Use of 9,10-diphenylanthracene as a contrast agent in chemiluminescence imaging: The observation of spreading of oxidative degradation in thin polypropylene films

Thin films of polypropylene were doped with a chemiluminescence (CL) activator, 9,10-diphenylanthracene (DPA), and were thermally oxidised in a CL imaging apparatus to determine whether heterogeneous oxidation processes such as spreading of oxidation could be observed. The presence of DPA resulted in significantly more intense CL images compared with undoped polymer, due to the efficient chemically induced electron exchange luminescence reaction between DPA and hydroperoxides. Hence, the CL images from DPA-doped PP were used to locate the position of hydroperoxides in the oxidising polymer. For thermal oxidation at 150 and 140 °C hydroperoxides were observed to form in localised regions of the films, whilst other areas remained hydroperoxide free. As the oxidation time increased the concentration of hydroperoxides in these areas increased and they were observed to spread to the remainder of the polymer. Time-resolved line maps from the images indicated that zones with high concentration of hydroperoxides travel through the polymer during oxidation. Integrals of CL images from the thermal oxidation of DPA-doped polymers indicated that a significant degree of oxidation had occurred by the end of the “induction period” for a conventional CL-intensity oxidation-time profile. This is a likely reason why spreading of oxidation has not previously been observed for undoped PP films.     

Nitridation of Niobium Pentoxide Films in Ammonia by Rapid Thermal Processing

The feasibility of niobium oxynitride formation through nitridation of niobium pentoxide films in ammonia by rapid thermal processing (RTP) was investigated. Niobium films 200 and 500 nm thick were deposited by sputtering on Si(100) wafers covered by a 100 nm thick thermally grown SiO₂ layer. These as‐deposited films exhibited distinct texture effects. They were processed in three steps using an RTP system. The as‐deposited niobium films were first nitridated in an ammonia atmosphere at 1000 °C for 1 min and then oxidised in molecular oxygen at temperatures ranging from 400 to 600 °C. Those samples in which a single Nb₂O₅ phase was determined after oxidation were additionally nitridated in ammonia at 1000 °C for 1 min. Investigations show that surface roughness of the samples after oxidation of niobium films first nitridated in ammonia is lower than after direct oxidation of as‐deposited films in oxygen, although the niobium pentoxide phase formed after annealing was the same in both cases. We explain this result as being due to the large expansion of the niobium lattice during the direct oxidation of the niobium film in molecular oxygen and also to the high oxidation rate of the as‐deposited niobium film in oxygen. By incorporation of oxygen in the crystal lattice of niobium and rapid formation of niobium pentoxide, substantial intrinsic stress was built up in the film, frequently resulting in delamination of the film from the substrate. Nitrogen hinders the diffusion of oxygen in nitridated films, which leads to a decrease of the oxidation rate and thus slower formation of Nb₂O₅. Nitridation of the completely oxidised niobium films in ammonia leads to the formation of niobium oxynitride and niobium nitride phases.     

Effect of cyclic oxidation on electrochemical corrosion of type 409 stainless steel in the simulated muffler condensates

The electrochemical corrosion behavior of 409 stainless steel after cyclic oxidation below 400 °C was investigated in the simulated muffler condensates by using surface analysis and electrochemical measurement techniques. In the cyclic processes of condensate-dipping and oxidation, specimens may form defective oxide films and weak Cr depletion underlying the oxide films. Sulfate from the condensate-dipping will give rise to sulfidation during the cyclic oxidation, being detrimental to both the oxidation and corrosion properties of stainless steel. The oxidation above 300 °C deteriorates the corrosion resistance, even leading to active corrosion in the acidic condensate solutions. Comparatively, specimens oxidized cyclically without condensate-dipping show much higher condensate corrosion resistance. It is suggested that the acidic condensate corrosion is accelerated by the synergetic effect of oxidation and condensation in the mufflers, and then may result in perforation through the defects such as cracks and nodules in oxide films on the stainless steel surface.     

Improved thermal oxidation stability of polypropylene films in the presence of β-nucleating agent

Thermal oxidation behavior of isotactic polypropylene (PP) films with and without nucleating agent was investigated at 100 °C in air. The crystal form of PP was modified with a specific aryl amide derivative as β-nucleating agent (β-NA). Fourier transform infrared spectroscopy (FTIR), polarized optical microscopy (POM), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and tensile tests were performed to determine the extent of chemical degradation and the variations of microstructure of the two kinds of PP films during thermal oxidation. It was found that the mechanism of thermal oxidation of PP films was not changed in the presence of β-NA, but the time to initiation and the rate of oxidation both declined. Moreover, during the thermal oxidation aging, the melting temperature of neat PP significantly decreased while only a slight decrease of the melting temperature occurred for β-PP. Overall, the investigation indicated that the thermal oxidative stability of β-PP was higher than that of neat PP. The underlying mechanism was further analyzed by considering the change in the physical structure, especially the crystalline and the amorphous structure, of PP in the presence of β-NA.     

Catalytic Oxidation of Toluene, Acetone and Ethyl Acetate on a New Pt-Pd/Stainless Steel Wire Mesh Catalyst

A new volatile organic compound (VOC) combustion catalyst of 0.1%Pt-0.5%Pd/stainless steel wire mesh (SSWM) was prepared via anodic oxidation treatment. The result of activity tests for complete oxidation of toluene, acetone, and ethyl acetate showed that 0.1%Pt-0.5%Pd/stainless steel wire mesh catalyst had good catalytic activity and thermal stability. The total oxidation temperature for toluene, acetone, and ethyl acetate was at 220, 260, and 280 °C for the catalyst calcined at 500 °C, respectively. The catalyst and stainless steel wire mesh support were characterized by means of scanning electron microscopy (SEM), X-ray photoelectron spectrum (XPS), and ultrasonic vibration tests. The SEM results indicated that a typical donga structure layer appeared on the surface of stainless steel wire mesh support after anodic oxidation procedure. This typical anodic oxidation film was favorable for dispersing Pd and Pt components.     

Characterisation of ultra-thin films of oxidised bacterial cellulose for enhanced anchoring and build-up of polyelectrolyte multilayers

The process of catalytic oxidation of bacterial cellulose (BC) ultra-thin films with 2,2,6,6-tetramethyl-1-piperidinyloxy was investigated along with their capability to adsorb oppositely charged polyelectrolytes of chitosan and alginate. The time-dependent oxidation of BC films was analysed by X-ray photoelectron spectroscopy and quartz crystal microbalance (QCM) experiments. A negatively charged surface was achieved by inserting carboxylic groups, which was augmented by prolonged media exposure (17.9 %), compared with a fast oxidation process (9.1 %). Polyelectrolyte deposition was followed by QCM, which indicated that BC oxidation increased the first layer uptake of chitosan 17-fold (?105.0?±?1.5 Hz) in comparison with unoxidised BC (?6.0?±?0.2 Hz), confirming the capability of oxidised BC surfaces to exhibit strong electrostatic interactions and to support the build-up of a thicker multilayer system. These findings indicate that oxidised BC surfaces are capable of immobilising and detecting several charged species.     

Low potential electrosyntheses of free-standing polyfluorene films in boron trifluoride diethyl etherate

High quality free-standing polyfluorene (PFe) films were synthesized electrochemically by direct anodic oxidation of fluorene in pure boron trifluoride diethyl etherate (BFEE) on stainless steel sheet. The oxidation potential of fluorene in this medium was measured to be only 1.1 V versus SCE, which was much lower than that determined in acetonitrile + 0.1 mol L⁻¹ TBATFB. PFe films obtained from this medium showed good electrochemical behavior, good thermal stability with conductivity of 0.25 S cm⁻¹, indicating that BFEE is a better medium than acetonitrile for the electrosyntheses of PFe films. FTIR and ¹H NMR spectral investigations indicated that the polymerization of fluorene occurred mainly at 2, 7 position. As-formed PFe films can be partly dissolved in acetone, acetonitrile, tetrahydrofuran, etc.     

Structural and morphological aspects considerations of bilayers actuators based on polypyrrole/polyethylene glycole composites

Polypyrrole-polyethylene glycol (PPy-PEG) composite films were synthesized on stainless steel electrode by electrochemical method. Presence of PEG as a plasticizing polymer in the solution of polymerization strongly affects the morphological and swelling characteristics of the composite films. Results indicated that the increase in PEG weight percent to 0.07 leads to bi-layer actuators that move faster 18% than those made by neat polypyrrole. However, with further increase in PEG weight percent, the rate of movement decreases. On the other hand, at the same time, the efficiency of electrical energy conversion to the mechanical work decreases as wt% of the PEG is increased. SEM pictures of electro-chemically synthesized PPy and PPy-PEG layers prepared at the presence of various amounts of PEG showed that the thick layer of PPy is a cauliflower and granular structure. However PPy-PEG composites have a more integrate structure and smooth surface including small pores required to penetrate the counter ions.     

Effect of thermal annealing of poly(3-octylthiophene) films covered stainless steel on corrosion properties

The effect of thermal annealing of poly(3-octylthiophene) (P3OT) coatings on the corrosion inhibition of stainless steel in an NaCl solution was investigated. P3OT was synthesized by direct oxidation of the 3-octylthiophene monomer with ferric chloride (FeCl₃) as oxidant. P3OT films were deposited by drop-casting technique onto 304 stainless steel electrode (304SS). 304SS coated with P3OT films were thermally annealed during 30 h at different temperatures (55°C, 80°C, and 100°C). The corrosion resistance of stainless steel coated with P3OT in 0.5 M NaCl aqueous solution at room temperature was investigated by using potentiodynamic polarization curves, linear polarization resistance, and electrochemical impedance spectroscopy. The results indicated that the thermal treatment at 80°C and 100°C of P3OT films improved the corrosion resistance of the stainless steel in NaCl solution; the speed of corrosion diminished in an order of magnitude with regard to the 304SS. In order to study the temperature effect in the morphology of the coatings before and after the corrosive environment and correlate it with corrosion protection, atomic force microscopy and scanning electron microscopy were used. Morphological study showed that when the films are heated, the grain size increased and a denser surface was obtained, which benefited the barrier properties of the film.     

Thermal oxidation of silicon studied by high resolution Rutherford backscattering

Rutherford backscattering provides a simple experimental technique for investigating the thermal oxidation of silicon containing heavy impurity species. The technique provides both mass and depth analysis of para-surface layers. Using conventional apparatus, typical depth resolution is 250Å N. This paper describes a simple method of improving the resolution to ～25 Å. The method is then illustrated with data on the analysis of thin (<300Å) layers of thermally oxidised silicon containing ion-implanted impurities. The effect of the type and dose of implanted ions on oxidation rate has been measured. The re-distribution of implanted ions during thermal oxidation is also investigated.     

Oxidation and biodegradation of polyethylene films containing pro-oxidant additives: Synergistic effects of sunlight exposure, thermal aging and fungal biodegradation

Synergistic effects of sunlight exposure, thermal aging and fungal biodegradation on the oxidation and biodegradation of linear low density poly(ethylene) PE-LLD films containing pro-oxidant were examined. To achieve oxidation and degradation, films were first exposed to the sunlight for 93 days during the summer months followed by their incubation with fungal strains previously isolated from the soil based on the ability to grow on the oxidized PE-LLD as a sole carbon source. Some films were also thermally aged at temperatures ranging between 45°C and 65 °C, either before or after fungal degradation. Films with pro-oxidant additives exhibited a higher level of oxidation as revealed by increase in their carbonyl index (COi). In addition to increase in the COi, films showed a slight increase in crystallinity and melting temperature (T_m), considerably lower onset degradation temperatures, and a concomitant increase in the % weight of the residues. The level of oxidation observed in thermally aged films was directly proportional to the aging temperature. The PE-LLD films with pro-oxidant exposed to sunlight followed by thermal aging showed even higher rate and extent of oxidation when subsequently subjected to fungal biodegradation. The higher oxidation rate also correlated well with the CO₂ production in the fungal biodegradation tests. Similar films oxidized and aged but not exposed to fungal biodegradation showed much less degradation. Microscopic examination showed a profuse growth and colonization of fungal mycelia on the oxidized films by one strain, while another spore-producing strain grew around the film edges. Data presented here suggest that abiotic oxidation of polymer's carbon backbone produced metabolites which supported metabolic activities in fungal cells leading to further biotically-mediated polymer degradation. Thus, a combined impact of abiotic and biotic factors promoted the oxidation/biodegradation of PE-LLD films containing pro-oxidants.     

锆离子改善十烷基磷酸组装膜结构及性能研究

利用烷基磷酸、金属锆离子和不锈钢电极表面的相互作用,通过表面自组装,在304不锈钢电极表面分别修饰了单层和双层烷基磷酸自组装膜,采用接触角和极化曲线对修饰电极进行测量.实验表明,双层烷基磷酸修饰膜具有更佳的耐腐蚀性能.     

锆合金初始氧化行为的原位近常压XPS研究

锆基合金由于具有低的热中子吸收截面、良好的耐腐蚀性能和力学性能等优点,通常被用于水冷核反应堆中的核燃料包壳和其他结构材料。通过在合金中添加适量的Nb元素可以有效地降低锆合金的氧化速率和吸氢分数,从而改善锆合金的耐腐蚀性能。尽管对锆合金的耐腐蚀性能得到了广泛的认识,但关于其在接近真实氧化腐蚀条件下的原位研究一直是具有挑战性的课题。本工作中利用近常压X射线光电子能谱(NAP-XPS)原位研究了1.3 × 10^-8 - 1.3 × 10^-1 mbar (1 mbar = 100 Pa)连续分压下室温到623 K温度时两种锆基合金表面在水,氧中的初始氧化腐蚀行为。结果表明,未添加Nb和添加1%Nb的锆合金表面在初始氧化过程中锆元素都会由金属态向多种氧化态过渡。水蒸气环境下两种合金的氧化速率都要低于氧气环境。室温下无论水蒸气还是氧气环境两种合金的氧化速率都要比623 K高温情况下的慢。在623 K的氧气气氛下,未添加Nb的锆合金相较于添加1%Nb的锆合金更容易被氧化,Nb的添加一定程度上会降低氧物种的吸附能力。在室温下和623 K低水蒸气压力下,1%Nb锆合金氧化速率更快,Nb促进OH^-在表面生成。而在623 K高水蒸气压力下,未添加Nb的锆合金有更易于被氧化的倾向,Nb在高温下向表面扩散并抑制OH^-键的断裂,但两种样品表面短时间内都无法被完全氧化。     

Thin Organic-Inorganic Anti-Fouling Hybrid-Films for Microreactor Components

Deposit formation and fouling in reactors for polymer production and processing especially in microreactors is a well-known phenomenon. Despite the flow and pressure loss optimized static mixers, fouling occurs on the surfaces of the mixer elements. To improve the performance of such parts even further, stainless steel substrates are coated with ultra-thin films which have low surface energy, good adhesion, and high durability. Perfluorinated organosilane (FOTS) films deposited via chemical vapor deposition (CVD) are compared with FOTS containing zirconium oxide sol-gel films regarding the prevention of deposit formation and fouling during polymerization processes in microreactors. Both film structures led to anti-adhesive properties of microreactor component surfaces during aqueous poly(vinylpyrrolidone) (PVP) synthesis. To determine the morphology and surface chemistry of the coatings, different characterization methods such as X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy as well as microscopic methods such as field-emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM) are applied. The surface free energy and wetting properties are analyzed by means of contact angle measurements. The application of thin film-coated mixing elements in a microreactor demonstrates a significant lowering in pressure increase caused by a reduced deposit formation.     

Adsorption on stainless steel surfaces of biosurfactants produced by gram-negative and gram-positive bacteria: Consequence on the bioadhesive behavior of Listeria monocytogenes

The ability of adsorbed biosurfactants (Pf and Lb) obtained from gram-negative bacterium (Pseudomonas fluorescens) or gram-positive bacterium (Lactobacillus helveticus) to inhibit adhesion of four listerial strains to stainless steel was investigated. These metallic surfaces were characterized using the following complementary analytical techniques: contact-angle measurements (CAM), atomic force microscopy (AFM), polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS) and X-ray photoelectron spectroscopy (XPS). Contact-angles with polar liquids (water and formamide) indicated that the stainless steel surface covered with adsorbed biosurfactant was more hydrophilic and electron-donating than bare stainless steel. The surface characterization by XPS and PM-IRRAS revealed that conditioning the stainless steel changes the substrate in two ways, by modifying the surface alloy composition and by leaving an thin adsorbed organic layer. AFM observations enabled to say that the layer covered entirely the surface and was probably thicker (with patches) in the case of Pf-conditioned surfaces compared to the Lb-conditioned ones, which seemed to be less homogeneous. Though the added layer was thin, significant chemical changes were observed that can account for drastic modifications in the surface adhesive properties. As a matter of fact, adhesion tests showed that both used biosurfactants were effective by decreasing strongly the level of contamination of stainless steel surfaces by the four strains of Listeria monocytogenes. The more important decrease concerned the CIP104794 and CIP103573 strains (>99.7%) on surface conditioned by L. helveticus biosurfactant. A less reduced phenomenon (75.2%) for the CIP103574 strain on stainless steel with absorbed biosurfactant from P. fluorescens was observed. Whatever the strain of L. monocytogenes and the biosurfactant used, this antiadhesive biologic coating reduced both total adhering flora and viable and cultivable adherent bacteria on stainless steel surfaces. This study confirms that biosurfactants constitute an effective strategy to prevent microbial colonization of metallic surfaces by pathogenic bacteria like the food-borne pathogen L. monocytogenes.     

Study in the effect of annealing on hydrogen retention properties of C‐90%SiC films

Carbon‐rich silicon carbide (C‐90%SiC) films as hydrogen barriers were deposited on the surface of stainless steel substrates with magnetron sputtering, and then bombarded by argon ion beam. In order to remove the argon atoms reserved during films preparation, some samples with the prepared C‐90%SiC films were thermally annealed for 30 min at 473, 673 and 873 K in vacuum, respectively. These samples together with the un‐annealed ones were then irradiated by a 5 keV hydrogen ion beam. SEM was used to investigate the surface micrograph of those films and SIMS was used to measure the mass spectra of positive species and the depth distribution of argon and hydrogen in the samples. A remarkable decrease in hydrogen intensity in the substrates with annealing indicates that annealing for removing argon can effectively improve hydrogen retention properties of the C‐90%SiC films. Copyright © 2008 John Wiley & Sons, Ltd.     

Direct growth of aligned multiwalled carbon nanotubes on treated stainless steel substrates

Growth of aligned carbon nanotubes (CNTs) on electrically conductive substrates is promising for many applications; however, the lack of complete understanding of the substrate effects on CNT growth poses a lot of technical challenges. Here, we report the direct growth of aligned multiwalled nanotubes (MWNTs) on chemically treated stainless steel (Type 304) using a chemical vapor deposition (CVD) process. A detailed X-ray photoelectron spectroscopy (XPS) analysis has been carried out for the various treated samples in order to better understand the correlation between the surface properties of the substrates and the MWNT growth. The XPS studies revealed that the CNTs prefer to grow on the enriched surface of iron oxides obtained by the chemical treatment rather than on the passive chromium oxide films present on the surface of the as-received stainless steel substrates. The density and alignment of the MWNTs could therefore be controlled by tuning the ratio of the iron oxides to chromium oxides through the chemical treatment on the stainless steel surfaces. On the basis of this method, selective growth of CNT patterns on stainless steel has also been demonstrated.     

Surface ozonation and photooxidation of polyethylene film

High-density polyethylene (HDPE) and low-density polyethylene (LDPE) films were oxidized by treatment with ozone and by photooxidation with a low-pressure mercury lamp. The changes that resulted in the surfaces of the films were followed by ESCA. On ozonation, the surface of LDPE initially is oxidized more rapidly than that of HDPE; however, extended ozonation produces a surface composition that corresponds to C₈O for HDPE and to C₁₈O for LDPE. The surface oxidation products are mainly carboxyl groups, with lower levels of carbonyl and C? O groups. For both polymers photooxidation provides more extensively oxidized surfaces than ozonation, although the surface of HDPE oxidizes slightly faster than that of LDPE treated under identical conditions. In both cases the surface stoichiometry after extensive photoxidation is C₆O. The functional groups formed are mainly carboxyl and C? O. The effects of ozonation and photooxidation on the polyethylene surfaces are compared with those produced by several other means of surface oxidation.     

RAMAN SPECTROSCOPIC STUDY ON THE CHAIN CONFORMATION OF ELECTROSYNTHESIZED POLY（p-PHENYLENE） FILMS

Poly（p-phenylene） （PPP） films have been electrochemically deposited on mirrorlike stainless steel （SS） electrode surfaces by direct oxidation of benzene in boron trifluoride diethyl etherate （BFEE） solutions at a constant applied potential of 1.7 V （versus Ag/AgCl）. The chain conformations of as-grown PPP films have been studied by Raman spectroscopy. The results demonstrated that high synthesis temperature favors the formation of planar PPP, and the conformation of planar PPP can be changed into torsional PPP by cooling treatment.     

Detergent-Induced Removal of β-Lactoglobulin from Stainless Steel Surfaces as Influenced by Surface Pretreatment

The adsorption of β-lactoglobulin to stainless steel and its subsequent removal were followed using in situ null ellipsometry. The influence of the surface pretreatment on the protein removal by the surfactant SDS and by sodium hydroxide was studied. All surfaces were precleaned in strongly alkaline solution. Some surfaces received no further pretreatment, while others were either passivated in nitric acid or plasma-cleaned prior to experiments. Stainless steel surfaces subjected to different surface pretreatments showed considerable differences in cleaning behavior. Cleaning, using NaOH, of surfaces which had been precleaned with alkali only or with plasma resulted in practically complete β-lactoglobulin removal. In contrast, appreciable amounts of protein remained on passivated stainless steel. Protein removal by SDS was limited and comparable for all three surface pretreatments investigated. Only minor effects on the protein adsorption tendency were observed. The amounts of β-lactoglobulin adsorbed tended to be somewhat lower on the passivated surfaces.