Adsorption mode of ethyl pyruvate on platinum: an in situ XANES study

The adsorption of ethyl pyruvate on Pt(111) has been studied by in situ XANES measurements in the presence and absence of hydrogen. Depending on the hydrogen and ethyl pyruvate pressure, the C and O K‐edge spectra exhibit distinctly different angular dependence. Without hydrogen ethyl pyruvate is oriented preferentially perpendicular to the surface, indicating bonding via the O lone pairs. In the presence of hydrogen the mean orientation is more tilted towards the surface. Likely, ethyl pyruvate also interacts with Pt via its π system under these conditions. The observed angle‐dependent shift of the energy of the π* and σ* resonances indicates the coexistence of differently adsorbed ethyl pyruvate species. The experimental findings demonstrate the importance of the in situ approach for unraveling the adsorption mode of ethyl pyruvate in the enantioselective hydrogenation over cinchona‐alkaloid‐modified Pt. This revised version was published online in July 2006 with corrections to the Cover Date.     

The effect of nanoclays on the nucleation,crystallization, and melting mechanisms of isotactic polypropylene

The influence of organomodified nanoclay (montmorillonite) on the crystallization and melting mechanisms of isotactic polypropylene (iPP) was studied. Films of both neat polymer and clay nanocomposites were prepared after molecular weight optimization through melt extrusion. Products exhibited the tactoidlike morphology since no compatibilizers were used. The effect of introduction of nanoclay within the polymer was studied through isothermal crystallization and linear heating. The results indicated that low nanoclay concentrations induce the formation of the β‐crystalline structure, its formation being inhibited with high nanoclay contents. Dynamic nonisothermal bulk crystallization experiments indicated that nanoclays act as nucleating agents of iPP. Isothermal, bulk crystallization studies indicated that the crystallization process (induction time and crystallization kinetics) is proportionally accelerated by the nanoclay presence. There was also an accelerated formation of secondary crystallization when nanoclays were present in high concentrations. POLYM. ENG. SCI., 47:1889–1897, 2007. © 2007 Society of Plastics Engineers     

Modification of a carbon/carbon composite with a thermosetting resin precursor as a matrix by the addition of carbon black

Carbon/carbon composites were made through the pyrolysis of stabilized PAN felt and phenolic resin with the addition of 5 or 10 wt % carbon black to the matrix and then heat treatment at 600–2500°C. The effects of adding carbon black to the matrix precursor on the physical properties, microstructure, and mechanical properties of the resultant composites were investigated. Adding carbon black not only reduced the weight loss but also limited the shrinkage of the resultant composites. Adding carbon black also accelerated the formation of carbon basal planes in the matrix. At 2500°C, the crystalline stacking height in the composite with 10 wt % added carbon black was 200% greater than that with no additive. The flexural strength of the composite also increased from 15 to 42 MPa (almost 300%). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 333–337, 2006     

Synthesis and characterization of novel copolymers with acid‐labile ketal moieties derived from camphor

Novel diastereomeric acrylic ketal monomers derived from (+)‐camphor and (±)‐camphor were synthesized. To investigate the applications of the camphor derivatives on positive‐tone photoresists, the acrylic ketal monomers were copolymerized with methyl methacrylate, methacrylic acid, and n‐butyl methacrylate. The optical activities of the chiral monomers and polymers were all evaluated. After UV irradiation and postexposure baking, the optical activity of the polymers decreased because of the decomposition of the acid‐labile pendant chiral groups. The existence of alicyclic camphyl groups increased the etching resistance of the photoresists. The thermogravimetric properties of the copolymers, the exposure curves, the lithographic evaluation of the positive‐tone photoresists, and the effects of alicyclic groups on the plasma etching resistance of the copolymers were all investigated. A resolution of a line‐and‐space pattern of 0.3 μm was achieved. Acid‐catalyzed dehydration crosslinking was also found in this system. Sufficient UV irradiation and heat treatment could cause the acid‐catalyzed dehydration crosslinking of pendant carboxyl groups and thereby increase the efficiency of the thermal resistance of the polymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2969–2978, 2003     

中药企业MES系统的研发及应用

该文针对中药制造企业计划层与控制层相互脱节的现状,即决策管理层的管理信息如ERP和底层的控制系统(DCS)处于相对独立的状态,在对中药制造企业资源管理现状分析的基础上,利用过程运行信息,以产品产量、质量、节能降耗、过程优化等为目标,研究适合中药制造企业的MES系统,并针对某中药企业做应用研究,证实其有效提高了企业管理水平,并降低能耗.     

Kinetic study of radical polymerization. II. Solid‐state bulk polymerization of sodium methacrylate by differential scanning calorimetry

The solid‐state radical polymerization of sodium methacrylate was investigated. It was initiated by azobisisobutyronitrile, which was used as a radical initiator. Differential scanning calorimetry (DSC) was used to observe the endothermic and exothermic transitions during the polymerization reaction. Structural studies were performed with the DSC thermograms and Fourier transform infrared and ultraviolet–visible spectra, and all of the results confirmed the progress of the reaction. The obtained data revealed that the polymerization reaction proceeded completely with a 100% conversion. ΔH of this reaction was calculated with various amounts of the initiator, and the peak temperatures were determined at different heating rates. The activation energy (19.7 kcal mol^?1) was also obtained by the Kissinger method for this type of solid polymerization reaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1648–1654, 2003     

Rheological properties of hyperbranched polymer/poly(ethylene terephthalate) reactive blends

The rheological properties in solution, in shear and in uniaxial elongation of poly(ethylene terephthalate) (PET) reacted together with hyperbranched polymers (HBPs) were investigated. Two different PET grades, of low and high molecular weights, were compounded with sub‐ to over‐stoichiometric concentrations of HBPs of second and fourth pseudo‐generation, and subsequently subjected to a solid‐state polycondensation (SSP). The formation of microgels, which occurs at high HBP concentration, gave rise to a large increase in melt elasticity and a related decrease in melt strength. At low HBP concentrations, the complex viscosity of the unreacted HBP/PET was considerably reduced, thus demonstrating a lubrication effect of the HBP molecules. During SSP, the intrinsic and shear viscosities exhibited a gradual increase, which was similar for both PET and HBP/PET blends, and was correlated to an increase in molecular weight, through linear‐chain extension and branching reactions. The elongational viscosity of the reactive blends was also increased as a function of reaction time, and this increase was much larger in the case of the HBP/PET blends. A 400% increase in melt strength of the PET was obtained by combining SSP and trace amounts of an HBP of second generation, without any decrease in drawability.     

二甲基亚砜的生产与消费

分析了国内外二甲基亚砜的消费市场情况，介绍了二甲基亚砜的生产工艺，对国内发展二甲基亚砜生产技术提出了合理建议。     

Improved mechanical properties of shape‐memory polyurethane block copolymers through the control of the soft‐segment arrangement

High‐performance shape‐memory polyurethane block copolymers, prepared with two types of poly(tetramethylene glycol) (PTMG) used as soft segments, were investigated for their mechanical properties. Copolymers with a random or block soft‐segment arrangement had higher stresses at break and elongations at break than those with only one kind of PTMG. Random copolymers with fewer interchain interactions showed higher elongation than block copolymers. All the copolymers had shape‐recovery ratios higher than 80%. In dynamic mechanical testing, the glass‐transition behavior clearly depended on the soft‐segment arrangement: random copolymers had only one glass‐transition peak, whereas block copolymers showed two separate glass‐transition peaks. Overall, the control of the soft‐segment arrangement plays a vital role in the development of high‐performance shape‐memory polyurethane. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2410–2415, 2004     

Synergic influence of a surfactant and ultrasonication on the preparation of soluble,conducting polydiphenylamine/silica‐nanoparticle composites

Conducting polydiphenylamine was used to encapsulate silica nanoparticles through the oxidative polymerization of diphenylamine in the presence of ultrasonic irradiation. The polymerization was performed in the presence of sodium lauryl sulfate as a surfactant. Experiments performed in the absence of ultrasound clearly demonstrated that the application of ultrasonication played multiple roles in the preparation of a composite of polydiphenylamine with silica nanoparticles. Ultrasonication dispersed the silica nanoparticles, converted sodium lauryl sulfate to lauryl alcohol, and augmented the dispersion of the silica‐nanoparticle/polydiphenylamine composite in an organic medium. Silica‐nanoparticle/polydiphenylamine composites were also prepared in the absence of ultrasound and/or sodium lauryl sulfate. The silica‐nanoparticle/polydiphenylamine composites were characterized with Fourier trans form infrared spectroscopy, ultraviolet–visible/near‐infrared spectroscopy, and thermogravimetric analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3912–3918, 2006