Assessment of barium sulphate formation and inhibition at surfaces with synchrotron X-ray diffraction (SXRD)

The precipitation of barium sulphate from aqueous supersaturated solutions is a well-known problem in the oil industry often referred to as ‘scaling’. The formation and growth of barite on surfaces during the oil extraction process can result in malfunctions within the oil facilities and serious damage to the equipment. The formation of barium sulphate at surfaces remains an important topic of research with the focus being on understanding the mechanisms of formation and means of control.In situ synchrotron X-ray diffraction (SXRD) was used to investigate the formation of barium sulphate on a stainless steel surface. The effect of Poly-phosphinocarboxylic acid (PPCA) and Diethylenetriamine-penta-methylenephosphonic acid (DETPMP) which are two commercial inhibitors for barium sulphate was examined. The in situ SXRD measurements allowed the identification of the crystal faces of the deposited barite in the absence and presence of the two inhibitors. The preferential effect of the inhibitors on some crystal planes is reported and the practical significance discussed.     

The crack control during laser cladding by adding the stainless steel net in the coating

The generation of crack is one of the key problems which restrict the development of laser cladding technique. The purpose of this study is to control the cracks during laser cladding by adding a plastic phase—an austenitic stainless steel net in the coatings. With Ni-, Co- and Fe-based alloy powders, laser cladding experiments were carried out. The microstructure of the coatings and the stainless steel net was investigated. Experimental results show that the stainless steel net is partly melted and strongly bonded to the cladding powder materials and the substrate. Thus the crack density is significantly reduced. The amount of the reduction increases as the diameter of the stainless steel net increases. Without preheating the substrate, large area coatings which remain free of cracks can be achieved when adding the stainless steel net with appropriate diameter. The characteristics of the coatings were investigated and the results indicate that the hardness fluctuations of the coatings become larger and the wear resistance decreases when adding 316 stainless steel net.     

Effect of a small increase in the Ni content on the properties of a laser surface clad Fe-based alloy

Two Fe-based alloys with a small variation in the Ni content, Fe-15.2Cr-5.1Ni and Fe-15.7Cr-7.1Ni (wt.%), were fabricated on a martensitic stainless steel 1Cr13 substrate by laser surface cladding (LSC) using a CO₂ laser and Ar shielding gas that was blown into a molten pool. Both LSC alloys exhibited typical rapid directional solidification structures. However, 2 wt.% Ni increase led to ∼9% increase in the weight fraction of austenite, and ∼5% increase in the area proportion of interdendritic regions, which contained the higher Cr contents. These microstructural changes caused a great reduction in the microhardness and great improvements in the resistance to electrochemical corrosion in 0.5 M H₂SO₄ solution and high temperature oxidation in air at 900 °C. The reasons for these differences are discussed in detail.     

Laser-assisted decontamination—A wavelength dependent study

We present here the experimental results on cleaning of radioactive dielectric particulates, loosely deposited on stainless steel, by coherent light of 1064 nm wavelength and its three harmonics occurring at 532 nm, 355 nm and 266 nm, derived from an Nd-YAG laser. For the initial few exposures, the decontamination factor has been found to be highest when exposed to 1064 nm radiation. With increasing number of exposures, however, the radiation with reducing wavelength assumes a more important role as a cleaning agent. The observation of almost no cleaning with 1064 nm and much reduced cleaning with its harmonics when the contamination is deposited on a transparent substrate confirms the dominant role played by metal substrate towards expelling the loose particulates from its surface.     

Synthesis and electrochemical characteristics of Ta-N thin films fabricated by cathodic arc deposition

Ta-N thin films were deposited on AISI 317L stainless steel (SS) substrates by cathodic arc deposition (CAD) at substrate biases of −50 and −200 V. The as-deposited films were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray analysis (EDX). The results show that stoichiometric TaN with hexagonal lattice (3 0 0) preferred orientation was achieved at the bias of −200 V. On the other hand, Ta-rich Ta-N thin film deposited at −50 V shows amorphous nature. According to the XPS result, Ta element in the films surface exist in bonded state, including the Ta-N bonds characterized by the doublet (Ta 4f_7/2 = 23.7 eV and Ta 4f_5/2 = 25.7 eV). Electrochemical properties of the Ta-N coated stainless steel systems were investigated using potentiodynamic polarization and electrochemical impedance spectroscope (EIS) in Hank's solution at 37 °C. For the Ta-N coated samples, the corrosion current (i_corr) is two or three orders of magnitude lower than that of the uncoated ones, indicating a significantly improved corrosion resistance. Growth defects in the Ta-N thin films produced by CAD, however, play a key role in the corrosion process, especially the localised corrosion. Using the polarization fitting and the EIS modelling, we compared the polarization resistance (R_p) and the porosity (P) of the Ta-N coatings deposited at different biases. It seems that Ta-N film with comparatively lower bias (−50 V) shows better corrosion behavior in artifical physiological solution. That may be attributed to the effect of ion bombarding, which can be modulated by the substrate bias.     

Electron beam treatments of electrophoretic ceramic coatings

In this work a method to densify ceramic coating obtained by electrophoresis and to improve its adhesion to the substrate is proposed. It consists in irradiating the coating surface by electron beam (EB). Alumina and alumina-zirconia coatings were deposited on stainless steel substrates and treated by low power EB. SEM, XRD and TEM characterizations demonstrated that the sintering occurred. Moreover, it is shown that on alumina-zirconia coating the EB irradiation produced a composite material consisting principally of tetragonal zirconia particles immersed in an amorphous alumina matrix. The adhesion stress of EB treated coating was estimated by stud pull test and it was found to be comparable to that of plasma-sprayed coatings.     

On the spray-drying deposition of TiO2 photocatalytic films

The photocatalytic activity of TiO₂ films deposited on different substrates by the spray-drying method using suspensions of commercially available TiO₂ (Degussa P25 or Tronox) as starting material was studied. The influence of the type of the initial TiO₂, preparation conditions (temperature of the substrate during the film deposition, temperature of the post-deposition annealing), substrate material (glass, fused silica, stainless steel and graphite), the presence of additives in the spraying suspension (polyethylene glycol, ethylene glycol and acetylacetone) and its sonication before spraying on the morphology, size of crystallites and phase composition (rutile/anatase ratio) was studied. Optimal conditions for spray deposition of the films are suggested.     

Lanthanide-doped titanium dioxide layers as photocatalysts

Films (∼0.5 mg/cm²) from TiO₂ doped with 1-10 mol% Ln³⁺ (Ln = La or Gd) are deposited on different types of substrates by spray-pyrolysis using ethylene glycol solutions of Ti⁴⁺-Ln³⁺ citric complexes as starting material and O₂ as a carrier gas. The films are post-deposition heated at 500 °C. Their phase composition, crystal structure, morphology, sorption ability and photocatalytic activity are studied. Aqueous solution of methylene blue is applied as a model pollutant. A film with 5 mol% La on Ti-coated stainless steel substrate shows significantly higher photocatalytic activity than the best performing samples produced from commercially available titania.     

Biological response of stainless steel surface modified by N2O/O2 glow discharge plasma

Stainless steel wafers were treated with the glow discharge plasma of mixed N₂O and O₂ at different molar ratios at a certain discharge condition to create desirable biological characteristics to the surfaces. It was found that the molar ratio of N₂O to O₂ in the mixture at 1:1 used for plasma surface modification caused high apoptotic percentage. Contact angle measurement showed that the surface of stainless steel samples became very hydrophilic after the plasma modification with a value of 15°-30°. The control stainless steel chips without plasma treatment had a contact angle of 40 ± 2°. The data of Electron Spectroscopy for Chemical Analysis (ESCA) indicated that there was a certain amount of oxynitrites formed on the plasma treated surfaces, which was considered to play an important role to cell apoptosis and anti-clot formation in cell culture tests. The ESCA depth profile of up to 250 Å from the top surface showed the change of elemental compositions within 40-50 Å of the surface by the plasma treatment. The decreased platelet attachment, combined with increased apoptosis in fibroblasts is a distinct combination of biological responses arising from the mixed gas plasma treatment. These initial results suggest it may be of particular use relative to stainless steel stents where decreased platelet attachments are advantageous and induction of apoptosis could limit in-stent restenosis.     

Damage zone produced by the bombardment of stainless steel using Ti nitride PVD coatings

This paper presents the damage zone and defects produced by TiN thin film deposition on stainless steel using DC magnetron sputtering to produce collisions between the TiN ions and the substrate. The PVD process used a low operative pressure, reducing the bombardment damage on the substrate, in comparison with other methods.Internal friction (IF) and elastic modulus measurements were carried out in TiN-PVD coated AISI 304 stainless steel, using a sub-resonant torsion pendulum (f ≅ 1 Hz) and a vibrant-reed instrument (f ≅ 10³ Hz). Some experiments showed several internal friction peaks, which are attributed to dislocation relaxation and to martensitic transformation from γ to α′. The characterization was carried out with X-ray, AFM and SEM. Analysis of X-ray peaks indicates a residual deformation in the order of 0.0005-0.0009 for γ-phase and 0.0006-0.00204 for α′-phase. Two methods are presented to determine the adhesion energy by IF in coated materials: for the first the enthalpy is determined by means of isochronal IF measurements, while for the second it is determined using isothermal measurements. These produce an image of damage caused by the bombardment on the substrate, especially of the residual defects.     

Effect of charged deep states in hydrogenated amorphous silicon on the behavior of iron oxides nanoparticles deposited on its surface

Langmuir-Blodgett technique has been used for the deposition of ordered two-dimensional arrays of iron oxides (Fe₃O₄/Fe₂O₃) nanoparticles onto the photovoltaic hydrogenated amorphous silicon (a-Si:H) thin film. Electric field at the a-Si:H/iron oxides nanoparticles interface was directly in the electrochemical cell modified by light soaking and bias voltage (negative or positive) pretreatment resulting in the change of the dominant type of charged deep states in the a-Si:H layer. Induced reversible changes in the nanoparticle redox behavior have been observed. We suggest two possible explanations of the data obtained, both of them are needed to describe measured electrochemical signals. The first one consists in the electrocatalytical effect caused by the defect states (negatively or positively charged) in the a-Si:H layer. The second one consists in the possibility to manipulate the nanoparticle cores in the prepared structure immersed in aqueous solution via the laser irradiation under specific bias voltage. In this case, the nanoparticle cores are assumed to be covered with surface clusters of heterovalent complexes created onto the surface regions with prevailing ferrous or ferric valency. Immersed in the high viscosity surrounding composed of the wet organic nanoparticle envelope these cores are able to perform a field-assisted pivotal motion. The local electric field induced by the deep states in the a-Si:H layer stabilizes their “orientation ordering” in an energetically favourable position.     

Growth of thin Fe(0 0 1) films for terahertz emission experiments

The electrical and magnetic properties of thin iron (Fe) films have sparked significant scientific interest. Our interest, however, is in the fundamental interactions between light and matter. We have discovered a novel application for thin Fe films. These films are sources of terahertz (THz) radiation when stimulated by an incident laser pulse. After intense femtosecond pulse excitation by a Ti:sapphire laser, these films emit picosecond, broadband THz frequencies. The terahertz emission provides a direct measure of the induced ultrafast change in magnetization within the Fe film. The THz generation experiments and the growth of appropriate thin Fe films for these experiments are discussed. Several criteria are used to select the substrate and film growth conditions, including that the substrate must permit the epitaxial growth of a continuous, monocrystalline or single crystal film, yet must also be transparent to the emitted THz radiation. An Fe(0 0 1) film grown on the (0 0 1) surface of a magnesium oxide (MgO) substrate makes an ideal sample. The Fe films are grown by physical vapor deposition (PVD) in an ultrahigh vacuum (UHV) system. Low energy electron diffraction (LEED) and Auger electron spectroscopy (AES) are used to characterize the Fe(0 0 1) films. Two substrate surface preparation methods are investigated. Fe(0 0 1) films grown on MgO(0 0 1) substrates that are used as-received and films grown on MgO(0 0 1) substrates that have been UV/ozone-cleaned ex vacuo and annealed in vacuo produce the same results in the THz generation experiments. Either substrate preparation method permits the growth of samples suitable for the THz emission experiments.     

Investigations on the invalidated process and related mechanism of PEG during copper via-filling process

The invalidated process and related mechanism of PEG during copper via-filling process were investigated by means of electrochemical polarization and electrochemical impedance (EIS) measurements, and infra-red spectrum (IR) measurement was employed to analyses the invalidated products of PEG. The results suggest that the adsorption strength of PEG on cathode surface and its inhibition to copper reduction decrease gradually with the increase of passed charges (PC). Both the anodic and the cathodic electrifying process can cause the invalidation of PEG, but their invalidated courses are different. PEG will further polymerize to form new PEG with bigger MW on the anode surface, which causes the dispersive ability of plating solution to decrease. As a result, super-filling behavior cannot be obtained and many small wales formed on the specimen surface during copper via-filling process. Inversely, PEG will decompose to form new PEG with smaller MW on the cathode surface, which results in the decrease of PEG adsorption ability and inhibition. As a result, super-filling behavior cannot be obtained and the brightness of the specimen surface decreases during copper via-filling process. The decomposition of PEG is easily to happen than its polymerization when the anodic and cathodic reactions happen in the same plating solution simultaneously. So the main invalidated product of PEG during copper via-filling process is PEG with smaller MW.     

Optical second harmonic generation as a surface probe of silver electrodes

Surface second harmonic (SH) signals generated at a polycrystalline silver surface are studied as the electrode undergoes electrochemical cycling in sulfate electrolytes of variable pH. The SH intensity profiles are correlated with the ionic adsorption and surface chemistry occurring at the electrode interface. The dramatic differences in the optical response of these solutions is attributed to the formation of silver oxides. Detection of monolayer coverages of adsorbed sulfate ions demonstrate the inherent sensitivity of this nonlinear optical technique. The effect on the SH efficiency of trace amounts of oxygen in the electrolyte is also discussed.     

Variations in the structural, optical and electrochemical properties of CeO2-TiO2 films as a function of TiO2 content

Alcohol based sols of cerium chloride (CeCl₃·7H₂O) and titanium propoxide (Ti(OPr)₄) in ethanol mixed in different mole ratios have yielded mixed oxide films on densification at 500 °C. The reversibility of the intercalation/deintercalation reactions has shown electrochemical stability of the films. Addition of TiO₂ in an equivalent mole ratio manifests in producing highly transparent films with appreciable ion storage capacity. The electrochemical studies have revealed the significant role of TiO₂ in controlling the ion storage capacity of the films, as it tends to induce the disorder. In addition, the films prepared from an aged sol are observed to exhibit a much higher ion storage capacity than the films deposited using the as-prepared sol. The X-ray photoelectron spectroscopic studies have provided information on the variation of Ce⁴⁺/Ce³⁺ ratio as a function of increased TiO₂ content in the films. This study has led to a better understanding of the increased ion storage capacity with the increased TiO₂ proportion. The transmission electron microscopic study has demonstrated the presence of CeO₂ nanograins even in films, which are amorphous to X-rays. Elucidation of the structural, optical and electrochemical features of the films has yielded information on aspects relevant to their usage in transmissive electrochromic devices. The films have been found to exhibit properties that can find application as counter electrode in electrochromic smart windows in which they are able to retain their transparency under charge insertion, high enough for practical uses. Also, the fastest coloration-bleaching kinetics for the primary electrochromic electrode (WO₃) working in combination with Ce/Ti (1:1) electrode stimulates the use of latter in electrochromic windows (ECWs).     

The adsorption behavior and corrosion inhibition mechanism of anionic inhibitor on galvanic electrode in 1% NaCl solution

The adsorption behavior of dodecanoic acid and its sodium salt (DDAS) as an anionic inhibitor on the galvanic electrode has been investigated by using electrochemical methods, Fourier transform infrared spectroscopy (FT-IR), and atomic force microscopy (AFM). The galvanic electrode was prepared by coupling N80 carbon steel (CS) and S31803 stainless steel (SS), and all experiments were performed in NaCl solution at pH 4 in the presence or absence of DDAS. Electrochemical experiments reveal SS and CS carry positive and negative excess charges in NaCl solution at pH 4, and DDAS is mainly anodic type inhibitor for the galvanic corrosion. FT-IR and AFM were used to analyze the protective layer formed on the electrodes, a stronger adsorbability of the inhibitor on the anode (CS) of GE was measured. Results indicate the protective layer formed on the single CS electrode is less compact than which on the coupled CS. The adsorption regulation of anionic inhibitor on the galvanic electrode is summarized based on the results obtained from electrochemical methods, FT-IR and AFM.     

The effect of back electrode on the formation of electrodeposited CoNiFe magnetic nanotubes and nanowires

The electrodeposition of cobalt + nickel + iron alloy nanostructures in aqueous sulfate solution has been studied using vitreous templates placed on highly ordered porous anodic alumina oxide (AAO). During the deposition process some electrochemical bath parameters such as ion content, deposition voltage, pH and temperature of solution were kept constant. The morphological properties of the nanostructures were studied by scanning electron microscopy (SEM) and the chemical composition was determined by examination of the energy dispersive X-ray (EDX) spectra. The magnetic behaviour of the arrays was determined with a vibrating sample magnetometer (VSM). Voltammetric and galvanostatic results indicate that the back electrodes placed on AAO plays the main role in obtaining nanowire or nanotube structured material.     

Growth, modulation and photoresponse characteristics of vertically aligned ZnO nanowires

Vertically aligned, c-axis oriented zinc oxide (ZnO) nanowires were grown on Si substrate by metal organic chemical vapor deposition (MOCVD) technique, where sputtered aluminum nitride (AlN) film was used as an intermediate layer and thermally evaporated barium fluoride (BaF₂) film as a sacrificial layer. The aspect ratio and density of the nanowires were also varied using only Si microcavity without any interfacial or sacrificial layer. The UV detectors inside the microcavity have shown the higher on-off current ratio and fast photoresponse characteristics. The photoresponse characteristics were significantly varied with the aspect ratio and the density of nanowires.     

Recent development of non-oriented electrical steel sheet for automobile electrical devices

This paper describes non-oriented electrical steel sheet for automobile motors and reactors. Electrical steel sheets for energy efficient motors show high magnetic flux density and low iron loss. They are suitable for HEV traction motors and EPS motors. A thin-gauge electrical steel sheet and a gradient Si steel sheet show low iron loss in the high-frequency range. Therefore, the efficiency of high-frequency devices can be greatly improved. Since a 6.5% Si steel sheet possesses low iron loss and zero magnetostriction, it contributes to reduce the core loss and audible noise of high-frequency reactors.     

In situ characterization of localized corrosion of stainless steel by scanning electrochemical microscope

Scanning electrochemical microscopy (SECM) area scan measurements have been performed to investigate the localized corrosion of type 304 stainless steel in neutral chloride solution. Variations in the Faradaic current measured at selected tip potential values can be related to changes in the local concentration and electrochemical activities of electroactive species involved in corrosion reactions occurring at the substrate as a function of immersion times of the substrate and polarized currents or potentials applied on the substrate. To further verify the results acquired from cyclic voltammetric experiments, SECM measurements were employed to in situ study the compositions and electrochemical activity distribution profile of the pitting corrosion products of stainless steel. It has been demonstrated that the combination of feedback current mode with generation-collection (G-C) mode of SECM is suitable to elucidate the possible reaction mechanisms and paths involved in the localize corrosion of stainless steel in neutral chloride solution.