Phase separation mechanism during membrane formation by dry‐cast process

Phase separation mechanisms during the membrane formation by dry‐cast process were investigated by light scattering in the cellulose acetate/dimethylformamide (DMF)/2‐methyl‐2,4‐pentanediol system. Phase separation occurred by spinodal decomposition (SD) when paths of the composition changes due to the evaporation of DMF were close to the critical point in the phase diagram. Characteristic properties of the early stage of SD such as an apparent diffusion coefficient and an interface periodic distance were obtained from the Cahn theory. Phase separation occurred by nucleation and growth (NG) when paths of the composition changes were far from the critical point. SEM observation confirmed that the membrane formed by the SD mechanism had interconnected structure, whereas that by the NG mechanism had the closed cell porous structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 776–782, 2000     

Studies on phase separation rate in porous polyimide membrane formation by immersion precipitation

Phase separation rate during porous membrane formation by immersion precipitation was investigated by light scattering in a polyimide/N‐Methylpyrrolidone (NMP)/water system. In the light scattering measurement, plots of scattered intensity against scattered angle showed maxima in all cases, which indicated that phase separation occurred by a spinodal decomposition (SD). Characteristic properties of the early stage of SD, such as an apparent diffusion coefficient D_app and an interphase periodic distance Λ, were obtained. The growth process of Λ was also followed by light scattering. The growth rate had the same tendency as D_app when water content in the nonsolvent bath and the polymer concentration in the cast solution were changed. The pore size of the final membrane increased with decreasing water content, which was opposite to the tendency of Λ growth rate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 292–296, 2003     

Poly(ethylene‐co‐vinyl acetate)‐graft‐poly(methyl methacrylate) (EVA‐graft‐PMMA) as a modifier of epoxy resins

Conventional approaches to toughen thermosets are: (1) the polymerization‐induced phase separation of a rubber or a thermoplastic, or (2) the use of a dispersion of preformed particles in the initial formulation. In the present study it is shown that it is possible to combine both techniques by using graft copolymers with one of the blocks being initially immiscible and the other that phase separates during polymerization. This is illustrated by the use of poly(ethylene‐co‐vinyl acetate)‐graft‐poly(methyl methacrylate) (EVA‐graft‐PMMA) as modifier of an epoxy resin. EVA is initially immiscible and PMMA phase separates during polymerization. Blends of an epoxy monomer based on diglycidylether of bisphenol A (DGEBA, 100 parts by weight), piperidine (5 parts by weight), and PMMA (5 parts by weight), showed the typical polymerization‐induced phase separation of PMMA‐rich domains before gelation of the epoxy network. Replacing PMMA by EVA‐graft‐PMMA (5 parts by weight), yielded stable dispersions of EVA blocks, favoured by the initial solubility of PMMA blocks. Phase separation of PMMA blocks in the course of polymerization led to a dispersion of in situ generated biphasic particles (plausibly composed of EVA cores surrounded by PMMA shells), with average diameters varying from 0.3 to 0.6 µm with the cure temperature. This procedure may be used to generate stable dispersions of biphasic particles for toughening purposes. © 2002 Society of Chemical Industry     

Characterization of styrene-ethylene oxide and methyl methacrylate-styrene block copolymers by light scattering

Several polystyrene-poly(ethylene oxide)-polystyrene (PS-PEO-PS) and poly(methyl methacrylate)-polystyrene-poly(methyl methacrylate) (PMMA-PS-PMMA) block copolymers, synthesized by free-radical polymerization, were studied in various solvents by using a light-scattering technique. The copolymers, which have different lengths of central blocks, had molecular weights within the range 3.0 × 10⁴ to 1.6 × 10⁶. It was found that almost all of them were confirmed as block copolymers from the variation of the product $\text{M}{}_{\mathrm{<mtext>app</mtext>}}\text{〈S}{}^2{}_{\mathrm{<mtext>app</mtext>}}\text{〉}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ with $\text{W}{}_{\mathrm{<mtext>A</mtext><mtext>v</mtext><mtext>A</mtext>}}\text{v}$, although they were rather heterogeneous. The copolymer compositions determined either from the additivity of the refractive index increments of its constituent parts and the copolymer or from ultra-violet analysis were in excellent agreement with each other.     

Formation of porous poly(ethylene‐co‐vinyl alcohol) membrane via thermally induced phase separation

Crystalline poly(ethylene‐co‐vinyl alcohol) (EVOH) membranes were prepared by a thermally induced phase separation (TIPS) process. The diluents used were 1,3‐propanediol and 1,3‐butanediol. The dynamic crystallization temperature was determined by DSC measurement. No structure was detected by an optical microscope in the temperature region higher than the crystallization temperature. This means that porous membrane structures were formed by solid–liquid phase separation (polymer crystallization) rather than by liquid–liquid phase separation. The EVOH/butanediol system showed a higher dynamic crystallization temperature and equilibrium melting temperature than those of the EVOH/propanediol system. SEM observation showed that the sizes of the crystalline particles in the membranes depended on the polymer concentration, cooling rate, and kinds of diluents. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2449–2455, 2001     

Effect of diluents on the crystallization behavior of poly(4‐methyl‐1‐pentene) and membrane morphology via thermally induced phase separation

The effect of diluents on polymer crystallization and membrane morphology via thermally induced phase separation(TIPS) were studied by changing the composition of the mixed‐diluents systematically, in the system of poly(4‐methyl‐1‐pentene) (TPX)/dibutyl‐phthalate (DBP)/di‐n‐octyl‐phthalate (D‐n‐OP) with TPX concentration of 30 wt %. The TPX crystallization was observed with differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD). The membranes were characterized with scanning electron microscopy (SEM), porosity, and pore size measurement. As the content of D‐n‐OP increased in mixed‐diluents, the solubility with TPX increased, inducing the phase separation changing from liquid–liquid phase separation into solid–liquid phase separation, which changed the membrane morphology and structure. When the ratios of DBP to D‐n‐OP were 10 : 0, 7 : 3; 5 : 5, and 3 : 7, membranes were formed with cellular structure and well connected pores, while the ratio was 0 : 10, discernable spherulities were found with not well‐formed pore structure. The effect of composition of the mixed‐diluents on membrane morphology was more remarkable in TPX/dioctyl‐sebacate (DOS)/dimethyl‐phthalate (DMP) system, since good cellular structure was formed when the ratios of DOS to DMP were 10 : 0, 7 : 3, while spherulites were observed when 5 : 5. Dual endotherm peaks behavior on DSC melting curves emerged for all the samples in this study, which was attributed to the special polymer crystallization behavior, primary crystallization, and secondary crystallization occurred when quenching the samples. As the content of D‐n‐OP increased, the secondary crystallization enhanced which induced the first endotherm peak on DSC melting curves moving to a lower temperature and the broadening of the overall melting peak, as well as the increasing of the overall crystallinity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Light‐scattering study of poly(hydroxy ester ether) in N,N‐dimethylacetamide solution

Static and dynamic light‐scattering techniques were used to study biodegradable thermoplastic poly(hydroxy ester ether) in N,N‐dimethylacetamide (DMAc). A weight‐average molecular weight M_W = 6.4 × 10⁴ g/mol, radius of gyration R_G = 9.4 nm, second‐virial coefficient A₂ = 1.05 × 10^?3 mol mL/g², translational diffusion coefficient D = 1.34 × 10^?7 cm²/s, and hydrodynamic radius R_H = 8.3 nm are reported. In addition, the effect of H₂O on the polymer chain's conformation and architecture in a DMAc/H₂O solution is evaluated. Results suggest that H₂O makes the mixed solvent poorer as well as promotes polymer chain branching via intramolecular transesterification. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1737–1745, 2001     

Polymerization of methyl methacrylate in the presence of a nonpolar hydrocarbon solvent. I. Construction of a complete ternary phase diagram through an in situ polymerization

This article presents the ternary phase diagram for methyl methacrylate (MMA), poly(methyl methacrylate) (PMMA), and n‐hexane system at 70°C. It was constructed by both theoretical calculations and online laser light scattering (LLS) technique. In situ polymerization of MMA in a nonpolar nonsolvent carried out in a LLS cell provides a new means for the accurate detection of the cloud points of highly viscous polymer mixtures, with polymer weight fractions over 0.6. The ternary phase diagram measured in this study can be used to design the reaction conditions for the precipitation and/or dispersion polymerization in a nonpolar nonsolvent medium where polymerization kinetics as well as polymer particle morphologies are strongly affected by thermodynamic phase separation phenomena. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and thermal properties of poly(methyl methacrylate)‐poly(L‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer

Poly(methyl methacrylate)‐poly(L ‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer was prepared using atom transfer radical polymerization (ATRP). The structure and properties of the copolymer were analyzed using infrared spectroscopy, gel permeation chromatography, nuclear magnetic resonance (¹H‐NMR, ¹³C‐NMR), thermogravimetry, and differential scanning calorimetry. The kinetic plot for the ATRP of methyl methacrylate using poly(L ‐lactic acid) (PLLA) as the initiator shows that the reaction time increases linearly with ln[M]₀/[M]. The results indicate that it is possible to achieve grafted chains with well‐defined molecular weights, and block copolymers with narrowed molecular weight distributions. The thermal stability of PLLA is improved by copolymerization. A new wash‐extraction method for removing copper from the ATRP has also exhibits satisfactory results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fouling reduction of a poly(ether sulfone) hollow‐fiber membrane with a hydrophilic surfactant prepared via non‐solvent‐induced phase separation

Membrane fouling is still a crucial problem, especially in applications for water treatment. When fouling takes place on membrane surfaces, it causes flux decline, leading to an increase in production cost due to increased energy demand. The selection of the right membrane material and a special treatment of the membrane are required to avoid membrane fouling. This article reports the fouling resistance of a poly(ether sulfone) (PES) hollow‐fiber membrane modified with hydrophilic surfactant Tetronic 1307. Experiments on several methods of fouling were carried out to investigate the effect of the addition of nonionic surfactant Tetronic 1307 on membrane fouling. The effectiveness of a chemical agent [sodium hypochlorite (NaClO)] in the reduction of bovine serum albumin (BSA) deposition on the membrane surface was also evaluated. Permeation results showed that the fouling of a PES blend membrane with Tetronic 1307 was lower than that of the original PES membrane in the case of BSA filtration. A treatment with a 100 ppm NaClO solution was capable of removing BSA cake formation and effective at improving the relative permeability. The permeability of a PES blend membrane with Tetronic 1307 was almost 2 times higher than the original permeability when the membrane was treated with a 100 ppm NaClO solution because both BSA and Tetronic 1307 could be decomposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Dynamical study on the late stage of demixing in poly(methyl methacrylate) and poly(vinyl acetate) blends

A dynamical study was made on demixing of an immiscible polymer blend, whose specimens were prepared by solvent casting and had very finely phase separated structures in the initial stage of the demixing. Light scattering experiments showed the applicability of a scaling rule to the later stage of the growth of phase separation structures. The demixing can be described by a scaling theory proposed by Furukawa.     

Polymerization‐induced phase separations in branched poly(methyl methacrylate) synthesis

Methyl methacrylate and ethylene glycol dimethacrylate or 1,6‐hexanediol dimethacrylate (HDDMA) were copolymerized in the presence of a nonsolvent (heptane) for poly(methyl methacrylate) (PMMA) to examine the phenomenon of polymerization‐induced phase separations (PIPS) in branched PMMA synthesis. The process was dependent upon the amount of nonsolvent and crosslinker in the reaction mixture. Gel particles were obtained in the majority of phase‐separated systems, and their formation was promoted by the preferential partition of monomer and crosslinker into the precipitated polymer phase during the phase separation process. Experimental data showed that, because of its lower solubility parameter, HDDMA can be used as crosslinker to minimize gel particle formation in systems where PIPS is present. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1462–1468, 2005     

Small‐angle X‐ray scattering study of modified porous suspension–poly(vinyl chloride) particles

Small‐angle X‐ray scattering (SAXS) was applied to investigate the microstructure of unmodified and modified porous commercial suspension‐type poly(vinyl chloride) (PVC) particles. The modified PVC particles were prepared by an in situ stabilizer‐free polymerization/crosslinking of particles absorbed with a monomer/crosslinker/peroxide solution. The modifying polymers include styrene with or without divinyl benzene (DVB) as a crosslinker and methyl methacrylate (MMA) with or without ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The SAXS method was used to highlight the effect of polystyrene (PS) on the microstructure of PVC particles and to evaluate the characteristic lengths, both in the PVC/PS and the PVC/XPS (PS crosslinked with 0 and 5% DVB, respectively) systems. A model is suggested, where during the synthesis modification process, swelling of PVC by styrene and styrene polymerization occur simultaneously. PVC swelling by styrene causes destruction of the PVC subprimary particles, whereas styrene polymerization leads to phase separation resulting from incompatibility of the polymers. It was further suggested that because of PVC swelling by styrene, structure of the subprimary particles is lost. Therefore the characteristic lengths of PVC/PS and PVC/XPS, as calculated from the SAXS measurements, were attributed to the size of the phase‐separated PS and XPS inclusions, respectively. The SAXS method also shows that PMMA and XPMMA do not influence the PVC microstructure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1024–1031, 2005     

Preparation of porous poly(oxymethylene) membrane with high durability against solvents by a thermally induced phase‐separation method

Porous poly(oxymethylene) membranes were prepared as new solvent‐resistant membranes by a thermally induced phase‐separation method. Porous structures were formed by solid–liquid phase separation (polymer crystallization) rather than liquid–liquid phase separation. The pores existed in the intraspherulitic and interspherulitic regions. The effects of the polymer weight percentage and cooling rate on toluene permeance and solute rejection were investigated. The solvent resistance of the membranes was tested by the immersion of the membranes in organic solvents for 1 month, and high durability against the solvents was confirmed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1993–1999, 2002     

Electro‐membrane process for the separation of amino acids by iso‐electric focusing

BACKGROUND: Amino acids (AAs) are usually produced commercially using chemical, biochemical and microbiological fermentation methods. The product obtained from these methods undergoes various treatments involving extraction and electrodialysis (ED) for salt removal and AA recovery. This paper describes an electro‐membrane process (EMP) for the charge based separation of amino acids. RESULTS: Iso‐electric separation of AAs (GLU–LYS) from their mixture, using ion‐ exchange membranes (IEMs) has been achieved by an efficient and indigenous EMP. It was observed that electro‐transport rate (flux) of glutamic acid (GLU) at pH 8.0 (above its pI) was extremely high, while that for lysine (LYS) (pH 9.6) across the anion‐exchange membrane (AEM) was very low, under similar experimental conditions. Under optimum experimental conditions, separation of GLU from GLU–LYS mixture was achieved with moderate energy consumption (12.9 kWh kg^?1), high current efficiency (CE) (65%) and 85% recovery of GLU. CONCLUSIONS: On the basis of the electro‐transport rate of AA and membrane selectivity, it was concluded that the separation of GLU–LYS mixture was possible at pH 8.0, because of the oppositely charged nature of the two amino acids due to their different pI values. Moreover, any type of membrane fouling and deterioration in membrane conductivity was ruled out under experimental conditions. This work clearly demonstrates the great potential of EMP for industrial applications. Copyright © 2010 Society of Chemical Industry     

DNA adsorption on a poly‐L‐lysine‐immobilized poly(2‐hydroxyethyl methacrylate) membrane

The DNA adsorption properties of poly‐L ‐lysine‐immobilized poly(2‐hydroxyethyl methacrylate) (pHEMA) membrane were investigated. The pHEMA membrane was prepared by UV‐initiated photopolymerization and activated with epichlorohydrin. Poly‐L ‐lysine was then immobilized on the activated pHEMA membrane by covalent bonding, via a direct chemical reaction between the amino group of poly‐L ‐lysine and the epoxy group of pHEMA. The poly‐L ‐lysine content of the membrane was determined as 1537 mg m^?2. The poly‐L ‐lysine‐immobilized membrane was utilized as an adsorbent in DNA adsorption experiments. The maximum adsorption of DNA on the poly‐L ‐lysine‐immobilized pHEMA membrane was observed at 4 °C from phosphate‐buffered salt solution (pH 7.4, 0.1 M; NaCl 0.5 M) containing different amounts of DNA. The non‐specific adsorption of DNA on the plain pHEMA membrane was low (about 263 mg m^?2). Higher DNA adsorption values (up to 5849 mg m^?2) were obtained in which the poly‐L ‐lysine‐immobilized pHEMA membrane was used. Copyright © 2003 Society of Chemical Industry     

Effect of the addition of the surfactant Tetronic 1307 on poly(ether sulfone) porous hollow-fiber membrane formation

Poly(ether sulfone) (PES) hollow-fiber membrane was prepared via a nonsolvent-induced phase-separation method, and the effect of the addition of the surfactant Tetronic 1307 on the membrane performance and characteristics was investigated. The phase diagram of the PES/N-methyl-2-pyrrolidone (NMP)/water system was clarified. When the polymer solution involved Tetronic 1307, the amount of water required to induce the phase separation decreased, which indicated that Tetronic 1307 was one kind of nonsolvent. The kinetics of phase separation for the PES/NMP/Tetronic 1307 system were studied by light-scattering measurements. With the addition of Tetronic 1307, delayed phase separation was observed, and the structure growth rate decreased. Scanning electron microscopy images for all of the membranes showed the formation of fingerlike macrovoids through the cross section. Membrane surface morphologies were measured by atomic force microscopy. The obtained results indicated that membrane with 7 wt % Tetronic 1307 had higher roughness parameters than original membrane without the addition of surfactant. Ultrafiltration experiment results showed that the addition of Tetronic 1307 brought about an increase in water permeability and decreased the rejection of dextran with a molecular weight of about 10,000. The contact angles of water on the membrane outer surface decreased with the addition of Tetronic 1307. This mean the membrane surface became more hydrophilic. Thus, the addition of Tetronic 1307 was useful for improving the water permeability and for obtaining a hydrophilic membrane surface. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Cloud‐point measurements for salt + poly(ethylene glycol) + water systems by viscometry and laser beam scattering methods

The phase separation of salt + poly(ethylene glycol) + water systems was studied by cloud‐point measurements using viscometry and laser beam scattering methods. The Flory–Huggins model was applied to determinate the condition for salt‐induced liquid–liquid phase separation in the system. A temperature‐ and concentration‐dependent interaction parameter was employed to fit the phase diagrams for the systems. The temperature and concentration functionality of the interaction parameter was determined and used to predict cloud‐point curves for the systems. The cloud‐point curves were found to be in quantitative agreement with experimental data. Also, the effect of various salts on the measured cloud points was studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1983–1990, 2003     

Preparation of poly(lactic acid) fiber by dry‐jet‐wet‐spinning. I. Influence of draw ratio on fiber properties

Poly(lactic acid) fiber was prepared by dry‐jet‐wet spinning of the polymer from chloroform solution and with methanol as the precipitating medium. The as‐spun fiber was subsequently made into high strength fiber by two‐step process of drawing at a temperature of 90°C and subsequent heat setting in the temperature range of 120°C. The draw ratio had significant influence on the crystallinity and the tensile strength of the fiber. The fiber with the tenacity of 0.6 GPa and modulus of 8.2 GPa was achieved at a draw ratio of 8. The differential scanning calorimetry revealed an increase in the glass‐transition temperature with the increase in the draw ratio, which suggests the orientation of chains during the drawing process. The surface morphology of the filament as revealed by scanning electron microscopy shows that fibers are porous in nature, but a significant reduction in the porosity and pore size of the fiber was observed with the increase in the draw ratio. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1239–1246, 2006     

Effect of tacticity of poly(methyl methacrylate) on the miscibility with poly(styrene‐co‐acrylonitrile)

Isotactic, atactic, and syndiotactic poly(methyl methacrylates) (PMMAs) (designated as iPMMA, aPMMA, and sPMMA) with approximately the same molecular weight were mixed separately with poly(styrene‐co‐acrylonitrile) (abbreviated as PSAN) containing 25 wt % of acrylonitrile in tetrahydrofuran to make three polymer blend systems. Differential scanning calorimetry (DSC) was used to study the miscibility of these blends. The results showed that the tacticity of PMMA has a definite impact on its miscibility with PSAN. The aPMMA/PSAN and sPMMA/PSAN blends were found to be miscible because all the prepared films were transparent and showed composition dependent glass transition temperatures (T_gs). The glass transition temperatures of the two miscible blends were fitted well by the Fox equation, and no broadening of the glass transition regions was observed. The iPMMA/PSAN blends were found to be immiscible, because most of the cast films were translucent and had two glass transition temperatures. Through the use of a simple binary interaction model, the following comments can be drawn. The isotactic MMA segments seemed to interact differently with styrene and with acrylonitrile segments from atactic or syndiotactic MMA segments. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2894–2899, 1999