Nonlinear rheological behavior of silica filled solution‐polymerized styrene butadiene rubber

The reinforcement and nonlinear viscoelastic behavior have been investigated for silica (SiO₂) filled solution‐polymerized styrene butadiene rubber (SSBR). Experimental results reveal that the nonlinear viscoelastic behavior of the filled rubber is similar to that of unfilled SSBR, which is inconsistent with the general concept that this characteristic comes from the breakdown and reformation of the filler network. It is interesting that the curves of either dynamic storage modulus (G′) or loss tangent (tan δ) versus strain amplitude (γ) for the filled rubber can be superposed, respectively, on those for the unfilled one, suggesting that the primary mechanism for the Payne effect is mainly involved in the nature of the entanglement network in rubbery matrix. It is believed there exists a cooperation between the breakdown and reformation of the filler network and the molecular disentanglement, resulting in enhancing the Payne effect and improving the mechanical hysteresis at high strain amplitudes. Moreover, the vertical and the horizontal shift factors for constructing the master curves could be well understood on the basis of the reinforcement factor f(φ) and the strain amplification factor A(φ), respectively. The surface modification of SiO₂ causes a decrease in f(φ), which is ascribed to weakeness of the filler–filler interaction and improvement of the filler dispersion. However, the surface nature of SiO₂ hardly affects A(φ). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2594‐2602, 2007     

Role of Na(+)-Ca2+ exchange system in the pathogenesis of myocardial ischemia-reperfusion damage

Results from a systematic experiment on isolated perfused rat heart and isolated myocytes of adult rat showed that the mechanism of calcium influx during myocardial ischemia-reperfusion is due to the development of intracellular sodium overload during ischemic period; on reperfusion, the high intracellular Na+ content activated the reverse direction of Na(+)-Ca2+ exchange over myocardial sarcolemma (SL), thus a large quantity of extracellular Ca2+ fluxed over the SL to the intracellular space, forming a condition of intracellular Ca2+ overload, which leads to irreversible damage of the myocardium.     

Improvement of least-squares finite difference method on simulating slider air bearings in head disk systems

Least-squares finite difference (LSFD) method, one of mesh-free methods, is used to solve slider air bearings problem through discritizing the generalized Reynolds equation into nonlinear systems of algebraic equations. Two approximation schemes for the linearization of these equations are presented and compared. And, some new techniques to search supporting points for the reference node in the mesh-free method were proposed and explored. Therefore, these improvements eliminate some potential limitation of the LSFD method previously published and further facilitate its employment in complex slider models. Advanced step slider as an example of negative pressure sliders is simulated and verified using the improved LSFD mesh-free method in head disk systems.     

A comparison of spin relaxation and local motion between symmetrically and asymmetrically ring-substituted bisphenol units in dissolved polycarbonates

Carbon-13 and proton spin-lattice relaxation times were measured at two field strengths on solutions 10% by weight of two polycarbonates in C₂D₂Cl₄ from ?20 to +120°C. The first polycarbonate is an asymmetrically substituted form with one chlorine on one of the two phenylene aromatic rings of the bisphenol unit, whereas the second polycarbonate is symmetrically substituted with two chlorines on each of the two rings. The nuclear spin relaxation data are interpreted in terms of several local motions likely in these polymers. Segmental motion was described by the Hall–Helfand correlation function. Segmental motion in the monosubstituted polycarbonate is somewhat slower than in unsubstituted polycarbonate, whereas segmental motion in the tetrasubstituted polycarbonate is considerably slower. Phenylene ring rotation is observed in unsubstituted polycarbonate and in the monosubstituted polycarbonate above 40°C. Below 40°C in the monosubstituted species, and at all temperatures in the tetrasubstituted species, ring rotation is replaced by ring libration as the predominant motion contributing to spin lattice relaxation. In addition, the rotational motion of the two types of rings in the asymmetric monosubstituted form are very similar although not identical. The substituted ring is slightly less mobile than the rings of unsubstituted polycarbonate. This indicates a strong coupling of ring motion, although the coupling leads to less than synchronous motion. Methyl group rotation is present in both polymers and is little affected by the various structural modifications.     

Some results on the unramified principal series ofp-adic groups

Supported in part by NSF grant No. DMS-9003999     

Synthesis of grafted poly(p‐phenyleneethynylene) with energy donor–acceptor architecture via atom transfer radical polymerization: Towards nonaggregating and hole‐facilitating light‐emitting material

In this contribution, we demonstrate a new effective methodology for constructing highly efficient and durable poly(p‐phenyleneethynylene) (PPE) containing emissive material with nonaggregating and hole‐facilitating properties through the introduction of hole‐transporting blocks into the PPE system as the grafting coils as well as building the energy donor–acceptor architecture between the grafting coils and the PPE backbone. Poly(2‐(carbazol‐9‐yl)ethyl methacrylate) (PCzEMA), herein, is chosen as the hole‐transporting blocks, and incorporated into the PPE system as the grafting coils via atom transfer radical polymerization. The chemical structure of the resultant copolymer, PPE‐g‐PCzEMA, was characterized by NMR and gel permeation chromatography, showing that the desirable copolymer was obtained with the narrow polydispersity. The increased thermal stability of PPE‐g‐PCzEMA was confirmed by thermogravimetric analysis and differential scanning calorimetry along with its macroinitiator. The optoelectronic properties of this copolymer were studied in detail by ultraviolet‐visible absorption, photoluminescence emission and excitation spectra, and cyclic voltammogram (CV). The results indicate that PPE‐g‐PCzEMA exhibits the solid‐state luminescent property dominated by individual lumophores, and also the energy transfer process from the PCzEMA blocks to the PPE backbone with a relatively higher energy transfer efficiency in the solid‐state compared to that of the solution state. Additionally, the hole‐injection property is greatly facilitated due to the presence of PCzEMA, as confirmed by CV profiles. All these data indicate that PPE‐g‐PCzEMA is a good candidate for use in optoelectronic devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3776–3787, 2007     

Synthesis and nuclear magnetic resonance analysis of starch‐g‐poly(1,4‐dioxan‐2‐one) copolymers

A new biodegradable starch graft copolymer, starch‐g‐poly(1,4‐dioxan‐2‐one), was synthesized through the ring‐opening graft polymerization of 1,4‐dioxan‐2‐one onto a starch backbone. The grafting reactions were conducted with various 1,4‐dioxan‐2‐one/starch feed ratios to obtain starch‐g‐poly(1,4‐dioxan‐2‐one) copolymers with various poly(1,4‐dioxan‐2‐one) graft structures. The microstructure of starch‐g‐poly(1,4‐dioxan‐2‐one) was characterized in detail with one‐ and two‐dimensional NMR spectroscopy. The effect of the feed composition on the resulting microstructure of starch‐g‐poly(1,4‐dioxan‐2‐one) was investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3417–3422, 2004     

Pd (II)‐catalyzed vinyl addition polymerization of novel functionalized norbornene bearing dimethyl carboxylate groups

Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl‐type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo‐norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis‐norbornene‐exo‐2,3‐dimethyl carboxylates) (PNB‐dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007     

Ethylene–propylene copolymerization with bis(β‐enaminoketonato) titanium complexes activated with modified methylaluminoxane

Ethylene–propylene copolymerization, using [(Ph)NC(R₂)CHC(R₁)O]₂TiCl₂ (R₁ = CF₃, Ph, or t‐Bu; R₂ = CH₃ or CF₃) titanium complexes activated with modified methylaluminoxane as a cocatalyst, was investigated. High‐molecular‐weight ethylene–propylene copolymers with relatively narrow molecular weight distributions and a broad range of chemical compositions were obtained. Substituents R₁ and R₂ influenced the copolymerization behavior, including the copolymerization activity, methylene sequence distribution, molecular weight, and polydispersity. With small steric hindrance at R₁ and R₂, one complex (R₁ = CF₃; R₂ = CH₃) displayed high catalytic activity and produced copolymers with high propylene incorporation but low molecular weight. The microstructures of the copolymers were analyzed with ¹³C NMR to determine the methylene sequence distribution and number‐average sequence lengths of uninterrupted methylene carbons. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5846–5854, 2006     

Epoxy resin containing polyphenylsilsesquioxane: Preparation,morphology, and thermomechanical properties

Polyphenylsilsesquioxane (PPSQ) was incorporated into an epoxy resin to prepare organic–inorganic composites, and two strategies were adopted to afford composites with different morphologies. Phase separation induced by polymerization occurred in the physical blending system. However, nanostructured composites were obtained when a catalytic amount of aluminum triacetylacetonate was added to mediate the reaction between PPSQ and diglycidyl ether of bisphenol A (DGEBA). The intercomponent reaction significantly suppressed the phase separation on the micrometer scale. Organic–inorganic composites with different morphologies displayed quite different thermomechanical properties. Both differential scanning calorimetry and dynamic mechanical analysis showed that the nanostructured composites possessed higher glass‐transition temperatures than the phase‐separated composites with the same loading of PPSQ, although the intercomponent reaction between PPSQ and DGEBA reduced the crosslinking density of the epoxy matrix. This result was ascribed to the presence of nanosized PPSQ domains in the nanostructured composites, which acted as physical crosslinking sites and thus reinforced the epoxy networks. The nanoreinforcement of the PPSQ domains afforded the enhanced dynamic storage modulus for the nanostructured composites in comparison with the phase‐separated composites with a PPSQ concentration less than 15 wt %. In terms of thermogravimetric analysis, the organic–inorganic composites displayed improved thermal stability and flame retardancy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1093–1105, 2006