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1.
A circulating fluidized reactor of polyethylene was modeled with the proper hydrodynamics for a riser and downer and combined with a kinetic model based on the moment equations. The hydrodynamic model was able to predict the profiles of the following parameters through the riser and downer: cluster velocity, bed porosity, concentration of potential active sites, active sites, gas‐phase components, molecular weights, and reactor temperature. It was shown that one could control the monomer consumption and molecular weight, which are crucial in the reactor behavior and production properties, respectively, by setting different operating hydrodynamic conditions, such as the gas velocity in the riser and the solid circulation rate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011 相似文献
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Parameter identification is quite challenging in mixing, which is extensively employed in chemical process industry. Agitated pulp chests are more difficult to characterize because they handle non-Newtonian pulp suspensions and non-ideal flows such as short circuiting, recirculation and channeling. In the present study, we characterize the agitated pulp chests in the continuous time domain, which obviates the restrictions imposed by the discrete time approach. For this purpose, a robust and efficient hybrid genetic algorithm is utilized along with a differential-algebraic model of mixing. Necessary derivatives including auxiliary differential equations are obtained for gradient search. Using realistic large sets of mixing data, both the algorithm and the model are successfully validated before characterizing laboratory-scale agitated pulp chests. Superior characterizations are obtained compared to those yielded by the discrete time domain approach. This outcome highlights the benefit of the continuous time domain approach developed in this work. 相似文献
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In this study, intelligent systems (ANN-GA and GMDH) was employed to develope a model based on experimental data to predict the performance of the pervaporation process. The ANN system was coupled with the genetic algorithm (GA) to choose initial connection weights and biases of the multi-layer feed forward neural network (FFNN). The input parameters were the feed concentration, membrane thickness, and Reynolds number, while the outputs were total flux and permeate concentration. The RMSE of the estimated total flux for the ANN-GA and GMDH were 0.09170 and 0.0903, respectively. Also, the RMSE of estimated permeate concentration for the ANN-GA and GMDH were 0.0994 and 0.0975, respectively. The results indicated that the models had sufficient accuracy, but that GMDH could provide a better outcome. Finally, the relative importance of input variables on the network outputs was determined. Sensitive analysis showed that the membrane thickness and feed concentration are the most effect on the total flux and permeate concentration, respectively. Other variables also have important effect on the PV process and cannot be ignored. 相似文献
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Frontal polymerization is a process in which a spatially localized reaction zone propagates through a monomer by converting it into a polymer. In particular, the heat produced during the curing process is exploited to promote the reaction of the monomer lying next to the propagating front, making this latter able to self‐sustain. This approach represents an alternative solution to traditional polymerization methods and can be successfully applied to the preparation of many polymeric materials. In this study, frontal polymerization was numerically modeled to better understand it and to provide the basis for processing simulation. A finite‐difference method was used to solve the thermal problem coupled with the equation describing the cure evolution for a reactor with a cylindrical geometry. The implicit backward time–centered space method was used. First, a one‐dimensional model, able to describe the process in an adiabatic tube, was developed. The front ignition was simulated as if it were a hot surface warming one end of the reactor to trigger reactant polymerization. The model was able to predict the formation of a reactive front advancing in the unreacted zone with a constant speed. The influence of the chemical and physical properties of the resin on process evolution was also investigated. By applying the alternate direction implicit method, a more detailed two‐dimensional model able to describe a three‐dimensional problem for a cylindrical reactor was also developed. With this model, it was possible to study the influence of boundary conditions on process evolution, considering a convective heat exchange with the environment through the reactor walls. Diglycidyl ether of bisphenol A, cured with diethylenetriamine (DETA), was used as the model system. Differential scanning calorimetry was used to produce a phenomenological model able to describe the cure process and to determine the physical properties of the resin. The validity of the approach was confirmed experimentally using a small cylindrical reactor. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1756–1766, 2005 相似文献
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This study was concerned with the chemical modification process of an atactic polypropylene from polymerization reactor byproducts with p‐phenylen‐bismaleamic acid to obtain a new grafted polymer supposed to play an important role as an interfacial agent in heterogeneous systems based on polymers. The grafting process was undertaken with the aid of the Box–Wilson experimental worksheet, with two independent variables (or controlled factors), the level of polar monomer to be grafted in the polymer and the concentration of the initiator, and with the agitation rate kept constant. Each item of the experimental design was performed at four different reaction times. This latter let us ascertain the transient nature of the process and the existence of a critical point in the concentration of both reactants conducting the system to the maximum grafting yield. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2202–2209, 2003 相似文献
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In this paper, the optimal policies for bulk polymerization of n‐butyl methacrylate (BMA) are determined in a nonisothermal batch reactor. Four objectives are realized for BMA polymerization based on a detailed process model. The objectives are: (i) maximization of monomer conversion in a specified operation time, (ii) minimization of operation time for a specified, final monomer conversion, (iii) maximization of monomer conversion for a specified, final number average polymer molecular weight, and (iv) maximization of monomer conversion for a specified, final weight average polymer molecular weight. For each objective, the optimal temperature policy of heat‐exchange fluid inside reactor jacket is determined. The temperature of the heat‐exchange fluid is considered as a function of a specified variable. Necessary equations are provided to suitably transform the process model in terms of a specified variable other than time, and to evaluate the elements of Jacobian to help in the accurate solution of the process model. A genetic algorithm‐based optimal control method is applied to realize the objectives. The resulting optimal policies of this application reveal considerable improvements in the batch production of poly(BMA). © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2799–2809, 2006 相似文献
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Taek Hyeon Kim 《应用聚合物科学杂志》2004,94(5):2117-2122
A monomeric antioxidant, bearing carbamate groups, was synthesized from the reaction of 3,5‐di‐tert‐butyl‐4‐hydroxybenzyl alcohol and azidomaleimide. Another antioxidant was prepared from the reaction of N‐(4‐hydroxyphenyl)maleimide and 3‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl) propionic chloride in the presence of triethylamine. These fictional antioxidants were grafted onto polyethylene (PE) via melt processing with free‐radical initiators in a minimax molder. The IR spectra of the grafted PE showed that the monomeric antioxidants were added to PE. IR spectroscopy methods were used for the quantitative determination of the extent of grafting of the monomeric antioxidants. Also, the extent of crosslinking was determined from the gel content. To optimize the reaction conditions, we investigated the effects of the initiator concentration, monomeric antioxidant, reaction time, and temperature on the extent of grafting. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2117–2122, 2004 相似文献
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A novel processing method of combining dynamic vulcanization with the silane‐grafted water‐crosslinking technique to improve the comprehensive properties of polyethylene (PE) is reported. PE was grafted with vinyl triethoxysilane (VTEO) first, and then, N,N,N′,N′‐ tetragylcidyl‐4,4′‐diaminodiphenylmethane epoxy resin was dynamically cured in a PE‐g‐VTEO matrix through a twin‐screw extruder to prepare PE‐g‐VTEO/epoxy blends. Polyethylene‐graft‐maleic anhydride (PE‐g‐MAH) was used as a compatibilizer to improve the interaction between PE‐g‐VTEO and the epoxy resin. The results show that the novel processing method improved the strength, stiffness, and toughness of the blends, especially the heat resistance of the blends, by the addition of the dynamically cured epoxy resin as the reinforcement. PE‐g‐MAH increased the compatibility between PE‐g‐VTEO and the epoxy resin, which played an important role in the improvement of the comprehensive properties of the blends. In addition, after treatments in both hot air and hot water, the comprehensive properties of blends were further improved, thanks to the further curing reaction of epoxy with PE‐g‐VTEO. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011 相似文献
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This study was concerned with the structural features and mechanical properties of polypropylene (PP)/low‐density polyethylene (LDPE) blends, which after compounding were modified by the free‐radical grafting of itaconic acid (IA) to produce [PP/LDPE]‐g‐IA in the course of reactive extrusion. To analyze the structural features of the [PP/LDPE]‐g‐IA systems, differential scanning calorimetry and relaxation spectrometry techniques were used. The data were indicative of the incompatibility of PP and LDPE in the [PP/LDPE]‐g‐IA systems on the level of crystalline phases; however, favorable interactions were observed within the amorphous phases of the polymers. Because of these interactions, the crystallization temperature of PP increased by 5–11°C, and that of LDPE increased by 1.3–2.7°C. The rapprochement of their glass‐transition temperatures was observed. The single β‐relaxation peak for the [PP/LDPE]‐g‐IA systems showed that compatibility on the level of structural units was responsible for β relaxation in the homopolymers used. Variations in the ratios of the polymers in the [PP/LDPE]‐g‐IA systems led to both nonadditive and complex changes in the viscoelastic properties as well as mechanical characteristics for the composites. Additions of up to 5 wt % PP strengthened the [PP/LDPE]‐g‐IA blended systems between the glass‐transition temperatures of LDPE and PP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1746–1754, 2006 相似文献
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用RAP法(reactivo atmosphere process)处理KCl熔体,在不改变生长气氛和RAP继续处理的情况下,提拉生长KCl晶体,以解决高纯、大尺寸、生长速度快、成品率高和有较大经济效益的问题。 相似文献
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Seyyed Abbas Mousavi‐Saghandikolaei Masoud Frounchi Susan Dadbin Sylvain Augier Elisa Passaglia Francesco Ciardelli 《应用聚合物科学杂志》2007,104(2):950-958
The chemical modification of isotactic polypropylene was performed by the free‐radical‐promoted grafting of 1,1,1‐trimethylolpropane trimethacrylate (TMPTMA) in the presence of dicumyl peroxide (DCP) as the initiator. The reaction was carried out both in a batch internal mixer and in a corotating twin‐screw extruder; the effects of the peroxide and monomer concentrations on the extent of modification in terms of the grafting efficiency and polymer chain structure variations were investigated. The modified samples were characterized with Fourier transform infrared to determine the structure of the grafted groups and the degree of functionalization, with gel permeation chromatography and the melt flow index to evaluate changes in the molecular weight, and with differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical thermal analysis to measure the final thermal properties. In addition, solvent extraction with xylene was performed to highlight the presence of gel and its extent. The structure of the grafted groups was determined, and the number of grafted groups was quantitatively evaluated. The degree of functionalization increased with an increasing TMPTMA/DCP molar ratio. Thermal analysis results hinted at the presence of grafted chains with an increased percentage of TMPTMA. Although degradation reactions predominated at high amounts of peroxide, grafting and branching processes became competitive at high levels of TMPTMA. The balance between competing β‐scission and grafting/branching reactions could be adjusted on the basis of feed conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 950–958, 2007 相似文献
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Maurizio Penco Stefania Della Sciucca Elisa Passaglia Guido Giordani Serena Coiai Luca Di Landro 《应用聚合物科学杂志》2008,109(2):1014-1021
Linear low-density polyethylene (LLDPE)/polybutadiene (PB) and LLDPE/poly(styrene-b-butadiene-b-styrene) (SBS) binary blends were prepared by simple melt mixing or by reactive blending in the presence of a free-radical initiator, and for comparison, pure LLDPE was treated under the same conditions with a comparable free-radical initiator concentration. The effect of the reactive melt mixing on the morphology of the blends was studied with transmission electron microscopy, and the corresponding particle size distributions were analyzed and compared to highlight the effects of the crosslinking and grafting phenomena. Thermal properties of the obtained materials were investigated with differential scanning calorimetry and dynamic mechanical thermal analysis (DMTA). In particular, the effect of the reactive mixing parameters on the amorphous phase mobility was investigated. The influence of the chemical modification on the crystallization behavior of LLDPE, neat and blended with PB and SBS, was also studied with dynamic and isothermal differential scanning calorimetry tests, and the isothermal thermograms were analyzed in light of the Avrami equation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
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Comparative analysis was conducted to learn the grafting of itaconic acid (IA) and glycidyl methacrylate (GMA) onto polypropylene (PP) in the course of reactive extrusion. Seven organic peroxides, which satisfactorily dissolve in PP, but do not dissolve in the monomer, were used to initiate free‐radical reactions. The grafting of IA and GMA onto PP initiated by certain peroxides gave approximately equal amounts of grafted product. It was learned that the nature of peroxide initiators is decisive for grafting efficiency and degree of macromolecular degradation. To ensure a high yield of grafted product, it is advisable to use peroxides, which have thermodynamic affinity with PP and the temperature range of decomposition of which corresponds to the thermal regime of reactive extrusion. Di(tert‐butyl peroxy‐isopropyl)‐benzene (P‐14) appeared to meet for the most these requirements for grafting both GMA and IA. Grafting is accompanied by β‐decomposition of the chains irrespective of the type of peroxide and monomer used; hence, the MFI increases. A considerable rise in MFI was observed at a minimum peroxide concentration (0.1wt %). Degradation of PP during modification eases its crystallization from the melt. In this case the crystallization temperature is 5 to 8.5°C higher than of the original PP, and the crystallinity degree increases by 20 to 60%. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 64–72, 2002 相似文献
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Multistream heat exchangers (MHEXs), typically of the plate‐fin or spiral‐wound type, are a key enabler of heat integration in cryogenic processes. Equation‐oriented modeling of MHEXs for flowsheet optimization purposes is challenging, especially when streams undergo phase transformations. Boolean variables are typically used to capture the effect of phase changes, adding considerable difficulty to solving the flowsheet optimization problem. A novel optimization‐oriented MHEX modeling approach that uses a pseudo‐transient approach to rapidly compute stream temperatures without requiring Boolean variables is presented. The model also computes an approximate required heat exchange area to determine the optimal tradeoff between operating and capital expenses. Subsequently, this model is seamlessly integrated in a previously‐introduced pseudo‐transient process modeling and flowsheet optimization framework. Our developments are illustrated with two optimal design case studies, an MHEX representative of air separation operation and a natural gas liquefaction process. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1856–1866, 2015 相似文献
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In this work, a new methodology is developed that describes the viscoelastic scaling of a polymer‐physical foaming agent (PFA) solution in a detailed and internally consistent manner. The approach is new in that while previous researchers have largely focused on scaling down experimentally obtained high pressure polymer‐PFA solution viscosity data onto a master curve for the viscosity of the undiluted polymer melt at a reference temperature and atmospheric pressure, we have generated the shear viscosity data required for our simulations by systematically scaling up the viscosity values obtained from measurements on a pure polymer melt to the desired temperature, pressure, and concentration values characterizing the flow. Simulations have been run for the flow of a polymer‐PFA solution through an extrusion foaming die with an abrupt axisymmetric contraction and good qualitative agreement is obtained with experimental pressure drop measurements obtained previously in our laboratory. The pressure drop rates and temperature rise rates have been estimated at the surface of incipient nucleation. Because of the short residence times in the die for the microcellular foaming process, approximating the flow through the die as a single phase flow in our simulations still gives useful insights into the dynamics of the flow. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 相似文献
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Phasemorphology and mechanical properties of blends of high‐impact polystyrene (HIPS) and polycarbonate (PC) blends compatibilized with a polystyrene (PS) and polyarylate (PAr) (PS–PAr) block copolymer were investigated. Over a broad range of composition from 50/50 through 30/70, HIPS/PC blends formed cocontinuous structures induced by the flow during the extrusion or injection‐molding processes. These cocontinuous phases had heterogeneity between the parallel and perpendicular directions to the flow. The micromorphology in the parallel direction to the flow consisted of stringlike phases, which were highly elongated along the flow. Their longitudinal size was long enough to be longer than 180 μm, while their lateral size was shorter than 5 μm, whereas that in the perpendicular direction to the flow showed a cocontinuous phase with regular spacing due to interconnection or blanching among the stringlike phases. The PS–PAr block copolymer was found to successfully compatibilize the HIPS/PC blends. The lateral size of the stringlike phases could be controlled both by the amount of the PS–PAr block copolymer added and by the shear rate during the extrusion or injection‐molding process without changing their longitudinal size. The HIPS/PC blend compatibilized with 3 wt % of the PS–PAr block copolymer under an average shear rate of 675 s?1 showed a stringlike phase whose lateral size was reduced almost equal to the rubber particle size in HIPS. The tensile modulus and yield stress of the HIPS/PC blends could be explained by the addition rule of each component, while the elongation at break was almost equal to that of PC. These mechanical properties of the HIPS/PC blends can be explained by a parallel connection model independent of the HIPS and PC phases. On the other hand, the toughness factor of the HIPS/PC blends strongly depended on the lateral size of the stringlike phases and the rubber particle size in the HIPS. It was found that the size of the string phases and the rubber particle should be smaller than 1.0 μm to attain a reasonable energy absorbency by blending HIPS and PC. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2347–2360, 2001 相似文献