Counterion and solvent effects on the dilute solution viscosity of polystyrene ionomers

We present an analysis of data on the intrinsic viscosity [η] of sulfo-polystyrene ionomers in several solvents for a variety of sulfonation levels and counterions. For solvents of low dielectric constant, 2 < ε < 18, [η] decreases from the base polymer value [η]₀ with increasing substitution level. This behavior was attributed to intramolecular association of ionic dipoles. The ratio [η]/[η]₀ was found to depend on a single reduced variable α_Aα_Sx, where x is the fractional substitution, α_A depends only on the counterion, and α_S ∝ ε^?1 depends only on the solvent. For solvents of high dielectric constant, 36 < ε < 47, [η] increases approximately as x³, and counterion effects are small. This behavior was attributed to ionic dissociation, giving rise to a polyelectrolyte effect. Implications of the low ε results are discussed in relation to association-induced gelation behavior and possible generalizations of the reduced variables approach.     

The phase diagram of a single polymer chain: New insights from a new simulation method

We present simulation results for the phase behavior of a single chain for a flexible lattice polymer model using the Wang-Landau sampling idea. Applying this new algorithm to the problem of the homopolymer collapse allows us to investigate not only the high temperature coil–globule transition but also an ensuing crystallization at lower temperature. Performing a finite size scaling analysis on the two transitions, we show that they coincide for our model in the thermodynamic limit corresponding to a direct collapse of the random coil into the crystal without intermediate coil–globule transition. As a consequence, also the many chain phase diagram of this model can be predicted to consist only of gas and crystal phase in the limit of infinite chain length. This behavior is in agreement with findings on the phase behavior of hard-sphere systems with a relatively short-ranged attractive square well. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2542–2555, 2006     

Synthesis and characterization of polyimides derived from (3‐amino‐2,4,6‐trimethylphenyl)‐(3′‐aminophenyl)methanone and aromatic dianhydrides

A series of new polyimides were prepared via the polycondensation of (3‐amino‐2,4,6‐trimethylphenyl)‐(3′‐aminophenyl)methanone and aromatic dianhydrides, that is, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride. The structures of the polyimides were characterized by Fourier transform infrared and NMR measurements. The properties were evaluated by solubility tests, ultraviolet–visible analysis, differential scanning calorimetry, and thermogravimetric analysis. The two different meta‐position‐located amino groups with respect to the carbonyl bridge in the diamine monomer provided it with an unsymmetrical structure. This led to a restriction on the close packing of the resulting polymer chains and reduced interchain interactions, which contributed to the solubility increase. All the polyimides except that derived from BPDA had good solubility in strong aprotic solvents, such as N‐methyl‐2‐pyrrolidinone, N,N′‐dimethylacetamide, N,N‐dimethylformamide, and dimethyl sulfone, and in common organic solvents, such as cyclohexanone and chloroform. In addition, these polyimides exhibited high glass‐transition values and excellent thermal properties, with an initial thermal decomposition temperature above 470 °C and glass‐transition temperatures in the range of 280–320 °C. The polyimide films also exhibited good transparency in the visible‐light region, with transmittance higher than 80% at 450 nm and a cutoff wavelength lower than 370 nm. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1291–1298, 2006     

Preparation and characterization of optically active polystyrene via a chiral nitroxide‐mediated polymerization

2,2,6,6‐Tetramethyl‐4‐[d‐(+)‐10‐camphorsulfonyl]‐1‐piperidinyloxy was synthesized and used as a chiral nitroxide for the bulk polymerizations of styrene initiated with benzoyl peroxide (BPO), tetraethylthiuram disulfide (TETD), and thermal initiation. The results showed that the polymerizations proceeded in a controlled/living way; that is, the kinetics presented approximately first‐order plots, and the number‐average molecular weights of the polymers with narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight) increased with the monomer conversion linearly. The molecular weight distributions in the case of thermal initiation were narrower than those in the case of BPO and TETD, whereas the polymerization rate with BPO or TETD as an initiator was obviously faster than that with thermal initiation. In addition, successful chain‐extension reactions were carried out, and the structures of the obtained polymers were characterized by gel permeation chromatography and ¹H NMR. The specific rotations of the polymers were also measured by polarimetric analysis. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1522–1528, 2006     

Synthesis and polymerization of a new nitrogen‐containing bis‐ortho‐diynylarene monomer

This study focuses on the preparation, characterization, and optical properties of new bis(3,4‐diphenylethynylphenyl)phenylamine. This is the first nitrogen‐containing bis‐ortho‐diynylarene (BODA) monomer having a nitrogen atom as the spacer group. BODA monomers are usually prepared from common bisphenols, thereby providing great synthetic versatility and the opportunity to develop a wide array of novel polyarylene thermosets by varying the aromatic spacer group. The new bis(3,4‐bisphenylethynylphenyl)phenylamine was synthesized in five steps. This compound emits an intense blue color (λ = 438 nm) upon irradiation by UV light and may be suitable for use as an emitting layer in electroluminescent devices. Bis‐(3,4‐bisphenylethynylphenyl)phenylamine and its polymer have photoluminescence quantum yields 34 and 38%, respectively, and long excited‐state lifetimes of 3.2 and 3.6 ns, respectively. The structure of the monomer and its polymer were characterized using spectroscopic techniques including Ultraviolet–visible Spectrophotometer, Photoluminescence Spectrophotometer, Fourier Transform infrared spectroscopy, and Gel Permeation Chromatography. The polymerizations were studied by Differential Scanning Calorimeter. The amount of weight loss and the thermostability of the nitrogen‐containing polymer were determined from thermogravimetric analysis. The electrical conductivity of neat HCl‐doped BODA‐derived polymer film was measured according to the standard four‐point probe technique. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6988–6996, 2006     

Polymer electrolyte membranes for the direct methanol fuel cell: A review

The direct methanol fuel cell (DMFC) has the potential to replace lithium‐ion rechargeable batteries in portable electronic devices, but currently experiences significant power density and efficiency losses due to high methanol crossover through polymer electrolyte membranes (PEMs). Numerous publications document the synthesis and characterization of new PEMs for the DMFC. This article reviews this research, transport phenomena in PEMs, and experimental techniques used to evaluate new PEMs for the DMFC. Although many PEMs do not show significant improvements over Nafion®, the benchmark PEM in DMFCs, experimental results show that several new PEMs exhibit lower methanol crossover at similar proton conductivities and/or higher DMFC power densities. These results and recommendations for future research are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Parts B: Polym Phys 44: 2201–2225, 2006     

QCD corrections to the forward-backward asymmetries of c and b quarks at the Z pole

Measurements of the forward-backward production asymmetry of heavy quarks in Z decays provide a precise determination of . The asymmetries are sensitive to QCD effects, in particular hard gluon radiation. In this paper QCD corrections for and are discussed. The interplay between the experimental techniques used to measure the asymmetries and the QCD effects is investigated using simulated events. A procedure to estimate the correction needed for experimental measurements is proposed, and some specific examples are given. Received: 26 February 1998 / Published online: 2 June 1998     

Mixed block elimination for linear systems with wider borders

The paper is about the stable solution of possibly ill-conditionedbordered linear systems. Given stable solvers for matrix A andfor A^T, we prove that the Govaerts Mixed Block Elimination (BEM)method constitutes a stable solver for the matrix consistingof A or A^T with a border of width 1, and hence by recursionfor a border of any width. We express the algorithm in an efficient,iterative, form. We analyse its operation count, and verifythe theory by extensive numerical experiments. ^*Senior Research Associate of the Belgian National Fund of ScientificResearch NFWO.     

Studies on solution cast perfluorocarbonsulfonic acid ionomers

The thermal properties of perfluorocarbonsulfonic acid ionomer films cast from solution and their temperature-dependent far infrared spectra have been investigated. In addition to the endotherms and spectral changes associated with the loss of solvent as the films were heated, a significant exotherm has been observed and assigned to the relaxation associated with rearrangements resulting in partially crystallized phases in insoluble thermally treated membranes. © 1993 John Wiley & Sons, Inc.