Control of self‐organized low‐dimensional morphology in poly(styrene‐b‐4vinylpyridine)/polystyrene blend thin films

The surface morphologies of poly(styrene‐b‐4vinylpyridine) (PS‐b‐P4VP) diblock copolymer and homopolystyrene (hPS) binary blend thin films were investigated by atomic force microscopy as a function of total volume fraction of PS (?_PS) in the mixture. It was found that when hPS was added into symmetric PS‐b‐P4VP diblock copolymers, the surface morphology of this diblock copolymer was changed to a certain degree. With ?_PS increasing at first, hPS was solubilized into the corresponding domains of block copolymer and formed cylinders. Moreover, the more solubilized the hPS, the more cylinders exist. However, when the limit was reached, excessive hPS tended to separate from the domains independently instead of solubilizing into the corresponding domains any longer, that is, a macrophase separation occurred. A model describing transitions of these morphologies with an increase in ?_PS is proposed. The effect of composition on the phase morphology of blend films when graphite is used as a substrate is also investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3496–3504, 2004     

Novel fixed‐site–carrier polyvinylamine membrane for carbon dioxide capture

Fixed‐site–carrier membranes were prepared for the facilitated transport of CO₂ by casting polyvinylamine (PVAm) on various supports, such as poly(ether sulfone) (PES), polyacrylonitrile (PAN), cellulose acetate (CA), and polysulfone (PSO). The cast PVAm on the support was crosslinked by various methods with glutaraldehyde, hydrochloric acid, sulfuric acid, and ammonium fluoride. Among the membranes tested, the PVAm cast on polysulfone and crosslinked by ammonium fluoride showed the highest selectivity of CO₂ over CH₄ (>1000). The permeance of CO₂ was then measured to be 0.014 m³ (STP)/(m² bar h) for a 20 μm thick membrane. The effect of the molecular weight of PVAm and feed pressure on the permeance was also investigated. The selectivity increased remarkably with increasing molecular weight and decreased slightly with increased pressure in the range of 1 to 4 bar. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4326–4336, 2004     

Pressure and temperature dependence of the gas‐transport properties of dense poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] membranes

The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH₄ > N₂ > O₂ > CO₂. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO₂ decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO₂‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004     

Relationship between the dynamic softening transition and wet sliding friction of elastomer compounds

For properly chosen elastomer compounds, thermorheological characterization is combined with an examination of the variation of the wet sliding friction with temperature. A conceptual argument leads to the assumption that the wet sliding friction should maximize at the energy dissipation peak associated with the dynamic softening transition at a characteristic frequency determined by the sliding speed and the effective smallest surface asperity scale. The dynamic softening transition is characterized with the peak in tan δ/G′ⁿ, where tan δ is the loss tangent, G′ is the elastic modulus, and n is a constant between 0 and 1. The William–Landel–Ferry transform is uncritically applied for extrapolating the position of the peak in tan δ/G′ⁿ at high frequencies. Even based on the criterion of tan δ, the results obtained on a concrete surface indicate that the effective smallest asperity scale is of order of 100 μm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2467–2478, 2004     

Differential scanning calorimetry and thermogravimetric analysis investigation of the thermal properties and degradation of some radiation‐grafted films and membranes

The influence of irradiation and grafting on the crystallinity of three base polymers has been investigated with differential scanning calorimetry. Grafting has the largest effect on the base polymer crystallinity and results in a reduction of the crystallinity. The thermal degradation of the base polymers and grafted films has been investigated with thermogravimetric analysis. The extent of the fluorination of the base polymer, the irradiation method, and the graft level all influence the thermal degradation and its activation energy. It is proposed that the variation of the chain lengths of the grafted polystyrene chains is actually a primary underlying factor responsible for the influence of these various parameters on the degradation process. The first results of a comparative thermal analysis of some fuel‐cell membranes are also presented, and the promise and shortcomings of this method are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2612–2624, 2004     

Nowhere zero 4‐flow in regular matroids

Jensen and Toft 8 conjectured that every 2‐edge‐connected graph without a K₅‐minor has a nowhere zero 4‐flow. Walton and Welsh 19 proved that if a coloopless regular matroid M does not have a minor in {M(K_3,3), M*(K₅)}, then M admits a nowhere zero 4‐flow. In this note, we prove that if a coloopless regular matroid M does not have a minor in {M(K₅), M*(K₅)}, then M admits a nowhere zero 4‐flow. Our result implies the Jensen and Toft conjecture. © 2005 Wiley Periodicals, Inc. J Graph Theory     

Efficient synthesis of an aldehyde‐capped polythiophene containing fluorinated electron‐withdrawing groups

To incorporate an acceptor type polythiophene segment onto a supramolecular block copolymer for potential light harvesting applications, effective synthetic routes for the end‐functionalized and acceptor‐substituted polythiophenes are critical. The Ullmann coupling reaction can be utilized to obtain electron‐deficient polythiophenes and to attach terminal thiophene units that carry functional groups. In this article, the reactions involving a 2,5‐dibromothiophene monomer containing an electron‐withdrawing fluorinated ester and 5‐bromo‐2‐thiophenecarboxaldehyde (the end‐capper) were studied in detail. It was found that the Ullmann coupling reaction of the dibromide is very fast (completed in a few minutes) and the terminal bromine group does not survive long under the reaction condition. These findings lead to the development of an effective procedure for aldehyde end‐capping of electron‐deficient polythiophenes. Polymers with molecular weights around 4000 Da are routinely obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 41–47, 2007     

Stability control of the electrooptic effect with new maleimide copolymers containing photoreactive tricyanopyrrolidene‐based chromophores

New photocrosslinkable maleimide copolymers have been synthesized by the attachment of a tricyanopyrrolidene‐based chromophore. The 2‐(3‐cyano‐4‐(2‐{4‐[hexyl‐(6‐hydroxy‐hexyl)‐amino]‐phenyl}‐vinyl)‐5‐oxo‐1‐{4‐[4‐(3‐oxo‐3‐phenyl‐propenyl)‐ phenoxy]‐butyl}‐1,5‐dihydro‐pyrrol‐2‐ylidene)‐malononitrile chromophore exhibits nonlinear optical activity and contains a chalcone moiety that is sensitive to UV light (λ = 330–360 nm) for crosslink formation. The maleimide monomers have also been functionalized with chalcone moieties. The resultant copolymers exhibit great processability, and one of them shows a maximum electrooptic coefficient of 90 pm/V at 1300 nm. We could control the thermal stability of the electrooptic coefficient with the newly synthesized photoreactive copolymers successfully. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 531–542, 2007     

Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Glass transitions and mixed phases in block SBS

Differential scanning calorimetry (DSC) does not allow for easy determination of the glass‐transition temperature (T_g) of the polystyrene (PS) block in styrene–butadiene–styrene (SBS) block copolymers. Modulated DSC (MDSC), which deconvolutes the standard DSC signal into reversing and nonreversing signals, was used to determine the (T_g) of both the polybutadiene (PB) and PS blocks in SBS. The T_g of the PB block was sharp, at ?92 °C, but that for the PS blocks was extremely broad, from ?60 to 125 °C with a maximum at 68 °C because of blending with PB. PS blocks were found only to exist in a mixed PS–PB phase. This concurred with the results from dynamic mechanical analysis. Annealing did not allow for a segregation of the PS blocks into a pure phase, but allowed for the segregation of the mixed phase into two mixed phases, one that was PB‐rich and the other that was PS‐rich. It is concluded that three phases coexist in SBS: PB, PB‐rich, and PS‐rich phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 276–279, 2005