Annealing behavior of gel‐spun polyethylene fibers at temperatures lower than needed for significant shrinkage

The annealing at 373 K of ultrastrong, gel‐spun polyethylene (PE) has been studied. At this temperature, the fibers show no significant shrinkage. Still, a significant decrease in the mechanical properties is observed. The fibers have been analyzed with differential scanning calorimetry (DSC), temperature‐modulated differential scanning calorimetry (TMDSC), atomic force microscopy (AFM), and small‐angle X‐ray scattering (SAXS). During the annealing, the glass transition of the intermediate phase is exceeded, as shown by DSC. When split for structure analysis by AFM, the annealed fibers undergo plastic deformation around the base fibrils instead of brittle fracture. The quasi‐isothermal TMDSC experiments are compared to the minor structural changes seen with SAXS and AFM. The loss of performance of the PE fibers at 373 K is suggested to be caused by the oriented intermediate phase, and not by major changes in the structure or morphology. The overall metastable, semicrystalline structure is shown by TMDSC to posses local regions that can melt reversibly. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 403–417, 2003     

Review of chiral perturbation theory

A review of chiral perturbation theory and recent developments on the comparison of its predictions with experiment is presented. Some interesting topics with scope for further elaboration are touched upon.     

Modeling hyperelastic behavior of rubber: A novel invariant‐based and a review of constitutive models

A constitutive phenomenological model completing the Gent‐Thomas concept is carried out to formulate laws governing the hyperelastic behavior of incompressible rubber materials. It is shown that the phenomenological Gent‐Thomas model (1958) and the constrained chain model (1992) give similar precise results at small to moderate deformation. On the other hand, comparisons of the outcome of the proposed model with that of the molecular model from the combined concepts of Flory‐Erman and Boyce‐Arruda (2000), and with those of the phenomenological models of Ogden (1982), Yeoh‐Fleming (1997), Pucci‐Saccomandi (2002) and Beda (2005) are made. Residual inconveniences raised by attractive continuum models in rubber elasticity literature have been successfully overcome. Results from both the statistical and phenomenological mechanics concepts are compared with the data of some useful classical materials (rubbers of Treloar, Rivlin‐Saunders, Pak‐Flory and Yeoh‐Fleming). The results permit one to see salient equivalence of the two theories for a more reliable prediction of stress‐stretch response for all states of any mode of deformation. A complete and exhaustive analysis of the Mooney plot that combines small and very large extension‐compression has been quite essential in assessing the validity of models. A method of identification of material parameters is presented and data of the simple tension suffice for the determination of the parameter values. It is shown that the ordinary identification procedures, such as the usual least squares, a very much used numerical method in materials investigation, can be unsuitable in some cases of hyperelastic modeling. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1713–1732, 2007     

Influence of preparation methods on structure and properties of PA6/PA66 blends: A comparison of melt‐mixing and in situ blending

The blends composed of polyamide 6 (PA6) and polyamide 66 (PA66) were obtained using two different preparation methods, one of which was the melt‐mixing through a twin‐screw extruder and the subsequent injection molding; and the other, the in situ blending through anionic polymerization of ε‐caprolactam in the presence of PA66. For the former, there existed a remarkable improvement in toughness but a drastic drop in strength and modulus; however, for the latter, a reverse but less significant trend of mechanical properties change appeared. Various characterizations were conducted, including the analyses of crystalline morphology, crystallographic form, and crystallization and melting behaviors using polarized optical microscopy (POM), wide‐angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC), respectively; observation of morphology of fractured surface with scanning electron microscope (SEM); measurement of glass transition through dynamic mechanical analysis (DMA); and the intermolecular interaction as well as the interchange reaction between the two components by Fourier transform infrared spectrometry (FT‐IR) and ¹³C solution NMR. The presence and absence of interchange reaction was verified for the in situ and melt‐mixed blends, respectively. It is believed that the transreaction resulted in a drop in glass transition temperature (T_g) for the in situ blends, contrary to an increase of T_g with increasing PA66 content for the melt‐mixed ones. And the two kinds of fabrication methods led to significant differences in the crystallographic form, spherulite size and crystalline content and perfection as well. Accordingly, it is attempted to explain the reasons for the opposite trends of changes in the mechanical properties for these two blends. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1176–1186, 2007     

Synthesis and optoelectronic properties of silole‐containing polyfluorenes with binary structures

2,5‐Bis(2‐bromofluorene‐7‐yl)silole was prepared by a modified one‐pot synthesis with a reverse addition procedure, from which novel silole‐containing polyfluorenes with binary random and alternating structures (silole contents between 4.5 and 25% and high M_w up to 509 kDa were successfully synthesized. The well‐defined repeating unit of the alternating copolymer comprises a terfluorene and a silole ring. Optoelectronic properties including UV absorption, electrochemistry, photoluminescence (PL), and electroluminescence (EL) of the copolymers were examined. The different excitation energy transfers from fluorene to silole of the copolymers in solution and in the solid state were compared. The films of the copolymers showed silole‐dominant green emissions with high absolute PL quantum yields up to 83%. EL devices of the copolymers with a configuration of ITO/PEDOT/copolymer/Ba/Al displayed exclusive silole emissions peaked at around 543 nm and the highest EL efficiency was achieved with the alternating copolymer. Using the alternating copolymer and poly(9,9‐dioctylfluorene) as the blend‐type emissive layer, a maximum external quantum efficiency of 1.99% (four times to that of the neat film) was realized, which was a high efficiency so far reported for silole‐containing polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 756–767, 2007     

Insight into chain dimensions in PEO/water solutions

Small‐Angle Neutron Scattering has been performed from poly(ethylene oxide) in deuterated water at temperature ranging from 10 to 80 °C. A simple fitting model was used to obtain a correlation length and a Porod exponent. The correlation length L characterizes the average distance between entanglements in the semidilute region and is proportional to the individual coil sizes in the dilute region. L was found to increase with temperature in the semidilute region but it decreases with temperature in the dilute region. This decrease is the precursor to the single‐chain collapse which applies to very dilute polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2196–2200, 2007     

The effect of nanoparticle shape on polymer‐nanocomposite rheology and tensile strength

Nanoparticles can influence the properties of polymer materials by a variety of mechanisms. With fullerene, carbon nanotube, and clay or graphene sheet nanocomposites in mind, we investigate how particle shape influences the melt shear viscosity η and the tensile strength τ, which we determine via molecular dynamics simulations. Our simulations of compact (icosahedral), tube or rod‐like, and sheet‐like model nanoparticles, all at a volume fraction ? ≈ 0.05, indicate an order of magnitude increase in the viscosity η relative to the pure melt. This finding evidently can not be explained by continuum hydrodynamics and we provide evidence that the η increase in our model nanocomposites has its origin in chain bridging between the nanoparticles. We find that this increase is the largest for the rod‐like nanoparticles and least for the sheet‐like nanoparticles. Curiously, the enhancements of η and τ exhibit opposite trends with increasing chain length N and with particle shape anisotropy. Evidently, the concept of bridging chains alone cannot account for the increase in τ and we suggest that the deformability or flexibility of the sheet nanoparticles contributes to nanocomposite strength and toughness by reducing the relative value of the Poisson ratio of the composite. The molecular dynamics simulations in the present work focus on the reference case where the modification of the melt structure associated with glass‐formation and entanglement interactions should not be an issue. Since many applications require good particle dispersion, we also focus on the case where the polymer‐particle interactions favor nanoparticle dispersion. Our simulations point to a substantial contribution of nanoparticle shape to both mechanical and processing properties of polymer nanocomposites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1882–1897, 2007     

Graphitic nanofillers in PMMA nanocomposites—An investigation of particle size and dispersion and their influence on nanocomposite properties

Mechanical, thermal, and electrical properties of graphite/PMMA composites have been evaluated as functions of particle size and dispersion of the graphitic nanofiller components via the use of three different graphitic nanofillers: “as received graphite” (ARG), “expanded graphite,” (EG) and “graphite nanoplatelets” (GNPs) EG, a graphitic materials with much lower density than ARG, was prepared from ARG flakes via an acid intercalation and thermal expansion. Subsequent sonication of EG in a liquid yielded GNPs as thin stacks of graphitic platelets with thicknesses of ～10 nm. Solution‐based processing was used to prepare PMMA composites with these three fillers. Dynamic mechanical analysis, thermal analysis, and electrical impedance measurements were carried out on the resulting composites, demonstrating that reduced particle size, high surface area, and increased surface roughness can significantly alter the graphite/polymer interface and enhance the mechanical, thermal, and electrical properties of the polymer matrix. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2097–2112, 2007     

Dibutyltin-3-hydroxyflavone titrates a dissociable component (cofactor) of mitochondrial ATP synthase: An energy-transfer component linked to the ubiquinone pool

Dibutyltin-3-hydroxyflavone, Bu₂Sn(of), is a new fluorescence probe inhibitor of F₁F₀-ATPase and oxidative phosphorylation which inhibits by titration of an unidentified component of F₀. Its site of action is closely related to that of the trialkyltins and of venturicidin. This F₀ component is part of a pool of this component which is present in the heart mitochondrial inner membrane at levels of 5–7 nmol (mg protein)^?1 [18 ± 3 Bu₂Sn(of) sites per mol F₁F₀-ATPase]. However, ATPase activity in submitochondrial particles is near maximally inhibited by titration of approx. three Bu₂Sn(of) sites per mol F₁F₀-ATPase. Over 60% (60–80%) of the Bu₂Sn(of) interaction sites can be lost during the purification of F₁F₀-ATPase from submitochondrial particles. The number of Bu₂Sn(of) interaction sites in various F₁F₀-ATPase preparations is variable. The high numbers of Bu₂Sn(of) sites per mol F₁F₀-ATPase for heart mitochondria (18–21) and submitochondrial particles (15–19.5) decline in ATP synthase (11–15) to the low values obtained in Complex V (7–10.5) and the minimal values observed in highly purified F₁F₀?ATPase (3.5–5.6), thus indicating a variable dissociable component or cofactor of ATP synthase. The Bu₂Sn(of) interaction site, a component of ATP synthase, is responsive to the redox status of the respiratory chain and the interaction with Bu₂Sn(of) is with the reduced form of this component. Fluorescence titration studies show that this component is in redox equilibrium with the ubiquinone pool of the respiratory chain. It is proposed that this redox component serves as an inhibitor titratable cofactor pool which cycles through an F₀ interaction site (or sites) via a system which serves as an energy-transfer link between the respiratory chain and ATP synthase.     

Deactivation reactions in the modeled 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐mediated free‐radical polymerization of styrene: A comparative study with the 2,2,6,6‐tetramethyl‐1‐piperidinyloxy/acrylonitrile system

The competitiveness of the combination and disproportionation reactions between a 1‐phenylpropyl radical, standing for a growing polystyryl macroradical, and a 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) radical in the nitroxide‐mediated free‐radical polymerization of styrene was quantitatively evaluated by the study of the transition geometry and the potential energy profiles for the competing reactions with the use of quantum‐mechanical calculations at the density functional theory (DFT) UB3‐LYP/6‐311+G(3df, 2p)//(unrestricted) Austin Model 1 level of theory. The search for transition geometries resulted in six and two transition structures for the radical combination and disproportionation reactions, respectively. The former transition structures, mainly differing in the out‐of‐plane angle of the N? O bond in the transition structure TEMPO molecule, were correlated with the activation energy, which was determined to be in the range of 8.4–19.4 kcal mol^?1 from a single‐point calculation at the DFT UB3‐LYP/6‐311+G(3df, 2p)//unrestricted Austin Model 1 level. The calculated activation energy for the disproportionation reaction was less favorable by a value of more than 30 kcal mol^?1 in comparison with that for the combination reaction. The approximate barrier difference for the TEMPO addition and disproportionation reaction was slightly smaller for the styrene polymerization system than for the acrylonitrile polymerization system, thus indicating that a β‐proton abstraction through a TEMPO radical from the polymer backbone could diminish control over the radical polymerization of styrene with the nitroxide even more than in the latter system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 232–241, 2007