in the presence of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

Corrosion and time–dependent oxide film growth on AA5052 Aluminum alloy in 0.25M Na₂SO₄ solution containing H₂O₂ was studied using electrochemical impedance spectroscopy, potentiodynamic polarization, chronoamperometric and open circuit potential monitoring. It was found that sequential addition of H₂O₂ provokes passivation of AA5052 which ultimately thickens the oxide film and brings slower corrosion rates for AA5052. H2O2 facilitates kinetics of oxide film growth on AA 5052 at 25° and 60 °C which is indicative of formation of a thick barrier film that leads to an increment in the charge transfer resistance. Pitting incubation time increases by introduction of H₂O₂ accompanied by lower pitting and smoother surface morphologies. At short exposure (up to 8 h) to H₂O₂–containing solution, the inductive response at low frequencies predominantly determined the corrosion mechanism of AA5052. On the other hand, at prolonged exposure times (more than 24 h) to 0.25M Na₂SO₄+1vol% H₂O₂ solution, thicker oxide layers resulted in the mixed inductive–Warburg elements in the spectra.     

Corrosion Behavior and Microhardness of Ni-P-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Nano-composite Coatings on Magnesium Alloy

In the present work, nano-composites of Ni-P-SiO₂-Al₂O₃ were coated on AZ91HP magnesium alloy. The surface morphology of the nano-composite coating was studied by field emission scanning electron microscopy (FESEM). The amount of SiO₂ in the coating was determined by energy-dispersive analysis of x-ray (EDX), and the crystalline structure of the coating was examined by x-ray diffractometer (XRD). All the experiments concerning the corrosion behavior of the coating carried out in 3.5 wt.% NaCl solution and evaluated by electrochemical impedance spectroscopy (EIS) and polarization technique. The results showed that an incorporation of SiO₂ and Al₂O₃ in Ni-P coating at the SiO₂ concentration of 10 g/Land 14 g/LAl₂O₃ led to the lowest corrosion rate (i _corr = 1.3 µA/cm²), the most positive E _corr and maximum microhardness (496 VH). Furthermore, Ni-P-SiO₂-Al₂O₃ nano-composite coating possesses less porosity than that in Ni-P coating, resulting in improving corrosion resistance.     

Microstructural and electrochemical properties of Ti-doped Al<Subscript>2</Subscript>O<Subscript>3</Subscript> coated LiCoO<Subscript>2</Subscript> films

We studied the microstructural and electrochemical properties of Ti-doped Al₂O₃ (Ti-Al₂O₃) coated LiCoO₂ thin films depending on the Ti composition. The 1.27 at.% Ti-Al₂O₃ coated films had an amorphous structure with better conductivity than that of pure Al₂O₃ films. The Ti-Al₂O₃ coating layer effectively suppressed the dissolution of Co and the formation of lower Li conductivity SEI films at the interface between the LiCoO₂ film and electrolyte. The Ti-Al₂O₃ coating improved the cycling performance and capacity retention at high voltage (4.5 V) of the LiCoO₂ films. The Ti-Al₂O₃ coated LiCoO₂ films showed better electrochemical properties than did the pure Al₂O₃ coated LiCoO₂ films. These results were closely related to the enhanced Li-conductivity and interfacial quality of the Ti-Al₂O₃ film.     

The role of Ce ions in electrochemical corrosion of 304 SS in Ce(NO<Subscript>3</Subscript>)<Subscript>3</Subscript>.6H<Subscript>2</Subscript>O

Effects of temperature and potential on the electrochemical corrosion behavior of alloy AISI 304 (UNS S30400) Stainless steel were investigated in 3 wt.% cerium nitrate (Ce[NO₃]₃.6H₂O) solution. With an increase in electrolyte temperature from ambient temperature to 90°C, the corrosion potential of the alloy shifted towards the noble direction, and the resistance to polarization increased due to the formation of Ce-oxide on the electrode surface. The oxide films formed at the open circuit potential (OCP) and a passive potential of 0.4 V_SCE were examined by x-ray photoelectron spectroscopy (XPS). The oxide film formed at 50°C and a passive potentialof 0.4 V_SCE consists of mixed oxides of Ce and Cr, whereas that at OCP consists of only Cr oxide. The formation of Cr oxides on the electrode surface was primarily due to the nitrate (NO₃ ⁻) ions in Ce(NO₃)₃.6H₂O electrolyte.     

The Influence of Electrophoretic Potential on Ni—Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Nano-Composite Coating

In this study, the effect of electrophoretic voltage changes on Ni—Al₂O₃ nano-composite coating via two step process electrophoretic, and electrochemically on 1100 Al substrate on morphology, corrosion and wear behaviour were studied. In the first step of deposition for determining the optimum amount of Teri Ethanol Amin activator in electrophoretic suspension Transmission Electron Microscopy (TEM) was used. The amount of alumina particles, Nickel ions in the coating and morphology were studied by Energy-dispersive X-ray spectroscopy (EDX) and Field-Emission Electron Microscopy (FESEM). Nanoparticles distribute more homogenous in deposit within using 40 V voltage. Corrosion behaviour of coating was investigated by polarization technique in 3.5 wt % NaCl which shows a decrease in corrosion current from 13.7 μA/cm² to 1.46 μA/cm² versus bare sample.     

Electrodeposition of composite chromium coatings from Cr(III) sulfate-oxalate solution suspensions containing Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, SiC,Nb<Subscript>2</Subscript>N,and Ta<Subscript>2</Subscript>N particles

The effect of concentration and nature of particles (dielectric Al₂O₃, broadband semiconducive SiC, and conductive Nb₂N and Ta₂N) on the adhesion of particles to the surface of coatings and the composition of electrochemical composite coatings deposited from Cr(III) sulfate-oxalate solution suspensions of various concentrations is studied. Adding particles of any nature to the solution does not affect the character of the formation of an X-ray amorphous chromium matrix and the content of hydrogen in the coating. The mechanisms of inclusion of Al₂O₃, SiC, Nb₂N + Ta₂N particles in chromium layers are different. In the former case (Al₂O₃ and SiC), the inclusion of particles is determined by kinetic factors (in the absence of current, there is no adhesion of particles), while, in the latter case, the particles demonstrate a strong adhesion in the absence of current. Accordingly, the distribution of SiC and Al₂O₃ particles depends on the depth by contrast to Nb₂N and Ta₂N particles, whose concentrations close to the substrate do not noticeably differ from those in the bulk and surface layers of the coating. An increase in the temperature of solution promotes the codeposition of chromium and these particles.     

Kinetics of formation and growth of epitaxial SrTiO<Subscript>3</Subscript> films of single-crystal (001) SrTiO<Subscript>3</Subscript> supports

The aim of this study was to quantitatively estimate the kinetics of the formation and growth of oxide SrTiO₃ (STO) films using the method of the in situ reflection high-energy electron diffraction (RHEED) and compare the obtained results with the known growth models and theoretical estimates. The kinetics of the relaxation and crystallization of particles is studied under pulsed laser deposition (PLD) from oxide targets onto (001) STO supports or onto the surface of STO film growth at 650–800°C. Deposition frequencies of 0.1–10 Hz typical of PLD were used. The surface morphology and film structure was studied ex situ using the methods of AFM and X-ray-structural analysis. It was found that the time of relaxation of deposited particles is within the range of 2–20 s, which greatly exceeds or is comparable to the relative pulse duration. It was experimentally shown that structural distortions in epitaxial films for temperatures of ≤900°C are mainly due to the high rate of deposition and limited surface mobility of particles. The effect of structural relaxation in films is observed after the end of deposition; the time constant of bulk structural relaxation is ∼10 − ∼10² s or more. The obtained kinetic parameters of the formation of an oxide structure may be useful for the development of crystallization theory, as well as to optimize the conditions of epitaxial oxide film growth.     

Dielectric properties of ZrTiO<Subscript>4</Subscript> thin films synthesized by sol-gel method

ZrTiO₄ thin films were successfully prepared on Pt/Ti/SiO₂/Si(100) substrates by a sol-gel process and gel films were heat-treated at various temperatures. The surface morphology, crystal structure, and dielectric properties of the thin films were investigated. It was possible to obtain ZrTiO₄ phase at temperatures above 650 °C for 2 h, which is much lower than the bulk sintering temperature. The microstructure of well-crystallized ZrTiO₄ thin films was a fine-grained microstructure less than 70 nm in grain size and the surface morphology was smooth with 22.4 rms roughness. The dielectric constant and loss of ZrTiO₄ thin films were 38 and 0.006, respectively, for thin films with 450 nm thickness heat-treated at 900 °C for 2 h.     

Reaction Time and Film Thickness Effects on Phase Formation and Optical Properties of Solution Processed Cu<Subscript>2</Subscript>ZnSnS<Subscript>4</Subscript> Thin Films

Copper-zinc-tin-sulfide (Cu₂ZnSnS₄ or CZTS) is a promising p-type semiconductor material as absorber layer in thin film solar cells. The sulfides of copper and tin as well as zinc and sulfur powders were dissolved in hydrazine. The effect of chemical reaction between precursor species, at room temperature, was assessed for 6 to 22 h. For 22 h reaction time, the effect of spin coated film thickness on the resulting composition, after annealing under N₂ flow at 500 °C for 1 h, was investigated. The morphology, composition, and optical properties of the annealed films were determined by means of x-ray diffraction, scanning electron microscope, and spectrophotometer studies. It was found that, for less than optimal reaction time of 22 h or film thickness below 1.2 µm, other ternary phases namely Cu₄SnS₄, Cu₅Sn₂S₇, and ZnS co-exist in different proportions besides CZTS. Formation of phase-pure CZTS films also exhibited a tendency to minimize film cracking during annealing. Depending on the processing conditions, the band gap (E _g) values were determined to be in the range of 1.55 to 1.97 eV. For phase-pure annealed CZTS film, an increase in the E _g value may be attributed to quantum confinement effect due to small crystallite size.     

Room temperature,ion energy-controlled deposition of silicon nitride films in a SiH<Subscript>4</Subscript>-N<Subscript>2</Subscript> plasma

In this study, silicon nitride films were deposited in SiH₄-N₂ plasma using a plasma-enhanced chemical vapor deposition system at room-temperature. The radio frequency bias power impact on the films characteristics (deposition rate, refractive index, and surface roughness) was examined. Ion energy information (energy level, energy flux) collected using an ion energy analysis system was correlated with the film characteristics. Increasing the bias power increased the ion energy, more noticeably with the high ion energy. For the same variations in the bias power, the ion energy flux initially decreased considerably and then varied little. A similar variation was noticed in both film characteristics. Both the deposition rate and the refractive index were strongly correlated with the ratio of high ion energy to low ion energy rather than high or low ion energy. A similar dependency was also observed for the refractive index. The dependency of surface roughness changed from ion energy to ion energy flux. The roles of the ion energy flux were further examined by implicating them in AFM images. The low ion energy flux was identified as a contributor to the extreme peaks that significantly deteriorated the surface roughness. The highest deposition rate, highest refractive index, and smallest surface roughness obtained were 183 Å/min, 2.06, and 0.230 nm, respectively.     

Electrochemical Corrosion of HVOF-Sprayed NiCoCrAlY Coatings in CO<Subscript>2</Subscript>-Saturated Brine

The effect of pre-oxidation treatment and surface preparation of optimized NiCoCrAlY coatings deposited by high-velocity oxygen fuel (HVOF) spraying and exposed to a low-temperature corrosive environment is reported herein. Coatings with two surface finish conditions (as-sprayed and ground) were heat treated under two different oxygen partial pressures (air and argon). The electrochemical corrosion behavior was evaluated in CO₂-saturated brine via potentiodynamic polarization, polarization resistance, and electrochemical impedance measurements. The results show that the grinding process and pre-oxidation treatment in argon enhanced growth and formation of α-Al₂O₃ scale. The potentiodynamic polarization results show that both pre-oxidation and surface treatment had a positive influence on the corrosion resistance of the coating. The reduction of the porosity and the formation of a dense, uniform, and adherent oxide scale through pre-oxidation treatment led to an increase of the corrosion resistance due to a decrease in active sites and blocking of diffusion of reactive species into the coating. However, according to the results, complete transformation from metastable alumina phases to α-Al₂O₃ in addition to formation and growth of dense α-Al₂O₃ is required to ensure full protection of the coating and base material over long periods.     

Preparation of ZrO<Subscript>2</Subscript> dielectric layers by subsequent oxidation after Zr film deposition with negative substrate bias voltage

ZrO₂ dielectric layers were prepared by a two-step process, a deposition of pure Zr film with and without a negative substrate bias voltage and a subsequent oxidation of the Zr films. We focused on the effect of the negative substrate bias voltage on the Zr film deposition and the subsequent oxidation of the Zr films. As a result, the Zr film deposited at the substrate bias voltage of −50 V (Vs = −50 V) was found to have a high intensity peak of Zr (100) and a uniform and smooth surface. From the capacitance-voltage and current-voltage measurements of the ZrO₂ films, a high dielectric constant of 21 and the equivalent oxide thickness (EOT) of 2.6 nm were obtained on the oxidation layer of the Zr film deposited at Vs = −50 V. On the other hand, a low dielectric constant of 15 and the EOT of 3.6 nm was obtained on that of the Zr film deposited at Vs = 0 V. The leakage current density of the ZrO₂ film (Vs = −50 V) was 5.69×10⁻⁴ A/cm², and this value was much lower than the 1.21×10⁻⁴ A/cm² for the ZrO₂ film (Vs = 0 V). It was found that the two-step process by subsequent oxidation after film deposition using a negative substrate bias voltage is useful for obtaining high-quality dielectric layers.     

Oxidation Behavior of NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript> Spinel-Coated Interconnects in Wet Air

Corrosion of boilers and heat exchangers is accelerated in the presence of vanadium, sodium, and sulfur from low-grade fuels. Several iron- and nickel-based alloys were immersed in 60 mol% V₂O₅–40Na₂SO₄ salt for 1000 h in order to investigate their degradation behavior at 600 °C in air. Materials performance was analyzed by means of substrate recession rate and metallographic characterization. Their corrosion mechanism is characterized by the formation of a sulfide/oxide layer adjacent to the metal, the dissolution of scale oxides in the molten deposit, and their precipitation near the outer surface of the deposit. High Ni- and Cr-containing alloys show the lowest metal loss rates. Al addition was detrimental due to low-melting eutectic AlVO₄–V₂O₅ formation. Fe–Cr-based alloys showed the highest metal loss rates. In such alloys, high Cr additions (above 20%) did not improve the performance due to the negative synergetic effect by simultaneous dissolution of Fe₂O₃ and Cr₂O₃. The predominant salt composition at the corrosion front varied from vanadate rich to sulfate rich during the exposure. This change in the attacking salt makes it difficult to find a protective material for mixed sulfate–vanadate-induced corrosion.     

Structure and electrical resistance of dispersion-strengthened vacuum-deposited Cu–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposites

Methods of X-ray diffraction and transmission electron microscopy were used to study the microstructure of dispersion-strengthened Cu-Al₂O₃ nanocomposites obtained by the method of simultaneous deposition of Cu and Al₂O₃ from the vapor phase. The effect of the size of particles of the oxide (Al₂O₃) and of their content on the electrical resistance of the composite has been considered. The results obtained make it possible to suppose that the main structural factor that determines the electrical resistance of the composite are nanodispersed particles of Al₂O₃ with a size of less than 20 nm.     

Corrosion Behavior of Novel Al-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Composites in Aerated 3.5% Chloride Solution

The corrosion behavior of novel Al-Al₂O₃ MMCs was evaluated in aerated 3.5% NaCl solution through potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). These materials corrode almost spontaneously by pitting in aerated 3.5% NaCl solution. Observations indicate that intermetallic particles in these composites appear to play an important role in this pitting corrosion behavior. Addition of Al₂O₃ particles to the base alloys did not appear to increase their corrosion resistance significantly, although corrosion rate was affected by these reinforcement particles. In cyclic polarization experiments, the small difference between the pitting potentials and the repassivation potentials for these MMCs indicated their low resistance to pitting corrosion. EIS measurements indicate adsorption/diffusion phenomena at the interface of the composites. Electrically equivalent circuits are proposed to describe and substantiate the corrosion processes occurring in these materials.