Studies on syntheses and permeabilities of special polymer membranes. VI. Permeation characteristics of cellulose nitrate membranes and cellulose membranes

The permeation characteristics of cellulose nitrate membranes and cellulose membranes were investigated using aqueous solutions of poly(ethylene glycol) as feed. To gain cellulose membranes the nitro groups in cellulose nitrate were converted to hydroxyl groups. It was found that cellulose nitrate membranes separate poly(ethylene glycol) 6000 but not any cellulose membrane did separate poly(ethylene glycol) 20 000.     

Recent progress of two-dimensional nanosheet membranes and composite membranes for separation applications

Two-dimensional (2D) materials have emerged as a class of promising materials to prepare high-performance 2D membranes for various separation applications. The precise control of the interlayer nanochannel/sub-nanochannel between nanosheets or the pore size of nanosheets within 2D membranes enables 2D membranes to achieve promising molecular sieving performance. To date, many 2D membranes with high permeability and high selectivity have been reported, exhibiting high separation performance. This review presents the development, progress, and recent breakthrough of different types of 2D membranes, including membranes based on porous and non-porous 2D nanosheets for various separations. Separation mechanism of 2D membranes and their fabrication methods are also reviewed. Last but not the least, challenges and future directions of 2D membranes for wide utilization are discussed in brief.     

Preparation of thermosensitive cellophane-graft-N-isopropylacrylamide copolymer membranes and permeation of solutes through the membranes

Thermosensitive membranes with high mechanical strength were prepared by heterogeneous graft copolymerization of N-isopropylacrylamide (NIPAAm) onto cellophane in a nitric acid solution using cerium ammonium nitrate as an initiator, and the permeation behavior of solutes such as lithium chloride and poly(ethylene glycol)s (PEGs) through the membranes at various temperatures was investigated. The degree of graft copolymerization of NIPAAm on cellophane depended on temperature, time, initiator concentration, and so on. The copolymer membranes having a high content of the NIPAAm moiety could be obtained at 25°C for 24 h. The permeation of Li⁺ through the membranes was affected by temperature, i.e., the permeation rate of Li⁺ increased with increasing temperature up to 32°C and then decreased rapidly above 35°C. The permeation rate of Li⁺ through the copolymer membranes at 40°C decreased considerably, but that at 20°C decreased slightly with an increasing amount of the NIPAAm moiety in the membranes. The permeation rate of PEGs with a molecular weight more than 1000 through the cellophane-g-NIPPAm copolymer membranes was considerably suppressed and only the permeation rate of PEG300 increased with increasing temperature up to 35°C and then decreased at 40°C. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 209–216, 1997     

Modification of carbon membranes and preparation of carbon-zeolite composite membranes with zeolite growth

A novel method for the modification of carbon membranes was developed by zeolite growth on the surface of porous carbon tubes using a hydrothermal synthesis method and carbon-zeolite composite membranes were successfully obtained. Zeolite seeds for the zeolite growth were introduced to the inner surface of the tubes by using a slip-casting technique in 1 wt.% seed ethanol solution and continuous and highly intergrown zeolite layers on the seeded tubes were formed by subsequent hydrothermal synthesis. Different types of zeolite layers can be grown on porous carbon tubes by using different types of zeolite seeds. Without zeolite seeds, a zeolite layer could not be formed on the carbon surface. SEM, XRD and pure gas permeation characterization indicates that the carbon-zeolite membranes are continuous and defect-free.     

Phase diagrams and membranes

Over the past two decades, membrane technology has found application in a variety of industries, ranging from water desalination to gas separations. These new applications have come about because of the availability of high-performance, permselective membranes. A key element in the development of these new membranes has been the discovery of “skinned” or asymmetric membranes. These membranes typically have an effective thickness on the order of 0.1 to 0.2 μm. They are essentially composite structures, consisting of a dense skin supported by a finely porous substrate. We now recognize that an understanding of the mechanism of formation of these asym-metric membranes is available through binary and ternary phase diagrams. Membranes for microfiltration, ultrafiltration, reverse osmosis, and gas separations are now routinely produced by some form of “phase inversion” process, amenable to explanation through phase diagram considerations.     

Catalysis with membranes or catalytic membranes?

This paper considers the application of inorganic membranes in conjunction with catalysis and discusses attempts which have been made to affect changes in the yields and product distributions in a number of catalytic reactions with a number of different conformations of catalyst and membrane. Various possible reactor conformations are first considered and then some results obtained for catalytically-active perm-selective membranes are presented to illustrate some of the problems encountered with such membranes. The use of non-perm-selective wall-and-tube reactors is then considered. Finally, the results of model calculations are presented which show that the most promising confirmation for the use of perm-selective membranes is one in which the membrane and catalyst are in separate units and external recirculation of reactants and products is carried out.     

Preparation of plasma-polymerized membranes from fluoroalkyl acrylates and methacrylates and gas permeability through the membranes

Summary Plasma-polymerized membranes were prepared from fluoroalkyl acrylates and methacrylates by two different directions of monomer injection and the permeation rates of O₂ and n₂ through the membranes were investigated. The chemical structure and composition of the plasmapolymerized membranes varied significantly by the direction of monomer injection. The optimum plasma conditions to yield maximum gas separation characteristics was obtained by the remote plasma excitation at the W/FM value of 20 J/mg, where W is the discharge power, F is the monomer flow rate and M is the molecular weight of the monomer.     

渗透汽化膜的制备及其应用进展

渗透汽化（pervaportion, PV）作为一种新颖的分离技术在工业范围内得以应用,至关重要的是它在恒沸混合物、近沸混合物分离方面的显著优势。相比分馏、精馏、萃取等传统分离方法,渗透汽化技术具有经济、高效、便于管理的优点,但目前缺少优质的渗透汽化膜材料和先进的膜制备方法。本文综述了近年来渗透汽化技术以及渗透汽化膜的研究现状,首先介绍了PV技术的分离机理、PV膜的制备方法、PV技术在工业上的应用领域等,并重点讨论了料液温度、料液浓度、料液流速、膜上下游蒸汽压差、膜材料等关键因素对渗透汽化分离性能的影响。文中提出未来渗透汽化技术应在膜材料方面积极探索,选用聚合物为材料,并结合先进的膜制备方法来进一步降低膜的厚度,从而明显地提高膜渗透通量。     

Synthesis and characterization of polyethersulfone membranes

Phase inversion method was used to prepare polyethersulfone (PES) ultrafiltration (UF) membranes. Polyethylene glycol (PEG); N, N-dimethyl formamide (DMF) and water were utilized as pore-forming additive, solvent and non-solvent, respectively. Effects of PES and PEG concentrations in the casting solution, PEG molecular weight (MW) and coagulation bath temperature (CBT) on morphology of the prepared membranes were investigated. Taguchi experimental design was applied to run a minimum number of experiments. 18 membranes were synthesized and their permeation and rejection properties to pure water and human serum albumin (HSA) solution were studied. It was found out that increasing PEG concentration, PEG MW and CBT, accelerates diffusional exchange rate of solvent (DMF) and non-solvent (water) and consequently facilitates formation of macrovoids in the membrane structure. The results showed that, increasing PES concentration, however, slows down the demixing process. This prevents instantaneous growth of nucleuses in the membrane structure. Hence, a large number of small nucleuses are created and distributed throughout the polymer film and denser membranes are synthesized. A trade-off between water permeation and HSA rejection was involved, with membranes having higher water permeation exhibited lower HSA rejection, and vice versa. Hence, optimizing preparation variables to achieve high pure water permeation flux along with reasonable HSA rejection was inevitable. Analysis of variance (ANOVA) showed that all parameters have significant effects on the response (water flux and HSA rejection). However, CBT and PES concentration were more influential factors than PEG concentration and MW on the responses.     

Photochemically modified thin-film composite membranes. I. Acid and ester membranes

A photochemically active membrane was made by the interfacial copolymerization of 3-diazo-4-oxo-3,4-dihydro-1,6-naphthalene disulfonylchloride and naphthalene-1,3,6-trisulfonylchloride with 1,6-hexanediamine. The chemical functionality of the membrane surface was modified on irradiation of the surface of the membrane in the presence of various nucleophiles. Surface analysis techniques of attenuated total reflectance-Fourier transform infrared and scanning electron microscopy have been used to monitor the changes in the chemistry of the thin-film composite membranes. The surface functionality of the membrane was shown to affect the reverse osmosis flux and separation of various solutes. Results for membranes which have been converted to acid, and ester forms are presented. © 1993 John Wiley & Sons, Inc.     

Selective permeability of PVA membranes. I. Radiation-crosslinked membranes

The water and salt transport properties of ionizing radiation crosslinked poly(vinyl alcohol) (PVA) membranes were investigated. The studied membranes showed high permeabilities and low selectivities for both water and salt. The results were found to be in accord with a modified solution–diffusion model for transport across the membranes, in which pressure-dependent permeability coefficients are employed.     

Selective permeability of PVA membranes. II. Heat-treated membranes

The water and salt transport properties of untreated and heat-treated poly(vinyl alcohol) (PVA) membranes were investigated. Water and salt permeabilities decreased abruptly as a result of heat treatment. The effect of heat treatment on the water and salt transport in PVA is expressed mainly by changes in the activation energies of the corresponding permeability coefficients. Due to the fact that the decrease in the salt permeability with heat treatment was considerably greater than the decrease in the water permeability, a pronounced improvement in the salt rejection of PVA membranes was found as a result of heat treatment.     

Permselectivity of ion exchange membranes from sorption data and its relation to nonuniformity of membranes

Transport numbers of the hydrogen ion within the cation permselective membranes equilibrated with sulfuric acid solutions have been calculated employing sorption data. Calculations were performed according to the equation of Arnold and Swift. The validity of this equation and resulting t _+(app) has been verified by independent determination of transport numbers by the EMF method. The equation has been derived which relates the permselectivity of membranes to the parameters describing their nonuniformity, i. e. to the nonuniformity factor Z and volume fraction of nonselective domains (Δ?).     

正渗透膜技术及其应用

<正>渗透技术为水资源和环境问题提供了低能耗、高效率的解决方法,同时正渗透技术还是一种绿色能源技术,可以将自然界中常见的渗透能直接转化为电能。近年来,正渗透技术在国际上得到了广泛的重视,探索和研究工作正不断发展。本文就正渗透技术中的膜材料最新进展和正渗透技术在海水淡化、绿色能源、污水回用、航空航天、食品浓缩等行业的应用进行了详实的综述,并展望了我国在该领域的发展前景。     

Self-standing nanoparticle membranes and capsules

We perform coarse-grained molecular dynamics simulations of self-standing nanoparticle membranes observed in recent experiments (K. E. Mueggenburg et al., Nat. Mater., 2007, 6, 656). In order to make our simulations feasible, we model 2-3 times smaller gold nanoparticles (core radius of r(core) ≈ 0.8 nm) covered with alkanethiol ligands (length of l(ligand) ≈ 0.5-2.6 nm). We study the structure, stability, and mechanical properties of these membranes and show that these characteristics are controlled by the ratio of R(LC) = l(ligand)/r(core). For R(LC) ≈ 0.6, the ligated nanoparticles form well ordered monolayers with hexagonal packing, in agreement with the experiments (R(LC) ≈ 0.44). For R(LC) ≈ 1.6, the nanoparticles form less organized multilayers, which are more stable and flexible. We show that these membranes could potentially form stable capsules for molecular storage and delivery.     

均孔膜

为进一步提高膜分离过程的精度,同步提升选择性和渗透性,分离膜孔径均一化是必然途径,均孔膜因此应运而生。首先讨论了均孔膜概念及其结构特点。均孔膜是孔径均一、孔道形状一致且垂直贯穿整个分离层的分离膜。然后介绍了制备均孔结构的不同方法,探讨了这些方法的优势和固有缺陷。利用嵌段共聚物微相分离的特性,可获取规整排列的、孔径在10～50 nm范围内连续可调的均孔结构,具有方法简便、无须特殊设备、易于放大制备等突出优势,是最有可能实现规模化生产的均孔膜制备方法。着重介绍了两亲嵌段共聚物选择性溶胀成孔方法的原理及其在孔径和孔型调节(圆柱孔、槽形孔)、自发永久亲水和制备过程绿色少污染等方面的特点。最后,讨论了嵌段共聚物基均孔膜发展的瓶颈,并指出应加强在孔径小于10 nm的均孔膜、孔型调变和应用领域等方面的研究。认为均孔膜不仅是一种新结构的分离膜,更代表着膜分离的发展方向。     

Inorganic membranes and membrane reactors

The inorganic membrane reactor is a combined unit operation of chemical reactions and membrane separations. By having a membrane reactor, the downstream separation load can be reduced. Also, the yields can be increased and conversion can be improved for equilibrium limited reactions. However, many of the industrial chemical reactions take place at high temperature that the conventional polymeric membranes cannot withstand. A great deal of research has been done recently to develop ion-conducting ceramic membranes. Many of these have been successfully employed to form membrane reactors for many industrially relevant chemical reactions, such as hydrogenation, dehydrogenation, oxidation, coupled reactions, and decomposition reactions. An overview is given for the area of inorganic membrane preparations and membrane reactors. Many examples of petrochemical interests are presented, including hydrocarbon conversions and fuel cell applications.     

Oxidative degradation of polyamide reverse osmosis membranes: Studies of molecular model compounds and selected membranes

Selected aromatic amides were used to model the chemical reactivity of aromatic polyamides found in thin‐film composite reverse osmosis (RO) membranes. Chlorination and possible amide bond cleavage of aromatic amides upon exposure to aqueous chlorine, which can lead to membrane failure, were investigated. Correlations are made of the available chlorine concentration, pH, and exposure time with chemical changes in the model compounds. From the observed reactivity trends, insights are obtained into the mechanism of RO membrane performance loss upon chlorine exposure. Two chemical pathways for degradation are shown, one at constant pH and another that is pH‐history dependent. An alternative strategy is presented for the design of chlorine‐resistant RO membranes, and an initial performance study of RO membranes incorporating this strategy is reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1173–1184, 2003