Polyacrylic desalination membranes. I. Synthesis and characterization

A new class of desalination membranes has been developed. The membranes were prepared by polymerizing mixtures of two hydrophilic monomers (N-methyloacrylamide and acrylic acid), a hydrophobic monomer (ethyl acrylate) and a hydrophobic crosslinking monomer (trimethylol propane trimethacrylate) followed by heat treatment. The membranes were homogeneous, averaging about 6 mils in thickness. They were characterized by measuring water contents and salt distribution coefficients using an immersion technique. The fractional water contents in the membranes varied between 0.16 and 0.44 as the molal salt distribution coefficients increased from ca. 0.22 to 0.43. Increasing contents of the hydrophobic monomer and/or crosslinking monomer led to decreased water and salt contents, as expected. A model is postulated in which the water is assumed to be distributed within the polymer in two forms: (1) as primary water, hydrogen-bonded with hydrophilic polymer groups, and (2) secondary water, imbibed with salt from the external solution into hydrophilic regions or defects within the polymer matrix. It was found that primary water content was approximately constant for all compositions and varied between ca. 2–3 moles of primary water/mole of hydrophilic monomer in the membrane.     

Pervaporative desalination of water using natural zeolite membranes

Several deposits of dense natural clinoptilolite, including one from British Columbia, Canada, have been identified which exhibit both high zeolite content and essentially no macroporosity or intercrystalline voids. Sections of zeolite mineral from the British Columbia deposit were machined into thin membranes and used in the pervaporative desalination of water samples with varying salinity levels, including synthetic seawater. Essentially complete rejection of Mg²⁺ and Ca²⁺ (99.99% and 98.52%) and high levels of rejection of Na⁺ and K⁺ (over 97.5%) were observed when using a synthetic seawater feed at 75 °C and 1 atm feed-side pressure. Water flux through the natural zeolite membranes was dependent on the ion concentration in the feed, the operating temperature and the feed salinity. At 93 °C, water fluxes of 2.5 kg/m²·h and 0.39 kg/m²·h were obtained for feed concentrations of 100 mg/L Na⁺ and 5500 mg/L Na⁺, respectively. The high ion rejection and water flux observed for these rugged and economical natural clinoptilolite membranes indicates their potential utility for desalination applications.     

Formation of ordered macroporous membranes from random copolymers by the breath figure method

In this paper, well-ordered macroporous membranes were fabricated from random poly(styrene-co-acrylonitrile) using tetrahydrofuran as solvent by the breath figure method. Influencing factors were investigated systematically including the relative humidity of atmosphere, the concentration of polymer solutions and the temperature. The pore size and the patterns were affected by these factors. The mechanism of pattern formation was also discussed.     

Hydrophilic hollow fiber membranes for water desalination by the pervaporation method

Hydrophilic ion-exchange membranes based on sulfonated polyethylene hollow fibers were manufactured, and their suitability for a water pervaporation process was studied for possible application in water desalination systems. The effects of the following parameters on the average water flux were determined: membrane properties (diameter (0.4–1.8 mm) and wall thickness (0.05–0.18 mm)); charge density (0.6–1.2 meq g⁻¹); and operating conditions (brine inlet temperature (30–68°C), air sweep velocity (0–6 m s⁻¹), and salt concentration in the feed brine (0–3 M)). A water flux of 0.8–3.3 kg m⁻² h⁻¹ was obtained using this type of hollow fiber with an inlet brine temperature of 25–65°C. It was found that, for our application, the optimal specifications for the ion-exchange hollow fibers were an outside diameter of 1.2 mm, a wall thickness of 0.1 mm, and an ion-charge density of about 1.0 meq g⁻¹. This information is required as basic data for the design of a prototype water desalination system based on a pervaporation system that uses this type of ion-exchange hollow fiber membrane.     

Waste water recycling by ion-exchange: I. Complete desalination

Recycling of waste water by ion-exchange was studied on a bench scale. Secondary municipal effluent, which had undergone lime flocculation, served as a feed for the ion-exchange system. It was found that both the salt concentration and the organic matter content of the effluent could be reduced to produce high quality water, suitable for a wide range of agricultural and industrial applications. Salt concentrations was reduced from 15 meq/l (750 ppm as CaCO³) to about 1 meq/l (50 ppm as CaCO³) and the organic matter, from 70–100 mg/l COD (chemical oxygen demand) to 20 mg/l. The anion exchanger was regenerated with Ca(OH)₂ according to a new method recently developed. The treatment cost for a 2000 m³/day plant was calculated to be 18.0 ¢/m³.     

Novel chitosan-piperazine composite nanofiltration membranes for the desalination of brackish water and seawater

A novel chitosan (CS)-piperazine (PIP) composite nanofiltration (NF) membrane with satisfied characteristics for brackish water and seawater desalination was successfully developed. PIP was mixed with CS during the interfacial polymerization (IP) process to enhance the NF membrane permeate flux. The resultant NF membranes were characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), atomic force microscope (AFM), contact angle. Effects of CS concentration, trimesoyl chloride (TMC) concentration, reaction time and the mixing ratio of CS/PIP on NF membrane performance were investigated thoroughly. When PIP in the aqueous phase monomers reached to 25% (w/w), the PWF (60.6 L·m^?2·h^?1) was synergistically improved by nearly 2 times without a significant reduction of Na₂SO₄ rejection (89.1%). Moreover, the NF membranes possessed excellent performance for the desalination of brackish water and seawater, which showed high potential to be applied in the desalination process for water treatment.     

The cocrystallization behavior of binary blends of isotactic polypropylene and propylene-ethylene random copolymers

Rapidly crystallized blends of metallocene isotactic polypropylene and propylene-ethylene random copolymers with an ethylene content varying from 0.76 to 7 mol% were found to cocrystallize to different degrees depending on the composition of the comonomer and content of copolymer in the blend. The degree of molecular mixing was studied using differential scanning calorimetry and solvent extraction techniques. A high extent of cocrystallization is obtained in the whole composition range of blends with a copolymer having up to ～ 2 mol% of ethylene. The degree of cocrystallization decreases gradually with increasing ethylene content or with increasing copolymer content in the blend. It is found that for ethylene contents as high as 5–7 mol% the copolymer rich blends show partial separate crystallization of the propylene ethylene copolymer. Thus, these crystals were selectively extracted at temperatures just above the dissolution temperature of the pure copolymer. In these blends, the fractional content of segments from the copolymer molecules incorporated in the cocrystal is low, yet it prevents extraction of these molecules at temperatures above the dissolution temperature of the copolymer. The degree of cocrystallization is explained by differences in crystallization kinetics of the pure components. The percentage of extracted material was found to be directly related to the dissolution temperature of the cocrystal which was also found to be a linear function of the inverse of the crystallite thickness. The high extent of cocrystallization observed for these polypropylene blends contrasts with comparable blends of polyethylenes. The blends of linear PE with a copolymer of 4 mol% branch units and higher, form separate crystals even after rapid crystallization.     

Application of random phase approximation to the dynamics of polymer blends and copolymers

The dynamics of melts of homopolymer mixtures and copolymers is studied with RPA. The first cumulant and the zeroth-order time moment of the measured dynamic scattering function S(q,t) are expressed-in terms of their counterparts in the non-interacting system of bare chains. The qualitative behaviour of these quantities as function of the wave number q and the interaction parameter χ_F are obtained using Rouse dynamics for bare chains, and the results are presented graphically as a guide to the interpretation of dynamic scattering experiments on such systems. The q-dependent threshold for spinodal decomposition in the case of copolymers, and the variation of the growth rate of the mean response with q in the unstable regime are also discussed qualitatively in both systems.     

Emerging R&D on membranes and systems for water reuse and desalination

Sustainable production of clean water is a global challenge. While we firmly believe that membrane technologies are one of the most promising solutions to tackle the global water challenges, one must reduce their energy consumption and fouling propensity for broad sustainable applications. In addition, different membranes face various challenges in their specific applications during long-term operations. In this short review,we will summarize the recent progresses in emerging membrane technologies and system integration to advance and sustain water reuse and desalination with discussion on their challenges and perspectives.     

Preparation and characterization of membranes obtained from blends of acrylonitrile copolymers with poly(vinyl alcohol)

New microfiltration and ultrafiltration membranes were obtained using acrylonitrile‐vinyl acetate copolymers in mixture with poly(vinyl alcohol) (PVA). Thus, a blend polymer solution was prepared in dimethylsulfoxide (DMSO) and used to obtain bicomponent polymer membranes by phase inversion. The rheological behavior of the DMSO polymer solutions was, mostly, dilatant at low shear gradients and pseudo plastic with quasi Newtonian tendency at higher gradients. Membranes were characterized by Fourier transform infrared spectrometry (FTIR), optical microscopy, atomic force microscopy, thermal gravimetric analysis‐differential thermal gravimetry, and pure water flux (PWF). FTIR spectra displayed the characteristic bands for acrylonitrile, vinyl acetate, and PVA. The morphology and the porosity can be tailored by the preparation conditions. PVA allows controlling the size of the pores and enables, in principle, to use the resulted membranes as supports for enzyme immobilization. PVA content influences the thermal stability. PWF values depend on the copolymer, on the content in PVA, but also on the coagulation bath composition. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41013.     

Electrospun fiber membranes from blends of poly(vinylidene fluoride) with fouling‐resistant zwitterionic copolymers

Nonwoven super‐hydrophobic fiber membranes have potential applications in oil–water separation and membrane distillation, but fouling negatively impacts both applications. Membranes were prepared from blends comprising poly(vinylidene fluoride) (PVDF) and random zwitterionic copolymers of poly(methyl methacrylate) (PMMA) with sulfobetaine methacrylate (SBMA) or with sulfobetaine‐2‐vinylpyridine (SB2VP). PVDF imparts mechanical strength to the membrane, while the copolymers enhance fouling resistance. Blend composition was varied by controlling the PVDF‐to‐copolymer ratio. Nonwoven fiber membranes were obtained by electrospinning solutions of PVDF and the copolymers in a mixed solvent of N,N‐dimethylacetamide and acetone. The PVDF crystal phases and crystallinities of the blends were studied using wide‐angle X‐ray diffraction and differential scanning calorimetry (DSC). PVDF crystallized preferentially into its polar β‐phase, though its degree of crystallinity was reduced with increased addition of the random copolymers. Thermogravimetry (TG) showed that the degradation temperatures varied systematically with blend composition. PVDF blends with either copolymer showed significant increase of fouling resistance. Membranes prepared from blends containing 10% P(MMA‐ran‐SB2VP) had the highest fouling resistance, with a fivefold decrease in protein adsorption on the surface, compared to homopolymer PVDF. They also exhibited higher pure water flux, and better oil removal in oil–water separation experiments. © 2018 Society of Chemical Industry     

硼掺杂二氧化硅杂化膜的制备及渗透汽化脱盐性能

以1,2-双（三乙氧基硅基）乙烷（BTESE）和硼酸为前体,通过溶胶-凝胶法制备了硼掺杂的二氧化硅（B-BTESE-SiO₂）杂化膜。采用FTIR、XRD、XPS、TEM、SEM等系列表征手段对合成溶胶及膜的结构和形貌进行了分析,结果表明：硼元素成功掺杂进入SiO₂骨架中,形成了水热稳定的B—O—Si键,能明显影响膜表面的微观结构、亲疏水性、膜孔径大小从而提高膜的脱盐性能和稳定性。当溶胶中的H₃BO₃/BTESE比为0.25时所优化制备SiO₂膜的亲水性最强,脱盐过程中活化能最低,传质阻力最小,膜孔径约为0.61 nm,故表现出最佳的脱盐性能。在60℃以3.5%（质量） NaCl溶液为进料液时,该膜的水通量高达16.5 kg·m^-2·h^-1,盐截留率近乎100%,并且表现出优异的长时间稳定性（>168 h）和高浓度盐水溶液[4.2%~15.0%（质量） NaCl]脱盐性能,在海水淡化和高盐废水处理等领域具有潜在的应用前景。     

Blends of propylene-ethylene and propylene-1-butene random copolymers: I. Morphology and structure

Samples of propylene-ethylene (EP) and propylene-(1-butene) (BP) random copolymers with various comonomer content (2-3.1 wt% ethylene, 9.9 wt% 1-butene), were melt-mixed in Brabender internal mixer at various compositions (25/75, 50/50, 75/25). Films of copolymers and blends, as well as of a homopolymer sample (iPP), obtained by compression moulding and with different thermal history were characterized by optical and scanning electron microscopy (OM, SEM), small-angle light scattering (SALS), small- and wide angle X-ray scattering (SAXS, WAXS) and differential scanning calorimetry (DSC). It was found that all copolymers and blends studied crystallized exclusively in monoclinic α-modification forming spherulitic structure in a very broad undercooling range. The average size of spherulites is smaller in the copolymer containing 1-butene as compared to those containing ethylene or to iPP homopolymer, due to enhanced heterogeneous nucleation in BP copolymer. SEM microscopic observations demonstrated that EP and BP copolymers were miscible at all examined compositions and form homogeneous blends. Structural and morphological analysis indicated that the comonomer units are incorporated into growing crystallites in both EP and BP copolymers, while the non-crystallizing material is rejected out of the crystallites. For small concentrations of comonomer some of non-crystallizing species are pushed ahead of the front of growing spherulite into interspherulitic regions. For higher comonomer concentration these species are mostly trapped in intraspherulitic regions. Melting behavior of copolymers reflects the incorporation of comonomer into crystalline phase: melting temperature and crystallinity degree decrease in copolymers and blends as compared to plain iPP.     

Enhanced chlorine-resistant and low biofouling reverse osmosis polyimide-graphene oxide thin film nanocomposite membranes for water desalination

The effect of graphene oxide (GO) loading (0.03, 0.06, 0.09, 0.12, and 0.30 wt%) in the aqueous phase on the performance of reverse osmosis (RO) polyimide (PI) thin film composite (TFC) membrane was investigated. TFC and thin film nanocomposite (TFN) membranes were produced through interfacial polymerization and the imide linkage was confirmed by attenuated total reflection Fourier transform infrared spectroscopy. The spongy-like structure with vertical fingers of RO PI-GO TFN membranes was explored by top-surface and cross-sectional field emission scanning electron microscope (FE-SEM). The roughness of the membranes was determined. All PI-GO TFN membranes exhibited enhanced desalination performance in comparison with PI membranes. Samples with 0.06 wt% GO performed the best with a water flux of 31.80 L/m²/h, salt rejection of 98.8%, and very good antibiofouling properties. This hydrophilic membrane displayed significantly enhanced chlorine-resistance with water flux of 36.3 L/m²/h and salt rejection of 98.5%. This work provides a promising start for designing rapid water permeation PI-GO TFN membranes in water desalination.     

Morphology and mechanical properties in the binary blends of isotactic polypropylene and novel propylene-co-olefin random copolymers with isotactic propylene sequence 1. Ethylene-propylene copolymers

The additive effects of the novel ethylene-propylene random (EP) copolymers with high isotacticity in propylene sequence on the morphology and mechanical properties of isotactic polypropylene (iPP) were investigated using polarized optical microscopy, transmission electron microscopy, dynamic mechanical analysis and tensile behavior. According to these results, the EP copolymers with a propylene content of more than 84 mol% were miscible with iPP, in which the crystallizable PP sequences in these EP copolymers were incorporated in crystal lattice of iPP and the other portions in the EP chains were excluded to the amorphous phases. Consequently, they act as tie molecules linking between adjacent lamellae, leading to enhancement of yield toughness of iPP. On the other hand, the EP copolymers with a propylene-unit content of less than 77 mol% were incompatible with iPP. The iPP/EP blends showed the phase-separated morphology.     

Fabrication of microfiltration membranes from polyisobutylene/polymethylpentene blends

An approach for fabrication of microfiltration membranes by solvent extraction of one of the immiscible components from a polymer blend was developed. Poly(4‐methyl‐1‐pentene) (PMP) was the membrane material, and poly(isobutylene) (PIB) was the extractable component. The PIB content varied in the wide range 0–45 wt%, and all blends could be melted and processed at a temperature of 240 °C. A rheological study demonstrated a pronounced non‐Newtonian behavior of PMP/PIB blends and their very low viscosity due to interlayer slip. With a PMP content of 55 and 60 wt%, it was possible to fabricate microfiltration membranes with a water permeability of 31 and 3.7 m³ m^?2 h^–1 bar^–1, respectively. The microfiltration membranes based on both compositions demonstrated good rejection performance at the level of 93%–98% for submicron particles of phthalocyanine dye with a size of 240 nm. These results indicate that the PMP/PIB system can be utilized for fabrication of filtration membranes by means of 3D printing followed by solvent extraction. © 2019 Society of Chemical Industry     

Appropriate mineral content of desalination water — theory and drinkers' reaction. Part I

This paper aims to establish guidelines for the mineral content of potable water produced by desalination. The optimal ranges of TDS, hardness and specific ionic content are indicated in terms of the available general criteria and standards. The optimal ranges identified are 200–400 mg/l for TDS, 12–20 French degrees of hardness, 30–150 mg/l chloride, 0–100 sodium, 50–75 calcium, 0–10 magnesium, 0–0.05 iron and copper, 0–200 sulphate, 0–35 carbonate. The minimum value for TDS is 120 mg/l. Preliminary results of a taste test conducted in Sydney are also reported.     

A binary interaction model for miscibility of copolymers in blends

Miscibility windows often exist in polymer blend systems when the chemical structure of one of the components is systematically varied, e.g. a random copolymer may be miscible with another polymer when neither limiting homopolymer is. A binary interaction model is developed which explains such behaviour. From this prediction, the general notion is advanced that many cases exist where the net exothermic heat of mixing required for miscibility of high molecular weight polymer mixtures may result from appropriate considerations of both intermolecular and intramolecular interactions of component units without an exothermic interaction existing between any individual pair of units. However, it is shown that for a net exothermic mixing the individual interaction parameters for the pairs of units must differ from those predicted by solubility parameter theory. Moreover, the departures from the geometric mean assumption of the solubility parameter theory need not be large to achieve conditions for miscibility. Several examples of the use of such a model are given including one where the homologous series of aliphatic polyesters is treated as ‘copolymers’ by considering their CH_x and COO constituents as the ‘monomers’.     

Properties of random and block copolymers of butadiene and styrene. I. Dynamic properties and glassy transition temperatures

The effect of monomer sequence on physical properties was investigated for butadienestyrene solution copolymers made by organolithium initiation. The polymers varied from random copolymers of uniform composition along the polymer chain to ideal block polymers of specific block sequence arrangement and included rubbers of intermediate degrees of randomness. Uniform composition random copolymers exhibit a single glass transition temperature and a very narrow dynamic loss peak corresponding to this transition. The glass transition can be predicted from the styrene content and the microstructure of the butadiene portion of the rubber. Random copolymers in which composition varies along the polymer chain, and to some extent between molecules, exhibit a single glass transition, but the dynamic loss peak is broadened. The extent of this broadening is shown to be compatible with the sequence distribution, polymer segments of various compositions losing mobility at different temperatures. This indicates a tendency for association between segments of different temperatures. This indicates a tendency for association between segments of different chains which are similar in composition. Block copolymers display two transitions, corresponding to T_g for each type of block. The position and width of the dynamic loss peaks are related to block length and compositional purity of the blocks.     

Mercapto‐modified copolymers in polymer blends. II. The compatibilization of NBR/EVA blends

Ethylene‐vinyl acetate (EVA) copolymer functionalized with mercapto groups (EVALSH) has been used as compatibilizing agent in nitrile rubber/EVA blends. The tensile strength and elongation at break of the system were measured as a function of the EVALSH content and blend composition. The compatibilization affects the mechanical properties of these blends. The highest improvement of the tensile strength has been achieved in the composition range corresponding to the co‐continuous phase morphology. The co‐continuity of these blends has been studied by both dissolution studies and scanning electron microscopy. The addition of EVALSH as an interfacial modifier did not change the region of co‐continuity but influences the percolation threshold for both dispersed nitrile rubber phase and dispersed EVA phase. From optical microscopy and differential scanning calorimetry analysis, it is possible to assume that the functionalized EVALSH copolymer affects the crystallization of the EVA phase. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 193–202, 2001