Protein separation by cellulose acetate/sulfonated poly(ether imide) blend ultrafiltration membranes

A process for purifying aqueous solutions containing macromolecular proteins such as bovine serum albumin (BSA), egg albumin (EA), pepsin, and trypsin has been investigated. Protein removal from food and biorelated industrial waste streams are gaining increased visibility due to environmental concern and saving precious materials. Ultrafiltration (UF) processes are largely being applied for protein separation from aqueous streams. In this work, an attempt has been made to separate the valuable proteins using cellulose acetate (CA)/sulfonated poly(ether imide) (SPEI) blend UF membranes prepared in the absence and presence of the additive, polyethyleneglycol (PEG600) in various compositions. The blend membranes were subjected to the determination of pore statistics and molecular weight cut‐off (MWCO). Porosity and pore size of the membranes increased with increasing concentrations of SPEI and PEG600 in the casting solution. Similarly, the MWCOs of the blend membranes ranged from 20 to greater than 69 kDa, depending on the various polymer blend compositions. Surface morphology of the blend membranes were analyzed using scanning electron microscopy. Studies were carried out to find the rejection and permeate flux of proteins. On increasing the concentration of SPEI and PEG600, the rejection of proteins is decreasing, whereas the permeate flux has an increasing trend. The effect of hydrophilicity of SPEI on fouling of protein for CA/SPEI blend membranes was also discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Asymmetric cellulose acetate dialysis membranes: Synthesis,characterization, and performance

Cellulose acetate (CA) is highly comparable to other synthetic polymer materials and is effective in the hemodialysis process. In this work, asymmetric CA membranes were synthesized with the phase‐inversion method. CA with a molecular weight of 52,000, poly(ethylene glycol) (PEG) with a molecular weight of 400, and 1‐methyl‐2‐pyrrolidone (NMP) were used as the polymer, additive, and solvent, respectively. The effects of the CA and PEG concentrations and coagulation bath temperature (CBT) on the morphology, pure water permeability (PWP), insulin/human serum albumin (HSA) transmission, and finally thermal and chemical stability of the prepared membranes were determined and investigated. In general, increasing the PEG concentration and CBT and reducing the CA concentration resulted in increased PWP and insulin/HSA transmission. Also, these variations facilitated the formation of macrovoids in the membrane sublayer. On the other hand, increasing the PEG and CA concentrations and reducing CBT resulted in increased thermal and chemical stability of the prepared membranes. Also, ratios of 15.5/10/74.5 and 17.5/10/72.5 (w/w) for the CA/PEG/NMP casting solutions and their immersion into coagulation baths with CBTs of 0 and 25°C, respectively, resulted in the preparation of membranes that had not only optimum sieving properties and higher PWP but also thermal and chemical stability better than that of conventional CA hemodialysis membranes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Diffusion of poly(vinylpyrrolidone) through cellulose ester membranes

Diffusion coefficients of poly(vinylpyrrolidone) in aqueous solutions were ascertained by the diaphragm method as a function of molecular weight and temperature using mixed cellulose ester (Millipore) membranes. The results agree satisfactorily with diffusion coefficients obtained by other methods. Separation of polymer according to molecular size takes place on diffusion as a function of membrane pore diameter. Also, interaction between the polymer and membrane has been observed resulting in a distribution coefficient between solution and membrane larger than 1. The energy and entropy of activation, repectively, increase with polymer chain length, and their magnitudes are in agreement with the view that segment mobility is operative for the diffusion process.     

Cellulose acetate and sulfonated polysulfone blend ultrafiltration membranes. I. Preparation and characterization

Modification of polymeric membrane materials by incorporation of hydrophilicity results in membranes with low fouling behavior and high flux. Hence, Polysulfone was functionalized by sulfonation and ultrafiltration membranes were prepared based on sulfonated polysulfone and cellulose acetate in various blend compositions. Polyethyleneglycol 600 was employed as a nonsolvent additive in various concentrations to the casting solution to improve the ultrafiltration performance of the resulting membranes. The total polymer concentration, cellulose acetate, and sulfonated polysulfone polymer blend composition, additive concentration, and its compatibility with polymer blends were optimized. The membranes prepared were characterized in terms of compaction, pure water flux, membrane resistance, and water content. The compaction takes place within 3–4 h for all the membranes. The pure water flux is determined largely by the composition of sulfonated polysulfone and concentration of additive. Membrane resistance is inversely proportional to pure water flux, and water content is proportional to pure water flux for all the membranes. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1749–1761, 2002     

Effect of poly(vinyl pyrrolidone) concentration and coagulation bath temperature on the morphology,permeability, and thermal stability of asymmetric cellulose acetate membranes

Cellulose acetate (CA) is widely used in membrane processes. In this study, CA (weight‐average molecular weight = 52,000) was mixed with poly(vinyl pyrrolidone) (PVP; weight‐average molecular weight = 15,000) as an additive in 1‐methyl‐2‐pyrrolidone as a solvent. The phase‐inversion method was used for the preparation of flat‐sheet membranes. The effects of PVP concentration and coagulation bath temperature (CBT) on the morphology, pure water permeation flux, and thermal stability of the prepared membranes were studied and are discussed in this article. The solute rejection of the developed CA membranes was quantified with an insulin protein solution. The results showed that an increase in the CBT levels from 0 to 23°C along with an increase in the PVP concentration in the cast film from 0 to 1.5 wt % resulted in an increase in the macrovoid formation in the membrane sublayer, an increase in the pure water flux (PWF), and a decrease in insulin rejection. Further increases in the PVP concentration from 1.5 to 3, 6, and 9 wt % resulted in gradual suppression of the macrovoid formation, a decrease in PWF, and an increase in insulin rejection. Higher PVP concentrations and lower CBT levels also appeared to result in higher glass‐transition temperatures. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of antifouling poly(vinylidene fluoride) blended membranes

Poly(vinylidene fluoride) (PVDF) membranes have been widely used in microfiltration and ultrafiltration because of their excellent chemical resistance and thermal properties. However, PVDF membranes have exhibited severe membrane fouling because of their hydrophobic properties. In this study, we investigated the antifouling properties of PVDF blended membranes. Antifouling PVDF blended membranes were prepared with a PVDF‐g‐poly(ethylene glycol) methyl ether methacrylate (POEM) graft copolymer. The PVDF‐g‐POEM graft copolymer was synthesized by the atom transfer radical polymerization (ATRP) method. The chemical structure and properties of the synthesized PVDF‐g‐POEM graft copolymer were determined by NMR, Fourier transform infrared spectroscopy, and gel permeation chromatography. To investigate the antifouling properties of the membranes, we prepared microfiltration membranes by using the phase‐inversion method, which uses various PVDF/PVDF‐g‐POEM concentrations in dope solutions. The pure water permeabilities were obtained at various pressures. The PVDF/PVDF‐g‐POEM blended membranes exhibited no irreversible fouling in the dead‐end filtration of foulants, including bovine serum albumin, sodium alginate, and Escherichia coli broth. However, the hydrophobic PVDF membrane exhibited severe fouling in comparison with the PVDF/PVDF‐g‐POEM blended membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚醚砜/磺化聚醚醚酮共混膜的制备和性能

采用流延法制备了聚醚砜(PES)含量不同的PES/磺化聚醚醚酮(SPEEK)共混膜。PES与SPEEK具有良好的相容性。所制备PES/SPEEK共混膜的含水率、溶胀度和甲醇透过系数均随PES含量的增加而降低。虽然共混膜的质子传导性能有所降低.但阻醇性能和溶胀性能提高,这说明PES/SPEEK共混膜是一种很好的直接甲醇燃料电池用固体高分子电解质膜材料。     

Phase structure in the blend of atactic poly(vinyl alcohol) with atactic poly(vinyl alcohol‐block‐vinyl acetate)

An almost fully saponified atactic poly(vinyl alcohol) and an atactic poly(vinyl alcohol‐block‐vinyl acetate) of which degree of saponification is 89 mol % were blended by a solution casting method. The phase structure of the blend film was analyzed by optical microscopy, ¹³C‐NMR, and differential scanning calorimetry. The most remarkable structure of the blend was composed of cylindrical domains penetrating the film. The swelling behavior of the blend films was also investigated in the dimethylsulfoxide and water mixed solvents to find differences in solubility and diffusion behavior between the matrix and the domain. The cylindrical domains could be selectively dissolved away in water and the film became porous. We tried to change the size of the cylindrical domain with various film preparation conditions. This aimed to turn the film into the useful filter membrane. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1807–1815, 2002     

Cellulose acetate–poly(ether sulfone) blend ultrafiltration membranes. II. Application studies

Ultrafiltration membranes are largely applied as macromolecular solutes and heavy‐metal‐ion separation from aqueous streams. Cellulose acetate and poly(ether sulfone) blend ultrafiltration membranes were prepared by the precipitation phase‐inversion technique in 100/0, 95/5, 85/15, and 75/25% polymer blend compositions in the absence and presence of a polymeric additive, poly(ethylene glycol) 600, at different additive concentrations and were used for the rejection of proteins trypsin, pepsin, egg albumin, and bovine serum albumin; a maximum of 94% rejection was achieved. The toxic heavy metal ions copper, nickel, and cadmium from dilute aqueous solutions were subjected to rejection by the blend membranes by complexation of the ions with the water‐soluble polymeric ligand, polyethyleneimine (PEI). Permeate flux studies of proteins and metal ions were performed simultaneously with the rejection experiments. The atomic absorption spectra results reveal maximum rejection for copper complex and a minimum rejection of about 60% for the cadmium complex. The rejection and permeate flux of the blend membranes were compared with those of pure cellulose acetate membranes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3659–3665, 2004     

Gas permeabilities of cellulose nitrate/poly(ethylene glycol) blend membranes

The permeability (P) of cellulose nitrate (CN)/poly(ethylene glycol) (PEG) blend membranes for N₂, O₂, and CO₂ has been measured as a function of film composition. The system CN/PEG-300 showed excellent miscibility, and films of the composition from 100/0 to 50/50 could be used for permeability measurements. P for each gas has been found to be almost constant or rather slightly lowered up to ca. 20 wt % PEG-300 content and then increased appreciably with increasing fraction of PEG. The increment of permeability was most remarkable for CO₂, and hence the permselectivity for CO₂ was considerably enhanced. Such a behavior of P has been found to be attributable to the plasticizing effect of PEG molecule lowering the glass transition temperature of the blend polymers. The effect of the molecular weight of PEG and that of closed voids generated in glassy blend membranes fabricated from acetone cast on gas permeabilities have been also discussed.     

Effects of nucleating agents on the morphologies and performances of poly(vinylidene fluoride) microporous membranes via thermally induced phase separation

The effects of nucleating agents on the morphology and performance of poly(vinylidene fluoride) (PVDF) microporous membranes via thermally induced phase separation were investigated. The nucleating agents studied were dicyclohexyl benzene amide (TMB‐5), 2,2‐methylene bis(4,6‐tertiary butyl phenol) sodium phosphate (TMP‐1), and 1,3 : 2,4‐di‐p‐methylbenzylidene sorbitol (DM–LO). Light transmittance experiments and differential scanning calorimetry (DSC) were performed to obtain phase diagrams of PVDF/tributyl citrate/di(2‐ethylhexyl) phthalate/nucleating agent doped solutions. The morphology and performance of the prepared PVDF microporous membranes were characterized with scanning electron microscopy and microfiltration experiments. The results show that the thermodynamics of liquid–liquid phase separation were not affected by the addition of the nucleating agents, but solid–liquid phase separation was influenced. The system with 0.3 wt % TMB‐5 had the fastest crystallization rate and a better nucleation ability. The PVDF microporous membranes had a partly closed, lacy bicontinuous structure with TMP‐1 and DM–LO, whereas the membrane with 0.3 wt % TMB‐5 had an interconnected bicontinuous structure. The pore size distribution became narrower with the addition of nucleating agent. With 0.3 wt % TMB‐5, the membrane had the minimum mean pore size (0.095 μm), a porosity of 80.3%, and a pure water flux of 270 L·m^?2·h^?1; these values were higher than those of the pure PVDF membrane. The performances of the membranes decreased with additions of TMB‐5 of greater than 0.3 wt %. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

烷基聚噻吩和聚醋酸乙烯酯梯度构造膜的自组装过程及导电性能研究

以烷基聚噻吩（PAT-6）和聚醋酸乙烯酯（PVAc）共混液为原料通过浇注方式制膜。通过控制干躁速度,在膜厚度方向可自组装形成梯度膜。沿膜厚方向对导电性进行检测,发现导电性随着PAT-6组分的增加而增强。     

Preparation of polyelectrolyte complex membranes based on sodium cellulose sulfate and poly(dimethyldiallylammonium chloride) and its permeability properties

In this study, polyelectrolyte complex (PELC) membranes prepared by the simultaneous interfacial reaction between aqueous solutions of sodium cellulose sulfate (NaCS) as polyanion and poly(dimethyldiallylammonium chloride) (PDMDAAC) as polycation were proposed. The preparation conditions were optimized. The influence of two important factors, molecular weight (MW) of PDMDAAC and reaction time on the membrane formation procedure and permeability was investigated. Membranes with the preparation conditions as NaCS 3.5% (w/v), PDMDAAC (MW = 200–350 kDa) 7.0% (w/v), the reaction time 30 min, hold a favorable performance, and steady state in water flux experiment. To testify the feasibility of the membrane used in salt separation, membrane performances and selectivity of the inorganic salts as well as their relations to the preparation conditions, the operation parameters, the species of inorganic salts, etc., were investigated in the pressure‐driven experiments. The results showed that this single‐layer PELC membrane afforded higher rejections of divalent ions (SO) to that of monovalent ions (Cl⁻), which indicated the potential application of this membrane system in the salt rejection process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Fibrous membranes of cellulose acetate and poly(vinyl pyrrolidone) by electrospinning method: Preparation and characterization

Fibrous membranes of cellulose acetate (CA), poly(vinyl pyrrolidone) (PVP) and composite membranes of these polymers, were obtained by the electrospinning method. Using systematic method, the optimal conditions for preparation of fibrous membranes were found. Both CA and PVP a concentration of 8% weight was found. The CA was dissolved in a acetone:water solution, volume ratio 80 : 20 and the PVP is dissolved in ethanol:water solution, ratio volume 85 : 15. The flow rate for both polymers was 1.5 mL h^?1. The same applied voltage value and the distance between the needle and collection plate were for polymer both, 15 kV and 15 cm respectively. The morphology of fibrous membranes and composite membranes were evaluated by scanning electron microscopy (SEM). The CA fibers showed ribon morphology, while the PVP fibers were cilindric, in both cases with diameters in the micrometer range. Thermogravimetric analysis showed that CA had a complete degradation to 445°C, while the fibrous membranes PVP required a value of temperature for degradation of up to 571°C. Fibrous composite membrane PVP/CA/PVP shows a higher value of strain at break (%), and a lower value of tensile strength (MPa) compared to CA/PVP/CA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of compatibility of cellulose acetate/poly(vinyl butyral) blends on pervaporation behavior of their membranes for methanol/methyl tert‐butyl ether mixture

Binary blends and their blend membranes of cellulose acetate (CA) and poly(vinyl butyral) (PVB) are prepared by solution blending. The compatibility of the blends is studied by viscometry and Fourier transform IR. It is found that the incompatibility of the blends is markedly manifested when the weight fraction of PVB in the CA/PVB blends (W_PVB) is located at higher regions. On the other hand, compatibility is obtained for the CA/PVB blends with lower W_PVB values, especially at about 0.2. This compatibility is believed to play a key role in the good pervaporation behavior of CA/PVB blend membranes. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2434–2439, 2002     

Preparation and characterization of konjac glucomannan/poly(diallydimethylammonium chloride) blend films

A novel preservative film was prepared by blending konjac glucomannan (KGM) and poly (diallydimethylammonium chloride) (PDADMAC) in aqueous system. The effects of PDADMAC content on the miscibility, morphology, thermal stability, and mechanical properties of the blend films were investigated by density determination, scanning electron microscopy (SEM), attenuated total reflection infrared spectroscopy (ATR‐IR), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and tensile tests. The results of the density determination predicted that the blends of KGM and PDADMAC were miscible when the PDADMAC content was less than 70 wt %. Moreover, SEM and XRD confirmed the result. ATR‐IR showed that strong intermolecular hydrogen bonds interaction occurred between the negative charge groups of KGM and the quaternary ammonium groups of PDADMAC in the blends. The tensile strength and the break elongation of the blends were improved largely to 106.5 MPa and 32.04%, when the PDADMAC content was 20 wt %. The thermal stability of the blends was higher than pure KGM. Results from the film‐coating preservation experiments with lichi and grapes showed that the blend film had excellent water‐holding and preservative ability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation of polyethyleneglycol (PEG) and cellulose acetate (CA) blend membranes and their gas permeabilities

Miscible blend membranes containing 10 wt % PEG of low molecular weight 200, 600, 2000, and 6000, and 10 wt %, 20 wt %, 30 wt %, 40 wt %, 50 wt %, and 60 wt % of molecular weight 20,000 were prepared to investigate the effect of PEG on gas permeabilities and selectivities for CO₂ over N₂ and CH₄. The permeabilities of CO₂, H₂, O₂, CH₄, and N₂ were measured at temperatures from 30 to 80°C and pressures from 20 cmHg to 76 cmHg using a manometric permeation apparatus. It was determined that the blend membrane, which contained 10% PEG 20,000, exhibited higher permeability for CO₂ and higher permselectivity for CO₂ over N₂ and CH₄ than those of the membranes that contained 10% PEG of the molecular weight ranging from 200 to 6000. The high PEG 20,000 content blend membranes showed remarkable permeation properties such that the permeability coefficients of CO₂ and the ideal separation factors for CO₂ over N₂ reached above 200 barrer and 22, respectively, at 70°C and 20 cmHg. Based on the data of gas permeability coefficients, time lags, and characterization of the membranes, it is proposed that the apparent solubility coefficients of all CA and PEG blend membranes for CO₂ were lower than those of the CA membrane. However, almost all of the blend membranes containing PEG 20,000 showed higher apparent diffusivity coefficients for CO₂, resulting in higher permeability coefficients of CO₂ than those of the CA membrane. It is attributed to the high diffusivity selectivities of CA and PEG 20,000 blend membranes that their ideal separation factors for CO₂ over N₂ were higher than those of the CA membrane in the temperature range from 50 to 80°C, even though the ideal separation factors of all CA and PEG blend membranes for CO₂ over CH₄ became lower than those of the CA membrane over nearly the full temperature range from 30 to 80°C. © 1995 John Wiley & Sons, Inc.     

Reaction‐induced phase separation in poly(vinyl acetate)/polyester blend

In blends of unsaturated polyester (UP), poly (vinyl acetate) (PVAc), and styrene, a reaction‐induced phase separation occurs upon curing that is due to the crosslinking between styrene and the UP molecules. The evolution of the morphology was observed by optical microscopy on a heated stage. Light transmission was used in parallel to precisely detect the onset of phase separation and the formation of microvoids. Using Fourier transform IR spectroscopy in the same conditions, the conversions at phase separation and at microvoiding were evaluated. Phase separation occurs at a very low degree of conversion and microvoiding develops at around 60% of conversion. The final morphology of the blend was investigated by scanning electron microscopy. The relative influences of the cure temperature, the concentration in PVAc, and the molecular weight of PVAc were investigated. It was confirmed that the early stages of the reaction at high temperature determine the final morphology of the blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3877–3888, 2006     

Anisotropic membranes from electrospun mats of sulfonated/nonsulfonated poly (ether ketone)s containing ion-rich paths as proton exchange membranes

Anisotropic proton exchange membranes composed of five layers with different contents of ionic groups across the membrane were prepared by simultaneous electrospinning of sulfonated and nonsulfonated poly(ether ketone) (PEK)s. To prepare nonporous and defect- free membranes from electrospun mats, nonsulfonated fibers as hydrophobic part of the membrane were melted by hot-pressing so that covered sulfonated fibers (hydrophilic part). Prepared membranes showed better thermal and dimensional stability compared to Nafion 115. Proton conductivity of membranes was comparable with Nafion especially at higher temperatures. Water uptake of prepared membranes and mechanical strength of them were in an acceptable range. The results showed that the difference between sulfonated PEK fibers in surface and center of the membranes affect proton conductivity and mechanical properties of the membranes.     

Performance evaluation and antifouling analyses of cellulose acetate/nanodiamond nanocomposite membranes in water treatment

In this study, nanocomposite membranes based on cellulose acetate (CA) and nanodiamond (ND) were prepared by applying phase inversion methods. In order to achieve efficient dispersion and more hydrophilic NDs, they were functionalized via heat treatment (ND‐COOH). The prepared nanocomposite membranes were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), contact angle, porosity measurement, tensile strength, and abrasion resistance techniques. Furthermore, the governing fouling mechanisms were determined by using classic models as well as combined fouling models. Moreover, the effect of precoagulation with polyaluminum chloride (PAC) on the humic acid (HA) filtration was investigated. The obtained results showed that in the presence of ND‐COOH, the abrasion resistance of nanocomposite CA membrane was three times higher than that of pristine CA membrane. Besides, the nanocomposite membranes with 0.5 wt % of raw and functionalized ND exhibited excellent hydrophilicity and PWF. The analysis of fouling mechanism based on Hermia's model revealed that the cake formation is prevailing mechanism for CA and CA/ND (0.5 wt %) membranes while for CA/ND‐COOH (0.5 wt %) membrane, experimental results are fitted by combined cake filtration‐complete blocking (CFCB) model. It confirms that pretreatment with PAC can significantly mitigate fouling and improve HA removal. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44873.