Blend membranes from cellulose/konjac glucomannan cuprammonium solution

The blend membranes were prepared from cellulose/konjac glucomannan (KGM) cuprammonium solution by coagulating with aqueous 10 wt% NaOH solution, 20°C and 40°C water, respectively. Miscibility, pore morphology, structure, water permeability and mechanical properties of the blend membranes were investigated. The complex forms of cellulose/KGM in the mixed solutions, the effect of various coagulants and the percent content of KGM (w_KGM) on the structure and properties of the blend membrane are discussed. SEM and mechanical relaxation analysis indicate that the blend membranes are miscible in the range of 0–30 wt% of w_KGM. When w_KGM was smaller than 20 wt%, the tensil strength of the blend membrane coagulated by alkali aqueous solution was enhanced, corresponding to homogeneous structure and small pore size. However, blend membranes having a larger pore size (366 nm by SEM) and water permeability (560 ml/m² h mmHg) were obtained by coagulating the cellulose/KGM (70:30) cuprammonium solution with 40°C water, where ca. 20% of KGM as pore former were removed from the membrane.     

CELLULOSE ACETATE AND EPOXY RESIN BLEND ULTRAFILTRATION MEMBRANES: REPARATION,CHARACTERIZATION, AND APPLICATION

ABSTRACT

Membranes based on cellulose acetate used in ultrafiltration applications lack good, chemical, mechanical and thermal resistance. In order to prepare membranes with improved properties, modification of cellulose acetate with epoxy resin through solution blending was attempted. In the present work, the membrane casting solutions with different polymer blend compositions of cellulose acetate and diglycidyl ether of bisphenol-A (DGEBA) were prepared at 30±2°C. The maximum percent compatibility of the two polymers, cellulose acetate and diglycidyl ether of bisphenol-A, was estimated to be 60/40%. Ultrafiltration blend membranes based on various blend compositions were prepared, characterized in terms of compaction, pure water flux, water content, membrane hydraulic resistance and molecular weight cut-off. The application of these membranes, in rejection of proteins of various molecular weights, are discussed.     

Ferroelectric polarization switching in nylon-11

Cold-drawn Nylon-11 films, which were prepared by stretching the melt-quenched films to a draw ratio of 2.8: 1 at room temperature, were found to exhibit an electric displacement versus electric field hysteresis loop. The results confirmed that the Nylon-11 film exhibited ferroelectric behavior at or below room temperature. The coercive fields were 65, 98, 125, 160, and 215 MV/m at 20, 0, ?20, ?40, and ?60°C and the remanent polarization at ?20°C (where there was considerably less dc conduction) was 56 mC/m². Switching of the polarization was almost completed within 20 ms.     

Maleic Anhydride Crosslinked Alginate-Chitosan Blend Membranes for Pervaporation of Ethylene Glycol-Water Mixtures

Calcium alginate-chitosan (CA/CS) blended membranes were prepared and crosslinked with maleic anhydride (MA) for the pervaporation (PV) separation of ethylene glycol (EG)/water mixtures at 30°C. The structure and properties of blend membranes were studied with the aid of FTIR, XRD, TGA, and SEM. The effect of experimental parameters such as feed composition, membrane thickness, and permeate pressure on separation performance of the MA crosslinked membranes were determined in terms of flux, selectivity, and pervaporation separation index. Sorption studies were carried out to evaluate the extent of interaction and degree of swelling of the blend membranes in pure, as well as in binary mixtures. The experimental results suggested that the crosslinked membrane (M-CA/CS) exhibited a good selectivity of 302 at a normalized flux of 0.38 kg.m^{? 2}.h^{? 1}.10 μ m at 30°C for 96.88 wt% EG aqueous solution.     

p-Nitrophenol permeability and temperature characteristics of an acryloyl-L-proline methyl ester-based porous gel membrane

Thermoresponsive porous gel membranes were synthesized by a simultaneously occurring process consisting of radiation-induced polymerization and crosslinking in aqueous solutions at various concentrations of acryloyl-L -proline methyl ester(A-ProOMe) without a crosslinker. Permeation of p-nitrophenol (PNP) through a thermoresponsive porous gel membrane obtained at a monomer concentration of 80% (w/w) drastically reduced around 14°C, the lower critical solution temperature (LCST) of linear poly(A-ProOMe) in water, from 0.60 × 10⁻³ cm/min at 10°C to no permeation at 18°C, accompanied by changes in both size and shape of pores associated with gel shrinkage. Moreover, it was found that porous gel membranes with a porosity of approximately 60% had a greater PNP permeability constant through porous gel membranes with mutually connected pores obtained at a monomer concentration of 50% (w/w) than individually supported pores obtained at a monomer concentration of 70% (w/w). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1495–1500, 1998     

Lithium-iodine solid electrolyte galvanic cells using iodine adducts of nylon-6 as active materials of positive electrodes

Iodine and nylon-6 form adducts containing 70–90 wt-% of iodine on heating at 115–145°C. The adducts have electrical conductivities ranging from 10^?7 to 10^?3 S cm^?1 at 25°C, and the electrical conductivity increases with increasing content of iodine of the adduct. The activation energies of the electrical conduction for the adducts prepared at 115°C and containing 69.2, 81.8, 87.1, and 90.0 wt-% of iodine are 94.6, 67.0, 52.9, and 46.1 kJ/mol, respectively. Polyamides other than nylon-6 also form similar semiconducting adducts with iodine. IR and NMR spectroscopic analyses of the iodine—nylon-6 adducts indicate profound changes in the structure of nylon-6 on adduct formation and suggest the formation of a ?CN⁺H species. The iodine-nylon-6 adducts prepared at 115°C and containing more than 82 wt-% of iodine serve as good active materials of positive electrodes in lithium-iodine solid electrolyte galvanic cells (outer diameter = 11.6 mm; outer thickness = 2.0 mm). The current efficiencies of the galvanic cells at 500 kΩ load are about 50% based on the iodine added. Discharge at 100 kΩ load gives lower current efficiencies. The galvanic cell has an internal resistance of about 5 kΩ at 25°C before discharge, and the internal resistance increases to about 100 kΩ at about 40% discharge. The dependence of the internal resistance during discharge have been determined.     

Polymer electrolyte membranes by in situ polymerization of poly(ethylene carbonate‐co‐ethylene oxide) macromonomers in blends with poly(vinylidene fluoride‐co‐hexafluoropropylene)

Salt‐containing membranes based on polymethacrylates having poly(ethylene carbonate‐co‐ethylene oxide) side chains, as well as their blends with poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP), have been studied. Self‐supportive ion conductive membranes were prepared by casting films of methacrylate functional poly(ethylene carbonate‐co‐ethylene oxide) macromonomers containing lithium bis(trifluorosulfonyl)imide (LiTFSI) salt, followed by irradiation with UV‐light to polymerize the methacrylate units in situ. Homogenous electrolyte membranes based on the polymerized macromonomers showed a conductivity of 6.3 × 10^?6 S cm^?1 at 20 °C. The preparation of polymer blends, by the addition of PVDF‐HFP to the electrolytes, was found to greatly improve the mechanical properties. However, the addition led to an increase of the glass transition temperature (T_g) of the ion conductive phase by ～5 °C. The conductivity of the blend membranes was thus lower in relation to the corresponding homogeneous polymer electrolytes, and 2.5 × 10^?6 S cm^?1 was recorded for a membrane containing 10 wt % PVDF‐HFP at 20 °C. Increasing the salt concentration in the blend membranes was found to increase the T_g of the ion conductive component and decrease the propensity for the crystallization of the PVDF‐HFP component. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 79–90, 2007     

Preparation and some properties of nylon-4,2

An attempt was made to produce a new short-chain alphatic polyamide nylon-4,2. This polyoxamide can be prepared by polycondensation of tetramethylene diamine and diethyl oxalate. A high molecular weight polymer (η_inh = 1.9 from 0.5% solutions in 96% sulphuric acid) has been obtained by employing a two-step polycondensation method; the precondensation was carried out in solution at low temperatures (20–140°C) and the postcondensation in the solid state at high temperatures (250–300°C). The effect of solvent composition and reaction temperature on the prepolymerization and the effect of reaction time and temperature on the postcondensation was studied. We also investigated the influence of moisture during washing, storing, and the solid-state reaction on the polymerizability by the postcondensation. Nylon-4,2 is soluble only in highly polar solvents such as trifluoroacetic acid (TFA), dichloroacetic acid, and 96% sulphuric acid. Films were cast from TFA. With these films we studied the IR spectrum, WAXS pattern, water absorption, and melting behavior. Nylon-4,2 was found to melt at 388–392°C, has a crystallinity of 70%, and a low water absorption (3.1% at 50% RH). The glass transition temperature of the dry sample was found to be at ～120°C and for the wet sample at ?15°C.     

Dynamic mechanical analysis of RIM nylon-6

The β relaxation process was shown to occur at different temperatures and exhibit a different activation energy for dry and wet samples prepared by reaction injection molding (RIM) of Nylon-6. By employing a low operating frequency and controlled low moisture levels, it became possible to distinguish the two β relaxation processes, β₁ and β₂, in one sample by dynamic mechanical spectroscopy. It was shown that while β₁ was associated with moisture in the sample, β₂ was related to a structural mechanism independent of moisture. The effect of moisture content on the chain-chain association (α relaxation process) and chain-water association (β₁, relaxation process) in nylon-6 was assessed. The annealing mechanism of RIM Nylon-6 at 85°C was probed by both dynamic mechanical spectroscopy and x-ray diffraction.     

Effect of polyethyleneglycol (PEG) on gas permeabilities and permselectivities in its cellulose acetate (CA) blend membranes

The effect of polyethyleneglycol (PEG) on gas permeabilities and selectivities was investigated in a series of miscible cellulose acetate (CA) blend membranes. The permeabilities of CO₂, H₂, O₂, CH₄, N₂ were measured at temperatures from 30 to 80°C and pressures from 20 to 76 cmHg using a manometric permeation apparatus. It was determined that the blend membrane having 10 wt% PEG20000 exhibited higher permeability for CO₂ and higher permselectivity for CO₂ over N₂ and CH₄ than those of the membranes which contained 10% PEG of the molecular weight in the range 200–6000. The CA blend containing 60 wt% PEG20000 showed that its permeability coefficients of CO₂ and ideal separation factors for CO₂ over N₂ reached above 2 × 10⁻⁸ [cm³ (STP) cm/cm² s cmHg] 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 the blend membranes containing PEG20000 showed higher apparent diffusivity coefficients for CO₂, resulting in higher permeability coefficients of CO₂ with relation to those of the CA membrane. It is attributed to the high diffusivity selectivities of CA and PEG20000 blend membranes that their ideal separation factors for CO₂ over N₂ were higher than those of the CA membrane in the range 50–80°C, even though the ideal separation factors of almost all PEG blend membranes for CO₂ over CH₄ became lower than those of the CA membrane over nearly the full range from 30° to 80°C.     

The effect of preparation temperature on some properties of a temperature-sensitive hydrogel

The physical and chemical characteristics of temperature-sensitive hydrogel, poly(N-isopropylacrylamide), were strongly dependent upon the preparation temperature and the kind of accelerator used for free radical polymerization. N, N,N′,N′-tetramethyl-ethylenediamine (TEMED) was a better accelerator for consistent gelation near room temperatures (17–24 °C) compared with sodium metabisulfite. Using TEMED, gelation time was 3.6 min at 18 °C, but decreased to 1.8 min at 23 °C. When the gel was prepared in a glass cylinder of 37 mm ID and 191 mm height at temperatures of 18 °C and below, it was completely transparent. The gel became more opaque starting from the core part of the gel cylinder, when prepared at higher temperatures. The gel became totally opaque at preparation temperatures of 23 °C and above. The transparent gel had better physical strength as determined by Instron, and higher transition temperature for volume change (lower critical solution temperature) as determined by differential scanning calorimetry. The transparent gel also had a better volume change capacity when the gel underwent temperature swings between 28 °C and 37 °C.     

Concentration of Whey Proteins by Using Temperature-Sensitive Polymer Gel Poly(N-isopropylacrylamide)

Summary: In this work, the use of a temperature-sensitive polymer gel, poly(N-isopropylacrylamide), for the concentration of whey proteins was studied. The studied variables were: gel mass/solution volume ratio and concentration temperature. The concentration percentage and the selectivity were determined. The gel 20 × 5 (20% w/w total monomer/solution and 5% w/w crosslinking agent/total monomer), contacted with whey proteins solutions, at 5 °C and at 20 °C, was capable of concentrating the solution, in protein, from 10 to 33%, depending on the gel mass/solution volume ratio. The separation efficiencies, for the different studied systems, varied from around 40 to 80%. The results were discussed in the context of gels thermodynamics and through correlations between synthesis parameters and structure of the obtained gels. The obtained results for the concentration of whey proteins solutions, by using temperature-sensitive polymer gel, poly(N-isopropylacrylamide), showed that the Gel Process can indeed be used as an advantageous alternative for such separation, either from an economic or from an environmental view point.     

Solutions of nylon-6 in antimony trichloride

Dilute solution viscosity measurements of nylon-6 in molten SbCl₃ reveal a polyelectrolyte effect that becomes more pronounced with increased molecular weight of the polymer sample. Intrinisic viscosities result in a relationship of [η] = 2.35 × 10^?6M^1.45_w for nylon-6 in SbCl₃ at 100°C, which indicates a high polymeric chain extension in molten SbCl₃ in the limit of zero concentration. Infrared (IR) and nuclear magnetic resonance (NMR) spectra indicate that a substantial fraction of the amide groups in each polymer chain remains unaffected, whereas the rest is interacted, probably, with SbCl₄-ions originating from the self-ionization of SbCl₃.     

Copolyamides of nylon-4,6 and nylon-4,T

Copolyamides of nylon-4,6 and nylon-4,T were prepared by a two-step method: (1) a prepolymerization in an autoclave (40 min at 210°C) and (2) a postcondensation in the solid state (4 h, 260°C). On these materials was studied the melting behavior with DSC, the crystalline structure with WAXS, the water absorption, and the mechanical properties with a torsion pendulum. In these copolyamides the order was found to remain high, but the crystalline structures of -4,6 and -4,T were not isomorphous. The torsion moduli increased with -4,T content both at RT and at 140°C.     

Effect of chemical crosslinking on mechanical and electrical properties of ultrahigh-molecular-weight polyethylene-carbon fiber blends prepared by gelation/crystallization from solutions

In an attempt to improve the mechanical property of polyethylene composite at high temperature, crosslinking of ultrahigh-molecular-weight polyethylene (UHMWPE) and carbon fiber (CF) blends was carried out by using dicumyl peroxide (DCP). The specimens were prepared by gelation/crystallization from solutions. The effect of chemical crosslinking on mechanical and electrical properties of UHMWPE/CF blends with composition of 1/0, 1/0.25, and 1/1 (w/w) were investigated in detail. Electrical conductivity and thermal mechanical properties of the blends with the 1/1 composition were greatly improved by incorporation of enough content of CF and adequate crosslinking network formation. Surprisingly, the Young’s modulus of the 1/1 blend reached 20 GPa at room temperature (20 °C). On the other hand, heat treatment at 135 °C played an important role for obtaining a high PTC effect for the UHMWPE-CF blend in which the PTC intensity reached 10⁷.     

Brill transition of nylon-6 in electrospun nanofibers

Electrospun nylon-6 fibers were prepared from its polyelectrolyte solution in formic acid with different concentrtaions. In situ Fourier transform infrared (FTIR), wide-angle X-ray diffraction and small-angle X-ray scattering (SAXS) were performed on the nylon-6 fibers heated to various temperatures until melting. For comparison, stepwise annealing of the solution-cast film having exclusively the α-form was also carried out to elucidate the structural evolution. Our results showed that Brill transition in the electrospun fibers occurs at a lower temperature than that in the solution-cast film due to the crystal size difference. Differential scanning calorimetry heating traces on the as-spun fibers exhibited a unique crystalline phase with a melting temperature of ～235?°C, higher than the equilibrium melting temperature of nylon-6. The content of high melting temperature (HMT) phase increased with increasing nylon-6 concentration; a maximum of 30?% of the fiber crystallinity was reached for fibers obtained from the 22?wt.% solution regardless of the heating rates used. Based on the SAXS and FTIR results, we speculated that the HMT phase is associated with thick α-form crystals developed from the highly oriented nylon-6 chains that are preserved in the skin layer of the as-spun fibers. A plausible mechanism for the formation of the skin/core fiber morphology during electrospinning was proposed.     

Fabrication of porous collagen/chitosan scaffolds with controlling microstructure for dermal equivalent

Two sets of homemade apparatus have been utilized to fabricate collagen/chitosan porous membranes by quenching its acetic solution and subsequently extracting the solvent with ethanol. The influence of chitosan concentration on the surface morphology of the collagen/chitosan membranes was studied using a quenching cold plate (apparatus 1). The pore size was enlarged along with an increase in the chitosan content, accompanied with the emergence of a sheet‐like microstructure. Due to the large thermal conductivity of the membrane‐forming platform (stainless steel), collagen/chitosan membranes prepared using apparatus 1 at freezing temperature between ?60 to ?20 °C present similar pore size (2–4 nm) and surface morphology. However, a large difference in pore size is generated using apparatus 2 (membrane preparation in a cold ethanol bath) and using a membrane‐forming platform of poor thermal conductivity (polymethylmethacrylate), e.g. ～10 to 20 μm at freezing temperature of ?60 to ?40 °C, and 265 μm at ?20 °C accompanied with the transformation from fiber‐ to sheet‐dominated morphology. The spongy collagen/chitosan membranes with pore sizes ranging from tens to hundreds of micrometers and porosity higher than 95%, which could be used as dermal regeneration template, have thus been fabricated. Copyright © 2003 John Wiley & Sons, Ltd.     

Morphology and mechanical properties of poly(vinyl alcohol) and starch blends prepared by gelation/crystallization from solutions

 In an attempt to produce biodegradation materials, poly(vinyl alcohol) (PVA)–starch (ST) blends were prepared by gelation/crystallization from semidilute solutions in dimethyl sulfoxide (Me₂SO) and water mixtures and elongated up to 8 times. The content of mixed solvent represented as Me₂SO/H₂O (volume percent) was set to be 60/40 assuring the greatest drawability of PVA homopolymer films. The PVA/ST compositions chosen were 1/1, 1/3, and 1/5. The elongation up to 8 times could be done for the 1/1 blend but any elongation was impossible for blends whose ST content was beyond 50%. When the blends were immersed in water at 20 or 83 °C, the solubility became considerable for an undrawn blend with 1/5 composition and a drawn 1/1 blend with λ=8. To avoid this phenomenon, cross-linking of PVA chains was carried out by formalization under formaldehyde vapor. Significant improvement could be established by the cross-linking of PVA chains. For the 1/1 blend, the amount of ST dissolved in water at 23 °C was less than 3% for the undrawn state and 25% for the drawn film. The decrease in the ST content was enough for use as biodegradation materials. Namely, the water content relating to the biodegradation in soil is obviously different from such a serious experimental condition that a piece of blend film was immersed in a water bath. At temperatures above 0 °C, the storage modulus of the formalization blends became slightly higher than those of the nonformalization blends. The Young's modulus of the drawn films with a draw ratio of 8 times was 2 GPa at 20 °C. Received: 23 June 2000 Accepted: 30 October 2000     

Fast responsive poly(<Emphasis Type="Italic">N,N</Emphasis>-diethylacrylamide) hydrogels with interconnected microspheres and bi-continuous structures

We prepared thermo-responsive polymer hydrogels by γ-ray irradiation of aqueous solutions of N, N-diethylacrylamide at different temperatures below and above its lower critical solution temperature (LCST). Poly(N, N-diethylacrylamide) gel had a transparent and homogeneous structure when the radiation-induced polymerization and crosslinking were carried out below the LCST (25 °C) of the polymer. On the other hand, cloudy and heterogeneous gels were formed at temperatures above the LCST of the polymer (>35 °C). From environmental scanning electron microscopy observations, the gels prepared at 35 and 40 °C were seen to show sponge-like bi-continuous porous structures, while those prepared at 50 °C showed a porous structure consisting of interconnected microspheres. For temperature changes between 10 and 40 °C, gels with porous structures showed rapid volume transitions on a time scale of about a minute, not only for shrinking but also for swelling processes, which is in remarkable contrast to the porous poly(N-isopropylacrylamide) hydrogels.     

How xerogel carbonization conditions affect the reactivity of highly disperse SiO<Subscript>2</Subscript>–C composites in the sol–gel synthesis of nanocrystalline silicon carbide

A transparent silicon polymer gel was prepared by sol–gel technology to serve as the base in the preparation of highly disperse SiO₂–C composites at various temperatures (400, 600, 800, and 1000°C) and various exposure times (1, 3, and 6 h) via pyrolysis under a dynamic vacuum (at residual pressures of ~1 × 10^–1 to 1 × 10^–2 mmHg). These composites were X-ray amorphous; their thermal behavior in flowing air in the range 20–1200°C was studied. The encapsulation of nascent carbon, which kept it from oxidizing in air and reduced the reactivity of the system in SiC synthesis, was enhanced as the carbonization temperature and exposure time increased. How xerogel carbonization conditions affect the micro- and mesostructure of the xerogel was studied by ultra-small-angle neutron scattering (USANS). Both the carbonization temperature and the exposure time were found to considerably influence structure formation in highly disperse SiO₂–C composites. Dynamic DSC/DTA/TG experiments in an inert gas flow showed that the increasing xerogel pyrolysis temperatures significantly reduced silicon carbide yields upon subsequent heating of SiO₂–C systems to 1500°C, from 35–39 (400°C) to 10–21% (1000°C).