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71.
72.
The rotational isomeric state model was employed to provide a better understanding of the role of chain microstructure on the conformational behavior of homogeneous ethylene-1-olefin copolymers. The chain microstructure was assembled in accordance with the copolymerization theory using a set of conditional probabilities in direct relation to the reactivity ratios and the feed compositions of the comonomers. The catalytic inversion influence on the tacticity of the polymeric microstructure was also taken into account by considering the replication probability during the Monte Carlo simulation. Statistical weight factors of the rotational isomeric states were evaluated using molecular dynamics runs of the various homopolymers according to the earlier work of Mattice et al. Probability distribution surfaces constructed by the integration of the molecular dynamics trajectories of sufficient length to sample all of the conformational space indicated the increase of the probability of g±t joint states at the expense of g±g± pairs with the increase in the side chain length of the 1-olefin comonomers. It was also indicated that this behavior had a maximum around poly(1-butene)/poly(1-hexene) with an apparent reversal in case of poly(1-octene) due to the side chain crowding, which forces the chain to favor more of the g±g± joint states. The characteristic ratios calculated for the copolymers on the basis of the rotational isomeric state model also indicated the increased extension of the polymer backbone with the increase in the side chain length. The lower characteristic ratio calculated for the octene polymers may, in fact, explain the experimental observation that poly(1-octene) has a lower melting point than those of other poly(1-olefin)s of shorter side chains. A complete account of the role of tacticity on the characteristic ratio and the radial distribution function is also given. 相似文献
73.
This paper presents further results and extensions of our previous point defect model for time-dependent growth of passive oxide films on metal surfaces. Specifically, by accounting for vacancies as material species rather than just holes in the oxide lattice, the model incorporates more plausible expressions for interfacial reactions and associated kinetic rate expressions. We use the model to explore the general effects of varying metal valence and electrolyte pH on passive film growth. Furthermore, we examine key assumptions concerning the thickness dependence of the electric field within the film. When the electric field inside the film remains constant and the rate constant for oxygen vacancy production varies with applied potential, the model predicts trends in thickness versus potential in reasonable agreement with experimental data for a variety of metal/metal oxide systems. This represents a considerable improvement upon the previous ‘high-field’ form of the model which assumed rate constants independent of potential and electric field in the film varying with thickness. 相似文献
74.
A number of polyphosphazenes with negatively charged β‐alanine (β‐Ala) and γ‐amino butyric acid (GABA) side groups were synthesized and studied for their ability to initiate the growth of hydroxyapatite (HAp) during exposure to simulated body fluid (SBF). All the polymers were hydrolytically sensitive, with the final hydrolysis rate dependent on the specific active side groups (GABA > β‐Ala). These systems also underwent extensive mineralization, with calcium phosphate deposited across their entire surface during exposure to SBF (up to 115 wt % gain after 4 weeks). This degree of deposition is a major advance over previously reported polyphosphazene systems, which underwent a maximum of 27 wt % gain after immersion in SBF for 4 weeks. The extent of mineralization over the surface was monitored using environmental scanning electron microscopy (ESEM) coupled with energy dispersive X‐ray spectroscopy (EDS). In addition, X‐ray diffraction (XRD) was used to determine the identity of the mineralized material. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41741. 相似文献
75.
Dr. Thomas Hauch Fenger Prof. Dr. Harry Brumer 《Chembiochem : a European journal of chemical biology》2015,16(4):575-583
A series of N‐bromoacetylglycosylamines and bromoketone C‐glycosides were synthesised from complex xyloglucan oligosaccharide (XyGO) scaffolds as specific active‐site affinity labels for endo‐xyloglucanases. Compounds based on XXXG (Xyl3Glc4) and XLLG (Xyl3Glc4Gal2) oligosaccharides exhibited strikingly higher affinities and higher rates of irreversible inhibition than known cellobiosyl and new lactosyl disaccharide congeners when tested with endo‐xyloglucanases from two distinct glycoside hydrolase (GH) families. Intact‐protein mass spectrometry indicated that inactivation with XyGO derivatives generally resulted in a 1:1 labelling stoichiometry. Together, these results indicate that XyGO‐based affinity reagents have significant potential as inhibitors and proteomic reagents for the identification and analysis of diverse xyloglucan‐active enzymes in nature, to facilitate industrial enzyme applications. 相似文献
76.
Harry Charalambous Shikhar Krishn Jha Kent Harrison Christian Ryan Thomas Lay Thomas Tsakalakos 《Journal of the European Ceramic Society》2018,38(10):3689-3693
In conventional flash sintering, the current rises nonlinearly to a set current limit, accompanied by a spike in the power density. This sudden power spike may cause hot spot formation, in which current preferentially channels through a small area, causing localized melting while other areas remain unsintered. By using a controlled current ramp early on the sudden power spike can be avoided. In addition, by changing the ramp rate material properties such as porosity, grain size and conductivity can be tuned. 相似文献
77.
The investigation of phase transformations in metastable ceramic systems such as zirconia often requires local phase analysis within the areas of interest. Electron backscatter diffraction is a suitable method in combination with focused ion beam sample preparation. The interaction between ion beam and sample has to be carefully considered. In case of metastable Y-PSZ and Mg-PSZ, phase transformations were observed after FIB preparation with 30?kV, 30?nA and 5° incidence angle. Damage was the dominating effect for angles of 72°. The expected local temperature increase due to the ion bombardment with 30?kV and 30?nA is 700?K for ZrO2. Thus, the observed phase transformations can be explained on the basis of the temperature increase in the corresponding Y-PSZ phase diagram. In case of Mg-PSZ, the transition temperature is 1083?°C. The local temperature increase was obviously lower. The excitation energy for the observed phase transformation was smaller than expected from the phase diagrams of the thermodynamic equilibrium. Using 5?kV, 4.8?nA and 5° incidence angle, no phase transformations and no damage were observed. Thus, these conditions are well suited for the FIB preparation of metastable zirconia. 相似文献
78.
Sadegh Salehzadeh Michael D. Ward Harry Adams 《Inorganic chemistry communications》2009,12(5):433-435
Cadmium(II) complexes of some potentially heptadentate tripodal Schiff base ligands with the general formula N{(CH2)nNCHC5H4N}2{(CH2)mNCHC5H4N}) (where n = m = 2, L222; n = 2, m = 3, L322; n = 3, m = 2, L332) have been studied. These ligands are products of the full condensation of a number of tripodal tetraamines with 2-pyridinecarboxaldehyde. An unusual reaction of an additional 2-pyridine-carboxaldehyde with a methylene group adjacent to the imine bond only during template preparation of [Cd(L332)]2+ was observed. The latter reaction is a novel chelate-assisted C?C bond formation because it is occurred only where a rigid five-membered chelate ring is present. 相似文献
79.
Kirsi S. Mikkonen Susanna Heikkinen Annemai Soovre Marko Peura Ritva Serimaa Riku A. Talja Harry Helén Lea Hyvönen Maija Tenkanen 《应用聚合物科学杂志》2009,114(1):457-466
The development of packaging films based on renewable materials is an important and active area of research today. This is the first extensive study focusing on film‐forming properties of an agrobiomass byproduct, namely, oat spelt arabinoxylan. A plasticizer was needed for cohesive film formation, and glycerol and sorbitol were compared. The tensile properties of the films varied with the type and amount of the polyol. With a 10% (w/w) plasticizer content, the films containing glycerol had higher tensile strength than the films containing sorbitol, but with a 40% plasticizer content, the result was the opposite. Sorbitol‐plasticized films retained their tensile properties better than films with glycerol during 5 months of storage. The films were semicrystalline with similar crystallinity indices of 0.20–0.26. The largest crystallites (9.5 nm) were observed in the film with 40% glycerol. The softening of films with 40% (w/w) glycerol started at a significantly lower relative humidity (RH) than that of the corresponding sorbitol‐containing films. The films with sorbitol also had lower water vapor permeability (WVP) than the films with glycerol. The films plasticized with 10% (w/w) sorbitol had a WVP value of 1.1 g mm/(m2·d·kPa) at the RH gradient of 0/54%. The oxygen permeability of films containing 10% (w/w) glycerol or sorbitol was similar: 3 cm3·μm/(m2·d·kPa) at 50–75% RH. A higher plasticizer content resulted in more permeable films. Permeation of sunflower oil through the films was not detected. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 相似文献
80.
Nazario D. Ramírez‐Beltrán Harry Rodríguez Vallés L. Antonio Estévez Horacio Duarte 《加拿大化工杂志》2009,87(5):748-760
Artificial neural networks (ANNs) and a group‐contribution approach were used to develop an algorithm to predict activity coefficients for binary solutions. The Levenberg–Marquardt algorithm was used to train the ANN and to predict the parameters of the Margules equation. The ANN was trained using phase‐equilibrium database from DECHEMA. The selected systems include alcohols, phenols, aldehydes, ketones, and ethers. The trim mean based on 20% data elimination was selected as the best representation of the Margules‐equation parameters. The algorithm was validated with 121 VLE systems and results show that the ANN provides a relative improvement over the UNIFAC method. 相似文献