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91.
The transitional behaviours of emulsion polymerisation for styrene and butyl acrylate (BA) monomers from zero-one to pseudo-bulk regime were mechanistically investigated. A dynamic mathematical model, which incorporates cross-over mechanism from zero-one to pseudo-bulk kinetics was developed for emulsion polymerisation and compared with experimental data for conversion, particle size and molar mass. Particles smaller than cross-over size follow zero-one kinetics and particles greater than cross-over size, they follow pseudo-bulk kinetics. In our mechanistic approach, particles nucleated from micelles, grow until the cross-over size is attained, based on zero-one kinetics, and subsequently continue to grow based on pseudo-bulk kinetics. Key findings from our work are that the developed transitional model predictions agree reasonably with experimental data on process and product attributes such as conversion, average molecular weight, molecular weight distribution (MWD), average particle size and particle size distribution (PSD). Optimal strategies for semibatch operation was developed using reaction temperature and monomer feed rate as process variables with specified initial conditions. 相似文献
92.
The effect of aluminum alkyls and BHT‐H on reaction kinetics of silica supported metallocenes and polymer properties in slurry phase ethylene polymerization 下载免费PDF全文
Muhammad Ahsan Bashir Vincent Monteil Christophe Boisson Timothy F. L. McKenna 《应用聚合物科学杂志》2018,135(2)
In slurry and gas phase catalytic ethylene polymerization processes, aluminum alkyl (AlR3) compounds are usually present inside the reactor and their role either as co‐catalyst or scavenger is of considerable importance. Silica supported metallocene/methyl aluminoxane (MAO) catalysts show specific interactions with AlR3 compounds. Therefore, this study shows an attempt to analyze and compare the effect of concentration as well as type of commonly used AlR3 on slurry phase ethylene homopolymerization kinetics of silica supported (n‐BuCp)2ZrCl2/MAO catalyst. The obtained results indicate that the lower the concentration of smaller AlR3 compounds, the higher the instantaneous catalytic activity. Concerning the polymer particle size distributions, a rise in fines generation has been observed with increasing AlR3 content inside the reactor. Finally, it has been shown that the addition of 2,6‐di‐tert‐butyl‐4‐methylphenol (a substituted phenol) into the reactor containing AlR3 reduces the influence of AlR3 compounds on the reaction kinetics of silica supported metallocene/MAO catalysts. Polyethylene properties remain similar in all the studied scenarios. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45670. 相似文献
93.
Vincent Martin Ulrike Werner-Zwanziger Josef W. Zwanziger Richard A. Dunlap 《International Journal of Applied Glass Science》2011,2(4):282-289
Recently an empirical model was established to predict the photoelastic response of a glass based on its composition and the crystalline structure of its constituents. In the present work the model was tested in detail by comparing the local structure assessed by a combination of nuclear magnetic resonance and Mössbauer spectroscopy with the model predictions and the measured photoelastic response. The system investigated was (SnO)x(P2O5)1−x. It was found that while the original simple model based on data on the pure components predicted the composition of the zero stress-optic glass to within about 15 mol%, inclusion of data on mixed systems, more reflective of the true glass structure, gave substantial improvement of the prediction. This finding further confirms the relation of local bonding structure to the photoelastic response of glass. 相似文献
94.
Cindy Belon Abraham Chemtob Céline Croutxé‐Barghorn Séverinne Rigolet Vincent Le Houérou Christian Gauthier 《大分子材料与工程》2011,296(6):506-516
A difunctional methacrylate oligomer was mixed with a variable amount of a MAPTMS precursor in the presence of both a radical and a cationic photoinitiator. The simultaneous photolysis of both photosensitive molecules upon UV irradiation allowed the single‐step generation of a type‐II polymethacrylate/polysiloxane nanocomposite film. Methacrylate and methoxysilyl conversions during irradiation were efficiently monitored by FTIR spectroscopy. The inorganic structure of the resulting silica‐based hybrid films was characterized using 29Si solid‐state NMR. Finally, the reinforcement ability of the resulting hybrid films was also assessed by using a unique range of characterization techniques: DMA, scratch test, and nanoindentation.
95.
Ernest B. Cady Ann Lorek Yakito Takei John S. Wyatt Juliet M. Penrice A. David Edwards Donald Peebles Marzena Wylezinska Huw Owen-Reece Vincent Kirkbride Christopher E. Cooper Richard F. Aldridge Simon C. Roth Guy Brown David T. Delpy E. Osmund R. Reynolds 《Magma (New York, N.Y.)》1994,2(3):437-439
The aim of this study was to reproduce the delayed (secondary) cerebral energy failure previously described in birth-asphyxiated newborn infants and to investigate relationships between primary insult severity and the extent of the delayed energy failure. Phosphorus (31P) magnetic resonance spectroscopy (MRS) at 7 T was used to study the brains of 12 newborn piglets during an acute, reversible, cerebral hypoxic-ischemic episode which continued until nucleotide triphosphates (NTP) were depleted. After reperfusion and reoxygenation, spectroscopy was continued for 48 h. High-energy metabolite concentrations returned to near normal levels after the insult, but later they fell as delayed energy failure developed. The time integral of NTP depletion in the primary insult correlated strongly with the minimum [phosphocreatine (PCr)]/[inorganic orthophosphate (Pi)] observed 24–48 h after the insult. (Linear regression analysis gave slope –8.04 h–1; ordinate intercept=1.23;r=0.92;P<0.0001.) This model is currently being used to investigate the therapeutic potential of various cerebroprotective strategies including hypothermia. 相似文献
96.
Modeling heterogeneous bacterial populations exposed to antibiotics: The logistic‐dynamics case 下载免费PDF全文
Pratik R. Bhagunde Michael Nikolaou Vincent H. Tam 《American Institute of Chemical Engineers》2015,61(8):2385-2393
In typical in vitro tests for clinical use or development of antibiotics, samples from a bacterial population are exposed to an antibiotic at various concentrations. The resulting data can then be used to build a mathematical model suitable for dosing regimen design or for further development. For bacterial populations that include resistant subpopulations—an issue that has reached alarming proportions—building such a model is challenging. In prior work, we developed a related modeling framework for such heterogeneous bacterial populations following linear dynamics when exposed to an antibiotic. We extend this framework to the case of logistic dynamics, common among strongly resistant bacterial strains. Explicit formulas are developed that can be easily used in parameter estimation and subsequent dosing regimen design under realistic pharmacokinetic conditions. A case study using experimental data from the effect of an antibiotic on a gram‐negative bacterial population exemplifies the usefulness of the proposed approach. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2385–2393, 2015 相似文献
97.
Carbon nanotubes-block copolymer composites were synthesized via reversible addition–fragmentation chain transfer living emulsion mechanism, based on zero–one and pseudo-bulk kinetics. In conjunction with multiwalled carbon nanotubes, ab initio reversible addition–fragmentation chain transfer homopolymerization of styrene and butyl acrylate, respectively, was carried out using xanthate-based reversible addition–fragmentation chain transfer agent through ultrasonified macroemulsion and miniemulsion. Then, the second and third monomer were applied at stage II and III, respectively, to produce multiwalled carbon nanotube diblock and triblock copolymer composites such as multiwalled carbon nanotube-b-poly(styrene)-co-polybutyl acrylate-co-polymethyl acrylate and multiwalled carbon nanotube-b-polybutyl acrylate-co-polymethyl acrylate-co-poly(styrene). As multiwalled carbon nanotube-homopolymer proceeds to diblock and triblock, thermal resistance of multiwalled carbon nanotube block composite products is enhanced. A mechanistic approach of reversible addition–fragmentation chain transfer living macroemulsion and miniemulsion polymerizations, with the purified multiwalled carbon nanotubes enables us to control the composite properties such as thermal degradation, mechanical strength, and glass transition temperature of multiwalled carbon nanotube-block copolymer composites, in conjunction with reaction conditions, monomer type, blocking sequence, particle size, and molecular weight. 相似文献
98.
99.
Isabelle L. Di Ma?o Pascale Barbier Diane Allegro Cédric Brault Vincent Peyrot 《International journal of molecular sciences》2014,15(8):14697-14714
The interaction between the microtubule associated protein, tau and the microtubules is investigated. A fluorescence resonance energy transfer (FRET) assay was used to determine the distance separating tau to the microtubule wall, as well as the binding parameters of the interaction. By using microtubules stabilized with Flutax-2 as donor and tau labeled with rhodamine as acceptor, a donor-to-acceptor distance of 54 ± 1 Å was found. A molecular model is proposed in which Flutax-2 is directly accessible to tau-rhodamine molecules for energy transfer. By titration, we calculated the stoichiometric dissociation constant to be equal to 1.0 ± 0.5 µM. The influence of the C-terminal tails of αβ-tubulin on the tau-microtubule interaction is presented once a procedure to form homogeneous solution of cleaved tubulin has been determined. The results indicate that the C-terminal tails of α- and β-tubulin by electrostatic effects and of recruitment seem to be involved in the binding mechanism of tau. 相似文献
100.
Zhongyan Chen Fan Wang Shuoqing Yan Yan Nie Zekun Feng Yajie Chen Vincent G. Harris 《Journal of the American Ceramic Society》2014,97(6):1873-1877
The effects of microwave calcination (MC) and conventional muffle furnace calcination (CC) on the microstructure and magnetic properties of M‐type hexagonal ferrite Ca0.15La0.39Sr0.46Fe11.7Co0.3O19 were investigated. The phase composition, microstructure, and magnetic properties of calcined materials were examined using X‐ray diffraction (XRD), scanning electron microscopy (SEM), and vibrating sample magnetometry. Experiments indicated that the MC method can achieve both pure phase, and fine and uniform grains for both calcined and sintered M‐type hexaferrites. MC treatments resulted in a magnetization at 15 kOe of 67 emu/g and an increase in coercivity by 12% over the CC technique. The improved magnetic properties resulting from microwave‐assisted calcination were attributed to the formation of a fine‐grained morphology, which yielded a narrow grain size distribution. The microwave calcinating technique was shown here to possess unique potential for fabrication of high‐performance ferrites and possibly other ceramics. 相似文献