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     

Voltage sag compensation with minimum energy injection by use of a micro‐SMES

This paper presents a method to compensate voltage sags with minimum energy injection for a series‐connected voltage restorer using a micro‐SMES. A circuit for extracting the fundamental symmetrical components from sag voltages and a minimum energy injection algorithm is described. Simulations of voltage sag compensation have been carried out using PSCAD/EMTDC for various faults. The simulation results confirm the validity of the proposed method and show the possibility of reducing the size of energy storage devices. © 2002 Wiley Periodicals, Inc. Electr Eng Jpn, 141(3): 70–80, 2002; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.10047     

Influence of ethyl methacrylate content on the volume‐phase transition of temperature‐sensitive poly[(N‐isopropylacrylamide)‐co‐(ethyl methacrylate)] microgels

A novel series of temperature‐sensitive poly[(N‐isopropylacrylamide)‐co‐(ethyl methacrylate)] (p(NIPAM‐co‐EMA)) microgels was prepared by the surfactant‐free radical polymerization of N‐isopropylacrylamide (NIPAM) with ethyl methacrylate (EMA). The shape, size dispersity and volume‐phase transition behavior of the microgels were investigated by transmission electron microscopy (TEM), ultraviolet–visible (UV–Vis) spectroscopy, dynamic light scattering (DLS) and differential scanning calorimetry (DSC). The transmission electron micrographs and DLS results showed that microgels with narrow distributions were prepared. It was shown from UV–Vis, DLS and DSC measurements that the volume‐phase transition temperature (VPTT) of the p(NIPAM‐co‐EMA) microgels decreased with increasing incorporation of EMA, but the temperature‐sensitivity was impaired when more EMA was incorporated, causing the volume‐phase transition of the microgels to become more continuous. It is noteworthy that incorporation of moderate amounts of EMA could not only lower the VPTT but also enhance the temperature‐sensitivity of the microgels. The reason for this phenomenon could be attributed to changes in the complicated interactions between the various molecules. Copyright © 2004 Society of Chemical Industry     

Phase behavior of ternary blends containing dimethylpolycarbonate,tetramethylpolycarbonate and poly[styrene‐co‐(methyl methacrylate)] copolymers (or polystyrene)

The miscibility and phase behavior of ternary blends containing dimethylpolycarbonate (DMPC), tetramethylpolycarbonate (TMPC) and poly[styrene‐co‐(methyl methacrylate)] copolymer (SMMA) have been explored. Ternary blends containing polystyrene (PS) instead of SMMA were also examined. Blends of DMPC with SMMA copolymers (or PS) did not form miscible blends regardless of methyl methacrylate (MMA) content in copolymers. However, DMPC blends with SMMA (or PS) blends become miscible by adding TMPC. The miscible region of ternary blends is compared with the previously determined miscibility region of binary blends having the same chemical components and compositions. The region where the ternary blends are miscible is much narrower than that of binary blends. Based on lattice fluid theory, the observed phase behavior of ternary blends was analyzed. Even though the term representing the Gibbs free energy change of mixing for certain ternary blends had a negative value, blends were immiscible. It was revealed that a negative value of the Gibbs free energy change of mixing was not a sufficient condition for miscible ternary blends because of the asymmetry in the binary interactions involved in ternary blends. Copyright © 2004 Society of Chemical Industry     

SHS of shape memory CuZnAl alloys

Aiming at preparation of shape memory alloys (SMAs), we explored the SHS of Cu_{1 − x} Zn_{1 − y} Al_{1 − z} alloys (0.29 < x < 0.30, 0.74 < y < 0.75, and 0.83 < z < 0.96). The most pronounced shape memory effect was exhibited by the alloys of the following compositions (wt %): (1) Cu(70.6)Zn(25.4)Al(4.0), (2) Cu(70.1)Zn(25.9)Al(4.0), and (3) Cu(69.9)Zn(26.1)Al(4.0). The effect of process parameters on the synthesis of CuZnAl alloys was studied by XRD, optical microscopy, and scanning electron microscopy (SEM). The grain size of CuZnAl was found to depend on the relative amount of the primary CuZn and AlZn phases. Changes in the transformation temperature and heat of transformation are discussed in terms of ignition intensity and compaction. Mechanism of the process depends on the level of the temperature attained relative to the melting point of components. At the melting point of AlZn, the process is controlled by the solid-state diffusion of AlZn into a product layer. The ignition temperature for this system depends on the temperature of the austenite-martensite transformation in CuZnAl alloys. The composition and structure of the products was found to markedly depend on process parameters. The SHS technique has been successfully used to prepare a variety of SMAs.      

Influence of a lipid phase on steam jet agglomeration of maltodextrin powders

The contribution of an oil phase to the agglomeration mechanisms of food powders was evaluated. Maltodextrin (DE 10), palm oil stearin and two palm oil oleins (up to 25% dry mass) were used as food models. Granulation runs were carried out in a pilot plant steam jet agglomerator. The powders containing oleins were more cohesive than those with stearin and the presence of oil changed the agglomeration mechanisms. The size increase mechanism of pure maltodextrin powder was controlled by surface plasticization and agglomerates with suitable instant properties were obtained. Small amount of oil degenerated drastically the rate of dispersion in water of the powders and their agglomerates but the average size and the mechanical resistance of the agglomerates increased when the oil content of the powders increased. SEM micrographs of agglomerates indicated that higher lipid content in the powders produced compact granules, favoring sinkability but hindering their disintegration. Agglomeration enhanced considerably the flowability of the particles containing oil. The dispersion behavior of the powders with higher lipid content could be correlated with the Hausner Number. A pre-agglomeration step favored the blend of the more cohesive powders producing larger and more resistant agglomerates.     

Performance evaluation of a water/silicone oil two‐phase partitioning bioreactor using Rhodococcus erythropolis T902.1 to remove volatile organic compounds from gaseous effluents

BACKGROUND: In the framework of biological processes used for waste gas treatment, the impact of the inoculum size on the start‐up performance needs to be better evaluated. Moreover, only a few studies have investigated the behaviour of elimination capacity and biomass viability in a two‐phase partitioning bioreactor (TPPB) used for waste gas treatment. Lastly, the impact of ethanol as a co‐substrate remains misunderstood. RESULTS: Firstly, no benefit of inoculation with a high cellular density (>1.5 g L^?1) was observed in terms of start‐up performance. Secondly, the TPPB was monitored for 38 days to characterise its behaviour under several operational conditions. The removal efficiency remained above 63% for an inlet concentration of 7 g isopropylbenzene (IPB) m^?3 and at some time points reached 92% during an intermittent loading phase (10 h day^?1), corresponding to a mean elimination capacity of 4 × 10^?3 g L^?1 min^?1 (240 g m^?3 h^?1) for a mean IPB inlet load of 6.19 × 10^?3 g L^?1 min^?1 (390 g m^?3 h^?1). Under continuous IPB loading, the performance of the TPPB declined, but the period of biomass acclimatisation to this operational condition was shorter than 5 days. The biomass grew to approximately 10 g L^?1 but the cellular viability changed greatly during the experiment, suggesting an endorespiration phenomenon in the bioreactor. It was also shown that simultaneous degradation of IPB and ethanol occurred, suggesting that ethanol improves the biodegradation process without causing oxygen depletion. CONCLUSION: A water/silicone oil TPPB with ethanol as co‐substrate allowed the removal of a high inlet load of IPB during an experiment lasting 38 days. Copyright © 2008 Society of Chemical Industry     

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.     

β″－Al_2O_3陶瓷的强化和韧化

研究了稳定ＺｒＯ＿２和部份稳定ＺｒＯ＿２对β″－Ａｌ＿２Ｏ＿３陶瓷的强化和韧化作用，观察了不同种类、不同含量的ＺｒＯ＿２对β″－Ａｌ＿２Ｏ＿３陶瓷的显微结构、力学性能和电导率的影响，探讨了β″－Ａｌ＿２Ｏ＿３的韧化机理。     

Importance of out-of-plane dispersion of the excitation spectrum of superconducting bilayers with Josephson coupling

We study the effect of Josephson coupling between adjacent superconducting layers on the BCS energy spectrum. We find that the interference between the gap functions of two layers can lead to vanishing condensation energy for perpendicular momenta corresponding to the formation of standing waves. We therefore predict a conventional energy spectrum for large interlayer spacings, if the gap of the single layers has no nodes, and in all cases a gapless spectrum for small spacings. Within the experimental error, our numerical results account for the low-temperature dependence of the penetration depth reported in Nd_1.85Ce_0.15CuO₄ and YBa₂Cu₃O_6.9.