Sulfonated poly(ether ether ketone)/clay-SO3H hybrid proton exchange membranes for direct methanol fuel cells Journal of Power Sources

A new type of sulfonated clay (clay-SO3H) was prepared by the ion exchange method with the sulfanilic acid as the surfactant agent. The grafted amount of sulfanilic acid in clay-SO3H was 51.8 mequiv. (100 g)(-1), which was measured by thermogravimetric analysis (TGA). Sulfonated poly(ether ether ketone) (SPEEK)/clay-SO3H hybrid membranes which composed of SPEEK and different weight contents of clay-SO3H, were prepared by a solution casting and evaporation method. For comparison, the SPEEK/clay hybrid membranes were produced with the same method.

A screening study on persistent bioaccumulation toxins (PBT) in fuel combustion soot

Persistent bioaccumulative toxins (PBTs) are organic substances that are persistent, bioaccumulative and can cause severe toxic effects (e.g. potential oncogens, mutagenic, endocrine disrupters) to human health or environment which are the ones that need special attention. PBT chemicals could be released to the environment from several types of sources and are ubiquitous in environment. However, fast and efficiency monitoring and assessment methods to investigate PBTs in environment are still lacking. In this study, a cleaning-up procedure of analyzing PBTs in fuels combustion soot was developed and its performance was assessed through comparing the chromatograms of crude extracts with their cleaned extracts after the cleaning-up procedure. The results showed that polycyclic aromatic compounds (PACs) were the main components in fuel combustion soot and the clean-up procedure developed in this paper can be well used as the method of analyzing PBTs in fuels combustion soot.

Surface modification of bioactive glass nanoparticles and the mechanical and biological properties of poly(L-lactide) composites

Novel bioactive glass (13G) nanoparticles/poly(L-lactide) (PLLA) composites were prepared as promising bone-repairing materials. The BG nanoparticles (Si:P:Ca = 29:13:58 weight ratio) of about 40 run diameter were prepared via the sol-gel method. In order to improve the phase compatibility between the polymer and the inorganic phase, PLLA (M-n = 9700 Da) was linked to the surface of the BG particles by diisocyanate. The grafting ratio of PLLA was in the vicinity of 20 wt.%. The grafting modification could improve the tensile strength, tensile modulus and impact energy of the composites by increasing the phase compatibility.

Novel proton exchange membranes based on water resistant sulfonated poly[bis(benzimidazobenzisoquinolinones)]

Novel water resistant sulfonated poly[bis(benzimidazobenzisoquinolinones)] (SPBIBIs) were synthesized from 6,6'-disulfonic-4,4'-binaphthy]-1,1',8,8'-tetracarboxylic dianhydride (SBTDA) and various aromatic ether tetraamines. The resulting polymers with IEC in the range of 2.17-2.87 mequiv g(-1) have a combination of desired properties such as high solubility in common organic solvents, film-forming ability, and excellent thermal and mechanical properties. Flexible and tough membranes, obtained by casting from m-cresol solution, had tensile strength, elongation at break, and tensile modulus values in the range of 87.6-98.4 MPa, 35.8-52.8%, and 0.94-1.07 GPa. SPBIBI membranes with a high degree of sulfonation displayed high proton conductivity and a good resistance to water swelling as well. SPBIBI-b with IEC of 2.80 mequiv g(-1) displayed the conductivity of 1.74 x 10(-1) S cm(-1) at 100 degrees C, which was comparable to that of Nafion (R) 117 (1.78 x 10(-1) S cm(-1), at 100 degrees C).

Novel sulfonated poly(arylene ether ketone) copolymers bearing carboxylic or benzimidazole pendant groups for proton exchange membranes

A novel strategy in which the benzimidazole group and sulfonic group are simultaneously attached to an aromatic polymer has been reported in this paper. For this purpose, sulfonated poly(arylene ether ketone) copolymers containing carboxylic acid groups (SPAEK-x-COOH, x refers to the molar percentage Of sulfonated repeating units) are prepared by the aromatic nucleophilic polycondensation of sodium 5,5'-carbonyl-bis(2-fluobenzene-sulfonate) (SDFBP), 4,4'-difluorobenzophenone (DFBP) and phenolphthalin (PPL). Then the carboxylic acid groups attached to the SPAEK-x-COOH are transformed to benzimidazole units through condensation reactions (referred to as SPAEK-x-BI). Fourier transform infrared spectroscopy and H-1 NMR measurements are used to characterize and confirm the structures of these copolymers.

Synthesis and characterization of novel sulfonated poly(arylene ether ketone) copolymers with pendant carboxylic acid groups for proton exchange membranes

A series of novel side-chain-type sulfonated poly(arylene ether ketone)s with pendant carboxylic acid groups copolymers (C-SPAEKs) were synthesized by direct copolymerization of sodium 5,5'-carbonyl-bis(2-fluorobenzenesulfonate), 4,4'-difluorobenzophenone and 4,4'-bis(4-hydroxyphenyl) valeric acid (DPA). The expected structure of the sulfonated copolymers was confirmed by FT-IR and H-1 NMR. Membranes with good thermal and mechanical stability could be obtained by solvent cast process. It should be noted that the proton conductivity of these copolymers with high sulfonation degree (DS > 0.6) was higher than 0.03 S cm(-1) and increased with increasing temperature. At 80 degrees C, the conductivity of C-SPAEK-3 (DS = 0.6) and C-SPAEK-4 (DS = 0.8) reached up to 0.12 and 0.16 S cm-1, respectively, which were higher than that of Nafion 117 (0.10 S cm(-1)).

Preparation and Bioactivity of the Composite of PLGA and Hydroxyapatite Nanocrystals Surface-grafted with L-lactic Acid Oligomer

The hydroxyapatite (HA) nanocrystals of 100-200 nm in length and 20-30 nm in width were hydrothermally synthesized by the reaction of phosphoric acid and calcium hydroxide. Lactic acid oligomer surface grafted HA(op-HA) nanoparticles were obtained by oligomeric lactic acid with a certain molecular weight grafting onto the HA surface to form a Ca carboxylate bond in the absence of any catalyst. The op-HA was further blended with poly(lactide-co-glycolide) (PLGA) to prepare the nanocomposite of op-HA/PLGA. FTIR, TGA, ESEM and EDX were used to analyze grafting reaction, the graft ratio of op-HA, surface topography and calcium deposition of the composites, respectively. The rabbit osteoblasts were seeded and cultured on the surface of composites in vitro. The cell morphology, adhesion, proliferation and gene expression were evaluated with FITC staining, NIH image J software and the analysis of real-time PCR, respectively. The results show that the graft ratio of op-HA is 8.3% (mass fraction). The op-HA/PLGA nanocomposite possessed more suitable surface properties, including roughness and plenty of calcium and phosphor. It exhibited better cell adhesion, spreading and proliferation of rabbit osteoblasts, compared to pure PLGA.

NOVEL COMPOSITES OF POLY(L-LACTIDE) AND SURFACE MODIFIED BIOACTIVE SiO2-CaO-P2O5 GEL NANOPARTICLES: MECHANICAL AND BIOLOGICAL PROPERTIES

Bioactive SiO2-CaO-P2O5 gel (BAG) nanoparticles with 40 nm in diameter were synthesized by the sol-gel route and further modified via the ring-opening polymerization of lactide on the surface of particles. Surface modified BAG (mBAG) was introduced in poly(L-lactide) (PLLA) matrix as bioactive filler. The dispersibility of mBAG in PLLA matrix was much higher than that of rough BAG particles. Tensile strength of the mBAG/PLLA composite could be increased to 61.2 MPa at 2 wt% filler content from 53.4 MPa for pure PLLA. The variation of moduli of the BAG/PLLA and mBAG/PLLA composites always showed an enhancement tendency with the increasing content of filler loading. The SEM photographs of the fracture surfaces showed that mBAG could be homogeneously dispersed in the PLLA matrix, and the corrugated deformation could absorb the rupture energy effectively during the breaking of materials. In vitro bioactivity tests showed that both BAG and mBAG particles could endow the composites with ability of the calcium sediment in SBF, but the surface modification of BAG particles could weaken this capability to some extent. Biocompatibility tests showed that both BAG and mBAG particles could facilitate the attachment and proliferation of the marrow cells on the surface of the composite.

Preparation and properties of sulfonated poly(ether ether ketone)s (SPEEK)/polypyrrole composite membranes for direct methanol fuel cells

Polypyrrole (Ppy) was successfully introduced into methyl substituted sulfonated poly(ether ether ketone) (SPEEK) membranes by polymerization in SPEEK solutions to improve their methanol resistance. Uniform polypyrrole (Ppy) distributed composite membranes were formed by this method by the interaction between SPEEK and Ppy. The properties of the composite membranes were characterized in detail. The composite membranes show very good proton conductive capability (25 degrees C: 0.05-0.06s cm(-1)) and good methanol resistance (25 degrees C: 5.3 x 10(-7) 1.1 x 10(-6) cm(2) s(-1)). The methanol diffusion coefficients of composite membranes are much lower than that of pure SPEEK membranes (1.5 x 10(-6) cm(2) s(-1)). The composite membranes show very good potential usage in direct methanol fuel cells (DMFCs).

Sol-gel-derived titanium oxide/copolymer composite based glucose biosensor

A new type of sol-gel-derived titanium oxide/copolymer composite material was developed and used for the construction of glucose biosensor. The composite material merged the best properties of the inorganic species, titanium oxide and the organic copolymer, poly(vinyl alcohol) grafting 4-vinylpyridine (PVA-g-PVP). The glucose oxidase entrapped in the composite matrix retained its bioactivity. Morphologies of the composite-modified electrode and the enzyme electrode were characterized with a scanning electron microscope. The dependence of the current responses on enzyme-loading and pH was studied. The response time of the biosensor was < 20 s and the linear range was up to 9 mM with a sensitivity of 405 nA/mM. The biosensor was stable for at least I month. In addition, the tetrathiafulvalene-mediated enzyme electrode was constructed for the decrease of detection potential and the effect of three common physiological sources that might interfere was also investigated.

Self-gelatinizable graft copolymer of poly(vinyl alcohol) with 4-vinylpyridine as an immobilization matrix for the construction of a tyrosinase-based amperometric biosensor

A tyrosinase-based amperometric biosensor using a self-gelatinizable graft copolymer of poly(vinyl alcohol) with 4-vinylpyridine (PVA-g-PVP) as an immobilization matrix was constructed. The 4-vinylpyridine component of PVA-g-PVP enhances the adherence to a glassy carbon electrode surface. The content of 4-vinylpyridine in this immobilization matrix plays a key role in retaining the activity of tyrosinase. A simple, milder method was adopted by simply syringing the copolymer-tyrosinase aqueous solution on to the electrode surface and allowing water to evaporate at 4 degrees C in a refrigerator. Several parameters, including copolymer composition; pH, applied potential and enzyme membrane composition, ware optimized. The enzyme membrane composition can be varied to obtain higher sensitivity or a wider linear detection range. The biosensor was used for the determination of phenol, p-cresol and catechol. The biosensor exhibited excellent reproducibility, stability and sensitive response and can be used in flow injection analysis. The biosensor showed an extended linear range in hydrophilic organic solvents and it can be used in monitoring organic reaction processes. The analytical performance demonstrated this immobilization matrix is suitable for the immobilization of tyrosinase.

IMPEDANCE STUDY OF THE INTERFACES BETWEEN LITHIUM, POLYANILINE, LITHIUM-DOPED MNO2 AND MODIFIED POLY(ETHYLENE OXIDE) ELECTROLYTE

Impedance study was carried out for the interfaces between lithium, polyaniline (PAn), lithium-doped MnO2 and modified poly(ethylene oxide) (PEO) electrolyte under various' conditions. The interfacial charge-transfer resistances R(ct) on PEO/PAn, R(ct) on PEO/LiMn2O4 increase with depth-of-discharge and decrease after the charge of the cell containing modified PEO as electrolyte. The charge-transfer resistance R(ct) on PEO/PAn is higher than R(ct) on PEO/LiMn2O4 under the same condition, since inserted species and mechanism are different for both cases. In the case of PAn, an additional charge-transfer resistance might be related to the electronic conductivity change in discharge/charge potential range, as it was evident from a voltammetry curve. With increasing cycle numbers, the charge-transfer resistance increases gradually. The impedance results also have shown that at low frequency the diffusion control is dominant in the process of the charge and discharge of Li/PEO/PAn or Li/PEO/LiMn2O4 cell. The diffusion coefficients have been calculated from impedance data.

Capillary electrochromatography with monolithic poly(styrene-co-divinylbenzene-co-methacrylic acid) as the stationary phase

A new kind of monolithic capillary electrochromatography column with poly(styrene-co-divinylbenzene-co-methacrylic acid) as the stationary phase has been developed. The stationary phase was found to be porous by scanning electron microscopy and the composition of the continuous bed was proved by IR spectroscopy to be the ternary polymer of styrene, divinylbenzene, and methacrylic acid. The effects of operating parameters, such as voltage, electrolyte, and organic modifier concentration in the mobile phase on electroosmotic flow were studied systematically, The retention mechanism of neutral solutes on such a column proved to be similar to that of reversed-phase high performance liquid chromatography. In addition, fast analyses of phenols, chlorobenzenes, anilines, isomeric compounds of phenylenediamine and alkylbenzenes within 4.5 min were achieved.

The interaction between poly(vinylpyrrolidone) and reversed micelles of water/AOT/n-heptane

The interactions between poly(vinylpyrrolidone) (PVP) and the reversed micelles composed of water, AOT, and n-heptane are investigated with the aid of phase diagram, measurements of conductivity and viscosity, Fourier transform infrared (FTIR) spectrum, and dynamic light scattering (DLS). The phase diagrams of water/AOT/heptane in the presence of and absence of PVP are given. The conductivity of the water/AOT/heptane reversed micelle without PVP initially increases and then decreases with the increase of water content, ω0 (the molar ratio of water to AOT), while the plots of conductivity (K) versus ω0 of the reversed micelle in the presence of PVP depend on the PVP concentrations. The plot of K versus ω0 with 2.0%wt PVP is similar to that without PVP. Only the ω0,max (the water content that the maximum conductivity corresponds to) is larger than that without PVP. Nevertheless, the conductivity of the reversed micelle containing more than 4%wt PVP always rises with the increase of the water content in the measured range. The DLS results indicate that the hydrodynamic radius (Rh) in the presence and absence of PVP rises with the increase of ω0. The plots with PVP and without PVP have almost the same value when ω0<17; and after that, it quickly increases with the increase of ω0. It is interesting to find that there is almost no effect of the PVP concentration on the viscosity and Rh of the reversed micelle at ω0 = 15. The FTIR results suggest that the contents of SO3--bound water and Na+-bound water both decrease with PVP added, while the content of the bulky-like water increases. However, the trapped water in the hydrophobic chain of the surfactant is nearly unaffected by PVP. It is also found from the FTIR that the carbonyl group stretching vibration of AOT is fitted into two sub-peaks, which center at 1740 and 1729 cm-1, corresponding to the trans and cis conformations of AOT, respectively.

Two-dimensional simulation of inductive plasma sources with self-consistent power deposition

A time averaged two-dimensional fluid model including an electromagnetic module with self-consistent power deposition was developed to simulate the transport of a low pressure radio frequency inductively coupled plasma source. Comparsions with experiment and previous simulation results show, that the fluid model is feasible in a certain range of gas pressure. In addition, the effects of gas pressure and power input have been discussed.