Verhalten von Magnesiumlegierungen für Anwendungen im Fahrzeugbau bei mechanisch‐elektrochemischer Komplexbeanspruchung: Einfluss passivierender Deckschichten und Mechanismen der lokalen Schädigung

Behavior of Magnesium‐Alloys for Automotive Applications under Mechanical and Environmental Loading: Influence of Passivating Films and Mechanisms of Local Breakdown To assure an efficient design of components under cyclic loading, all available data concerning fatigue have to be observed. Therefore the influences of manufacturing on the material condition, the mechanical loads and environmental effects have to be analysed. Magnesium‐alloys are of special interest for lightweight applications because of their excellent strength‐density ratio. The corrosion resistance of magnesium‐alloys depends on the same factors that are critical to other metals. The alloys have a good stability to atmospheric exposure and a good resistance to attack by alkali, chromic and hydrofluoric acids. However, because of the electrochemical activity of magnesium, the relative importance of some factors is greatly amplified. The nature and composition of passive films formed on magnesium‐alloys depend on the prevailing conditions, viz. alloy‐composition, passivation potential, pH, electrolyte composition and temperature. Passive films may be damaged by local breakdown. Because of this, magnesium‐alloys suffer a degradation of their properties when exposed to an aqueous environment. The main topic of the present investigations is the verification of mechanisms of the local breakdown of the protecting film. At least two mechanisms are possible for this localization: mechanical breakdown by slip steps and electrochemical breakdown (for e.g. by the effects of chloride ions). Corrosion and passivation of different high purity alloys have been studied in different solutions (neutral, alkaline with specific anions and cations) using electrochemical techniques. The diecasted alloys were tested as produced and machined. The results clarified that depending on alloy/material and surface condition/corrosion environment different mechanisms for electrochemical breakdown of the protecting films are possible. Hence fatigue life under environmental loading is influenced by surface and testing conditions.     

Monte Carlo simulation of gas phase polymerization of 1,3‐butadiene. Part II: Kinetics optimization and confirmation

Studies on the deactivations and initiations of gas phase polymerizations of 1,3‐butadiene have been achieved by Monte Carlo simulation. Initiation and deactivation control the reaction before and after the peak of the polymerization rate, respectively. The influence of polymerization temperature has been studied. Monte Carlo modeling of polymerization kinetics and mechanism was confirmed by the agreement of experimental data and simulation results of polymerizations run with a temporary evacuation of monomer. The balance of catalysts and active chains is established by both initiation and chain transfer reactions with cocatalyst, which causes a ‘pseudo‐stability’ stage. © 2003 Society of Chemical Industry     

Mixed oxide supported hydrodesulfurization catalysts—a review

Support effects form important aspect of hydrodesulfurization (HDS) studies and mixed oxide supports received maximum attention in the last two decades. This review will focus attention on studies on mixed oxide supported Mo and W catalysts. For convenience of discussion, these are divided into Al₂O₃ containing mixed oxide supports, TiO₂ containing mixed oxide supports, ZrO₂ containing mixed oxide supports and other mixed oxide supports containing all the rest. TiO₂ containing mixed oxides received maximum attention, especially TiO₂–Al₂O₃ supported catalysts. A brief discussion about their prospects for application to ultradeep desulfurization is also included. An overview of the available literature with emphasis on research carried out in our laboratory form the contents of this publication.     

Nitric oxide reduction and carbon monoxide oxidation over carbon-supported copper-chromium catalysts

Carbon supported copper-chromium catalysts are shown to be very active for both the reduction of nitric oxide with carbon monoxide and the oxidation of carbon monoxide with oxygen. Mixed copper-chromium oxide active phases have good activity in the simultaneous removal of nitric oxide and carbon monoxide from exhaust gases. The influence of several catalyst variables has been investigated. The activity per volume of catalyst increases with increasing loading, while the intrinsic activity shows a maximum around C/M=100−50. An optimum catalyst for nitric oxide reduction and carbon monoxide oxidation has a copper/chromium ratio of 2/1. The apparent activation energy for the carbon monoxide oxidation over carbon supported copper-chromium catalysts is 77 kJ/mol, suggesting that the Cu---O bond rupture is the rate-limiting process. The reduction of nitric oxide takes place at higher temperatures. Since all catalysts have a low selectivity for molecular nitrogen formation at lower temperatures, the dissociation of nitric oxide is probably rate determining, resulting in a slightly reduced catalyst system. In an excess of carbon monoxide the reaction is first-order in nitric oxide and zero-order in carbon monoxide. Moisture inhibits the reaction by reversible competitive adsorption, whereas carbon dioxide does not. Oxygen completely inhibits the reduction of nitric oxide due to the more rapid reoxidation of the catalytic sites compared to nitric oxide. Therefore, the reduction of nitric oxide takes place only when all oxygen has been converted and, hence, is shifted to higher temperatures. As a possible consequence, the production of nitrous oxide is reduced. Nitric oxide and molecular oxygen react preferentially with carbon monoxide, so, in an excess of oxidizing component, gasification of the carbon support occurs at higher temperatures after carbon monoxide has been completely consumed.     

Feasibility analysis of membrane reactors – discovery of reactive arheotropes

A feasibility analysis methodology adopted from reactive distillation is applied to membrane reactors. A model is formulated to depict the reactive liquid phase composition on the retentate side of a continuous type membrane reactor. The effects of both the chemical reaction kinetics and the membrane mass transfer kinetics on the feasible products are elucidated by means of retentate phase diagrams and bifurcation analysis. The proposed method can be applied to various membrane processes, independent of the specific structure of the membrane. Two quaternary reaction systems are considered to illustrate the methodology. In the first hypothetical system, it is shown how selective membranes can influence the sequence of effective volatilities which in turn affects the feasible products of the system. In the second example of practical importance, i.e. the heterogeneously catalysed synthesis of propyl acetate coupled with permeation through a porous polycarbonate membrane, the dusty gas model is applied to describe the component fluxes through the membrane. For the latter reaction system, the existence of reactive arheotrope is demonstrated. Arheotropes represent mass transfer controlled feasible products of membrane separation process.     

Corrosion Behavior of 316LN and 316 Stainless Steels During Long-term Exposure to Aerated 0.5 M NaCl Using Electrochemical Noise Technique

In the present work 316LN as well as 316 stainless steel (SS) coupons each of dimensions (0.025 × 0.018 × 0.006 m³) in well-polished condition were used as two nominal electrodes which were immersed in the aerated solution of 0.5 M NaCl. Correlated current and potential electrochemical noise (EN) signals were collected at 1 Hz sampling frequency for 1 h daily over a period of 30 days. The detrended EN data were used to calculate the noise resistance (R _N) as well as the spectral noise resistance at zero frequency (R _SN^o) values and other statistical parameters. To study the nature of pits and distribution of their diameters as well as depths, extensive observations of the pitted and the blank specimens were carried out using Confocal Laser Scanning Microscopy (CLSM). The current and the potential records of the two alloys showed distinct differences in their corrosion behavior. It was observed that within less than 4 h of immersion, 316SS showed signals indicative of unstable pitting and onset of stable pitting was noticed after 48 h of exposure. However, until about 24 h, 316LN showed just the random signals and unstable pitting was observed after 28 h. The signals clearly indicated continuous growth of the stable pits in 316SS as against the repassivation of the unstable pits in 316LN after 7 days exposure. It was observed that R _N values showed a continuous decrease in the case of 316SS, but were quite stable in the case of 316LN over the exposure period. Concurrent to these observations it was observed that 316SS specimen was extensively pitted. The frequency distributions of pit diameters as well pit depths were observed to be highest at 10-20 μm and 5-10 μm, respectively. However, pits with as large as 70-80 μm diameter and as deep as 20-25 μm too were observed. No pits were observed in case of 316LN even after 30 days of exposure, an observation that corroborates well with the stable R _N values. Thus, in the present investigation, the long-term tests using EN technique coupled with CLSM studies conclusively prove that many unstable pits initiated in 316SS turn into stable ones resulting in insidious localized corrosion attack whereas the unstable pits initiated in 316LN get passivated in the simulated coastal environment.     

探讨电石法PVC烟气治理方法

分析了电石法PVC生产链中电石炉烟气及电厂烟气二氧化硫的排放情况,指出利用电石炉烟气中的CO合成氨、再将合成氨用于燃煤电厂烟气的"氨法"脱硫是具有较大应用潜力的循环经济产业链。     

Effect of surfactants and liquid hydrocarbons on gas hydrate formation rate and storage capacity

Hydrate formation rate plays an important role in making hydrates for the storage and transport of natural gas. Micellar surfactant solutions were found to increase gas hydrate formation rate and storage capacity. With the presence of surfactant, hydrate could form quickly in a quiescent system and the energy costs of hydrate formation reduced. Surfactants (an anionic surfactant, a non‐ionic surfactant and their mixtures) and liquid hydrocarbons (cyclopentane and methylcyclohexane) were used to improve hydrate formation. The experiments of hydrate formation were carried out in the pressure range 3.69–6.82 MPa and the temperature range 274.05–277.55 K. The experimental pressures were kept constant during hydrate formation in each experimental run. The effect of anionic surfactant (sodium dodecyl sulphate (SDS)) on natural gas storage in hydrates is more pronounced compared to a non‐ionic surfactant (dodecyl polysaccharide glycoside (DPG)). The induction time of hydrate formation was reduced with the presence of cyclopentane (CP). Cyclopentane and methylcyclohexane (MCH) could increase hydrate formation rate, but reduced hydrate storage capacity The higher methylcyclohexane concentration, the lower the hydrate storage capacity. Copyright © 2003 John Wiley & Sons, Ltd.     

谢尔渣油气化油改气控制系统的改造

介绍了Shell渣油气化装置将渣油原料改为天然气时控制系统的改造方案。提出的改造思路不但可用于Shell渣油气化，也可用于德士古渣油气化的油改气工程中。     

Characterization and modification of fillers for paints and coatings

This paper highlights the possibility of inverse gas chromatography for the surface characterization of common fillers (CaCO₃, talc, SiO₂,) for paints and coatings. Divided solids are described, on the one hand, by the dispersive component of their surface energy and, on the other, by a specific parameter indicating their acid-base interaction potential. The role of the surface morphology at a molecular level is also examined. It is demonstrated that steric effects play an important role in the adsorption of probes on lamellar solids like talc. The consequences of surface treatments as well as examples of practical applications are also reported.