Characterization of Sb2O3 subjected to different ion and plasma surface treatments

This paper presents a study of Sb₂O₃ subjected to oxygen plasma and to ion beam bombardment (Ar⁺ and O₂⁺ ions of 4 keV) by x‐ray photoelectron and reflected electron energy‐loss spectroscopies. Changes in stoichiometry (i.e O/Sb ratio) and oxidation state of Sb have been detected and correlated with the chemical and ballistic effects of the beams used for alteration of the Sb₂O₃ surface. Thus, oxygen plasma treatments lead to a significant oxidation of the surface layers of this material with the formation of up to 51% Sb⁵⁺ species as found by Sb 4d curve‐fitting analysis. By contrast, O₂⁺ ion bombardment only produces a mild oxidation of the target with the formation of ～13% Sb⁵⁺ species. Argon ion bombardment induces a complex process where Sb⁵⁺ and Sb⁰ species are formed simultaneously. This result has been discussed in terms of a disproportionation reaction of the type Sb³⁺ → Sb⁵⁺ + Sb⁰. The changes in the electronic properties of the treated material are consistent with the loss upon oxidation to Sb⁵⁺ of the valence states associated to the 5s² electron pair of antimony. Approximate shapes of valence bands for Sb₂O₃ and Sb₂O₅ pure compounds have been extracted by applying factor analysis to valence band spectra of Sb₂O₃ subjected to different ion and plasma treatments. Copyright © 2003 John Wiley & Sons, Ltd.     

On the Interaction of Cold Atmospheric Pressure Plasma with Surfaces of Bio-molecules and Model Polymers

We review studies of surface-interaction mechanisms for a surface microdischarge (SMD) and an atmospheric pressure plasma jet (APPJ) with model polymers and biomolecules in our laboratory. We discuss the influence of plasma source type, operating parameters, and gaseous environments on surface modifications and biological deactivation. We focus on mild, remote conditions where the visible plasma plume does not contact the surface. For an APPJ fed with Ar, the interaction of the plasma plume with O₂ and/or N₂ gaseous environments leads to oxidation and surface-bound NO_x even on materials containing neither oxygen nor nitrogen. The APPJ also modifies photo-sensitive polymers. Using optical filters, these modifications were shown to result in part from irradiation with vacuum ultraviolet (VUV) photons in a spectral range corresponding to Ar excimer emission. No VUV-induced effects were seen for the SMD source operated with O₂/N₂. SMD treatments using O₂/N₂ mixtures result in surface oxidation and nitridation. A new surface-bound species, NO₃, has been measured on the polymers and biomolecules. Depending on the gas chemistry and film molecular structure, the NO₃ surface concentration can reach 10 %. Both surface NO₃ on plasma-treated films of lipopolysaccharide (LPS), an immune stimulating biomolecule found in bacteria such as E. c oli, and overall surface oxidation correlate with LPS biological deactivation as evaluated using an enzyme-linked immunosorbent assay. Ambient humidity was studied using the SMD and was found to decrease overall surface modifications including NO₃ and biodeactivation for O₂-rich conditions. Lastly, we discuss possible mechanisms and compare our results with published simulation studies.     

Surface modification of polypropylene under argon and oxygen-RF-plasma conditions

Polypropylene fabrics samples were surface functionalized under Ar and O₂ RF plasma conditions. Survey and high resolution photoelectron spectroscopy and attenuated total reflectance FTIR comparative evaluation of virgin and plasma treated substrat surfaces, and their pentafluorophenyl hydrazine-derivatized correspondents, indicate that both Ar and O₂-discharge treated PP surfaces undergo intense oxidation. C=O, O−C=O, and C−O linkages were identified on both inert and reactive gas plasma exposed surfaces. It was found that the relative surface atomic concentrations and the relative ratios of newly created functionalities are controlled by the external plasma parameters (RF power and treatment time). The oxidation of Ar-plasma treated surfaces has been related toex situ post plasma mechanisms. Dynamic contact angle measurements from unmodified and plasma exposed substrates demonstrated the presence of increased surface polarity, and its dependence on plasma parameters. AFM evaluations of plasma treated samples indicate the presence of rough surface morphologies. Paper based on the results presented during the workshop of the Engineering Research Center for Plasma-Aided Manufacturing held in Madison, Wisconsin, in Spring 1996.     

Effect of surface modification on the properties of plasma-polymerized hexamethyldisiloxane thin films

Plasma-polymerized hexamethyldisiloxane (pp-HMDSO) thin films have been deposited in a radiofrequency (RF) remote plasma-enhanced chemical vapor deposition (PECVD) system, on different types of substrates: silicon wafers, glass, quartz crystals, and chemiresistor structure. The as-grown thin films have been post treated in two types of reactive plasmas produced in SF₆ and O₂ gases. The effect of this surface modification on different properties of the as-grown pp-HMDSO thin film (chemical structure, elemental composition, surface morphology, film density and thickness, optical bandgap, and electrical resistivity) has been investigated. It is found that SF₆ plasma and O₂ plasma surface modifications of the as-grown pp-HMDSO thin film induce property changes different from each other. SF₆ plasma converted the as-grown pp-HMDSO film to a more porous material and caused a narrowing of its optical band gap of about 33%, while O₂ plasma induced a lowering of film electrical resistivity of about two orders of magnitude.     

Contribution from the solid-phase interactions of activating oxides to their nonlinear joint effect on the thermal oxidation of GaAs

The contribution from the solid-phase interactions in the PbO + Sb₂O₃ and PbO + Bi₂O₃ activating compositions to the multichannel process of GaAs thermal oxidation has been determined by spatial separation of the oxides. The solid-phase interactions make a positive contribution to the overall negative nonlinear effect in the dependence of the oxide film thickness on the GaAs surface on the activator batch composition. The contributions from the oxide interactions on the semiconductor surface and in the gas phase have been evaluated for the PbO + Sb₂O₃ composition.     

Preparation,properties, and catalytic activity of platinum-modified plasma electrolytic oxide structures on aluminum

Catalytically active Pt-containing oxide composites on aluminum have been prepared by plasma electrolytic oxidation (PEO) and by additional modification of the resulting coating by impregnation with an aqueous solution of chloroplatinic acid followed by calcination. The oxide film/metal composites have been characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and electron microscopy. The modified films contain the γ-Al₂O₃ and Pt crystalline phases. Platinum in the surface and subsurface layers is in the Pt⁰ state. There are platinum-rich areas on the surface of the PEO films. A higher catalytic activity in CO oxidation into CO₂ is shown by the samples whose oxide film contains nickel and copper along with platinum.     

An improvement on the adhesion‐strength of laminated ultra‐high‐molecular‐weight polyethylene fabrics: surface‐etching/modification using highly effective helium/oxygen/nitrogen plasma treatment

In this study, helium/oxygen/nitrogen (He/O₂/N₂)‐plasma was used to etch/modify the surface of ultra‐high‐molecular‐weight polyethylene (UHMWPE) fiber. After coated with polyurethane (PU), the plasma treated UHMWPE fabrics were laminated. It was found that the values of peeling strength between the laminated UHMWPE fabrics treated with He/O₂/N₂‐plasma were significantly higher (3–4 times) than that between pristine fabrics. The hydrophilic property and the value of the surface roughness of the UHMWPE fibers increased significantly after treated with He/O₂/N₂‐plasma. The mechanism of the oxidation/degradation of the polymers on the surface of the UHMWPE fiber during He/O₂/N₂‐plasma treatment was suggested. In addition, it was found that the higher content of functional groups (carbonyl, aldehyde, and carboxylic acid) on fiber surface and the higher value of surface roughness of the UHMWPE fiber treated with He/O₂/N₂‐plasma could significantly improve the adhesion‐strength of the laminated UHMWPE fabric. Especially, the micro‐aperture on the surface of UHMWPE fiber caused by the strenuous etching of He/O₂/N₂‐plasma treatment was also an important factor on improving the adhesion‐strength between the laminated UHMWPE fabrics. Copyright © 2010 John Wiley & Sons, Ltd.     

Surface modification of low density polyethylene (LDPE) film by low pressure O2 plasma treatment

In this work, low pressure glow discharge O₂ plasma has been used to increase wettability in a LDPE film in order to improve adhesion properties and make it useful for technical applications. Surface energy values have been estimated using contact angle measurements for different exposure times and different test liquids. In addition, plasma-treated samples have been subjected to an aging process to determine the durability of the plasma treatment. Characterization of the surface changes due to the plasma treatment has been carried out by means of Fourier transformed infrared spectroscopy (FTIR) to determine the presence of polar species such as carbonyl, carboxyl and hydroxyl groups. In addition to this, atomic force microscopy (AFM) analysis has been used to evaluate changes in surface morphology and roughness. Furthermore, and considering the semicrystalline nature of the LDPE film, a calorimetric study using differential scanning calorimetry (DSC) has been carried out to determine changes in crystallinity and degradation temperatures induced by the plasma treatment. The results show that low pressure O₂ plasma improves wettability in LDPE films and no significant changes can be observed at longer exposure times. Nevertheless, we can observe that short exposure times to low pressure O₂ plasma promote the formation of some polar species on the exposed surface and longer exposure times cause slight abrasion on LDPE films as observed by the little increase in surface roughness.     

Self-propagating synthesis of Pd-CeO2/Al2O3 automotive monolith catalysts

Pd-CeO₂ catalysts on a monolith support with a honeycomb structure have for the first time been prepared by surface self-propagating thermal synthesis (SSTS). Decomposition routes for the cerium precursors are deduced from TG-DTA data and from the mass spectra of decomposition intermediates. The Pd-CeO₂/Al₂O₃ monoliths prepared by SSTS are more active in CO oxidation, total hydrocarbon oxidation, and nitrogen oxide reduction than the catalysts obtained by conventional impregnation. This is explained by the fact that the SSTS products have a larger specific surface area and their active component has a smaller particle size.     

Reactivity of sites on Al2O3 surface modified by Ni

It has been established that CO oxidation with excess O₂ on Ni/Al₂O₃ forms an inhomogeneous NiO contact surface that smoothes critical effects in the sharp reactivity change.     

Study of the effect of laser treatment on the initial oxidation behaviour of Al‐coated NiCrAlY bond‐coat

In this study, the initial oxidation behaviour of laser‐treated Al/NiCrAlY bond‐coat is investigated. Two approaches, (i) Al film sputtering on the surface of bond‐coat and (ii) laser treatment, have been taken to enhance the oxidation resistance of NiCrAlY bond‐coat. Experimental results showed that after laser treatment, the Al/NiCrAlY bond‐coat exhibited a columnar dendritic microstructure without cracks and voids. A dense and continuous α‐Al₂O₃/Cr₂O₃ multilayer was found to form on the bond‐coat surface. Results on the cyclic oxidation at 1200 °C (for time ≤ 204 h) revealed that the laser‐treated Al/NiCrAlY bond‐coat exhibited better oxidation resistance compared to as‐sprayed NiCrAlY, Al/NiCrAlY and laser‐remelted NiCrAlY bond‐coat. The formation of θ‐Al₂O₃, NiO, Cr₂O₃ and NiCr₂O₄ spinel oxides was observed to be suppressed due to the preformed α‐Al₂O₃ scale during initial oxidation on the surface of laser pre‐oxidized Al/NiCrAlY bond‐coat. Copyright © 2013 John Wiley & Sons, Ltd.     

Influence of Vapor Phase Pretreatments of Epoxy Surfaces on the Nucleation of MOCVD Copper Thin Films

Vapor phase pretreatments of epoxy composite material reinforced with carbon fibers were carried out prior to the growth of Cu thin films by metal-organic chemical vapor deposition (MOCVD) using Cu (hfa)(COD) as copper precursor. These dry surface oxidation processes include H₂O/UV, O₂/UV and O₂/Plasma treatments. Oxygen plasma method is the most efficient to oxidize the surface and it has the greatest effect to improve the wettability of epoxy samples. As a consequence, the higher hydrophilicity of the plasma-modified epoxy surface induces a higher nucleation density in the Cu film. Furthermore, this treatment reduces drastically the induction period observed for the growth of the metal. Even though the O₂/UV pretreatment incorporates almost the same amount of oxygen in the epoxy surface than the plasma treatment, the functional groups are different, as revealed by XPS analyses, and the surface is less hydrophilic. Correlations between oxidation, wettability and nucleation density of the Cu films are discussed.     

Photoelectron spectroscopy (XPS) and thermogravimetry (TG) of pure and supported rhenium oxides 1. Pure rhenium compounds

To investigate the interaction of rhenium with several supports, a preliminary study on pure rhenium compounds has been carried out in order to achieve a better understanding of their surface chemical properties. To this end X-ray photoelectron spectroscopy (XPS) and thermogravimetry (TG) methods have been applied. The results show that metallic rhenium, ReO₂ and ReO₃ are covered with Re(VII). By heating in H₂, NH₄ReO₄ and rhenium oxides are reduced to metallic rhenium in different temperature ranges. In the case of Re₂O₇ a spillover effect has been found when platinum is present. For ReO₃ and ReO₂ a morphological model has been described on the basis of combined XPS, TG and surface area measurements. The binding energy values of the different rhenium oxidation states have been assessed and their variation with the oxidation number briefly discussed.     

Photochemical Removal of Gaseous Elemental Mercury in a Dielectric Barrier Discharge Plasma Reactor

The plasma process has the potential to serve as a low cost mercury oxidation technology that will facilitate elemental mercury removal in a downstream of Flue Gas Desulfurization system. The performance of the main gas constituents, such as H₂O, O₂ and HCl on elemental mercury oxidation under plasma atmosphere was investigated in simulated flue gas. Experiments were carried out in a dielectric barrier discharge reactor operated at 140?°C. Photochemical effects of nanocrystalline titania on oxidation of elemental mercury were also tested. The results indicated that both H₂O and O₂ promote the oxidation of elemental mercury significantly. Active radicals generated by ionization, such as O, O₂ and OH, play the crucial roles in oxidation process. The presence of HCl in N2/O2 stream in plasma system is a very effective way of oxidizing elemental mercury, the nearly complete oxidation of elemental mercury was observed by 4?kV of applied voltage only. The best photocatalytic activity of anatase TiO₂ which was calcined at 600?°C was found in our tests. Compared with the plasma process alone, the oxidation efficiency increased 18.7?C26.3?% with the addition of photocatalyst.     

<Emphasis Type="Italic">In situ</Emphasis> XPS study of InAs oxidation in glow-discharge plasma

This is the first in situ XPS study of the InAs oxidation kinetics in glow-discharge plasma in the atmosphere of O₂ and CO₂ gases and in a mixture of O₂ and NF₃ gases. Chemical composition of the oxide films produced by cathodic and anodic polarization of samples was examined. Main regularities and features of the oxide film formation on the InAs surface in the normal and dark glow discharge modes were revealed. Normal glow discharge in oxygen-containing plasma was shown to form bilayer oxide films on the InAs surface. The bottom layer with thickness of some nanometers, which consists of arsenic and indium oxides, forms at the initial oxidation steps, its thickness remaining virtually unchanged. The upper layer consists of Al₂O₃ produced by sputtering of cathode material; it serves as a barrier to oxygen diffusion, its thickness building up linearly with the treatment time in glow-discharge plasma. Chemical composition of the growing proper InAs oxide film and the stoichiometry of subsurface region of a semiconductor substrate strongly depend on the oxidation process parameters. The obtained regularities are discussed.     

Property and structure of various platinum catalysts for low-temperature carbon monoxide oxidations

The oxidation of carbon monoxide (CO) has received more attention in the last two to three decades owing to its importance in different fields. To control this CO pollution, catalytic converters have been investigated. Different types of catalysts have been used in a catalytic converter for CO emission control purposes. Platinum (Pt)-based noble metal catalysts show great potential for CO oxidation in catalytic converters with high thermal stability and tailoring flexibility. Pt metal catalysts modified with promoters such as alkali metals and reducible metal oxides have received great attention for their superior catalytic activities in CO oxidation. Temperature, close environment of the catalyst, and chemical composition in the surface layer of the catalyst have a huge effect on the active phase dispersion and O₂ adsorption capacity of the Pt metal catalysts. The main difference in activities of Pt metal catalyst for CO oxidation in O₂ or H₂ atmosphere has found. The addition of supports in Pt metal catalysts has improved their performances and reduced their cost. These improvement strongly depends on the surface structure, morphology, number of active sites, and various Pt-O interactions. Many research articles have already been published in CO oxidation over Pt metal catalysts, but no review article dedicated to CO oxidation is available in the literature.     

Influence of Plasma Regimes and Catalysts on Ethanethiol Oxidation

Plasma oxidation of ethanethiol in air was investigated using three plasma regimes: surface dielectric pulsed corona discharge, surface dielectric barrier discharge and pulsed corona discharge (PCD) in the plasma reactor. Catalytic plasma degradation of ethanethiol was also performed on the singular or binary metals doped ?èCAl₂O₃. The ethanethiol removal rate increased with increasing energy density but energy efficiency was first increased and then decreased with increasing energy density under three various types of discharges. PCD plasma required the lowest energy density at the similar ethanethiol removal performance compared with the other two plasma discharges. The main intermediate by-products of ethanethiol oxidation by plasma are CH₃CHO, HCHO, CO and CO₂. The sum of these intermediate products selectivities is 19?C43?%, implying that some other intermediates containing carbon were undetermined. When using PCD plasma combined with catalysts, ethanethiol removal rate and energy efficiency were all evidently improved. The maximum energy efficiency was achieved about 200?g kWh^?1 using Fe?CMn/?èCAl₂O₃ assisted PCD plasma, which was about 4.4 times when using PCD plasma alone. The mechanism of ethanethiol oxidation is also discussed.     

Two-Layer Nano-Oxide Composite Films on Fe-18Cr Alloys

A two-layer film composed of a reactive element (RE) oxide (ZrO₂, Y₂O₃, CeO₂, or La₂O₃) and aluminum oxide (Al₂O₃) was prepared on the surface of Fe-18Cr alloys by an electrochemical process combined with sintering. High-resolution field emission scanning electron microscopy (FE-SEM) was used to characterize the two-layer film, which showed nanostructure. SEM, EDS and mass gain measurement were used to study the oxidation resistance of the film on Fe-18Cr alloy. It is proved that this kind of film is effective in protecting the substrate from oxidation. The results also indicated that the two-layer film possesses superior oxidation resistance than a single Al₂O₃ film. The mechanisms accounting for such effects have been discussed.     

Characteristics of the Oxidation of Carbon Monoxide on Platinum and Palladium Acetylacetonates Immobilized on a Silica Surface

Characteristics of the kinetics of the oxidation of carbon monoxide on acetylacetonates of palladium and platinum immobilized on a silica surface have been studied. The bound metal complexes show no hysteresis in the dependence of the rate of reaction on the concentration of CO and O₂ and have a higher catalytic activity than Pt/SiO₂ and Pd/SiO₂. A mechanism is proposed for the oxidation of carbon monoxide on platinum and palladium complexes bound to a SiO₂ surface.     

Surface and Bulk Structure of Thin Spin Coated and Plasma-Polymerized Polystyrene Films

Polystyrene (PS) spin coated thin films were modified by O₂ and Ar plasma as well as by UV irradiation treatments. The modified PS samples were compared with plasma polymerized and commercial polystyrene. The effects of plasma (O₂ and Ar) and UV irradiation treatments on the surface and the bulk properties of the polymer layers were discussed. The surface properties were evaluated by X-ray Photoelectron Spectroscopy and Contact angle measurements and the bulk properties were investigated by FTIR and dielectric relaxation spectroscopy. As a result only one second treatment time was sufficient to modify the surface. However, this study was also dedicated to understand the effect of plasma and plasma irradiation on the deposited layers of plasma polymers. The dielectric measurements showed that the plasma deposited films were not thermally stable and underwent an undesired post-plasma chemical oxidation.