Preparation and characterization of poly(piperazineamide) composite nanofiltration membrane by interfacial polymerization of 3,3 ',5,5 '-biphenyl tetraacyl chloride and piperazine

Most nanofiltration (NF) membranes are composite and have a polyamide thin film prepared by interfacial polymerization. Their performances mainly correlate the structure of the thin film and monomers used for its preparation. In this work, a novel thin-film composite (TFC) nanofiltration membrane was successfully prepared from 3,3',5,5'-biphenyl tetraacyl chloride (mm-BTEC) and piperazine (PIP) through interfacial polymerization. Attenuated reflectance infrared (ATR-IR) and X-ray photoelectronic spectroscopy (XPS) were used to characterize the chemical composition of the membrane surface. The membrane performance was optimized by studying preparation parameters including monomer concentration, reaction time, and pH of aqueous phase.

Blends based on sulfonated poly[bis(benzimidazobenzisoquinolinones)] and poly(vinylidene fluoride) for polymer electrolyte membrane fuel cell

A new blend system consisting of an amorphous sulfonated poly[bis(benzimidazobenzisoquinolinones)] (SPBIBI) and the semi-crystalline poly(vinylidene fluoride) (PVDF) was prepared for proton exchange membranes. The miscibility behavior of a series of blends of SPBIBI with PVDF at various weight ratios was studied by WXRD, DSC and FTIR. The properties of the blend membranes were investigated, and it was found that the introduction of PVDF in the SPBIBI matrix altered the morphological structure of the blend membranes, which led to the formation of improved connectivity channels. For instance, the conductivity of the blend membrane containing 10 wt% PVDF displayed the highest proton conductivity (i.e., 0.086 S cm(-1)) at room temperature, a value almost twofold that of the pristine SPBIBI membranes (i.e., 0.054S cm(-1)) under identical conditions.

High proton conductive advanced hybrid membrane based on sulfonated Si-SBA-15

Composite membranes based on Sulfonated poly(ether ether ketone) (SPEEK) and sulfonated organically modified Si-SBA-15 (S-SBA-15) were investigated with the purpose of increasing the proton conductivity. The novelty of the composite membranes was attributed to two special structures and different ion exchange capacities (IEC) of S-SBA-15 fillers, which were embedded in membranes. The typical hexagonal channels array of S-SBA-15 was confirmed by XRD and TEM. The regular vermiculate and amorphous structures of the inorganic fillers were proved by SEM. Composite membranes were prepared through common solvent casting method. SEM images indicated that the inorganic filler with regular structure dispersed homogeneously in the composite membranes, but the amorphous filler caused an agglomeration phenomenon at the same loading content.

Pore-filling membrane for direct methanol fuel cells based on sulfonated poly(styrene-ran-ethylene) and porous polyimide matrix

We have synthesized a porous co-polyimide film by coagulating a polyimide precursor in the non-solvent and thermal imidization. Factors affecting the morphology, pore size, porosity, and mechanical strength of the film were discussed. The porous polyimide matrix consists of a porous top layer and a spongy sub-structure with micropores. It is used as a porous matrix to construct sulfonated poly(styrene-ran-ethylene) (SPSE) infiltrated composite membrane for direct methanol fuel cell (DMFC) application. Due to the complete inertness to methanol and the very high mechanical strength of the polyimide matrix, the swelling of the composite membrane is greatly suppressed and the methanol crossover is also significantly reduced, while high proton conductivity is still maintained. Because of its higher proton conductivity and less methanol permeability, single fuel cell performance test demonstrated that this composite membrane outperformed Nafion membrane.

Interaction between alpha-actinin and negatively charged lipids membrane investigated by surface plasmon resonance and electrochemical methods

alpha-Actinin has been shown to be capable of interacting with some special membrane phospholipids directly, which is important for its function. In this study, hybrid bilayer membranes composed of negatively charged lipids are constructed on the surface plasmon resonance gold substrate and on the gold electrode, respectively, and the interaction between alpha-actinin and negatively charged lipids membrane is investigated by surface plasmon resonance, cyclic voltammetry and electrochemical impedance spectroscopy methods. alpha-Actinin is proved to be able to interact with the negatively charged lipids membrane directly. It can also insert at least partly into the membrane or lead to some defect or lesion in the membrane, which increase the permeability of the membrane. This study would bring some insight on the interaction between the alpha-actinin and the cell membranes in vivo.

Preparation and evaluation of a proton exchange membrane based on oxidation and water stable sulfonated polyimides

A series of novel oxidation and water stable sulfonated polyimides (SPIs) were synthesized from 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BTDA), and wholly aromatic diamine 2,2'-bis(3-sulfobenzoyl) benzidine (2,2'-BSBB) for proton exchange membrane fuel cells. These polyimides could be cast into flexible and tough membranes from m-cresol solutions. The copolymer membranes exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendant groups. Moreover, all BTDA-based SPI membranes exhibited much better water stability than those based on the conventional 1,4,5,8-naphthalenecarboxylic dianhydride. The improved water stability of BTDA-based polyimides was attributed to its unique binaphthalimide structure. The SPI membranes with ion exchange capacity (IEC) of 1.36-1.90 mequiv g(-1) had proton conductivity in the range of 0.41 x 10(-1) to 1. 12 x 10(-1) S cm(-1) at 20 degrees C. The membrane with IEC value of 1.90 mequiv g(-1) displayed reasonably higher proton conductivity than Nafion((R)) 117 (0.9 x 10(-1) S cm(-1)) under the same test condition and the high conductivity of 0.184 S cm(-1) was obtained at 80 degrees C. Microscopic analyses revealed that well-dispersed hydrophilic domains contribute to better proton conducting properties. These results showed that the synthesized materials might have the potential to be applied as the proton exchange membranes for PEMFCs.

Synthesis and characterization of soluble poly(amideimide)s bearing triethylamine sulfonate groups as gas dehumidification membrane material

A series of soluble poly(amide-imide)s (PAIs) bearing triethylammonium sulfonate groups were synthesized directly using trimellitic anhydride chloride (TMAC) polycondensation with sulfonated diamine such as 2,2'-benzidinedisulfonic acid (BDSA), 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid (ODADS), and nonsulfonated diamine 4,4-diaminodiphenyl methane in the presence of triethylamine. The resulting copolymers exhibited high molecular weights (high inherent viscosity), and a combination of desirable properties such as good solubility in dipolar aprotic solvents, film-forming capability, and good mechanical properties. Wide-angle X-ray diffraction revealed that the polymers were amorphous. These copolymers showed high permeability coefficients of water vapor because of the presence of the hydrophilic triethylammonium sulfonate groups. The water vapor permeability coefficients (P-w) and permselectivity coefficients of water vapor to nitrogen and methane [alpha(H2O/N-2) and (alpha(H2O/CH4)] Of the films increased with increasing the amount of the triethylammonium sulfonated groups.

Surface-modified Nafion (R) membrane by casting proton-conducting polyelectrolyte complexes for direct methanol fuel cells

Surface-modified Nafion (R) membrane was prepared by casting proton-conducting polyelectrolyte complexes on the surface of Nafion (R). The casting layer is homogeneous and its thickness is about 900 nm. The proton conductivity of modified Nafion (R) is slightly lower than that of plain Nafion (R); however, its methanol permeability is 41% lower than that of plain Nafion (R). The single cells with modified Nafion (R) exhibit higher open circuit voltage (OCV = 0.73 V) and maximal power density (P-max = 58 mW cm(-2)) than the single cells with plain Nafion (R) (OCV = 0.67 V, P x = 49 mW cm-2). It is a simple, efficient, cost-effective approach to modifying Nafion (R) by casting proton-conducting materials on the surface of Nafion (R).

Loosely packed self-assembled monolayer of N-hexadecyl-3,6-di(p-mercaptophenylacetylene)carbazole on gold and its application in biomimetic membrane research

Dithiols of N-hexadecyl-3,6-di(p-mercaptophenylacetylene)carbazole (HDMC) have been synthesized and employed to form self-assembled monolayers (SAMs) on gold. One characteristic of the HDMC molecule is its peculiar molecular structure consisting of a large and rigid headgroup and a small and flexible alkyl-chain tail. HDMC adsorbates can attach to gold substrates by a strong Au-S bond with weak van der Waals interactions between the alkyl-chain tails, leading to a loosely packed hydrophobic SAM. In this way we can couple hybrid bilayer membranes (HBMs) to gold surfaces with more likeness to a cell bilayer than the conventional HBMs based on densely packed long-chain alkanethiol SAMs. The insulating properties and stability of the HDMC monolayer as well as the HDMC/lipid bilayer on gold have been investigated by electrochemical techniques including cyclic voltammetry and impedance spectroscopy. To test whether the quality of the bilayer is sufficiently high for biomimetic research, we incorporated the pore-forming protein a-hemolysin) and the horseradish peroxidase into the bilayers, respectively.

Phenolphthalein immobilized membrane for an optical pH sensor

A phenolphthalein immobilized cellulose membrane for an optical pH sensor was described. The phenolphthalein was first reacted with the formaldehyde to produce a series of prepolymers with many hydroxymethyl groups. In this paper, the prepolymers was abbreviated to phenolphthalein-formaldehyde (PPF). Then the PPF was covalently immobilized to the diacetylcellulose membrane via hydroxymethyl groups. Finally the membrane was hydrolyzed in the 0.1 M NaOH solution for 24 h to reduce the response time. Advantageous features of the pH-sensitive membrane include (a) a large dynamic range from pH 8.0 to 12.50, or even broader, (b) rapid response time (2-30 s), (c) easy of fabrication, and (d) a promising material for determination of high pH values. The immobilized PPF has a broader dynamic range from 8.0 to 12.50 than the free phenolphthalein from pH 8.0 to 11.0, and this was due to the newly produced methylenes in our investigation.

Extraction and separation of cadmium(II), iron(III), zinc(II), and europium(III) by Cyanex302 solutions using hollow fiber membrane modules

The mass transfer behaviors of Cd(II), Fe(III), Zn(II), and Eu(III) in sulfuric acid solution using microporous hollow fiber membrane (HFM) containing bis(2,4,4-trimethylpentyl)monothiophosphinic acid (commercial name Cyanex302) were investigated in this paper. The experimental results showed that the values of the mass transfer coefficients (K-w) decreased with an increase of H+ concentration and increased with an increase of extractant Cyanex302 concentration. The mass transfer resistance of Eu3+ was the largest because K-w value of Eu3+ was the smallest. The order of mass transfer rate of metal ions at low pH was Cd > Zn > Fe > Eu. Mixtures of Zn2+ and Eu3+ or of Zn2+ and Cd2+ were well separated in a counter-current circulation experiment using two modules connected in series at different initial acidity and concentration ratio. These results indicate that a hollow fiber membrane extractor is capable of separating the mixture compounds by controlling the acidity of the aqueous solution and by exploiting different mass transfer kinetics. The interfacial activity of Cyanex302 in sulfuric acid solution was measured and interfacial parameters were obtained according to Gibbs adsorption equation.

A new method of measuring alcohol clusters in polyimide membrane: combination of inverse gas chromatography with equilibrium swelling

A new method of measuring the mean size of solvent clusters in swollen polymer membrane is presented in this paper. This method is based on a combination of inverse gas chromatography (IGC) and equilibrium swelling. The mechanism is that weight fraction activity coefficient of solvent in swollen polymer is influenced by its clusters size. The mean clusters size of solvent in swollen polymer can be calculated as the quotient of the weight fraction activity coefficient of clustering system dividing the weigh fraction activity coefficient of non-clustering system. In this experiment, the weigh fraction activity coefficient of non-clustering system was measured with IGC. Methanol, ethanol and polyimide systems were tested with the new method at three temperatures, 20, 40, and 60degreesC. The mean clusters size of methanol in polyimide was five, four, and three at each temperature condition, respectively. Ethanol did not form clusters (the mean clusters size was one). In contrast to the inherent narrow temperature range in DSC, XRD, and FTIR methods, the temperature range in IGC and equilibrium swelling is broad. Compared with DSC. XRD. and FTIR, this new method can detect the clusters of solvent-polymer system at higher temperature.

Preparation and properties of microporous membrane from poly(vinylidene fluoride-co-tetrafluoroethylene) (F2.4) for membrane distillation

Flat-sheet microporous membranes from F2.4 for membrane distillation (MD) were prepared by phase inversion process. Dimethylacetamide (DMAC) and LiClO(4)(.)3H(2)O/trimethyl phosphate (TMP) were, respectively, used as solvent and pore-forming additives. The effects of casting solution composition, exposure time prior to coagulation and temperature of precipitation bath on F2.4 membrane structure were investigated. The morphology of resultant porous membrane was observed by scanning electron microcopy. Some natures of F2.4 porous membrane after drying in air, such as mechanical properties and hydrophobicity, were exhibited and compared with poly(vinylidene fluoride) (PVDF) membrane prepared by the same ways. Stress-at-break and strength stress of F2.4 microporous membrane are higher than that of PVDF membrane, and elongation percentage of F2.4 membrane at break is about eight-fold as great as that of PVDF membrane. Contact angle of F2.4 microporous membrane to water (86.6 +/- 0.51degrees) was also larger than that of PVDF mernbrane (80.0 +/- 0.78degrees). MD experiment was carried out using a direct contact membrane distillation (DCMD) configuration as final test to permeate performance of resultant microporous membrane.

Preliminary research on microporous membrane from F2.4 for membrane distillation

An asymmetric hydrophobic microporous membrane from the copolymer of tetrafluoroethylene and vinyliden fluoride (F2.4) has been fabricated by phase inversion process. Some characteristics, such as mechanical properties and hydrophobicity, have been examined and compared with polyvinylidenefluoride (PVDF) membrane. Experimental data exhibit F2.4 membrane excellent mechanical properties and hydrophobicity. F2.4 microporous membrane was approximately 6-8 times as high as PVDF membrane in stretching strain and extension ratio at break, and contact angle to distilled water of the fore (88.5degrees) was larger than the latter (80.0degrees), too. The results from membrane distillation (MD) process were well agreed with the fundamental laws of membrane distillation.