Multi-site phase transfer catalyst assisted radical polymerisation of glycidyl methacrylate using potassium peroxydisulphate as initiator – a kinetic study

In this work, the kinetics and mechanism of free-radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxydisulphate (PDS) as water soluble initiator in the presence of synthesized 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (TBMABDC) as multi-site phase transfer catalyst (MPTC) was studied. The polymerisation reactions were carried out under inert and unstirred conditions at constant temperature of 60 ± 1°C in cyclohexane/water biphase media. The role of concentrations of monomer, initiator, catalyst and volume fraction of aqueous phase, solvent polarity and temperature on the rate of polymerisation (Rp) was ascertained. The order with respect to monomer and initiator was found to be unity. The order with respect to catalyst was found to be 0.51. The rate of polymerisation is independent of ionic strength and pH of the medium. However, an increase in the polarity of solvent has slightly increased the Rp value. Based on the results obtained, a suitable kinetic scheme has been proposed to account for the experimental observations and its significance discussed.     

General Solution for the Dynamic Modeling of Parallel Robots

In this paper, we present a general method to calculate the inverse and direct dynamic models of parallel robots. The models are expressed in a closed form by a single equation in which all the elements needed are expressed. The solution is given in terms of the dynamic models of the legs, the dynamics of the platform and some Jacobian matrices. The proposed method is applied in this paper on two parallel robots with different structures. Categories (2), (3).     

Finite sample properties of estimators of spatial autoregressive models with autoregressive disturbances

The article investigates the finite sample properties of estimators for spatial autoregressive models where the disturbance terms may follow a spatial autoregressive process. In particular we investigate the finite sample behavior of the feasible generalized spatial two-stage least squares (FGS2SLS) estimator introduced by Kelejian and Prucha (1998), the maximum likelihood (ML) estimator, as well as that of several other estimators. We find that the FGS2SLS estimator is virtually as efficient as the ML estimator. This is important because the ML estimator is computationally burdensome, and may even be forbidding in large samples, while the FGS2SLS estimator remains computationally feasible in large samples. Received: 20 January 2001 / Accepted: 31 August 2001     

Influence of halide ions and alloy microstructure on the passive and localized corrosion behavior of alloy 22

Alloy 22 (N06022) is the current candidate alloy used to fabricate the external wall of the high-level nuclear waste containers for the Yucca Mountain repository. It was of interest to study and compare the general and localized corrosion susceptibility of Alloy 22 in fluoride and chloride solutions at 90 °C. Standard electrochemical tests such as cyclic potentiodynamic polarization, amperometry, and electrochemical impedance spectroscopy were used. Studied variables included the solution pH and the alloy microstructure (thermal aging). Results show that Alloy 22 is highly resistant to general corrosion in all the solutions tested. Thermal aging is not detrimental and even seems to be slightly beneficial for general corrosion at the higher solution pHs. Pitting corrosion was never observed. Crevice corrosion was found only for high chloride-containing solutions after anodic polarization. The presence of fluoride ions together with chloride ions seems to increase the susceptibility of Alloy 22 to crevice corrosion compared to pure chloride solutions. This article is based on a presentation made in the symposium “Effect of Processing on Materials Properties for Nuclear Waste Disposition,” November 10–11, 2003, at the TMS Fall meeting in Chicago, Illinois, under the joint auspices of the TMS Corrosion and Environmental Effects and Nuclear Materials Committees.     

Research on Marine Boiler＇s Pressurized Combustion and Heat Transfer

The effect of pressure on combustion and heat transfer is analyzed. The research is based on the basic combustion and heat transfer theorem. A correction for the heat calculation method for pressurized furnace is made on the basis of the normal pressure case. The correction takes the effect of pressurizing into account. The results show that the correction is reasonable and the method is applicable to combustion and heat transfer of the marine supercharged boiler.     

Organic matter release in low temperature thermal treatment of biological sludge for reduction of excess sludge production.

Thermal treatment applied in association with a biological system allows for a significant reduction in excess sludge production (approximately 50%). In general, heat treatment is described as a sludge disintegration technique. This paper offers a thorough study on the impact of heat treatment, at temperatures below 100 degrees C, on the solubilisation of the sludge COD and its biodegradability. Discontinuous heating experiments were performed on activated and digested sludge. At all temperatures tested the released COD for digested sludge was systematically higher than that for activated sludge (15 and 40%, respectively, at 95 degrees C for 40 min of contact time). For the first 30 min, a 1st order kinetic, with respect to the residual COD, was systematically found. In the range of 40-95 degrees C, digested sludge had a lower activation energy than activated sludge (26 kcal/mol compared to 70-160 kcal/mol). COD solubilisation is thus more positively influenced by temperature in the case of activated sludge. This may be due to the significant difference in the ratio of protein/carbohydrate in digested and activated sludge (1-5 and 0.2-0.7, respectively). The increase in the COD/TKN ratio in the solubilised fraction after thermal treatment of activated sludge suggests a preferential solubilisation of proteins over carbohydrates. Respirometric tests performed on the solubilised COD showed that whatever the sludge origin, only 40-50% of released COD is biodegradable at a conventional hydraulic retention time (i.e., 24 h). Hence, heat treatment would act more through organic matter solubilisation rather than by a biodegradability increase.     

Softwarekartographie

Zusammenfassung  Anwendungslandschaften in Unternehmen sind langlebige hoch-komplexe Strukturen bestehend aus hunderten bis tausenden von miteinander vernetzten betrieblichen Informationssystemen, die von Personen mit sehr unterschiedlichen Interessen und Erfahrungshintergrund konzipiert, erstellt, modifiziert, betrieben, genutzt und finanziert werden. Die Softwarekartographie zielt darauf ab, die Kommunikation zwischen diesen Personen durch zielgruppenspezifische verst?ndliche graphische Visualisierungen zu unterstützen, die Gesch?fts- und Informatik-Aspekte gleicherma?en berücksichtigen, und die speziell für langfristige und strategische Management-Betrachtungen geeignet sind. In diesem Beitrag fassen wir zun?chst die in der betrieblichen Praxis wohlbekannten Probleme beim Management von Anwendungslandschaften zusammen und diagnostizieren erhebliche Kommunikationsdefizite. Da Anwendungslandschaften als Systeme von Systemen mit Menschen als integrale Systembestandteile zu verstehen sind, werden Karten als attraktiver L?sungsansatz identifiziert und die wesentlichen Konzepte der Softwarekartographie anhand von Beispielen vorgestellt. Dabei werden Querbezüge zu anderen Fachgebieten der Informatik und Wirtschaftsinformatik hergestellt, und die bisherige Nutzung der Forschungsergebnisse in der Praxis gezeigt.     

Recrystallization of phenylbutazone using supercritical fluid antisolvent process

Phenylbutazone was recrystallized from its solutions by using a supercritical fluid antisolvent process. It was dissolved in acetone and supercritical carbon dioxide was injected into the solution, thereby inducing supersaturation and particle formation. Variation in the physical properties of the recrystallized phenylbutazone was investigated as a function of the crystallizing temperature and the carbon dioxide injection rate. The recrystallized particles showed cleaner surfaces and more ordered morphology compared to the particles obtained by other methods such as solvent evaporation. X-ray diffraction patterns indicated that the crystallinity of the particles had been modified upon the recrystallization. Differential scanning calorimetry measurement revealed that the crystallizing temperature influenced the thermal stability of the resulting crystals. Larger crystals were produced when the carbon dioxide injection rate was reduced.     

Photochemical reduction of molecular weight and number of double bonds in natural rubber film

Natural rubber (NR) can be degraded depending on various factors such as heat, mechanical force, chemical reaction, and light. Light is a very interesting factor because it can cause the NR to degrade under low temperature and pressure. The photo-degradation of NR films was carried out to investigate the effects of the light and the temperature on the reduction of the weight-average molecular weight (Mw) and the double bonds in the NR films. The NR films, with and without catalysts, titanium dioxide (TiO₂), and potassium persulfate (K₂S₂O₈), were exposed to light from a mercury light bulb at 7,000 and 36,000 lux, and at the temperature of 25 °C and 80 °C for 192 hrs. After exposure, the Mw of the NR films was analyzed by gel permeation chromatography (GPC). Changes in the Mw were used to construct a kinetic model for the process, (1/Mw)=(1/Mw₀)+(kt/2M₀) where k is the rate constant, and M₀ is the Mw of the monomer unit. The linear relationship between 1/Mw and time suggested pseudo first-order processes with random scission. The Mw distribution information from the GPC was used to calculate the number of double bonds in the NR films. The trend of the double bonds reduction curves was quite similar to the result obtained from the calculation from the FTIR spectra. This indicated that this calculation method might possibly be another alternative way to obtain the number of double bonds in the NR.     

在未来勘探开发中研发的推动作用

在过去的20年里,尽管油价和经营环境不断发生着变化,但勘探开发的产量和经济效益持续增长着,科学研究和先进技术起了关键作用。未来的勘探开发将更加依赖于先进的技术和科学的研究开发。 随着变化的经营环境和关键的先进科学技术强有力的结合,出现了新的研发模式和发展趋势。在这里我们