Fluid flow modeling in a sulfonated cation‐exchange membrane

Liquid permeation measurements of water, methanol, and 2‐propanol were carried out using a commercial cation‐exchange membrane Nafion‐117 (perfluorinated polyethylene with pendant ether‐linked side chains terminated with sulfonated groups). The experimental permeation data are treated and analyzed using the capillary model, leading to the determination of equivalent pore radius of the membrane structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of acrylic acid‐treated bacterial cellulose cation‐exchange membrane

The feasibility of using bacterial cellulose as a source for environmentally compatible ion‐exchange membranes (IEM) was studied. Bacterial cellulose was modified with cation‐exchangeable acrylic acid (AAc) by UV‐graft polymerization to prepare membranes having ion‐exchange capacity (IEC) and greater structural density. Fourier transform infrared (FTIR) spectra showed that acrylic acids were successfully bound to bacterial cellulose. Morphological changes of acrylic acid‐treated bacterial cellulose were examined through scanning electron microscopy. A dense structure of the membrane increased with increasing UV‐irradiation time. Acrylic‐modified bacterial cellulose membrane showed reasonable mechanical properties, such as tensile strength of 12 MPa and elongation of 6.0%. Also the prepared membranes were comparable to the commercial membrane CMX in terms of the electrochemical properties, ie IEC of 2.5 meq g^?1‐dry mem, membrane electric resistance of 3 ohm cm², and transport number of 0.89. Copyright © 2003 Society of Chemical Industry     

A new cation‐modified Al‐polyacrylamide flocculant for solid–liquid separation in waste drilling fluid

A new cation‐modified Al‐polyacrylamide (CAPAM) flocculant was prepared by the in situ polymerization of acrylamide (AM) and (2‐methacryloyloxyethyl) trimethyl ammonium chloride (DMC) with Al(OH)₃ sol. The optimum preparation conditions were obtained by a one‐factor experimental design: as the amount of AlCl₃ was fixed at 0.025 mol, the polymerization time, polymerization temperature, n(AM) : n(AlCl₃), n(DMC) : n(AlCl₃), and n(K₂S₂O₈) : n(AM) were 4 h, 70°C, 8, 0.9, and 1.82 × 10^?3, respectively. The CAPAM was characterized by thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, and transmission electron microscopy. The solid–liquid separation performance of the CAPAM was evaluated in terms of water content. The CAPAM showed better flocculation performance than cationic polyacrylamide and polyaluminum sulfate at a fixed concentration of 0.3% in waste drilling fluid and tended to perform well in alkaline solution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41641.     

合成4-氨基安替比林类试剂的新途径

4-氨基安替比林属于吡唑酮杂环类化合物,含-CC-、-CO、-NH3个官能团,可望形成具有一定长度、至少含O、N2种配位原子的有机试剂.由于吡唑酮环的稳定性,-CC-、-CO作为反应中心具有一定的局限性,因此有关的反应多发生在4位氨基上.已报道的合成方法有芳香醛与4-氨基安替比林的席夫碱反应、重氮盐反应、成硫脲反应、成酰胺反应等类型.通过4位氨基与卤代烃进行亲核取代,合成新试剂的路线尚未见报道.为此,我们选择芳环上连有硝基的卤代烃与4-氨基安替比林在适当的条件下反应,合成了3种新化合物,对4-氨基安替比林类试剂合成进行了成功的尝试.     

Electrospinning preparation of a graphene oxide nanohybrid proton‐exchange membrane for fuel cells

Proton‐exchange membrane (PEM) is a core component of fuel cells that provides a channel for proton migration and transport. Prevailing PEMs fabricated using well‐established casting techniques have several limitations such as low proton conductivity, high fuel permeability, and poor stability. To overcome these shortcomings, this article introduces a graphene oxide (GO)‐based nanohybrid Nafion nanofiber membrane prepared using a facile electrospinning technique. On the one hand, electrospinning nanofibers provide efficient transport paths for protons, which tremendously enhance the proton conductivity. On the other hand, GO doping in PEM improves the self‐humidification, stabilities (mechanical, thermal, and chemical), and proton conductivity and reduces the fuel permeability. In this research, nanofiber membranes were obtained from Nafion solutions containing 0, 0.1, and 0.2 wt % GO via electrospinning. The morphology, structure, mechanical properties, proton conductivity, water uptake, and swelling properties of the membranes were studied. The results demonstrated that the comprehensive performance of PEM was significantly improved. The new findings may promote the wide application of PEM fuel cells. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46443.     

Characterization of cation‐exchange membrane fouling during bipolar membrane electrodialysis of monosodium glutamate isoelectric supernatant

BACKGROUND: A novel procedure that involved regeneration and recycling of ammonia and sulfuric acid from monosodium glutamate isoelectric supernatant with bipolar membrane electrodialysis (BMED) was proposed. As the performance of the membranes deteriorated during the batch runs, fouling of the cation‐exchange membrane (CEM) in contact with the base cell was studied. RESULTS: During ten consecutive batches of BMED, some operating parameters deteriorated gradually. Using scanning electron microscopy observations, fouling deposits were found on the CEM surface on the base cell side. Using Fourier transform infrared spectroscopy and reversed‐phase high‐performance liquid chromatography (RP‐HPLC), the organic fouling fraction of the CEM foulants was found to contain eight amino acids. Using X‐ray energy‐dispersive analysis, the mineral fouling fraction was shown to be mainly O and Ca elements, and a little Mg. Using X‐ray diffraction, the inorganic foulant was identified as CaCO₃, mainly in the form of calcite and a little aragonite. CONCLUSION: The CEM was subject to membrane fouling consisting of an organic fouling fraction and a mineral fraction. The organic fraction occurred as ions with some positive charges from the isoelectric supernatant and probably existed in the form of amino acids or their peptides. The mineral fraction was mainly CaCO₃ calcite and aragonite, and probably a little amorphous Ca and Mg hydroxides. Copyright © 2011 Society of Chemical Industry     

A new way to conduct enzymatic synthesis in an active membrane using ionic liquids as catalyst support

Several active membranes were prepared by immobilization of Candida antarctica lipase B (CALB) onto the surface of ceramic membranes via three different ionic liquids (ILs): [bmim⁺][PF₆⁻], [emim⁺][NTf₂⁻] and [bmim⁺][NTf₂⁻] and compared to an active membrane obtained by simple enzyme adsorption. The performances of these various membranes were evaluated by studying the synthesis of butyl laurate by the acidolysis between butyl acetate and lauric acid in a hexane/water mixture (98:2, v/v). The results obtained show that all the membranes prepared with or without ILs were active and maintained their activity after several runs and during some months.     

Cation‐exchange kinetics and electrical conductivity studies of an ‘organic‐inorganic’ composite cation‐exchanger: Polypyrrole Th(IV) phosphate

Polypyrrole Th(IV) phosphate, an electrically conducting ‘organic‐inorganic’ cation‐exchange composite material was prepared by the incorporation of an electrically conducting polymer, i.e., polypyrrole, into the matrix of a fibrous type inorganic cation‐exchanger thorium(IV) phosphate. The composite cation‐exchanger has been of interest because of its good ion‐exchange capacity, higher chemical and thermal stability, and high selectivity for heavy metal ions. The temperature dependence of electrical conductivity of this composite system with increasing temperatures was measured on compressed pellets by using four‐in‐line‐probe dc electrical conductivity measuring instrument. The conductivity values lie in the semiconducting region, i.e., in the order of 10^?6 to 10^?4 S cm^?1 that follow the Arrhenius equation. Nernst–Plank equation has been applied to determine some kinetic parameters such as self‐diffusion coefficient (D₀), energy of activation (E_a), and entropy of activation (ΔS*) for Mg(II), Ca(II), Sr(II), Ba(II), Ni(II), Cu(II), Mn(II), and Zn(II) exchange with H⁺ at different temperatures on this composite material. These results are useful for predicting the ion‐exchange process occurring on the surface of this cation‐exchanger. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Physical and potentiometric properties of polyurethane‐based cation‐selective membranes

Lipophilic salts based on tetraphenylborate derivatives [e.g., potassium tetrakis(p‐chlorophenyl)borate (KTpClPB), sodium tetraphenylborate (NaTPB), and cesium tetrakis(3‐methylphenyl)borate are essential ingredients used in the preparation of solvent polymeric cation‐selective membranes. The effects of such lipophilic salts on the physical properties of a polyurethane (PU) matrix comprising 4,4′‐diphenylmethane diisocyanate, 1,4‐butanediol, and poly(tetramethylene ether glycol) were examined. Differential scanning calorimetry measurements revealed that the sodium and potassium salts doped in PU increased the glass‐transition temperatures (T_g) of the matrix, while the film containing cesium salt exhibited slightly decreased T_g. The temperature dependence of the ionic conductivity for PU60 films doped with KTpClPB is well described by the Arrhenius‐type equation, and that doped with NaTPB is described by the Vogel–Tammann–Fulcher (VTF)‐type equation. The temperature dependence of the ionic conductivity on the VTF‐type equation suggests that the transport of sodium ions in the PU60 matrix is more strongly coupled to the soft segmental motion, and potassium ions are decoupled from the polymer host and transported by activated hopping. The effect of added salt on the internal structure of PU membranes was investigated by measuring the ratio between the free and hydrogen‐bonded CO bands at 1703 and 1730 cm⁻¹, respectively. The results showed that the ether oxygens in the soft segment chains are strongly coupled to the potassium or sodium, but much less to cesium. The potentiometric properties of these lipophilic additive doped PU membranes were characterized by incorporating valinomycin and 4‐tert‐butylcalix[4]arene‐tetraacetic acid tetraethylester as potassium‐ and sodium‐selective ionophores, respectively. Their response behavior could be explained by the observed physical characteristics. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 618–625, 2001     

Synthesis and characterization of cation‐exchange membrane based on sulfonated sty/HEA/LMA terpolymer

A cation‐exchange membrane based on a styrene/hydroxyethyl acrylate/lauryl methacrylate (Sty/HEA/LMA) terpolymer was prepared via a postsulfonation reaction for various sulfonation times. Sulfonic groups were introduced into the membrane structure with sulfuric acid as the sulfonating agent and silver sulfate as an initiator in a nitrogen atmosphere. Sulfonated Sty/HEA/LMA terpolymer membranes were characterized by Fourier transform infrared (FTIR) spectrometry and nuclear magnetic resonance as well as by determining the degree of sulfonation (DS), ion‐exchange capacity (IEC), water uptake (WU), and electrical property of the membranes. The presence of sulfonic groups in the sulfonated Sty/HEA/LMA terpolymer was confirmed by FTIR, and the resulting membrane showed an IEC of 1.29 meq/g and an electrical resistance of 0.1 Ω cm². The WU of the prepared membranes increased with the DS at the reaction time. The surface morphology obtained by atomic force microscopy clearly showed an increase of roughness with reaction time. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A new and simple way of preparing polycation‐grafted fibrous cellulose

A new way of producing polycation‐grafted fibrous cellulose for its use as a retention aid in the papermaking process was conceived. It consists of adding, under intense stirring, to a cellulose fibers suspension at a basic pH a cationic polyacrylamide dissolved in water. As the cellulose fiber's surface is negatively charged because of its more or less acid groups, the cationic polymer adsorbs on it. The cationic‐grafted cellulose fibers are very similar to the cellulose fibers used in papermaking, since the polymer is (on a micrometer scale) homogeneously grafted on them as a film. It could so be used to increase the retention of the negatively charged fillers, fibers, and pigments during the process, without altering the properties of the resulting sheet of paper. The amount of polymeric grafts depends on the quantity of anionic groups on fiber's surface and varies monotonically with the grafting temperature and polyacrylamide's concentration in the blend. The grafted fibrous cellulose is well stable, even in drastic media and for lower M_w grafts, and the amount of grafted polymer also depends on the concentration and characteristics of fiber's suspension. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3149–3157, 2006     

Characterization of semi‐interpenetrating polymer network polystyrene cation‐exchange membranes

Polystyrene cation exchange membranes were prepared by a PVC‐based semi‐interpenetrating polymer network (IPN) method. The reaction behaviors during polymerization and sulfonation in the preparation method were investigated. The prepared membranes were characterized in terms of the physical and electrochemical properties. The membranes exhibited reasonable mechanical properties (tensile strength, 13 MPa, and elongation at break, 52%) for an ion‐exchange membrane with the ratio of polystyrene–divinylbenzene (DVB)/poly(vinyl chloride) (PVC) (R_St‐DVB/PVC) of below 0.9. Fourier transform infrared/attenuated total reflectance, differential scanning calorimetry, and scanning electron microscopy studies revealed the formation of a homogeneous membrane. The resulting membrane showed membrane electrical resistance of 2.0 Ω cm² and ion‐exchange capacity of 3.0 meq/g dry membrane. The current–voltage (I–V) curves of the membrane show that the semi‐IPN polystyrene membranes can be properly used at a high current density, and that the distribution of cation‐exchange sites in the membrane was more homogenous than that in commercial membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1488–1496, 2003     

A facile synthesis of a novel three‐phase nanocomposite: Single‐wall carbon nanotube/silver nanohybrid fibers embedded in sulfonated polyaniline

A three‐phase water‐soluble nanocomposite of single wall carbon nanotube/silver nanoparticle hybrid fibers embedded in sulfonated polyaniline has been synthesized by a simple chemical solution mixing process. The nanocomposite has been characterized by high resolution electron microscopy, X‐ray diffractometry, FTIR spectroscopy, Raman spectroscopy, and thermogravimetric analysis. Optical and electrical characteristics of the nanocomposite have been determined by UV–vis absorption spectroscopy, photoluminescence spectroscopy, and four‐probe electrical conductivity measurement. A surface plasmon absorption band obtained around 460 nm indicates the presence of silver nanoparticles in the composite. The optical band gap calculation for sulfonated polyaniline vis‐a‐vis the nanocomposite supported the conductivity measurement. Over 1300 times increase in DC electrical conductivity has been observed for the three‐phase nanocomposite, with a filler loading of 20 wt %, at 306 K. This observation could be explained by Mott's variable range hopping model considering a three‐dimensional conduction. Such a nanocomposite has immense potential for use as a cathode material in lithium‐ion batteries and supercapacitors. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41692.     

Effect of hydrophilic additive and PVC polymerization degree on morphology and electrochemical properties of PVC‐based heterogeneous cation‐exchange membrane

Membrane solution composition is one of the important factors that determine properties of ion‐exchange membranes. In this study, PVC‐based heterogeneous cation‐exchange membranes were prepared by the solution casting method. Effects of a hydrophilic additive [poly(ethylene glycol), PEG400] and degree of polymerization of poly(vinyl chloride) (PVC) on the morphology and electrochemical properties of the cation‐exchange membranes were investigated. The results revealed that the hydrophilic additive can improve membrane properties, including water uptake (Wu), ion‐exchange capacity (IEC), conductivity, and permselectivity. The improvements might be associated with an increase in accessibility of functional sites in the membrane matrix due to a higher hydrophilicity, indicated by a reduction of water contact angle and the greater void fraction shown by scanning electron microscopy. However, the permselectivity slightly decreased when the additive concentration was increased further. Meanwhile, increasing the degree of polymerization and PVC concentration resulted in higher permselectivity and lower conductivity, which might be due to a better resin distribution and a lower void fraction. Overall, the prepared membranes had relatively good conductivities (up to ～2.5 mS/cm) and permselectivities (up to ～0.92). In general the conductivity increased with increasing Wu and IEC, while the permselectivity showed the opposite trends. This could be associated with the efficacy of Donnan exclusion indicated by the IEC/Wu ratio and the Donnan equilibrium constant of the cation (K⁺). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46690.     

Characterization of glow‐discharge–treated cellulose acetate membrane surfaces for single‐layer enzyme electrode studies

Cellulose acetate membranes (CA) were modified by means of plasma polymerization of ethylene diamine (EDA) and n‐butylamine (n‐BA). The motivation for this work was the application of a modified membrane for the single‐layer enzyme electrode. A tubular reactor with the external radiofrequency (13.56 MHz) excitation was used. Surface modification was performed at 5, 10, and 15 W power (at 27 Pa working pressure) for 5, 10, 15 min. Modified surfaces were characterized in detail by FTIR–ATR, XPS (ESCA), contact angle, and enzyme immobilization activity. The best treatment results were obtained for EDA with 5 W and 30 min and 15 W and 10 min. These results are discussed using surface analysis data. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1341–1352, 2001     

A new macroinitiator for the synthesis of triblock copolymers PA12‐b‐PDMS‐b‐PA12

A new PDMS macroinitiator is proposed for the anionic ring‐opening polymerization of lactams. This α,ω‐dicarbamoyloxy caprolactam PDMS macroinitiator was readily obtained in quantitative yield, by an original synthesis scheme in two steps, which involved the scarcely reported reaction of isocyanates with silanol groups. It was then shown that this bifunctional macroinitiator enabled to synthesize triblock copolymers PA12‐b‐PDMS‐b‐PA12 by polymerization of lauryl lactam (LL) at high temperature (200°C) in inert atmosphere under conditions compatible with reactive extrusion processes. Another related high molar weight α,ω‐diacyllactam PDMS macroinitiator was also successfully used in the polymerization of LL under the same conditions, therefore overcoming the limitations formerly reported for this type of macroinitiators during the polymerization ε‐caprolactam (ε‐CL) at a much lower temperature (80°C). Triblock copolymers with a wide range of PA12 /molar weights (M_n: ～ 10,800–250,000 Da) were eventually obtained by using both types of macroinitiators. DMTA and DSC analyses showed that their thermal properties were strongly dependent upon their respective contents in soft and hard blocks. Such triblock copolymers already appear very promising for the highly effective in situ compatibilization of PA12/PDMS blends as shown by recent complementary results obtained in our laboratory. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2818–2831, 2006     

折流杆换热器数值模拟新方法

为了实现对换热器性能的整体数值模拟,阐述了一种"分段模拟,整体综合"的管壳式换热器数值模拟新方法,其核心思想是在对换热器的几何结构及其流道的流体力学和传热特性进行定性分析和结构分类的基础上,对换热器内部流道分段,建立典型流道的完整实体三维模型和网格模型,并且建立分段模型之间的数据联系方案,最后将数值模拟得出的局部数据进行综合处理。     

Simultaneous synthesis of structural‐constrained heat exchanger networks with and without stream splits

This paper presents a comprehensive simultaneous synthesis approach based on stage‐wise superstructure to design cost‐optimal heat exchanger network (HEN). It is well known that the simultaneous synthesis model has very complicated mixed integer nonlinear programming formulations, which are non‐convex, non‐continuous and have many local optima. Up till now, it cannot be expected that an algorithm can find, in polynomial time, the global solution to the simultaneous synthesis problem of HEN. In order to reduce computational complexity, some simplified assumptions for structures, such as no stream splits, stream splits with isothermal mixing, no stream split flowing through more than one exchanger, etc, are adopted to prune the search space at the expense of neglecting certain important alternatives in the network configuration. In this work, a flexible stage‐wise superstructure is proposed to control the solution performance and search space efficiently. At each stage of the superstructure, with or without stream splits is determined at random or by the experience of designers. In this way, various candidate series and split network designs featuring the lowest annual cost can be found. Moreover, an efficient two‐level optimisation algorithm is employed for solving the presented model utilising genetic algorithm and particle swarm optimisation algorithm. Three case studies are presented to show the applicability of the proposed methodology. In addition, the results show that the new approach is able to find more economical networks than those generated by other methods. © 2012 Canadian Society for Chemical Engineering     

A hybrid optimization strategy for simultaneous synthesis of heat exchanger network

The heat exchanger network synthesis problem often leads to large-scale non-convex mixed integer nonlinear programming formulations that contain many discrete and continuous variables, as well as nonlinear objective function or nonlinear constraints. In this paper, a novel method consisting of genetic algorithm and particle swarm optimization algorithm is proposed for simultaneous synthesis problem of heat exchanger networks. The simultaneous synthesis problem is solved in the following two levels: in the upper level, the network structures are generated randomly and reproduced using genetic algorithm; and in the lower level, heat load of units and stream-split heat flows are optimized through particle swarm optimization algorithm. The proposed approach is tested on four benchmark problems, and the obtained solutions are compared with those published in previous literature. The results of this study prove that the presented method is effective in obtaining the approximate optimal network with minimum total annual cost as performance index.