Sulfonated poly(arylene-co-naphthalimide)s synthesized by copolymerization of primarily sulfonated monomer and fluorinated naphthalimide dichlorides as novel polymers for proton exchange membranes

A novel sulfonated aromatic dichloride monomer was successfully prepared by the reaction of 2, 5-dichlorobenzophenone with fuming sulfuric acid. Copolymerization of this monomer in the form of sodium salt (1) with N-(4-chloro-2-trifluoromethylphenyl)-5-chloro-1,8-naphthalimide (2) or bis(N-(4-chloro-2-trifluoromethylphenyl)1,4,5,8-naphthalimide (3) generated two series of novel poly(arylene-co-naphthalimide) s I-x and II-x where x represents the content of the sulfonated monomer. The synthesized copolymers with the -SO3H group in the side chains possessed high molecular weights revealed by their high viscosity and the formation of tough and flexible membranes. The copolymers exhibited excellent stability toward water and oxidation due to the introduction of the hydrophobic CF3 groups. The sulfonated copolyimides that incorporated with 1,8-naphthalimide (I-x) exhibited better hydrolytic and oxidative stabilities than those with 1,4,5,8-naphthalimide. Copolymer I-50 membrane endured for more than 83 h in Fenton's reagent at room temperature. The mechanical properties of I-50 membrane kept almost unchanged after immersing membrane in boiling water for 196 h. The proton conductivities of copolymer films increased with increasing IEC and temperature, reaching values above 6.8 x 10(-1) S/cm at 80 degrees C.

Morphology of high impact polypropylene particles

Morphological features of isotactic polypropylene (iPP) and high impact polypropylene (hiPP) particles produced in a multistage polymerization process were investigated by field-emission electron microscopy (FESEM) and transmission electron microscopy (TEM) techniques. Study was mainly focused on architecture of iPP particle and distribution of elastomer phase (EPR) within the preformed iPP matrix. The iPP particle is an agglomerate of many subglobules (ca. several to hundred microns in diameter), while the subglobule in turn is formed by a great deal of primary globules (ca. 100 nm in diameter). Large macropores between the subglobules and finely distributed micropores within the subglobule constitute a network of pore inside the iPP particle. Ethylene/propylene comonomers can diffuse into the macro- and micropores and copolymerize on catalyst active sites located on periphery of the pores, forming elastomer phase inside.

The direct synthesis of wholly aromatic poly(p-phenylene)s bearing sulfobenzoyl side groups as proton exchange membranes

Sulfonated poly(p-phenylene)s (SPPs) containing sulfonic acid groups in their side chains had been directly synthesized by Ni(0) catalytic coupling of sodium 3-(2,5-dichlorobenzoyl)benzenesulfonate and 2,5-dichlorobenzophenone. The synthesized copolymers possessed high molecular weights revealed by their high viscosity, and the formation of tough and flexible membranes by casting from DMAc solution. The copolymers exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendent groups. Transmission electron microscopic (TEM) analysis revealed that these side-chain type SPP membranes have a microphase-separated structure composed of hydrophilic side-chain domains and hydrophobic polyphenylene main chain domains. The proton conductivities of copolymer membranes increased with the increase of IEC and temperature, reaching values above 3.4 x 10(-1) S/cm at 120 degrees C, which are almost 2-3 times higher than that of Nafion 117 at the same measurement conditions. Consequently, these materials proved to be promising as proton exchange membranes.

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).

Highly sensitive electrogenerated chemiluminescence produced at Ru(bpy)(3)(2+) in Eastman-AQ55D-carbon nanotube composite film electrode

The electrochemistry and electrogenerated chemilurninescence (ECL) of tris(2,2-bipyridyl)ruthenium(II) ion-exchanged in Eastman-AQ-carbon nanotube (CNT) composite films were investigated at a glassy carbon (GC) electrode. Eastman-AQ55D is a poly (ester sulfonic acid) cation exchanger available in a commercial dissolved form. It is much more hydrophilic than Nafion due to its unique structure, so Ru(bpy)(3)(2+) does not diffuse into the hydrophobic region where it may lose its electroactivity as that in Nafion. The interfused CNT could act as electronic wires that connect the electrode with Ru(bpy)(3)(2+), which made the composite film much more electronically which finally led to the increasing of Ru(bpy)(3)(2+) conductive. Besides, the negatively charged CNT could also absorb some Ru(bpy)(3)(2+). Moreover, the strong electrostatic interaction between AQ and Ru(bpy)(3)(2+) made the composite films much more stable. The combination of AQ and CNT brings excellent sensitivity with the detection limit as low as 3 x 10(-11) M for TPA.

The influence of arrangement of St in MBS on the properties of PVC/MBS blends

Three series of MBS core-shell impact modifiers were prepared by grafting styrene and methyl methacrylate onto PB or SBR seed latex in emulsion polymerization. All the MBS modifiers were designed to have the same total chemical composition, and MMA/Bd/St equals 30/42/28, which is a prerequisite for producing transparent blends with PVC. Under this composition, there were three different ways of arrangement for styrene in MBS, which led to the different structure of MBS modifier. The concentration of MBS in PVC/MBS blends was kept at a constant value of 20 wt.%. The effects of arrangement of St in MBS on the mechanical and optical properties of PVC/MBS blends were studied. The notched Izod impact test results showed that the MBS with a PB homopolymer core grafted with St had a lowest brittle-ductile transition (BDT) temperature and BDT temperature increased with the amount of St copolymerized with Bd in the core of MBS. The transparency of blends also increased with the amount of St copolymerized with Bd in the core. TEM results showed that the arrangement of St in MBS influenced the deformation behavior. Two deformation modes were observed in the blends: cavitation and shear yielding.

Deformation mechanism of polystyrene toughened with sub-micrometer monodisperse rubber particles

Core-shell polybutadiene-graft-polystyrene (PB-g-PS) rubber particles with different ratios of polybutadiene to polystyrene were prepared by emulsion polymerization through grafting styrene onto polybutadiene latex. The weight ratio of polybutadiene to polystyrene ranged from 50/50 to 90/10. These core-shell rubber particles were then blended with polystyrene to prepare PS/PB-g-PS blends with a constant rubber content of 20 wt%. PB-g-PS particles with a lower PB/PS ratio (<= 570/30) form a homogeneous dispersion in the polystyrene matrix, and the Izod notched impact strength of these blends is higher than that of commercial high-impact polystyrene (HIPS). It is generally accepted that polystyrene can only be toughened effectively by 1-3 mu m rubber particles through a toughening mechanism of multiple crazings. However, the experimental results show that polystyrene can actually be toughened by monodisperse sub-micrometer rubber particles. Scanning electron micrographs of the fracture surface and stress-whitening zone of blends with a PB/PS ratio of 70/30 in PB-g-PS copolymer reveal a novel toughening mechanism of modified polystyrene, which may be shear yielding of the matrix, promoted by cavitation.

Confining conducting polyaniline in a stable inorganic network

Water soluble conducting polyaniline with electrical conductivity of 10(-1)-10(-2) S/cm was prepared employing dopant induced water solubility technology. The water resistance of the conducting film was significantly improved employing,sol-gel hybrids method, especially when the conductive polyaniline loading was below 30 wt%. The reason for the improvement is that the conducting polyaniline chains are confined in a stable inorganic network.

Surface plasmon resonance studies on the electrochemical doping/dedoping processes of anions on polyaniline-modified electrode

The combination of in situ surface plasmon resonance (SPR) with electrochemistry was used to investigate the electrochemical doping/dedoping processes of anions on a polyaniline (PAn)-modified electrode. Electrochemical SPR characteristics of the PAn film before and after doping/dedoping were revealed. The redox transformation between the insulating leucoemeraldine, and the conductive emeraldine, corresponding to the doping/dedoping of anion, can lead to very distinct changes in both the resonance minimum angle and the shape of SPR curve. This is ascribed to the swelling/shrinking effect, and the change of the PAn film in the imaginary part of the dielectric constant resulted from the transition of the film conductivity. In situ recording the time evolution of reflectance change at a fixed angle permits the continuous monitoring of the kinetic processes of doping/dedoping anions. The size and the charge of anions, the film thickness, as well as the concentration of anions are shown to strongly influence the rate of ingress/egress of anions. The time differential of SPR kinetic curves can be well applied in the detecting electroinactive anion by flow injection analysis. The approach has higher sensitivity and reproducibility compared with other kinetic measurements, such as those obtained by amperometry.

Gold nanoparticles as fine tuners of electrochemical properties of the electrode/solution interface

Recently, a novel approach for preparing SERS and SPR substrates was developed, which indicates a potential application in tailoring the interfacial structure of an electrode surface. In this study, (3-mercaptopropyl)trimethoxysilane (MPTMS) was selected as a polymeric adhesive layer, and a low concentration of colloid Au solution was used to achieve a more accurate control over interface morphology at nanoscale dimensions due to slow self-assembling kinetics of gold nanoparticle's. Subsequent seeding growth of these MPTMS-supported submonolayers of gold nanoparticles in Au3+/NH2OH aqueous solution enlarges particle size and eventually results in the generation of conductive gold films (similar to previous (3-aminopropyl)trimethoxysilane-supported gold films). Such tunable interface structure was evaluated by atomic force microscopy (AFM). Also, ac impedance spectroscopy (ACIS) and cyclic voltammograms were performed to evaluate electrochemical properties of the as-prepared interfaces by using Fe(CN)(6) (3-/4-) couples as a probe. Furthermore, relevant theories of microarray electrodes were introduced into this study to explain the highly tunable electrochemical properties of the as-prepared interfaces. As a result, it is concluded that the electrochemical properties toward Fe(CN)(6) (3-/4-) couples are highly dependent on the active nanoelectrode (nanoparticles) area fraction and nanoparticles are fine-tuners of interfacial properties because the number density. (numbers/unit area) and size of nanoparticles are highly tunable by self-assembling and seeding growth time scale control. This is in agreement with the theoretical expectations for a microarray electrode if a single nanoparticle tethered to a blocking SAM is taken as a nanoelectrode and 2-D nanoparticle assemblies are taken as nanoelectrode arrays.

Sol-gel derived carbon ceramic electrode containing methylene blue-intercalted alpha-zirconium phosphate micro particles

Methylene blue-intercalated a-zirconium phosphate (MBZrP) micro particles in deionized water were deposited onto the surface of graphite powder to prepare graphite powder-supported MBZrP, which was subsequently dispersed into methyltrimethoxysilane-derived gels to yield a conductive composite. The composite was used as electrode material to fabricate a surface-renewable, rigid, leak-free carbon ceramic composite electrode, bulk-modified with methylene blue (MB). In the configuration, alpha-zirconium phosphate was employed as a solid host for MB, which acted as a catalyst. Graphite powder ensured conductivity by percolation, the silicate provided a rigid porous backbone and the methyl groups endowed hydrophobicity and thus limited the wetting section of the modified electrode. Peak currents of the MBZrP-modified electrode were surface-confined at low scan rates but diffusion-controlled at high scan rates. Square-wave voltammetric study revealed that MBZrP immobilized in carbon ceramic matrix presented a two-electron, three-proton redox process in acidic aqueous solution with pH ranged from 0.44 to 2.94. In addition, the chemically modified electrode showed an electrocatalytic activity toward nitrite reduction at +0.15 V (vs. Ag/AgCl) in acidic aqueous solution (pH=0.44). The linear range and detection limit are 1 x 10(-6)-4 x 10(-3) mol L-1 and 1.5 x 10(-7) mol L-1, respectively.

Synthesis and characterization of network liquid crystal elastomers and thermosets

A new series of network liquid crystal polymers were synthesized by graft copolymerization of the difunctional mesogenic monomer 4-allyloxy-benzoyloxy-4'-allyloxybiphenyl (M) upon polymethylhydrosiloxane (PMHS). Monomer M acted not only as a mesogenic unit but also as a crosslinker for the network polymers. The chemical structures of the polymers were confirmed by IR spectroscopy. DSC, TGA, and X-ray scattering were used to measure their thermal properties and mesogenic properties. The glass transition temperature (T-g) of these network liquid crystal polymers was increased when the monomer was increased, and T-d (temperature of 5% weight loss) at first went up and reached a maximum at P, then went down. The slightly crosslinked polymers (P, P,) show rubber-like elasticity, so it was called liquid-crystal elastomer. Network polymers will lose elasticity property with a highly crosslinked degree, and turn into thermosetting polymers (P-4, P-5). All polymers exhibited a smectic texture by X-ray scattering.

Study of electron transfer across the liquid/ice-like matrix interface by scanning electrochemical microscopy

In this work, we report the findings of a study on scanning electrochemical microscopy (SECM) to investigate the interfacial electron-transfer (ET) reaction between the 7,7,8,8-tetracyanoquinodimethane radical anion (TCNQ(.-)) in 1,2-dichloroethane and ferricyanide in an ice-like matrix (a mixture of insulting ice and conductive liquid) under low temperatures. Experimental results indicate that the formed liquid/ice-like matrix interface is superficially similar in electrochemical characteristics to a liquid/liquid interface at temperatures above -20 degreesC. Furthermore, imaging data show that the surface of the ice-like matrix is microscopically flat and physically stable and can be applied as either a conductive or an insulting substrate for SECM studies. Perchlorate ion was selected as the common ion in both phases, the concentrations of which controlled the interfacial potential difference. The effect of perchlorate concentration in the DCE phase on interfacial reactions has been studied in detail. The apparent heterogeneous rate constants for TCNQ(.-) oxidation by Fe(CN)(6)(3-) in another phase under different temperatures have been calculated by a best-fit analysis, where the experimental approach curves are compared with the theoretically derived relationships. Reaction rate data obey Butler-Volmer formulation before and after the freezing point, which is similar to most other known cases of ET reactions at liquid/liquid interfaces. However, there is a sharp change observed for heterogeneous rate constants around the freezing point of the aqueous phase, which reflects the phase transition. At temperatures below -20 degreesC, surface-confined voltammograms for the reduction of ferricyanide were obtained, and the ice-like matrix became an insulating one, which indicates that the aqueous phase is really a frozen phase.