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  • 101
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1617-1624 
    ISSN: 0887-6266
    Keywords: hydrogen-bonded living polymers ; supramolecular ; liquid crystalline polymers ; X-ray scattering ; Fourier transform infrared (FTIR) ; structure ; association chain polymers ; self-assembly ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A main chain hydrogen-bonded liquid crystalline polymer was formed by melt mixing two complementary components, A and B, which in their individual states do not exhibit liquid crystallinity. The structure of the polymer and the thermal stability of its mesophase were studied using synchrotron radiation SAXS/WAXS/DSC at Daresbury (UK) and by variable temperature Fourier transform infrared. The chain extension, or “polymerization” process, was accelerated at the point when the polymer formed a liquid crystalline phase upon cooling from the isotropic melt. The polymer has an aabb chain structure and forms a smectic layer with a length of the A-B repeating unit. The hydrogen-bonded main chain polymer studied here is a monotropic liquid crystal. Above 150°C, it exhibits kinetic stabilization of its monotropic smectic phase. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1617-1624, 1998
    Additional Material: 11 Ill.
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  • 102
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1703-1711 
    ISSN: 0887-6266
    Keywords: complex shear modulus ; ultrasonic measurements ; dynamic-mechanical measurements ; acrylic-type copolymers ; film formation ; glass-rubber relaxation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An ultrasonic shear wave reflection method was applied to study film formation and temperature dependence of the complex shear modulus (G*=G′ + iG″) in different amorphous films made of aqueous dispersions of acrylic-type copolymers. The data are compared with dynamic-mechanical measurements in the low frequency range. It is shown that the temperature dependence of the storage (G′) and the loss modulus (G″) for both methods can be fitted by the same set of parameters using the Havriliak-Negami function incorporating the Vogel-Fulcher-Tamman-Hesse equation for the temperature dependence of relaxation times. The temperature dependence of the relaxation times obtained from the fits to the ultrasonic shear modulus is compared to the shift factors of the dynamic-mechanical measurements. The agreement between both methods is good. This suggests an almost thermorheological simplicity of the samples for the main glass-rubber relaxation and demonstrates the capacity of the ultrasonic rheometer. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1703-1711, 1998
    Additional Material: 7 Ill.
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  • 103
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    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1679-1694 
    ISSN: 0887-6266
    Keywords: crystallization kinetics ; thermotropic liquid crystalline polymers ; polyimide ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have studied the nonisothermal and isothermal crystallization kinetics of an aromatic thermotropic liquid crystalline polyimide synthesized from 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA) and 1,3-bis[4-(4′-aminophenoxy) cumyl] benzene (BACB) by means of differential scanning calorimetry (DSC). Polarized light microscopy (PLM) and wide-angle X-ray diffraction (WAXD) results confirm that this polyimide exhibits a smectic texture. Nonisothermal crystallization showed two strong and one weak exothermic peaks during cooling. The phase transition from isotropic melt to liquid crystalline state is extremely fast which completes in several seconds. The mesophase transition has a small Avrami parameter, n, of approximate 1. The isothermal crystallization of 253-258°C has been examined. The average value n is about 2.6 and the temperature-dependent rate constant k changes about two orders of magnitude in the crystallization temperature range of 6°C. The slope of ln k versus 1/(TcΔT) is calculated to be -2.4 × 105, which suggests nucleation control, via primary and/or secondary nucleation for the crystallization process. During the annealing process, a new phase (slow transition) is induced, which grows gradually with annealing time. At lower annealing temperatures (220-230°C), the slow transition process seems not to be influenced by the crystals formed during cooling process and its Avrami parameter n is ca. 0.3-0.4. However, the slow transition was hindered by the crystals formed during cooling process when annealed at higher temperature (230-240°C). © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1679-1694, 1998
    Additional Material: 15 Ill.
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  • 104
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 901-911 
    ISSN: 0887-6266
    Keywords: activation volume ; relaxation ; pressure ; polymer ; reorientation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Second harmonic generation (SHG) was used to measure the temperature dependence of the reorientation activation volume of 4-(diethylamino)-4′-nitrotolane (DEANT) in poly(methyl methacrylate) (PMMA). The decay of the SHG signal from films of DEANT/PMMA was recorded at hydrostatic pressures up to 3060 atm and at different temperatures between 25°C below the glass transition temperature to 35°C above it. The activation volume, ΔV*αβ associated with the long range α-type motion of the polymer remained constant at 213 ± 10 Å3 between Tg - 25°C and Tg + 10°C. At higher temperatures, ΔV*αβ decreased linearly with increasing temperature. The activation volume, ΔV*αβ, associated with short range secondary relaxations was constant over the entire temperature range with a value of 77 ± 10 Å3. The data suggest that above Tg chromophore reorientation is coupled to both the long range and local motions of the polymer; whereas, well below Tg chromophore reorientation is closely coupled to the local relaxations of the polymer. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 901-911, 1998
    Additional Material: 8 Ill.
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  • 105
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    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1769-1780 
    ISSN: 0887-6266
    Keywords: polymer blends ; liquid crystalline polymer ; microfibers ; viscosity reduction ; rheology ; morphology ; X-ray scattering ; composite materials ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Immiscible blends of thermotropic liquid crystalline polymers (TLCP) and a flexible polymer matrix show viscosity reductions and extensive fiber formation under certain flow conditions. Here we study these phenomena by directly examining the TLCP component's molecular orientation and the dispersed phase morphology. The rheology and morphology of blends of polybutylene terephthalate and a thermotropic copolyester (HX-8000 series, DuPont) at concentrations varying from 5 to 30 wt % of TLCP are characterized. It is found that the blends show viscosity reduction as well as stable fiber formation at shear rates dependent on the TLCP content. Wide-angle X-ray scattering is performed to measure the degree of molecular orientation of the TLCP phase. A deconvolution scheme isolates the scattering from the TLCP in the blends and a molecular model enables extracting an experimental orientation factor. It was found that a highly microfibrillated TLCP phase is coupled with an increase in the TLCP molecular orientation to values close to the pure TLCP at similar processing conditions. Further, the microfibrillated TLCP phase is found to be stable within the testing time. Current hypotheses about fiber formation in immiscible blends are tested against the experimental observations. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1769-1780, 1998
    Additional Material: 10 Ill.
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  • 106
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1831-1837 
    ISSN: 0887-6266
    Keywords: block copolymer ; wormlike micelle ; fluctuations ; slow mode ; dynamic light scattering ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic light scattering (DLS) has been used to explore the properties of asymmetric styrene-isoprene (SI) block copolymers in concentrated solutions. Concentrations were always well below those necessary to access the order-disorder transition in neutral good solvents. The samples include SI (10-50), SI (36-9), and SIS (10-100-10), where the numerical suffixes denote the block molecular weights in kilodaltons; experimental emphasis was placed on SI (10-50). The DLS intensity correlation functions in the neutral good solvents, THF and toluene, were dominated by a slow mode that first appeared at a concentration c+ ≈ 4 c*, where c* is the coil overlap concentration. The decay rate of this mode scaled approximately as the third power of the scattering wavevector, and the excess scattered intensity decreased with increased scattering angle. These results were tentatively ascribed to the onset of substantial concentration fluctuations, that exhibited cylindrical, or wormlike structures. Measurements in solvents of known selectivity, dioxane and cyclohexane, and on a copolymer of the opposite composition, SI (36-9), indicated that the intermolecular association was driven by the effectively repulsive interactions between styrene and isoprene segments, rather than by solvent selectivity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1831-1837, 1998
    Additional Material: 8 Ill.
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  • 107
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    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1857-1872 
    ISSN: 0887-6266
    Keywords: hybrid polymers ; rheology ; reptation ; silsesquioxane polymers ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report on the viscoelastic behavior of linear thermoplastic nonpolar hybrid inorganic-organic polymers. These materials have been synthesized through copolymerization of an oligomeric inorganic macromer with 4-methylstyrene where the inorganic portion of the material is a well-defined polyhedral oligosilsesquioxane (POSS), R7(Si8O12)(CH2CH2C6H4C=CH2), with R = c-C6H11 or c-C5H9. A series of 4-methyl styrene copolymers with approximately 4, 8, and 16 mol % POSS macromer incorporation were investigated. Rheological measurements show that the polymer dynamics are profoundly affected as the percent of POSS increases. In particular, a high-temperature rubbery plateau develops (where a terminal zone is not observed), despite the fact that the parent poly 4-methylstyrene is unentangled. It is also observed that the thermal properties are influenced as the percent of POSS incorporation increases, with increases in the glass and decomposition temperatures. The results suggest that interchain interactions between the massive inorganic groups are responsible for the retardation of polymer chain motion, a mechanism similar to the “sticky reptation” model conceived for hydrogen-bonded elastomers and developed by Leibler et al. [Macromolecules, 24, 4701 (1991)]. Control over the interchain interactions would also give rise to the observed increases in glass transition and the establishment of a rubbery plateau. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1857-1872, 1998
    Additional Material: 14 Ill.
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  • 108
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1911-1918 
    ISSN: 0887-6266
    Keywords: polymer solutions ; supercritical fluids ; non-Newtonian viscosity ; free-volume ; polydimethylsiloxane ; carbon dioxide ; viscoelastic scaling theory ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recent measurements of the viscosity of polydimethylsiloxane (PDMS) melts swollen with dissolved carbon dioxide at 50 and 80°C by Gerhardt et al. have shown that classical viscoelastic scaling factors can be employed to superpose the viscosity curves for CO2-swollen melts onto the viscosity curve for pure PDMS at the same temperature and pressure. Here a free volume expression for the viscosity of a diluted polymer melt is combined with equation-of-state theories for the volumetric properties of PDMS-CO2 mixtures to develop models for the CO2 concentration-dependent viscoelastic scaling factors. Both the Sanchez-Lacombe and Panayiotou-Vera equations-of-state are investigated for this purpose. The predicted viscoelastic scaling factors are found to be in very good agreement with the data of Gerhardt et al. The model predictions show that mixing of gaseous carbon dioxide into the swollen PDMS phase is highly non-ideal, and that significant free volume is added to the melt upon carbon dioxide dissolution. The free volume added to the melt by dissolved carbon dioxide is the principal mechanism for viscosity reduction, relative to pure PDMS, in this system. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1911-1918, 1998
    Additional Material: 8 Ill.
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  • 109
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1947-1958 
    ISSN: 0887-6266
    Keywords: interfacial tension ; breaking thread ; polyamide ; polyethylene ; interface ; modifier morphology ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Compared to the dynamic mixing process used in melt blending operations, most techniques for measuring the interfacial tension can be considered as virtually static. For this reason, in order to measure the interfacial tension of an A-B immiscible system in the presence of an interfacial modifier, the problem of migrating the modifier to the interface is a central issue. In this study, the influence of the addition of an interfacial modifier, a polyethylene copolymer ionomer, on the interfacial tension between two high-density polyethylenes and a polyamide is investigated. The breaking thread method is used and the interfacial tension is measured as a function of ionomer content. In order to enhance the likelihood of placing the modifier in closer proximity to the interface, various sample preparations are compared. In all cases, the interfacial tension significantly drops with increasing ionomer content and tends to a limiting value. It is shown, however, that the preparation of the system for the breaking thread experiment via coextrusion using a conical die brings the modifier in closest proximity to the interface. With this approach an additional 1.45 times reduction of the interfacial tension at 10% compatibilizer concentration (based on the mass of HDPE) is observed compared to the classical technique of preparation. Confirmation of this effect is demonstrated using X-ray photoelectron spectroscopy where analysis of the thread surface of the system prepared by coextrusion indicates a more than fourfold enrichment of interfacial modifier. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1947-1958, 1998
    Additional Material: 9 Ill.
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  • 110
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1995-2003 
    ISSN: 0887-6266
    Keywords: semiflexible polymers ; persistence length ; viscosity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A numerical approach, based on the configurational distribution function of a polymer chain in flow, has been used to calculate the zero-shear rheological properties. Starting from a bead-spring representation of the chain, the stiffness is introduced by repulsive springs between next-nearest neighbors. The connection to models based on the bending equation and their limitation is discussed. To obtain a correct model of a semiflexible chain, an inhomogeneous spring constant has to be used. Calculations have been carried out for the free draining case, and a simple relation between the intrinsic viscosity, the translational diffusion coefficient and the persistence length for arbitrary solvent conditions is proposed. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1995-2003, 1998
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  • 111
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1987-1994 
    ISSN: 0887-6266
    Keywords: toughening ; impact strength ; blend ; nylon 6 ; core-shell impact modifier ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Super-tough nylon 6 was prepared by using maleic anhydride grafted polyethylene-octene rubber/semicrystalline polyolefin blend (TPEg) as an impact modifier. The morphology, dynamic mechanical behavior, mechanical properties, and toughening mechanism were studied. Results indicate that TPEg with a semicrystalline polyolefin core and a polyethylene-octane rubber shell, possesses not only a better processability of extruding and pelletizing with a lower cost, but also an improved toughening effect in comparison with the maleated pure polyethylene-octene rubber. The shear yielding is the main mechanism of the impact energy dissipation. In addition, the influence of melt viscosity of nylon 6 on toughening effectiveness was also investigated. High melt viscosity of matrix is advantageous to the improvement of notched Izod impact strength. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1987-1994, 1998
    Additional Material: 9 Ill.
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  • 112
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2019-2024 
    ISSN: 0887-6266
    Keywords: divinylbenzene ; porous copolymer ; excess adsorption isotherm ; active centers ; adsorption azeotropic point ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adsorptive properties of four porous copolymers were investigated. They contained different functional groups in the internal structure. Adsorption measurements were made using the static method. Three two-component and one three-component solutions with different physicochemical properties were used. The adsorptive centers of the copolymers were evaluated based on the analysis of excess adsorption isotherms of the polar solution component. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2019-2024, 1998
    Additional Material: 4 Ill.
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  • 113
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2057-2067 
    ISSN: 0887-6266
    Keywords: PTFE ; fillers ; UV radiation ; degradation ; morphology ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The first part of a series of two, this paper analyzes the degradation of pure and filled PTFE under high energy UV radiation. The polymer morphology is first investigated using differential scanning calorimetry, highlighting the respective nucleating efficiency of TiO2 and CaF2 during polymer crystallization. Then, the various polymers are exposed to excimer laser radiation and observed under an optical microscope. The results indicate that the degradation is closely connected with microstructural parameters. In pure PTFE, scattering by crystallites and reflection on piles of lamellae control the nature and extent of the degradation. In filled PTFE, nature and concentration of fillers are the most important features governing degradation. When absorbing particles are added to PTFE, the damage is restricted to the surface and photothermal processes can modify the degradation from heterogeneous to ablative, depending on the filler content. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2057-2067, 1998
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  • 114
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2103-2109 
    ISSN: 0887-6266
    Keywords: ethylene-vinyl alcohol copolymers ; multiple-pulse proton NMR ; spin diffusion ; comonomer content ; crystallinity ; long spacing ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Capitalizing on the superior sensitivity of proton NMR, relatively rapid estimates of three parameters, namely, comonomer content, crystallinity, and long spacing, are determined for three ethylene/vinyl alcohol copolymers using solid-state proton NMR measurements. Multiple-pulse techniques are utilized (a) in conjunction with magic angle spinning for measuring comonomer content, (b) in conjunction with a T1xz relaxation measurement for determining crystallinity, and (c) in conjunction with a T1xz-based spin diffusion measurement for determining the long spacing. These three parameters, extracted from data collected in a total spectrometer time of about 20 min, are compared with similar parameters obtained using more conventional DSC, SAXS (including synchrotron), and solution-state NMR measurements. Agreement is found to be good. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2103-2109, 1998
    Additional Material: 5 Ill.
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  • 115
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1393-1399 
    ISSN: 0887-6266
    Keywords: PNLC ; UV cure ; polyurethane acrylate ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer network liquid crystals (PNLC) have been prepared from ultraviolet-curable polyurethane acrylate (PUA) and a nematic liquid crystal mixture (BL002). Effects of monoacrylate type on film morphology, temperature-dependent off-state transmittance, and electro-optic performance of the film have been studied. Among three types of monoacrylates incorporated (EHA(2-ethyl hexyl acrylate), MMA (methylmethacryalte), NVP (N-vinylpyrrolidone)), EHA-based PUAs gave the greatest polymer-LC phase separation, lowest threshold (V10), and operating (V90) voltages, and the effect was more pronounced in monoacrylate/triacrylate systems than in monoacrylate/diacrylate systems. Contact angle measurement offers a clue to the observed morphology and electro-optic behavior. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1393-1399, 1998
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  • 116
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1419-1422 
    ISSN: 0887-6266
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 117
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1443-1450 
    ISSN: 0887-6266
    Keywords: poly(ethylene terephthalate) ; STEM ; dark field imaging ; chemical derivatization ; morphology ; semicrystalline ; amorphous ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Important chemical and mechanical properties in semicrystalline polymers are determined by the noncrystalline or nonordered regions. Hence, characterizing these regions is important in developing a morphological model to better define and predict the chemical and mechanical behavior of polymeric materials. With this objective, preferential tagging was accomplished by covalent linking of a heavy element to poly(ethylene terephthalate) (PET). In scanning transmission electron microscopy (STEM), contrast was obtained using a low concentration of thallium (0.4%), the tagging element, thus providing a map of the more accessible regions within the semicrystalline structure. Differential scanning calorimetry (DSC) and wide-angle x-ray scattering (WAXS) were used to characterize the PET film. Elemental analysis using energy dispersive x-ray analysis (EDAX) was used to confirm the presence of the heavy element in the tagged regions. The STEM imaging results were then compared with the characterization results from the DSC and WAXS measurements to gain an understanding of the domains and their size ranges in the semicrystalline microstructure of PET. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1443-1450, 1998
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  • 118
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1501-1506 
    ISSN: 0887-6266
    Keywords: intrachain coil-to-globule transition ; interchain aggregation ; laser light scattering ; poly(N-isopropylacrylamide) ; single-chain nanoparticle ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The coil-to-globule transition of two poly(N-isopropylacrylamide) (PNIPAM) ionomers with different ionic contents (0.8 and 4.5 mol %), but similar weight average molar masses, in deionized water was investigated by a combination of static and dynamic light scattering. In spite of the large difference in their ionic contents, both the ionomers have a nearly same lower critical solution temperature (LCST, ∼ 32.5°C). At temperatures higher than the LCST, the ionomer chains undergo a simultaneous intrachain coil-to-globule transition and interchain aggregation to form nanoparticles thermodynamically stable in water. The average size of the nanoparticles decreases respectively as the ionic content increases and the ionomer concentration decreases. The interchain aggregation can be completely suppressed in an extremely dilute ionomer solution (〈 ∼ 5 × 10-6 g/mL), so that the intrachain coil-to-globule transition leads to the collapse of the ionomer chains into individual single-chain nanoparticles. Our results clearly indicate that there is a hysteresis in the colling process (the globule-to-coil transition). © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1501-1506, 1998
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  • 119
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2069-2083 
    ISSN: 0887-6266
    Keywords: PTFE ; fillers ; UV radiation ; degradation ; multiple scattering ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The second part of the series, this article analyzes the way UV light propagates through pure and filled PTFE. We investigated the diffusiveness of the semicrystalline matrix as well as the effect of scattering and absorbing fillers (CaF2 and TiO2) on the attenuation. The UV-visible absorption curves have been determined by spectrophotometry. A theoretical calculation based on a four-flux multiple scattering approach allowed us to satisfactorily reproduce the experimental results, highlighting the respective importance of the coherent and the diffuse fields. In light of this model, we discuss the influence of multiple scattering on the extent of degradation when PTFE is exposed to a high energy UV radiation. This approach provides of a comprehensive view of the damaging effect of UV light on PTFE, showing a good agreement with the experimental results of the previous article. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2069-2083, 1998
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  • 120
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2111-2128 
    ISSN: 0887-6266
    Keywords: orientation ; physical aging ; free volume ; glass-transition ; dilatometry atactic-polystyrene ; bisphenol A polycarbonate ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has recently been demonstrated that hot-drawn samples of bisphenol A polycarbonate (PC) have a 50% higher volume relaxation rate than their isotropic counterpart even though the oriented samples have a lower initial free volume (i.e., higher density).1 In an attempt to better understand this paradox, samples of unaged, hot-drawn PC were characterized thermodynamically and kinetically as a function of orientation. Heat capacity, hole energy, and Tg data indicate that the chain mobility is actually decreasing slightly with orientation, possibly due to the hindered motion brought about by tighter packing, stronger intermolecular bonding, and reduced free volume. Nonetheless, this decrease in localized mobility is in contradiction to the enhanced volume relaxation rates observed for the oriented samples. In contrast, dynamic mechanical data indicate an increase in the relaxation strength of the β-transition (-100°C at 1 Hz) upon stretching for both the stretch and transverse directions. This implies that more segments are actively participating in the relaxation process for the oriented samples even though their individual localized mobility might be slightly lower. The net result is an increase in “effective” mobility for the oriented samples. It is conjectured that the enhanced relaxation strength of the oriented samples is a result of the stretching process somehow activating more of the chains into a higher energy state, and may be related to the physical aging concept of stress-induced rejuvenation/acceleration. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2111-2128, 1998
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  • 121
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1625-1636 
    ISSN: 0887-6266
    Keywords: mechanical behavior ; block copolymers ; affine strain ; SAXS ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Films of a blend of styrene-isoprene triblock copolymer and mineral oil have been simple-cast and roll-cast from a toluene solution. Their microstructure has been analyzed by transmission electron microscopy and small-angle X-ray scattering. The blend formed polystyrene spheres arranged on a body-centered cubic lattice in a matrix composed of polyisoprene and mineral oil, and the samples display large grain sizes and very long-range order. The roll-cast sample exhibits approximately uniaxial symmetry around the rolling direction, which corresponds to the [111] crystallographic direction of the lattice. The glassy spheres act as physical crosslinks of known crosslinking functionality in the soft rubbery matrix. The high-strain deformation mechanism of this oriented cubic material has been studied by a simultaneous tensile-SAXS experiment, where the sample was stretched up to 300% along the [111] direction. By monitoring the position of the (222) and (110) reflections, the deformation of the lattice is shown to be affine with the macroscopic deformation of the sample, and the Poisson's ratio is approximately 0.46. The first zero of the sphere form factor in the SAXS patterns remains also essentially unchanged up to 300% deformation indicating that the reinforcing glassy PS domains retain their spherical shape throughout the deformation. Deformation of the microstructure is totally reversible upon unloading. A model of {hk0} faults is proposed to describe the microstructural changes induced by high-strain deformation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1625-1636, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1669-1677 
    ISSN: 0887-6266
    Keywords: photo-assisted poling ; polymer dynamics ; polymer structure ; nonlinear optical polyimides ; high glass transition temperature ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have used combinations of light, heat, and electrostatic fields to investigate the orientation of nonlinear azo-chromophores chemically incorporated into high glass transition temperature (Tg) polyimides. A number of nonlinear optical polyimides have been synthesized in which the interaction between the nonlinear optical chromophore and the polymer main chain was systematically altered to determine to what extent this steric interaction influences the orientation of the nonlinear chromophore. Chromophores in polymers may be oriented by a number of methods: (a) polarized light at room temperature (i.e., photo-induced orientation or PIO), (b) polarized light and electric fields (i.e., photo-assisted poling or PAP) at temperatures ranging from room temperature to the polymer Tg, and (c) electric fields at Tg (thermal poling). While thermal poling and PIO are usually possible, PAP depends strongly on the molecular structure of the polymer. Previously we have shown that PIO can be accomplished at room temperature in a system where the nonlinear chromophore is embedded into the polyimide main chain via the donor substituent, and this orientation can only be thermally erased at temperatures approaching Tg. In this article we show that, whereas photoisomerization can efficiently depole donor-embedded polyimides in a matter of few minutes at room temperature, PAP does not induce any polar order. This behavior is in marked contrast to a structurally related, side-chain, nonlinear polyimide, in which the azo chromophore is tethered via a flexible linkage to the polymer backbone. In this case some PAP occurs even at room temperature, while no PAP is observed for a donor-embedded system with a similar Tg. We suggest that the orientation during PAP below Tg in the side-chain polyimide is primarily due to the movement of the azo side chains, and there is a very little coupling of this motion to the main chain. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1669-1677, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2691-2702 
    ISSN: 0887-6266
    Keywords: surface segregation ; polyolefin copolymers ; deuterium labeling effect ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have examined the effect of deuterium labeling on surface interactions in mixtures of random olefinic copolymers [C4H8]1-x[C2H3(C2H5)]x. Based on surface segregation data we have determined a surface energy difference χs between pure blend constituents. In each binary mixture components have different fractions x1, x2 of the group C2H3(C2H5), and one component is labeled by deuterium (dx) while the other is hydrogenous (hx). The mixtures are grouped in four pairs of structurally identical blends with swapped labeled constituent (dx1/hx2, hx1/dx2). For each pair the surface energy parameter χs increases when the component with higher fraction x is deuterated, i.e., χs(dx1/hx2) 〉 χs(hx1/dx2) for x1 〉 x2. A similar pattern has been found previously for the bulk interaction parameter χ. This is explained by the solubility parameter formalism aided by the lattice theory relating the surface excess to missing-neighbor effect. χs has also an additional contribution, insensitive to deuterium swapping effect, and related to entropically driven surface enrichment in a more stiff blend component with a lower fraction x. Both enthalpic and entropic contributions to χs seem to depend on the extent of chemical mismatch between blend components. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2691-2702, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2725-2735 
    ISSN: 0887-6266
    Keywords: blending ; polymorphism ; syndiotactic polystyrene (s-PS) ; amorphous polystyrene (a-PS) ; PPO ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray diffraction and optical microscopy characterization were performed to evaluate the phenomenon of alteration of polymorphism of syndiotactic polystyrene (s-PS) in the presence of other blending miscible polymers: poly(2,6-dimethyl-p-phenylene oxide) (PPO) or atactic polystyrene (a-PS). Both α and β crystal forms were observed in the neat s-PS sample, but only β-form crystal was found in miscible blends of s-PS with a-PS or PPO. The order and neighboring chain segments of neat s-PS are different from those of s-PS/PPO or s-PS/a-PS blends; thus, it is plausible that the greater randomness in the melt state of s-PS/a-PS or s-PS/PPO blends might be unfavorable for formation of α-form crystals from melts. The final spherulitic morphology the s-PS/a-PS or s-PS/PPO blends suggests that the amorphous-state miscibility of does not change much the spherulitic structure of s-PS. The radial growth rate is, in general, depressed with the presence of blending miscible polymers in s-PS of equal Tg or PPO of higher Tg. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2725-2735, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2745-2750 
    ISSN: 0887-6266
    Keywords: polymer blends ; hydrogen bonding ; small-angle neutron scattering ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Deuterium-labeled polystyrene modified by random distributions of the comonomer p-(1,1,1,3,3,3-hexaflouro-2-hydroxyisopropyl)-α-methyl-styrene [DPS(OH)] has been blended with poly(butyl methacrylate) (PBMA) and studied with small-angle neutron scattering (SANS). Miscibility is induced via hydrogen bonding between the DPS(OH) hydroxyl group and PBMA carbonyl groups. The data suggest that the nature of the miscible-phase structure in these blends differs from that of the usual homopolymer blends at small scattering angles, which we attribute to the short-range site specific nature of the hydrogen bond interaction. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2745-2750, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2771-2780 
    ISSN: 0887-6266
    Keywords: drying ; semicrystalline polymers ; poly(vinyl alcohol) ; solvent removal ; modeling ; diffusion ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The drying mechanism of semicrystalline poly(vinyl alcohol) (PVA) was investigated. PVA samples of various molecular weights were crystallized by annealing at temperatures slightly above the glass transition temperature of PVA, and swollen in water for different time periods. The water volume fraction in the sample was measured using a buoyancy technique. The samples were dried in air at constant temperatures, and the drying kinetics were investigated using thermogravimetric analysis. The change in degree of crystallinity of the swollen polymer during drying was measured by differential scanning calorimetry (DSC) as well as by Fourier transform infrared spectroscopy (FTIR). The degree of crystallinity of the samples increased during drying, which in turn was found to alter the drying rate. The drying kinetics were faster at higher temperatures, for lower molecular weights, and for lower degrees of crystallinity. A mathematical model was developed to predict drying rates of semicrystalline polymers by considering the crystallization kinetics during drying. The model predictions included the thickness of the polymer sample, the degree of crystallinity of the polymer, and the water weight loss as functions of drying time. Model predictions were found to agree reasonably well with the experimental results. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2771-2780, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2793-2803 
    ISSN: 0887-6266
    Keywords: activation volume ; relaxation ; pressure ; nonlinear optical polymer ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Second harmonic generation (SHG) was used to measure the temperature dependence of the reorientation activation volume of the side-chain copolymer poly(disperse red 1 methacrylate-co-methyl methacrylate) (DR1-MMA). The decay of the SHG signal from poled films of DR1-MMA was recorded at hydrostatic pressures up to 3060 atm and at different temperatures between 25°C below the glass transition temperature (Tg) to 35°C above it. The activation volume, ΔV*, decreased with increasing temperature. The data suggests that the coupling between chromophore reorientation and the long-range motion of the polymer is stronger for the DR1-MMA side-chain system than in previously measured guest-host systems. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2793-2803, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2829-2833 
    ISSN: 0887-6266
    Keywords: Raman ; LAM ; stress ; polyethylene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Raman longitude acoustical mode (LAM) study of axially stressed polyethylene-made microfilms gave evidence of the formation of the straight tie molecules localized in two neighboring crystals and in an amorphous layer situated between them. The samples were bicomponent blends composed of polyethylenes with different MW (7 × 104 and 2 × 106). Each MW fraction exhibits an individual LAM band responding to crystals with the size specific to a given fraction. Under tensile stress, the bands shift insignificantly towards an exciting laser line. In addition, the LAM localized on all-trans sequencies with the length exceeding the mean crystallite size appear in the spectrum of a stressed sample. The reversibility of these spectral changes depends on the draw ratio of samples. We conclude the effect is due to stress-induced gauch-to-trans transformations taking place in the amorphous layers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2829-2833, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2849-2863 
    ISSN: 0887-6266
    Keywords: nylon oligoamides ; new crystal structure ; morphology ; crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three-amide oligomers of nylon 6 and nylon 6 6 have been investigated using electron microscopy (imaging and diffraction), X-ray diffraction, and computational modeling. A new crystal structure has been discovered for the three-amide oligomer of nylon 6. This material crystallizes from chloroform/dodecane solutions into an unfolded crystal form that has progressively sheared hydrogen bonding in two directions between polar (unidirectional) chains. This structure is quite different from the usual room temperature α-phase structure of chain-folded nylon 6 crystals, in which alternatingly sheared hydrogen bonding occurs between chains of opposite polarity in only one direction. The occurrence of this new structure illustrates the extent to which progressively sheared hydrogen bonding is preferred over alternatingly sheared hydrogen bonding. Indeed, the progressive hydrogen bonding scheme occurs in the three-amide nylon 6 material even though it requires a disruption to the lowest potential energy all-trans conformation of the chain backbone, and requires all the chains in each hydrogen-bonded layer to be aligned in the same direction. We believe the presence of chain folding, which necessarily incorporates adjacent chains of opposite polarity into the crystal structure, prevents the formation of this new crystal structure in the nylon 6 polymer. In contrast, the three-amide nylon 6 6 crystal structure is analogous to the polymeric nylon 6 6 α-phase structure, found in both fibers and chain-folded crystals, and consists of progressive hydrogen-bonded sheets which stack with a progressive shear. In both structures, the molecules (≈ 3 nm in length) form smectic C-like layers with well-orchestrated stacking of 2.2 nm to form a three-dimensional crystal. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2849-2863, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2267-2274 
    ISSN: 0887-6266
    Keywords: poly(ether ether kotone) ; polyimide ; miscibility ; crystallization ; morphology ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Miscibility and crystallization behavior of solution-blended poly(ether ether ketone)/polyimide (PEEK/PI) blends were investigated by using DSC, optical microscopy and SAXS methods. Two kinds of PIs, YS-30 and PEI-E, which consist of the same diamine but different dianhydrides, were used in this work. The experimental results show that blends of PEEK/YS-30 are miscible over the entire composition range, as all the blends of different compositions exhibit a single glass transition temperature. The crystallization of PEEK was hindered by YS-30 in PEEK/YS-30 blends, of which the dominant morphology is interlamellar. On the other hand, blends of PEEK/PEI-E are immiscible, and the effect of PEI-E on the crystallization behavior of PEEK is weak. The crystallinity of PEEK in the isothermally crystallized PEEK/YS-30 blend specimens decreases with the increase in PI content. But the crystallinity of PEEK in the annealed samples almost keeps unchanged and reaches its maximum value, which is more than 50%. The spherulitic texture of the blends depends on both the blend composition and the molecular structure of the PIs used. The more PI added, the more imperfect the crystalline structure of PEEK. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2267-2274, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2301-2309 
    ISSN: 0887-6266
    Keywords: discrete dynamic compliance spectra ; nonlinear viscoelasticity ; creep ; stress relaxation ; constant strain rate tests ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The present work reports a discrete, stress-dependent dynamic compliance spectra method which may be used to predict the mechanical response of nonlinear viscoelastic polymers during strain-defined processes. The method is based on the observation that the real and complex parts of the discrete dynamic compliance frequency components obtained from creep measurements are smooth, easily fit functions of stress. Comparisons between experimental measurements and model calculations show that the model exhibits excellent quantitative agreement with the basis creep measurements at all experimental stress levels. The model exhibits good quantitative agreement with stress relaxation measurements at moderate levels of applied strain. However, the model underestimates the experimental stress relaxation at an applied strain of 3.26%. The stress relaxation error appears to be a real material effect resulting from the different strain character of creep and stress relaxation tests. The model provides a good quantitative agreement with experimental constant strain rate measurements up to approximately 4% strain, after which the model underestimates the experimental flow stress. This effect is explained by the time dependence of the stress-activated configurational changes necessary for large strains in glassy polymers. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2301-2309, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2737-2743 
    ISSN: 0887-6266
    Keywords: high-temperature zone-drawing ; high-tension multiannealing ; nylon 46 fiber ; high-modulus ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nylon 46 fibers produced by the high-temperature zone-drawing treatment were treated by repeating high-tension annealing treatments, that is, a high-tension multiannealing (HTMA) treatment to improve their tensile properties. The HTMA treatment was carried out at a repetition time of 10 times and treating temperature of 110°C under high tension (538.2 MPa) close to the tensile strength at break. Although the HTMA treatment was carried out at 110°C, which is much lower than the crystallization temperature of 265°C for nylon 46, the degree of crystallinity increased up to 59%. The orientation factor of crystallites increased dramatically up to 0.949 by the first high-temperature zone-drawing treatment and slightly during the subsequent treatments. This observation indicated that the orientation of crystallites due to slippage among molecular chains did not occur during the HTMA treatment. The treatments shifted the melting peak to slightly higher temperatures, and the HTMA fiber has a melting endotherm peaking at 285°C. The fiber obtained finally had a storage modulus of 12.5 GPa at 25°C. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2737-2743, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2761-2769 
    ISSN: 0887-6266
    Keywords: protein folding ; Lyapunov exponents ; computer simulations ; nonlinear dynamics ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A lattice model with Monte Carlo dynamics is used to carry out computer simulations of protein dynamics on a four α-helix bundle. The interaction energies in the model can be set so that either the helix bundle structure remains relatively stable or changed so that it unfolds. The computer model produces output that simulates experimental measurements relating to the structure. We show how this output can be used with analytical techniques of nonlinear dynamics to obtain important information about the complex underlying protein dynamics. Time-delay reconstruction plots of structural parameters of unfolding bundles resemble strange attractors in a space of dimension 3-4. We calculate Lyapunov exponents for these unfolding runs and find positive Lyapunov exponents implying chaotic dynamics. For stable runs the Lyapunov exponents are close to zero. We use these Lyapunov exponents to calculate the rate of loss of structural information during the unfolding process and show how the approach may be useful for investigating the folding dynamics of proteins. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2761-2769, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2805-2810 
    ISSN: 0887-6266
    Keywords: poly(dimethylsiloxane) ; DSC ; raman spectra ; thermal history ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(dimethylsiloxane) was studied by laser Raman spectroscopy and differential scanning calorimetry. The Si—O—Si skeletal mode at 489 cm-1 and the C—Si—C deformation bands at 188 cm-1 and 158 cm-1 were studied as functions of temperature from ambient to -130°C, and effects of temperature interpreted in accordance with results from thermal analysis. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2805-2810, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2821-2827 
    ISSN: 0887-6266
    Keywords: polypropylene ; composites ; gamma phase ; epitaxy ; X-ray scattering ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method for crystallizing oriented samples of the γ-phase of isotactic polypropylene (iPP) under atmospheric pressure in the presence of nucleating fibers has been developed. The technique uses iPP grades of high molecular weight and high isotacticity and produces a mixture of α and γ-phase crystals within the matrix of both pitch-based carbon and Kevlar®-reinforced composites. Two-dimensional wide-angle X-ray scattering (WAXS) patterns from these samples show that the content of the γ-phase decreases as the fiber loading in the composites decreases, suggesting that the γ-phase is directly nucleated by the fibers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2821-2827, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2835-2848 
    ISSN: 0887-6266
    Keywords: dielectric spectroscopy ; interfacial polarization ; Debye length ; particle size ; polymer blends ; laminates ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this article we will focus on the dielectric properties of laminates and blends of a partially conducting (the liquid crystalline copolyesteramide Vectra B950) and an insulating (polypropylene or mica) phase. Dielectric spectroscopy was used as a tool to obtain information about the influence of the dimensions of the conducting phase in these laminates and blends. With decreasing thickness of the conducting layer in the laminates, the measured permittivities deviate more and more from the values predicted using conventional dielectric mixture models. From this discrepancy it is possible to calculate the thickness of the charge layer (=Debye length) in the conducting phase and the thickness of this phase itself, using a model derived by Trukhan. This model incorporates not only conduction, but also diffusion of the charges. Similar experiments were performed on a system of Vectra B950 particles in a polypropylene matrix. After the derivation of a new model, which combines the Trukhan model for space charges with the Böttcher equation for dielectric mixtures, we could make a distinction between samples containing large and small particles. For samples containing small particles, it is even possible to determine the variation in particle sizes. However, the use of a Debye length of 1.1 µm obtained from the laminates resulted in particle sizes that were two times higher than the actual values. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2835-2848, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2869-2876 
    ISSN: 0887-6266
    Keywords: cyclopentadiene ; resins ; carbon yields ; carbon-carbon composites ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of thermosetting resins were synthesized via phase transfer reaction of allyl chloride and propargyl bromide with cyclopentadiene in the presence of a strong base. Feed ratios of 1 : 1, 3 : 1, and 5 : 1 allyl chloride to propargyl bromide were used to give resins with varying amounts of propargyl and allyl functionality. In all cases the resins could be thermally cured, without added catalyst, at temperatures below 275°C to give black, glassy, brittle materials with densities of 1.15. TGA evaluation of the resins, with heating to 1000°C, resulted in carbon yields ranging from 48 to 66% with increasing propargyl functionality causing increased values. Physical mixtures of ACP and PCP resins were also made and evaluated. Cure of the mixed materials also occurred below 275°C, and carbon yields were comparable to the corresponding APCP resin. APCP/carbon fiber composites gave good mechanical properties with flexural modulus values of 115-130 GPa and flexural strength values of 1000 MPa. Carbonization of 1 : 1 APCP/carbon fiber composites provided materials with interlaminar strength values of approximately 1.14 MPa. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2869-2876, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2895-2904 
    ISSN: 0887-6266
    Keywords: polyamide 11 ; dynamic rheo-optical spectra ; deformation mechanism ; thermal treatment ; hydrogen bonds ; crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic mechanical analysis, coupled with polarized step-scan FTIR transmission spectroscopy, has been used to monitor the submolecular motional behavior of uniaxially oriented polyamide 11. The dynamic in-phase spectra depend upon the morphology of the samples as well as on the polarization direction of the infrared radiation. The lineshape features of the dynamic in-phase spectra and their relationship to sample deformation are analyzed on the basis of changes of the internal coordinates, the reorientation movement of several functional groups, and the thickness change of the film during the stretching cycle. Dynamic infrared spectra are helpful for deconvolution of overlapping bands on the basis of their different responses to the external perturbation, which sometimes cannot be resolved well by derivative spectroscopy or curve-fitting analysis. The lineshape features have been used to follow microstructural changes after isothermal heat treatment. Near the N—H stretching frequency, two bands at 3270 cm-1 and 3200 cm-1 are resolved and analyzed in terms of Fermi resonance between the N—H stretching fundamental mode and the overtone and combination modes of the amide I and II vibrations. The dynamic response of the N—H stretching mode correlates with the modulation of hydrogen bond strength in uniaxially oriented PA-11. After thermal treatment at the highest temperature (190°C), the dynamic response in this region is mainly caused by the modulation of crystals. In amide I region, three bands at 1680 cm-1, 1648 cm-1, and 1638 cm-1 are separated and assigned to hydrogen bond-free, hydrogen-bonded amorphous, and hydrogen-bonded crystalline regions, respectively. The dynamic responses of the hydrogen-bonded regions are more sensitive to external perturbation. Two components are found in the amide II region, and the band at 3080 cm-1 is assigned to the overtone resonance of the component with perpendicular polarization. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2895-2904, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2941-2947 
    ISSN: 0887-6266
    Keywords: Case II diffusion ; stability ; multidimensional Stefan-like Problem ; asymptotic analysis ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A well-known model of one-dimensional Case II diffusion is reformulated in two dimensions. This 2-D model is used to study the stability of 1-D planar Case II diffusion to small spatial perturbations. An asymptotic solution based on the assumption of small perturbations and a small driving force is developed. This analysis reveals that while 1-D planar diffusion is indeed asymptotically stable to small spatial perturbations, it may exhibit a transient instability. That is, although any small perturbation is damped out over sufficiently long times, the amplitude of any perturbation initially grows with time. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2941-2947, 1998
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  • 140
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2961-2970 
    ISSN: 0887-6266
    Keywords: micelle ; blends ; crystallization ; morphology ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization, morphology, and crystalline structure of dilute solid solutions of tetrahydrofuran-methyl methacrylate diblock copolymer (PTHF-b-PMMA) in poly(ethylene oxide) (PEO) and PTHF have been studied with differential scanning calorimetry (DSC), X-ray, and optical microscopy. This study provides a new insight into the crystallization behavior of block copolymers. For the dilute PTHF-b-PMMA/PEO system containing only 2 to 7 wt % of PTHF content, crystallization of the PTHF micellar core was detected both on cooling and on heating. Compared the crystallization of the PTHF in the dilute solutions with that in the pure copolymer, it was found that the crystallizability of the PTHF micellar core in the solution is much greater than that of the dispersed PTHF microdomain in the pure copolymer. The stronger crystallizability in the solution was presumably due to a softened PMMA corona formed in the solution of the copolymer with PEO. However, the “soft” micelles formed in the solution (meaning that the glass transition temperatures (Tg) of the micelle is lower than the Tm of the matrix phase) showed almost no effects on the spherulitic morphology of the PEO component, compared with that of the pure PEO sample. In contrast, significant effects of the micelles with a “hard” PMMA core (meaning that the Tg of the core is higher than the Tm of the PTHF homopolymer) on the nucleation, crystalline structure, and spherulitic morphology were observed for the dilute PTHF-b-PMMA/PTHF system. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2961-2970, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3017-3023 
    ISSN: 0887-6266
    Keywords: liquid crystalline polymer ; shear alignment ; thermotropic polymer ; small-angle neutron scattering ; flow-induced structure ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle neutron scattering is utilized to determine the flow induced alignment of a model thermotropic liquid crystalline polymer (LCP) as a function of shear rate and temperature. The results demonstrate that the flow-induced structures in thermotropic liquid crystalline polymers have similarities and differences to those in lyotropic liquid crystalline polymer solutions. The shear rate dependence of the alignment shows that the flow-induced alignment correlates very well to the viscosity behavior of the LCP in the shear thinning regime, while temperature variation results in a change in the extent of alignment within the nematic phase. Relaxation results also demonstrate that the flow-induced alignment remains essentially unchanged for up to an hour after the shear field has been removed. Last, there exists a regime at low shear rate and low temperature where alignment of the LCP molecule perpendicular to the applied shear flow is stable. These results provide important experimental evidence of the molecular level changes that occur in a thermotropic liquid crystalline polymer during flow, which can be utilized to develop theoretical models and more efficiently process thermotropic polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3017-3023, 1998
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  • 142
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3065-3077 
    ISSN: 0887-6266
    Keywords: polyurethanes ; AFM ; atomic force microscopy ; phase separation ; crosslinking ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of polyurea urethanes was isothermally synthesized from toluene diisocyanate (TDI), water, and trifunctional poly(propylene oxide) in the temperature range of 50-150°C. Morphologies of the samples vary significantly as a function of reaction temperature. In this system, phase separation competes with polymerization and crosslinking. Both transmission electron microscopy and atomic force microscopy have shown a network type of structure for the 50°C samples, while the 150°C samples appear to be homogeneous. Infrared analysis shows that samples prepared at 150°C possess a morphology that is less strongly hydrogen bonded and has a broader distribution of hydrogen-bonded states compared to those prepared at lower temperatures. From this combination of techniques, it can be inferred that phase separation occurs faster than crosslinking at low temperatures; consequently, a phase-separated morphology forms. In contrast, crosslinking occurs faster than phase separation at higher reaction temperatures. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3065-3077, 1998
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  • 143
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3101-3113 
    ISSN: 0887-6266
    Keywords: block copolymer ; neutral solvent ; selective solvent ; gyroid ; order-order transition ; order-disorder transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phase behavior of a styrene-isoprene (SI) diblock copolymer, with block molecular weights of 1.1 × 104 and 2.1 × 104 g/mol, respectively, is examined in the neutral solvent bis(2-ethylhexyl) phthalate (DOP) and the styrene-selective solvent di-n-butyl phthalate (DBP). DBP is a good solvent for PS, but is near a theta solvent for PI at approximately 90°C. Small-angle X-ray scattering (SAXS), rheology, and static birefringence are used to locate and identify order-order (OOT) and order-disorder transitions (ODT); all three techniques gave consistent results. The neat polymer adopts the gyroid (G) phase at low temperatures, with an OOT to hexagonally-packed cylinders (C) at 185°C, and the ODT at 238°C. Upon dilution with the neutral solvent DOP, the C window is diminished, until for a polymer concentration φ = 0.65, a direct G to disorder (D) ODT is observed. These results reflect increased stability of the disordered state, based on the different concentration scalings of the interaction parameter, χ, at the OOT and ODT. The OOT follows the dilution approximation, i.e., χOOT ∼ φ-1, but the ODT is found to follow a stronger concentration dependence, i.e., χODT ∼ φ-1.4, similar to the scaling of φ-1.6 found previously for lamellar SI diblocks in toluene and DOP. Addition of the selective solvent DBP produces dramatic changes in the phase behavior relative to DOP and the melt state; these include transitions to lamellar (L) and perforated layer (PL) structures. The observed phase sequences can be understood in terms of trajectories across the SI melt phase map (temperature vs. composition): addition of a neutral solvent or increasing temperature corresponds to a “vertical” trajectory, whereas adding a selective solvent amounts to a “horizontal” trajectory. When the solvent selectivity depends on temperature, as it does for the SI/DBP system, increasing temperature results in a diagonal trajectory. For both neutral and selective solvents the domain spacing, d*, scales with φ and χ as anticipated by self-consistent mean-field theory. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3101-3113, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3147-3154 
    ISSN: 0887-6266
    Keywords: glass microfiber ; scattering ; polymer ; nonwoven fabrics ; polymer analogue ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Disordered fiber mats made of glass microfibers (GMF) were studied using small-angle light scattering (SALS), ultrasmall-angle X-ray scattering (USAXS), SEM, and optical microscopy. The morphological scaling of these materials in the micron scale was very similar to that of polymers in the nanometer scale. In some fiber mats, such as GMF, the structure is randomized at the time of formation, leading to a statistical analogy with the thermal randomization that occurs in nanometer-scale, high polymers. Analogues for the coil radius-of-gyration, persistence unit, and scaling regimes exist in such fiber mats and may be a useful feature both for modeling thermally equilibrated polymeric systems, as well as furthering the understanding of the physical properties of fiber mats through analogy with the theoretical understanding of thermally equilibrated polymeric systems. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3147-3154, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 105-112 
    ISSN: 0887-6266
    Keywords: polystyrene ; single-molecule single crystal ; radiation resistance ; lattice image ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of single-molecule single crystals of isotactic polystyrene (i-PS) was investigated by electron diffraction (ED). The nanoscale single-molecule single crystals were found to be more resistant to electron irradiation when compared to the larger crystals of many molecules, as indicated by both observation of ED and high-resolution electron microscopy with increasing radiation dose. It is proposed that since the single-molecule single crystals are very small, the secondary electrons escape more frequently from the crystal so that the radiation damage is reduced. Lattice imaging was achieved at room temperature in the case of single-molecule single crystals because of their stability to electron irradiation. Published 1998 John Wiley & Sons, Inc.This article is a US Government work and, as such, is in the public domain in the United States of America. J Polym Sci B: Polym Phys 36: 105-112, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 463-471 
    ISSN: 0887-6266
    Keywords: hydrogel ; free volume ; positron annihilation ; water ; density ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A copolymer of 2-hydroxyethyl methacrylate (HEMA) with 2-ethoxy ethyl methacrylate (EEMA) was synthesized and the molecular mobility, free volume, and density properties examined as a function of composition. These properties were correlated with the equilibrium water uptake in order to determine which of the properties were most influential in causing high water sorption, as these materials are suitable candidates for hydrogel systems. It was found that the polar HEMA repeat unit results in a rigid, glassy sample at room temperature due to the high degree of hydrogen bonding between chains whereas high EEMA content leads to rubbery samples with subambient glass transition temperatures. The free volume properties on the molecular scale measured by positron annihilation lifetime spectroscopy (PALS) showed that higher HEMA content led to smaller, fewer holes and a lower free volume fraction than EEMA. Therefore the high water uptake of HEEMA-containing copolymers is largely related to the high polarity of the HEMA unit compared to EEMA, despite the low content of free volume into which the water can initially diffuse. Trends in density with copolymer composition, as measured on a macroscopic level, differs to that seen by PALS and indicates that the two techniques are measuring different scales of packing. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 463-471, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 473-481 
    ISSN: 0887-6266
    Keywords: PET fiber ; continuous zone-drawing/zone-annealing ; high-modulus ; mechanical properties ; microstructure ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A continuous zone-drawing/zone-annealing method was applied to poly(ethylene terephthalate) fibers in order to improve their mechanical properties. Apparatus used for this treatment was assembled in our laboratory. The continuous zone-drawing treatment was carried out at a drawing temperature of 103°C under an applied tension of 6.6 MPa to fully orient amorphous chains in the drawing direction without inducing thermal crystallization. The continuous zone-annealing treatment was carried out twice at an annealing temperature of 160°C under 102.2 MPa and at 183°C under 161.1 MPa to crystallize the highly oriented amorphous chains. The fiber was continuously drawn and annealed at a rate of 420 mm/min. The fiber obtained had a birefringence of 0.260, a degree of crystallinity of 55%, a tensile modulus of 18 GPa, and a storage modulus of 21 GPa at 25°C. Despite the large difference in the treating speed between the continuous zone-annealing and zone-annealing, their values are approximately equal to those of the zone-annealed PET fiber that was reported previously. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 473-481, 1998
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  • 148
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 889-900 
    ISSN: 0887-6266
    Keywords: Pluronic P103 ; micellar formation and structure ; supramolecular structure ; laser light scattering ; small-angle X-ray scattering ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Both laser light scattering (LLS) and small-angle X-ray scattering (SAXS) were used to study the water-induced formation and structure of micelles and supramolecules of Pluronic P103 [(EO)17(PO)60(EO)17] in o-xylene, a selective solvent for the long middle block. In pure o-xylene, P103 molecules exist as unimer coils with an equivalent hard-sphere radius of 1.6 nm even at fairly high concentrations. Micelles with a PEO/water core and a PPO dominated corona were formed in the presence of water when the P103 concentration ≥0.046 g/mL. The size and structure of micelles have been studied as a function of solubilized water content Z (the molar ratio of water to EO units) in micelles. The micelles change from a somewhat open structure with some EO units either dangling out of the micellar core or being incorporated into neighboring micellar cores at low Z values to a flower-like structure with relatively sharp interface at high Z values. At low Z values (〈 about 2.9), micelles tend to have a structure with part of the poorly solvated PEO blocks present in the corona. With more water added to the core, the PEO blocks in the corona gradually entered into the core, and the PPO blocks backfolded to form loops. With increasing Z, the micellar core radius, Rc, and the hard-sphere volume fraction, φ, of micelles increased; the aggregation number, N, kept nearly a constant; but the hydrodynamic radius, 〈Rh〉0, and the corona thickness, Rs, decreased. At high Z values (〉 about 2.9), micelles have a flower-like structure with the two end PEO blocks belonging to the small micellar core. With increasing Z, the values of Rc, φ, and N increased, while Rs kept nearly a constant. In the concentrated regime (C 〉 0.30 g/mL), a stiff polymer network at a critical φ value of 0.49 was formed. The supramolecular structures with a face-center cubic packing, and a possible hexagonal packing at higher polymer concentrations (i.e. 〉 0.55 g/mL), were observed, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 889-900, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1129-1139 
    ISSN: 0887-6266
    Keywords: polymer diffusion ; ambient temperature ; fluorescence ; latex films ; poly(butyl methacrylate) ; poly((acetoacetoxy)ethyl methacrylate-co-ethylhexyl methacrylate) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer diffusion across interfaces at room temperature (21°C) was analyzed by direct nonradiative energy transfer (DET) in labeled latex films. Two modellatex polymers were examined: poly(butyl methacrylate) [PBMA, Mw = 3.5 × 104, Tg (dry) = 21°C] and a copolymer of 2-ethylhexyl methacrylate with 10 wt % (acetoacetoxy)-ethyl methacrylate [P(EHMA-co-AAEM), Mw = 4.8 × 104, Tg (dry) = -7°C]. Little energy transfer due to polymer diffusion was detected for the P(EHMA-co-AAEM) latex samples in the dispersed state or dried to solids content below ca. 90%, but above 90% solids, diffusion occurs among particles. For PBMA, diffusion occurs only after the film is dried (〉97% solids) and aged. In the dry PBMA films, it requires 4-5 days at 21°C to reach a significant extent of mixing (fm = 0.3-0.4). This corresponds to an estimated penetration depth dapp of 30-40 nm and a mean apparent diffusion coefficient (Dapp) of 5 × 10-4 nm2/s. The corresponding Dapp value for the dry P(EHMA-co-AAEM) sample is 5 × 10-2 nm2/s, and it takes about 25-40 min for this polymer to reach fm of 0.3-0.4 with dapp of 20-30 nm. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1129-1139, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1507-1512 
    ISSN: 0887-6266
    Keywords: interpenetrating polymer networks ; gelation ; phase separation ; kinetics ; poly(carbonate-urethane)/polyvinyl pyridine ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A possible model for the formation of interpenetrating polymer networks is suggested. Phase separation is assumed to be faster than gelation. This implies that domains rich in either component grow first until late stages of spinodal decomposition. In these domains, short linear chains are crosslinked, leading to large branched macromolecules. Growth of the domains is slowed down by the presence of crosslinked polymers. It is assumed that it is stopped when the sizes of the domains and of the branched macromolecules are comparable. The resulting domains are significantly larger than the average distance between crosslinks. These results are supported by recent neutron scattering results on a poly(carbonate-urethane)/polyvinyl pyridine interpenetrating network. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1507-1512, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1513-1528 
    ISSN: 0887-6266
    Keywords: free volume ; thermal expansion ; positron lifetime measurements ; semicrystalline polymers ; polyethylene ; polytetrafluoroethylene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Positron lifetime measurements, performed in the temperature range 80-300 K, are reported for polyethylene (PE) and polytetrafluoroethylene (PTFE). The lifetime spectra have been analyzed using the data processing routines LIFSPECFIT and MELT. Two long-lived components appear, which are attributed to pick-off annihilation of ortho-positronium in crystalline regions and at holes in the amorphous phase. The ortho-positronium lifetimes, τ3 and τ4, are used to estimate the crystalline packing density and the size of local free volumes in the crystalline and amorphous phases. The interstitial free volume in the crystals exhibits a weak linear increase with the temperature which is attributed to thermal expansion of the crystal unit cell. In the amorphous phase, the hole volume varies between 0.053 and 0.188 nm3 (PE) and between 0.152 and 0.372 nm3 (PTFE). Its temperature variation may be fitted by two straight lines, the intersection of which is used to estimate a glass transition temperature of Tg = 195 K for both PE and PTFE. The slopes of the free volume in the glassy and crystalline phases with the temperature correlate well with each other. The coefficients of thermal expansion of the hole volume are compared with the macroscopic volume change below and above the glass transition. From this comparison a fractional hole volume at Tg of 4.5 (PE) and 5.7% (PTFE) and a number of 0.73 (PE) and 0.36 (PTFE) × 1027 holes/m3 is estimated. Finally, it is found that the intensity of o-Ps annihilation in crystals shows a different temperature dependence to that in the amorphous phase. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1513-1528, 1998
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  • 152
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1609-1616 
    ISSN: 0887-6266
    Keywords: polymer-surface interactions ; deuterium NMR ; block copolymers ; polymer micelles ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Anionically polymerized poly(α-deuterostyrene) and poly(β-deuterostyrene-b-2-vinylpyridine) (DSVP), selectively deuterated on the styrene backbone, were studied using deuterium wide-line NMR in bulk and adsorbed on silica and alumina. Changes in the segmental dynamics of the bulk and adsorbed polymers were inferred via changes in the NMR line shape with temperature. The DSVP bulk sample, which consisted of micellar aggregrates with a 2-vinylpyridine core, was more rigid than the homopolystyrene of a similar molecular weight. A significant change in mobility occurred at 20°C higher in the DSVP bulk sample than it did in homopolystyrene. The DSVP-adsorbed sample showed more restrictive mobility than bulk DSVP. The spectra of the adsorbed samples contained “rigid” Pake patterns with considerable intensity at temperatures where the collapse of the Pake pattern for the DSVP bulk sample was observed. DSVP bound to the silica surface was found to have a mobility similar to the same copolymer on alumina. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1609-1616, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1647-1655 
    ISSN: 0887-6266
    Keywords: thermodynamics ; phenolic ; PEO ; polymer blend ; PCAM ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermodynamic properties of novolac type phenolic resin blended with poly(ethylene oxide) (PEO) were investigated by the Painter-Coleman association model (PCAM). Equilibrium constants and enthalpy corresponding to the interaction between phenolic and poly(ethylene oxide) were calculated from the Fourier transform infrared spectroscopy of low molecular weight analogues in dilute solutions. The association parameters of the model compounds are transferred to the corresponding polymers, to predict the Gibbs free energy, phase behavior, and the degree of hydrogen bonding in the polymer blend. The heat capacity (CP) and the excess heat capacity (ΔCP) are used to verify the validity of PCAM model on predicting the thermodynamics properties of phenolic/PEO blend. It is found that the hydrogen bonding interaction dominates at moderate temperatures, which is outweighed by the dispersion force at higher temperature or high PEO compositions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1647-1655, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1657-1668 
    ISSN: 0887-6266
    Keywords: microstructure ; properties ; poly(1,3-cyclohexadiene) ; living anionic polymerization ; hydrogenated derivatives ; triblock copolymer ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relationship between the microstructure and the properties of poly(1,3-cyclohexadiene)s, obtained by living anionic polymerization with an alkyllithium/amine system, and their hydrogenated derivatives are reported. The 1,2-bond/1,4-bond molar ratio of poly(1,3-cyclohexadiene) was determined by measuring 2D-NMR with the H—H COSY method. The glass transition temperature of poly(1,3-cyclohexadiene) was found to rise with an increase in the ratio of 1,2-bonds to 1,4-bonds or with an increase of the number average molecular weight. The 1,2-bond of the polymer chain gives a high flexural strength and heat distortion temperature. Hydrogenated poly(1,3-cyclohexadiene) has the highest Tg (231°C) among all hydrocarbon polymers ever reported. 1,3-Cyclohexadiene-butadiene-1,3-cyclohexadiene triblock copolymer and 1,3-cyclohexadiene-styrene-1,3-cyclohexadiene triblock copolymer have high heat resistance and high mechanical strength. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1657-1668, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1739-1746 
    ISSN: 0887-6266
    Keywords: block copolymers ; molecular diffusion ; Forced Rayleigh scattering ; free volume ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Forced Rayleigh scattering was used to investigate the diffusion of a photoreactive dye molecule in two homogeneous poly(styrene-b-isoprene) (SI) diblock copolymers with overall molecular weights of approximately 2000. Although diffusion rates were intermediate to TTI transport in homopolymer polystyrene (PS) and polyisoprene (PI), system dynamics appear to be largely dictated in each case by the PI block. The size of the polymer jumping unit, on the other hand, is evaluated from a free-volume analysis of the data, and is found to be governed predominantly by the PS component of the copolymer. The mechanism for tracer diffusion in low-molecular-weight block copolymers appears analogous to transport in a high molecular weight SI diblock copolymer (Mn = 13,600) that has been solvated sufficiently in toluene to be microstructurally disordered. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1739-1746, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1793-1793 
    ISSN: 0887-6266
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1959-1969 
    ISSN: 0887-6266
    Keywords: miscibility ; transesterification ; kinetics ; polyarylate ; liquid crystalline copolyesters ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Blends of poly(oxybenzoate-p-ethylene terephthalate) (POB-PET) and polyarylate were confirmed to be a partially miscible system by differential scanning calorimetry. When 60/40 POB-PET/PAr blend was annealed at high temperature (above 270°C) for several minutes, the ester-ester interchange (transesterification) in the blend took place immediately, as evidenced by Fourier Transformed infrared analyses. The analysis of the blend annealed at 290°C by 1H-13C nuclear magnetic resonance disclosed that there were four new diads appearing in 15 min and an additional one produced in 60 min during the heat treatment. The miscibility between POB-PET and polyarylate increased with the mol concentration of these new diads judging from differential scanning calorimetry. The evolution of the concentration of the diad ethylene glycol-isophthalate during the annealing can be described by a second-order reaction. The activation energy of forming the diad ethylene glycol-isophthalate was 26.5 kcal/mol, and the preexponential factor for the transesterification reaction is 3.7 × 108 min-1. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1959-1969, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2047-2056 
    ISSN: 0887-6266
    Keywords: polypropylene ; spherulite ; cocrystallization ; lamellae ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: During spherulitic crystallization of polymers, there is a tendency for low molecular weight and other less crystallizable entities to be rejected from the body of the spherulites. This rejection process causes a segregation of these species to those areas where spherulites impinge. As a result of this segregation, lamellar and spherulite boundaries have a tendency to become weak, often resulting in premature mechanical failure. The objective of this work, anthropomorphically speaking, is to develop a melt miscible blend system in which a propylene copolymer “fools” a polypropylene homopolymer into rejecting the copolymer to the spherulite boundaries as an impurity. However, once the copolymer arrives at these boundaries, the copolymer subsequently connects adjacent spherulites through cocrystallization of the propylene copolymer segments. It was found that addition of either a random ethylene-propylene copolymer or an isotactic-atactic block copolymer was able to yield the desired effect. Cocrystallization was confirmed by calorimetry, and segregation of copolymer and subsequent reinforcement at the spherulite boundaries was directly observed microscopically. Using this approach, toughness was increased with little loss in stiffness. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2047-2056, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2085-2093 
    ISSN: 0887-6266
    Keywords: starch ; shear-thickening ; semidilute solution ; viscoelastic properties ; oscillatory shear flow ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The shear-thickening behavior of semidilute waxy maize (WM) starch solutions (90/10 DMSO/water) exhibit much of the behavior of classical nonlinear viscoelasticity. Small-amplitude oscillatory shear experiments were used to investigate the network structure formed during the shear-thickening regime. The solution viscoelastic properties of WM starch prior to the shear-thickening region could be described by the GLV model. The macromolecules behave as random coils with a longest relaxation time of 0.58 ± 0.03 s. For WM starch the observed shear-thickening region creates a stable, highly entangled network which resembles the behavior found in solutions in the concentrated regime. The longest relaxation time for the entangled solution is estimated to be 1.4 s. Semidilute solutions of normal maize (NM) starch in 90/10 DMSO/water do not exhibit a shear-thickening regime. The oscillatory shear data obtained before and after a thixotropic loop experiment were identical. The semidilute solution conformational dynamics of NM starch indicate some degree of rigidity in one of the components that constitute NM starch which might be associated with the helical structure obtained by amylose in DMSO. © 1998 John Wiley & Sons, Inc. This article is a US Government work, and, as such, is in the public domain in the United States of America. J Polym Sci B: Polym Phys 36: 2085-2093, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2129-2139 
    ISSN: 0887-6266
    Keywords: adhesion hysteresis ; poly(dimethylsiloxane) ; JKR technique ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The JKR technique was used to determine the source and nature of the adhesion hysteresis present in modified poly(dimethylsiloxane) (PDMS) networks. As controlled excess amounts of the tetrafunctional crosslinker were added to the networks, the adhesion hysteresis increased. It was found that by poisoning the catalyst with a thiol the hysteresis could be significantly lowered, and completely removed in some cases. We believe that the adhesion hysteresis in this system stems from a complexation between the excess crosslinker and the catalyst. We found that the work of adhesion in this case is a function of the unloading rate. The unloading rate dependence of this chemical adhesion hysteresis was attributed to the rate of bond dissociation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2129-2139, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2211-2224 
    ISSN: 0887-6266
    Keywords: starch ; mechanical properties ; percolation ; clustering ; diffusion ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The use of starch microcrystals as biodegradable particulate filler is evaluated by processing composite materials with a weight fraction of starch ranging from 0 to 60%. In a previous work [Macromolecules, 29, 7624] the preparation technique of a colloidal suspension of hydrolyzed starch and the processing of composite materials by freeze drying and molding a mixture of aqueous suspensions of starch microcrystals and synthetic polymer matrix were presented. Starch microcrystals with dimensions of a few nanometers were obtained from potatoes' starch granules, and it was found that this filler produces a great reinforcing effect, especially at a temperature higher than Tg of the synthetic matrix. Classical models for polymers containing nearly spherical particles based on a mean field approach could not explain this reinforcing effect. The morphology of these nanocomposite systems is discussed in light of aggregate formation and percolation concepts. The sorption behavior of these materials is also performed. Starch is a hygroscopic material, and it is found that the composites absorb more water, as the starch content is higher. The diffusion coefficient of the penetrant is predicted from modified mechanical three branch series-parallel model based on a percolation approach. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2211-2224, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2259-2265 
    ISSN: 0887-6266
    Keywords: polymer composite ; moisture-absorption ; dielectric loss ; thermal conductivity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the search for new packaging materials for the electrical/electronics industry, three types of polymer composites have been studied. Silicone/boron nitride powders, polyurethane/alumina powders, and polyurethane/carbon fibers have all been synthesized to study the moisture-absorption kinetics, thermal conductivities, and the dielectric loss spectra under various levels of humidity. The water uptake data indicate that water molecules are absorbed not only by the polymer matrix, but also by the interfaces introduced by the fillers. For all materials, the dielectric relaxation spectroscopy shows the presence of a peak in the 175-200 K range, which is largely due to absorbed water. The silicone/boron nitride samples absorbed the least amount of moisture. Incorporating this result with the thermal conductivity data of the three types of polymer composites, it is concluded that silicone polymers embedded with boron nitride can best serve as the coating for the electronic devices that require heat dissipation and moisture resistance, in addition to electrical insulation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2259-2265, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2291-2300 
    ISSN: 0887-6266
    Keywords: poly(hydroxyether of bisphenol A) ; poly(N-vinylpyrrolidone) ; polymer miscibility ; polymer blend ; solid-state (NMR) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The miscibility of poly(hydroxyether of bisphenol A) (phenoxy) and poly(N-vinyl pyrrolidone) (PVP) was investigated by differential scanning calorimetry (DSC) and high-resolution solid-state nuclear magnetic resonance (NMR) techniques. The DSC studies showed that the phenoxy/PVP blends have a single, composition-dependent glass transition temperature (Tg). The S-shaped Tg-composition curve of the phenoxy/PVP blends was reported, which is indicative of the strong intermolecular hydrogen-bonding interactions. To examine the miscibility of the system at molecular level, high-resolution solid-state 13C nuclear magnetic resonance (NMR) technique was employed. Upon adding phenoxy to system, the chemical shift of carbonyl carbon resonance of PVP was observed to shift downfield by 1.6 ppm in the 13C cross-polarization (CP)/magic angle spinning (MAS) together with the high-power dipolar decoupling (DD) spectra when the concentration of phenoxy is 90 wt %. The observation was responsible for the formation of intermolecular hydrogen bonding. The proton spin-lattice relaxation time T1(H) and the proton spin-lattice relaxation time in the rotating frame T1ρ(H) were measured as a function of the blend composition. The T1(H) result was in good agreement with the thermal analysis, i.e., the blends are completely homogeneous on the scale of 20 ∼ 30 nm. The six results of T1ρ(H) further indicated that the blends were homogeneous on the scale of 40 ∼ 50Å. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2291-2300, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2327-2337 
    ISSN: 0887-6266
    Keywords: surface tension ; surface energy ; contact angle ; liquid crystalline polymers ; thermotropic polymers ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have determined the surface energies (γs) of two liquid crystalline polyesters (Vectra™ A-950 [Hoechst Celanese, NJ] and Xydar™ [Amoco, GA]) and one polyesteramide (Vectra™ B-950 [Hoechst Celanese, NJ]) using contact angle techniques at room temperature. These LCPs were dissolved in bis-trifluoromethyl phenol and spin coated upon glass slides to form thin films. The contact angle measurements were carried out employing a Ramé-Hart Contact Angle Goniometer (Ramé-Hart, NJ). Pure water, glycerol, formamide, and diiodomethane were chosen as the testing liquids. Various surface energy calculation models were utilized to analyze the surface energies of these LCP films. Experimental data suggest that surface energy values did match between two-liquid geometric and three-liquid acid-base approaches if the correct combinations of testing liquid were used. However, the three-liquid Lifshitz-van der Waals acid-base method is more suitable for the surface energy calculation of these three LCPs, and provides much more information (e.g., acidity and basity of LCP surfaces). The average surface energies of Vectra™ A-950, Vectra™ B-950, and Xydar™ are 41.0, 41.9, and 42.3 mJ/cm2, respectively. In addition, all these three LCPs should be classed as monopolar Lewis bases because their Lewis acid components, γ+, are negligible. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2327-2337, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2355-2369 
    ISSN: 0887-6266
    Keywords: fracture ; fatigue ; polyethylene ; molecular weight distribution ; short chain branch content ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stepwise fatigue crack propagation in a range of polyethylene resins, some of which are candidates for use in pipes for natural gas distribution, was studied. Examination of the effect of molding conditions on fatigue crack propagation in a pipe resin indicated that fast cooling under pressure produced specimens with the same crack resistance as specimens taken from a pipe extruded from this resin. The mechanism of stepwise crack propagation in fatigue was the same as reported previously for creep loading. Observations of the region ahead of the arrested crack revealed a complex damage zone that consisted of a thick membrane at the crack tip followed by a main craze with subsidiary shear crazes that emerged from the crack tip at an angle to the main craze. The effects of molecular parameters, such as molecular weight, comonomer content, and branch distribution, on the kinetics of fatigue crack propagation were examined. Correlation of creep and fatigue crack resistance made it possible to relate fatigue fracture toughness to molecular parameters by invoking concepts of craze fibril stability developed for creep. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2355-2369, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 383-394 
    ISSN: 0887-6266
    Keywords: ion-selective membranes ; gel crystallization ; poly(siloxanes) ; crown-ethers ; calixarenes ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A one-step procedure for the preparation of ion-selective membranes is described. The method employs the thermally induced gel crystallization of ultrahigh molecular weight poly(ethylene) (UHMW-PE) from a dilute xylene solution. After evaporation of the xylene, a microporous UHMW-PE film remains, which can serve as the support for liquid and polymeric ion-selective membranes. The addition of a membrane solvent and suitable receptor molecules to the xylene solution allows a one-step incorporation of these membrane components into the UHMW-PE support. The influence of the preparation conditions of the UHMW-PE support on the rates of the p-tert-butylcalix[4]arene tetraethylester-mediated transport of NaClO4 was studied. Two concepts to improve the life-time of the membranes are introduced. In a first approach, the addition of photocrosslinkable nitril-substituted siloxane copolymers to the membrane phase has been evaluated. The enhanced viscosity of the membrane phase reduces leaching of carrier and solvent molecules from the membrane into the aqueous phases. In a second approach, the solvent is omitted and the membrane-phase merely consists of a benzo-15-crown-5 or calix[4]arene modified siloxane-copolymer, which is substituted to such a degree that ion transport no longer has to take place via diffusion of host-guest complexes but by jumping of the cations from one fixed carrier to a neighboring carrier. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 383-394, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 425-431 
    ISSN: 0887-6266
    Keywords: poly(arylene ether ketone) ; gas permeability ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this work we present the results from studies on novel poly(arylene ether ketone)s, including gas permeability, wide-angle x-ray diffraction (WAXD), and dynamic mechanical analysis (DMA). Poly(arylene ether ketone)s containing 2,2′- and 3,3′-dibenzoylbiphenyl (DBBP) moieties were characterized to study the effect of biphenyl substitution on gas transport properties. Gas permeabilities of naphthalene-containing poly(arylene ether ketone)s were also measured. Higher permeabilities were observed for polymers prepared with 6F-BPA, compared to 9,9-bis(4-hydroxyphenyl)fluorene (HPF). The naphthalene-containing polymers exhibited higher permeabilities than the DBBP polymers, except for a polymer having the 2,2′-DBBP and tetramethylbiphenyl moieties. Based on our work, and results reported in the literature, the 3,3′-DBBP polymers showed the lowest permeabilities for DBBP-containing poly-(arylene ether ketone)s. The low permeabilities are due to more efficiently packed chains brought on by greater flexibility of the backbone, compared to the other polymers studied. DMA studies confirmed the higher barriers to rotation which are believed to be responsible for 2,2′-DBBP polymers having similar selectivities compared to 3,3′-DBBP polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 425-431, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 455-462 
    ISSN: 0887-6266
    Keywords: photoreactive polymer blends ; photocrosslinking kinetics ; photodimerization of anthracene ; Kohlrausch-Williams-Watts relaxation ; poly(vinyl methyl ether) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mixtures of polystyrene derivatives (PSCS) and poly(vinyl methyl ether) (PVME) were made photocrosslinkable by chemically labeling PSCS chains with photoreactive anthracene. Miscibility of these anthracene-labeled PSCS/PVME blends was examined by light scattering under several crosslinking conditions in the one-phase region via photodimerization of anthracenes. As the reaction proceeds, the coexistence curve of PSCS/PVME blends shifts toward the low temperature side. By following the changes in concentration of anthracenes with irradiation time, it was found that the crosslinking reaction of PSCS chains in the blends does not follow the mean-field kinetics. However, it can be well expressed by the Kohlrausch-Williams-Watts (KWW) relaxation mechanism, indicating that the crosslinking reaction proceeds inhomogeneously in the blends. By scaling the reaction time with the average reaction rate obtained from the KWW equation modified for the reaction kinetics, all the crosslinking data obtained in the miscible region of the reacted blends fall on a single master curve. These experimental results suggest the universal behavior of the photocrosslinking kinetics obtained under the “shallow quench” conditions in the region far away from the coexistence curve of the reacting blends. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 455-462, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 537-542 
    ISSN: 0887-6266
    Keywords: sulfonated polyelectrolytes ; gelatin ; complex stoichiometry ; size-exclusion chromatography ; flow field-flow fractionation ; hydrodynamic size ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 655-664 
    ISSN: 0887-6266
    Keywords: PMMA ; ion beam ; scission ; G value ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chemical and physical effects induced by bombardment of nearly monodisperse Poly(methyl methacrylate) (PMMA) with energetic ions (He+) at 200 keV have been studied. Bond scission is the main results of low fluence ion irradiation but, at high fluence there is a regime transition of PMMA from positive tone resist behavior to negative tone. The ion-induced chemical reactions in the macromolecular film give rise to gas evolution and chemical changes in the solid residue. The gas formed during the bombardment has been studied by means of a mass spectrometer, while the solid polymer has been characterized by measuring the molecular weight distribution (MWD) and the absorption coefficient in the Near Infrared (NIR), visible, and ultraviolet regions. X-ray Photoelectron Spectroscopy (XPS) has been performed to learn what happens at the surface of the polymer after bombardment. The main result of these studies is that at fluence higher than 1013 cm-2 both chemical and physical effects follow a nonlinear behavior due to the transition from a single-track regime to a track overlap regime. This transition is explained in terms of progressive chemical change of the irradiated polymer from the pristine chemical structure to a new one depleted of the ester pendent groups. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 655-664, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 673-679 
    ISSN: 0887-6266
    Keywords: scanning force microscopy ; hectorite ; polystyrene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Many important layered silicate-polymer nanocomposite materials may be synthesized using an in-situ polymerization process. Using this technique, organic monomers are intercalated into the interlayer regions of the hosts, where subsequent polymerization may then occur. In this paper, we report on the in-situ polymerization of styrene in Cu(II)-exchanged hectorite thin films. Scanning force microscopy (SFM) images of the polymer surface reveal that the surface polystyrene is generally aggregated into groups of elongated strands. SFM imaging of the interclay regions, in conjunction with X-ray diffraction (XRD) and electron spin resonance (ESR) data, indicates that approximately 20-30% of these regions contain polystyrene, with minimal reduction in the majority of Cu2+ sites observed. XRD data shows little or no intercalation of the monomer into the true intergallery regions. Instead, the polymer likely forms in intercrystallite or planar defect regions. In addition, two distinct phases of polymeric material are found within these defect regions, a highly polymerized polystyrene in addition to a polystyrene form exhibiting greater material stiffness. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 673-679, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 755-761 
    ISSN: 0887-6266
    Keywords: positron annihilation lifetime spectroscopy ; free volume ; transition temperatures ; poly(silylenemethylene)s ; dynamic mechanical analysis ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Amorphous and crystalline poly(silylenemethylene)s with the repeating PhRSiCH2 (R : Me or Ph) units were characterized by positron annihilation lifetime spectroscopy (PALS) to gain insights into the molecular motions of these polymers. The temperature dependence of the ortho-positronium lifetime (τ3) and intensity (I3) was examined from 50 to 470 K for each sample. The glass transition temperature of each polymer was easily distinguished by a change in the slope of τ3 spectrum. Both polymers exhibited a steep drop of I3 at 130-140 K being probably assignable to the transition arising from the motions of phenyl groups, which was almost undetectable by means of differential scanning calorimetry or dynamic mechanical analysis. Several other transitions of these polymers detected by PALS are also discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 755-761, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 763-781 
    ISSN: 0887-6266
    Keywords: random copolyesters ; copolymers ; crystallization ; melting ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting behavior of poly(ethylene terephthalate co-1,4-cyclohexylene dimethylene terephthalate) [PET/CT] random copolyesters has been studied. The basis of this analysis was the triple melting behavior of PET homopolymers, which is commonly observed after a period of isothermal crystallization followed by linear heating in a differential scanning calorimeter. Both ET and CT homopolymers are able to crystallize, and as a consequence, the copolymer morphology depends on the ET/CT ratio. It has been reported that at low CT concentrations, the ET units can crystallize with complete rejection of the CT units and that at high CT concentrations, the CT units can cocrystallize with the ET units. In the present work, low CT concentrations were selected, as they are completely rejected from the ET crystals. The purpose was to further test the hypothesis that in the triple melting behavior of PET homopolymers, the second DSC melting endotherm is related to secondary species crystallized by material rejected from the primary crystals. This concept arose from our previous work, where it was speculated that increasing the average molecular-weight of PET would enhance molecular entanglement and increase secondary crystallization. This process would give rise to a higher amount of species being rejected from the main crystals, i.e., an increase of secondary crystallization would occur, and as a consequence the second melting endotherm would be enhanced. Similar to the effect of molecular weight, such behavior has been observed as a function of rejected copolymer content. This gives support to our previously proposed step-like crystallization and melting mechanism for PET homopolymers, and has the potential to be extended to other high temperature semicrystalline polymeric systems. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 763-781, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 815-825 
    ISSN: 0887-6266
    Keywords: dielectric spectroscopy ; interfacial tension ; liquid crystalline polymer ; blend ; interfacial polarization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric spectroscopy is an unexplored technique in the elucidation of the morphology of polymer blends. Especially the appearance of interfacial polarization can reveal important information about the microstructure of a polymer blend. A model system of liquid crystalline polymer fibers lined up in a thermoplastic matrix was investigated. After heating above the melting temperature of both phases, the fibers developed distortions which grew with time. Dielectric spectroscopy was used to follow the change in shape of the distorted fibers. The use of only two frequencies made it possible to increase the number of relevant data points in the initial stages of the fiber breakup process. From these measurements it was possible to calculate the growth rate and hence the interfacial tension between the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 815-825, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 873-888 
    ISSN: 0887-6266
    Keywords: crystallization ; polymer blends ; pattern formation ; numerical simulation ; syndiotactic polystyrene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The development of texture which exists in polymer spherulites grown from single phase melts containing an appreciable amount of noncrystallizable material was investigated. This texture generally consists of lamellar bundles separated by amorphous regions, both of which are typically 0.1-1 μm thick. A space-time finite element model previously developed by us was used to simulate the growth of a group of polymer lamellae. The model determines the impurity concentration field in the melt surrounding the growing lamellae and tracks the growth of each lamella. Important variables are the initial melt concentration of noncrystallizable material, the mass diffusion coefficient of noncrystallizable species, lamellar thickness, long period, and the rate of molecular attachment at the growth front. Under certain conditions, bundles did indeed develop during the simulations. These results were used to predict bundle thicknesses. The predictions of bundle texture were compared to actual textures observed in blends of syndiotactic and atactic polystyrene. It was found both experimentally and numerically that bundle thickness was a strong function of crystallization temperature and a relatively weak function of both the initial composition of noncrystallizable species and the degree of crystallinity of the lamellar stack. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 873-888, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 913-918 
    ISSN: 0887-6266
    Keywords: glass transition ; thermally stimulated currents (TSC) ; relaxation ; PVC ; dielectric ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermally stimulated current-thermal sampling (TSC-TS) technique was used to study the broadened glass transition in conventional “atactic” poly(vinyl chloride), PVC. The activated parameters obtained from the TSC-TS data, mainly the apparent activation energy (Ea), characterize the breadth of glass transitions in a very sensitive way. These results are compared with those values of Ea obtained from the literature, using a recently proposed method of analyzing a.c. dielectric constants and their derivatives, over the temperature range of -100-130°C. Both techniques detect weak cooperative glass transition-like relaxations well below the main glass transition of ca. 80°C. As is the case with “atactic” PMMA, the data suggest that compositional heterogeneity related to a small fraction of predominantly isotactic sequences contribute to the broad glass transition extending ca. 60°C below the main glass transition in atactic PVC. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 913-918, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 959-968 
    ISSN: 0887-6266
    Keywords: PTMSP ; cross-linking ; membranes ; permeability ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cross-linkable poly[1-(trimethylsilyl)-1-propyne] (PTMSP) films were cast from toluene solutions containing PTMSP and either 4,4′-diazidobenzophenone or 4,4′-(hexafluoroisopropylidene)diphenyl azide. The composite films were clear and homogeneous and were cross-linked by UV irradiation at room temperature or thermal annealing at 180°C. Low levels of the bis(aryl azide) (1-5 wt %) were effective in rendering the films insoluble in toluene and THF, both good solvents for PTMSP. The process is simple and effective, and thus PTMSP can be readily converted to mechanically stable membranes with permeabilities and separation factors comparable or higher than those of poly(dimethylsiloxane). The films were characterized by measuring their density, their permeability toward O2 and N2, and their spectroscopic properties. Compared to PTMSP, films containing bis(aryl azide) cross-linkers had lower permeabilities and higher separation factors, consistent with a reduction in free volume. When the films were cross-linked photochemically, the permeabilities declined further and the separation factor increased. Films cross-linked thermally had permeabilities comparable to their PTMSP/azide precursors, and density and swelling measurements suggest that higher free volumes are obtained in thermally cross-linked films. All films stored in air suffered from a slow decline in permeability which may reflect slow surface oxidation of the films. When stored in vacuum, cross-linked films were stable and showed no loss in permeability, but the permeability of uncross-linked PTMSP films stored under the same conditions fell to 70% of their original value in 1 month. We attribute the permeability decline to densification accelerated by impurities and solvents. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 959-968, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 999-1004 
    ISSN: 0887-6266
    Keywords: latex ; polystyrene ; luminescence ; particle ; micron-diameter ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A technique for rapid determination of the presence of polystyrene in individual micron-diameter polymer particles of mixed composition is presented. This technique is based upon observation of visible emission from conjugated regions of the polymer backbone, generated photochemically, while the particle is held in an optical trap. Particle emission characteristics are dependent upon particle size and suspending solvent. Emission spectra are provided for single component polystyrene particles and mixed polymer particles containing poly(methyl methacrylate), poly(N-vinyl pyrrolidone), and polystyrene. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 999-1004, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 991-997 
    ISSN: 0887-6266
    Keywords: poly(methyl methacrylate-co-lithium methacrylate)(P(MMA-co-LiMA)) ; ionomer ; polymer electrolyte ; ion content ; ion conductivities ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have prepared polymer electrolytes composed of poly(methyl methacrylate-co-lithium methacrylate) ionomer (P(MMA-co-LiMA)), low molecular weight PEG, and LiCF3SO3 salt. The ion groups in P(MMA-co-LiMA) could enhance the miscibility between the MMA units and PEG in the polymer electrolytes. This miscibility enhancement made the pathway of ion transport less tortuous, and consequently led to the increase in ion conductivity. The maximum ambient ion conductivities in these systems were measured to be in the range of 10-4-10-5 S/cm. The polymer electrolytes became transparent at the higher ion content owing to the enhanced miscibility. The mechanical stability of the polymer electrolytes was also improved through the introduction of ion groups into the PMMA. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 991-997, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1037-1050 
    ISSN: 0887-6266
    Keywords: polymer glasses ; glass transition ; diluents ; antiplasticization ; mixtures ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A mathematical model to describe the specific volume of glassy mixtures of a polymer and a low molecular weight diluent or additive is presented. The model is based on understandable physical assumptions and relies on parameters that can be determined experimentally or estimated from methods available in the literature. The predictions of the model show good agreement with the experimental data for mixtures of four polymers with diluents that in the pure state are liquid, glassy, or crystalline. The observed negative departure from volume additivity, as defined by simple additivity of the specific volume of the pure glassy polymer and the pure amorphous diluent, is the result of the relaxation of the excess volume of the glassy mixture relative to the equilibrium state caused by mixing two components with different glass transition temperatures. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1037-1050, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1081-1089 
    ISSN: 0887-6266
    Keywords: liquid crystals ; acrylate ; photopolymer network ; dynamic mechanical analysis ; infrared dichroism ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This article is concerned with molecular orientation in liquid crystal (LC) monomers and the retention of orientation in crosslinked network polymers formed from them by photopolymerization. This is of importance because anisotropic mechanical and physical properties can be beneficial in certain structural applications. To this end, linear viscoelastic behavior of liquid crystal photo-monomers was investigated with dynamic mechanical analysis, and molecular order was studied by infrared dichroism measured with Fourier transform infrared spectroscopy. Although the order parameter of the monomer could vary from 0.45 to 0.70, depending on temperature, the order parameters of the polymer samples varied only from 0.50 to 0.62 and depended on polymerization temperature and extent of cure. The mechanical anisotropy was found to be a complicated phenomenon that depended not only on the molecular order, but also on other factors such as free volume and network structure. The difference in the elastic modulus parallel and perpendicular to the alignment direction was as high as a factor of two in the glassy state, and a factor of three above Tg. In addition, different amounts of mechanical anisotropy could be induced by varying the cure conditions. Finally, different postcuring schemes could cause variations in mechanical behavior by advancing cure or by inducing secondary reactions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1081-1089, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1141-1151 
    ISSN: 0887-6266
    Keywords: polymer gel ; poly(N-isopropylacrylamide) ; PNIPA ; volume phase transition ; hydrogen bond ; hydrophobic interaction ; free volume ; positronium ; positron annihilation ; methanol-water mixed solvent ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The macroscopic volume shrinkage and swelling of poly(N-isopropylacryl-amide) (PNIPA) gel induced by the compositional change in the methanol-water mixed solvent is correlated to the change in the nanoscopic free volume size and numerical concentration formed in the PNIPA gels. The free volume size and numerical concentration are estimated from the longest component appearing in the positron annihilation lifetime curves. The apparent free volume fraction calculated by the free volume size and numerical concentration, and dispersion of the free volume deduced by the size distribution are utilized to analyze the origin and location of the free volumes. The free volume parameters obtained by analysis of the positron annihilation data show various nanoscopic phases occuring within the PNIPA gels during the volume change, implying the variation of the strength of the interactions among the solvent molecules and the polymer chains of the PNIPA. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1141-1151, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1211-1218 
    ISSN: 0887-6266
    Keywords: polyethylene ; slow crack growth ; γ-irradiation ; crosslinks ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of γ-irradiation were measured in a HDPE and in the resin after it was recrystallized. The fracture mode of the initial material transformed from crazing to complete brittle failure at a critical dose. The failure mode of the recrystallized material transformed from crazing to shear deformation, which produced an extremely long failure time, and finally, at a higher dose, its fracture became brittle. The relationship between morphology and slow crack growth is presented where crosslinking was the major factor. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1211-1218, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 805-813 
    ISSN: 0887-6266
    Keywords: collagen ; surfactants ; calorimetry ; segment-long-spacing ; anionic ; titration ; sodium lauryl sulfate ; castor oil ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Leather, a textile based on collagen, usually requires the addition of sulfated oils that have been recently found to cause instability when heated in critical manufacturing processes. Here reactions between collagen and sodium dodecyl sulfate (SDS), sulfated castor oil, or a synthetic sulfated oil are studied calorimetrically. Sodium lauryl sulfate below its critical micelle concentration (cmc) displayed an immediate exotherm due to equilibrium binding of the reagents with stoichiometry n = 12.6 ± 0.2, K = (2.02 ± 0.8) × 107 M-1, and enthalpy ΔH = 62 ± 2 Kcal/mol; and a delayed endotherm due to denaturation of collagen. The endotherms accompanying the reactions with sulfated oils with longer chains were smaller, with no apparent denaturation of collagen. The micellar nature of these surfactants was apparent from very large n for sulfated castor oil, 4082 ± 11 and a very small value of ΔH, 0.77 ± 0.01 cal/mol. The binding of sulfated castor oil at the polar bands of collagen crystallites, comprising extended molecules arranged side-by-side, was shown directly by electron microscopy. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 805-813, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 861-871 
    ISSN: 0887-6266
    Keywords: glass transition ; polymer blends ; free volume ; positron annihilation ; composition dependence of Tg ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High-Vinyl Polybutadiene (HVBD)/cis-Polyisoprene (CPI) blends were characterized by Differential Scanning Calorimetry (DSC) and Positron Annihilation Lifetime Spectroscopy (PALS). A single DSC glass transition temperature Tg is observed, whose composition dependence strongly deviates from additivity, and shows an apparent cusp when the weight fraction of HVBD ≈ 0.75. The free-volume hole size, Vh, and the scaled fractional free volume, hps/C, = I3Vh were determined by PALS from the orthopositronium (o-Ps) intensities, I3, and lifetimes, τ3, over a temperature range encompassing Tg and the temperature at which “positronium bubble” formation occurs. In the glass, Vh and hps/C are smaller for CPI than for HVBD, but the thermal expansion coefficient for hole volume, αf, is larger in the melt for CPI than for HVBD; thus, an iso-hole volume temperature occurs in these blends at Tiso ≈ -34°C. Above and below Tiso, Vh and hps/C each show a negative departure from additivity. A quantitative interpretation of the cusp in the composition dependence of Tg can be obtained, via a modified analysis of Kovacs, using free-volume quantities from PALS, with the ratio of scaling constants CCPI/CHVBD as an adjustable parameter. At high temperatures, the positron bubble size is smaller in CPI than in HVBD. This agrees with the observation that the thermal expansivity of hole volume, and, hence the internal pressure are larger in the equilibrium melt of CPI. The effect of e+-irradiation on the o-Ps intensity was investigated. I3 decreases more rapidly in the melt as T → Tg, and then more slowly in the glass, suggesting that the effect is due to trapping of radical or ionic species which inhibit o-Ps formation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 861-871, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 931-936 
    ISSN: 0887-6266
    Keywords: potentiometric titration ; mathematical simulation ; neighbor effect ; interpolymer complexes ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theory of the “neighbor effect” was applied for the description of the potentiometric titration curves of polyelectrolytes. Satisfactory results for poly(acrylic acid) were obtained by considering the effect of the two (at the right and at the left) nearest neighbors on the state of the monomeric unit in the limits of triads. The developed method was used for the determination of the degree of linkage of acidic groups in solutions of the interpolymer complexes. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 931-936, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 969-976 
    ISSN: 0887-6266
    Keywords: positron annihilation ; conducting polymers ; free volume in polymers ; electrical conductivity in polymer electrolytes ; analysis of positron lifetime spectra ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Positron lifetime spectroscopy has been applied to study the temperature dependence of free-volume properties in a solvent-free polymer-salt complex polyethylene oxide (PEO) doped with ammonium iodide (NH4I, with NH4+ ≈ 0.076) in the temperature range of 298-353 K. The observed lifetime spectra were resolved into three components and the longest lifetime, τ3, was associated with the pick-off annihilation of ortho-positronium (o-Ps) trapped by the free volume. The lifetime component, τ3, and its intensity, I3, both showed a significant variation with temperature, which followed a different course in the heating and cooling cycle. Changes in the temperature coefficient of τ3 and I3 were observed at T ≈ 328 K, the melting point of the sample. This behaviour is correlated to the temperature variation of the electrical conductivity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 969-976, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1005-1012 
    ISSN: 0887-6266
    Keywords: polylactide ; melt spinning ; fiber formation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(L-lactic acid) filaments were prepared by high speed melt spinning at take-up velocities up to 5000 m/min. The crystallinity, birefringence, tensile strength, Young's modulus and yield strength all exhibit maxima at take-up velocities between 2000 and 3000 m/min. The boiling water shrinkage exhibits a minimum in this range. The maximum tensile strength of the as-spun filaments was 385 MPa and the maximum modulus was 6 GPa. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1005-1012, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1051-1060 
    ISSN: 0887-6266
    Keywords: polymer mixtures ; film casting ; solvent selectivity ; incompatibility ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Blends of polystyrene/poly(oxyethylene) (PS/POE) and polystyrene/poly-(methyl methacrylate) (PS/PMMA) have been obtained by casting from solution. Differential Scanning Calorimetry, Optical Microscopy, and Scanning Electron Microscopy showed that two incompatible polymers can present relatively good miscibility (formation of domains smaller than 5 μm) when the solvent from which the films are obtained does not present any noticeable selectivity towards the two polymers of the blends. An increase of the casting temperature increases the miscibility of PS and PMMA because the selectivity of the solvent used, towards these polymers decreases with increasing temperature. On the contrary, an increase of the casting temperature in the case of the PS and POE mixture decreases their miscibility because the selectivity of the solvent used increases with increasing temperature. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1051-1060, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1107-1114 
    ISSN: 0887-6266
    Keywords: polyelectrolytes ; conformational change ; water-acetone mixture ; viscosity and conductivity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of a polyelectrolyte poly(methacryloylethyl trimethylammonium methylsulfate), PMETMMS, with molar masses Mw = 22-25 × 106 were examined with viscosity, static light scattering, and conductivity measurements in a water-acetone solvent. Because acetone is a nonsolvent for this polymer the measurements were performed to determine the influence of the solvent composition, the polymer concentration, and the presence of added ions on the conformation of the polyelectrolyte in mixed solvents. The possible influence of a hydrodynamic field on the polymer conformation was also studied. The viscosity of the polymer solutions as a function of polymer concentration, as well as of the solvent composition, was studied using a broad range of shear rates. When the mass fraction of acetone in the solvent, γ, is below 0.5, the solutions show a usual polyelectrolyte behavior. When γ ≥ 0.80, the polymer adopts a compact conformation. This is observed as a decrease of the radius of gyration, Rg, second virial coefficient, A2, the viscosity, and also as a change in the conductivity of the solution. The change in the polymer conformation may be induced also by dilution. When 0.60 ≤ γ 〈 0.80, a gradual decrease in the polymer concentration leads to a sudden decrease of the reduced viscosity, which indicates a decrease in the particle size. The values of Mw measured by static light scattering were constant in all experiments. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1107-1114, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1167-1189 
    ISSN: 0887-6266
    Keywords: poly(dimethylsiloxane) ; silica ; hydrolysis ; condensation ; gelation ; composites ; filled elastomers ; stress-strain isotherms ; reinforcement ; X-ray scattering ; neutron scattering ; fractal geometry ; disordered systems ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various synthetic protocols were used to prepare several classes of polysiloxane-silica filler systems. The structures of these fillers and their interactions with the polysiloxane matrices were studied using small-angle X-ray and neutron scattering. In addition, the mechanical properties of the composites were characterized using equilibrium stress-strain isotherms in elongation. The results indicated that manipulation of the chemical reactions used to generate the filler can lead to a wide range of complex structures and unusual properties. Some of the observed mechanical properties were correlated with information on the composite structures and on elastomer-filler interactions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1167-1189, 1998
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  • 192
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    Keywords: poly(methylphenylsiloxane) ; poly(dimethylsiloxane) ; titania ; silica ; composites ; reinforced elastomers ; morphology ; stress-strain isotherms ; scattering intensities ; differential scanning calorimetry ; transmission electron microscopy ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The work reported in the preceding article in this series is extended by consideration of polysiloxane-ceramic composites based on atactic poly(methylphenylsiloxane) (PMPS) elastomers instead of poly(dimethylsiloxane). The former is noncrystallizable because of its stereochemically irregular structure, while the latter is crystallizable. In addition, some composites were prepared by the in situ precipitation of titania instead of silica. The resulting materials were characterized using differential scanning calorimetry, equilibrium stress-strain measurements in elongation, small-angle neutron scattering, and transmission electron microscopy. The moduli of the PMPS elastomers were found to increase significantly with increase in amount of either type of filler, with reinforcing upturns at high elongation in the case of the silica. Because the PMPS elastomers were amorphous, it is obvious that strain-induced crystallization is not required for these upturns in modulus. Titania did not give as good reinforcement as did silica, at least in the case of PMPS. Differences in interactions between the polymer and the two fillers are obviously important in this regard, but differences in particle morphology probably also contribute. Specifically, the titania “particles” were significantly larger than the silica particles when observed in TEM, and appeared to be much more porous. The actual domain size as measured by scattering, however, was only approximately 5% larger. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1191-1200, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1247-1260 
    ISSN: 0887-6266
    Keywords: polyimides ; thin films ; infrared spectroscopy ; molecular structure ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular structure of poly[biphenyl dianhydride-p-phenylenediamine] (BPDA-PDA) polyimide in ultrathin (3-300 nm) films on silicon has been characterized by polarized infrared spectroscopy in conjunction with ellipsometry and X-ray reflectivity measurements. In spite of the high degree of crystalline packing of the polymer chains, the results show that an unexpected and significant content of imide rings exhibit local structural perturbations, including out-of-plane twisting. Further, the fraction of perturbed rings increases with increasing film thickness while, in contrast, the high degree of in-plane uniaxial film symmetry and planar stacking of the chains remain constant with thickness. These results reveal a new structural aspect of localized ring disorder that arises within the otherwise well-ordered, chain-stacked structure of BPDA-PDA polyimide films. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1247-1260, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1293-1303 
    ISSN: 0887-6266
    Keywords: extended-chain crystals ; low molecular weight linear polyethylene ; revision of Flory's theory of fusion ; interfacial free energy ; bulk-isothermal crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To analyze extended-chain crystalline systems composed of linear polyethylene, Flory's conventional theory of fusion is reconsidered by introducing a new concept of crystallinity. When this new treatment is applied to a melting case of a low molecular weight polyethylene fraction (Mn = 5600) isothermally bulk crystallized, a certain result that very large lamellar thickness was caused by a very small increase in crystallization temperature can satisfactorily be explained by a significant change in interfacial free energy of the crystallite end. Further, it shows 14-17 kJ/mol as a nonequilibrium value range of interfacial free energy for highly crystalline polyethylene fractions of low molecular weight Mn ≦ 5600 by using the previous data presented by other workers. A similar result is also obtained on the Mn = 5600 fraction by analyzing from a standpoint of equilibrium crystallinity. In either case, the estimated range of interfacial free energy is consistent with the conventional range. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1293-1303, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1335-1348 
    ISSN: 0887-6266
    Keywords: PEEK ; growth rate ; crystallization ; kinetics ; regime ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An optical microscope equipped with a video photograph system was used to follow the growth of spherulites. Under nitrogen atmosphere, the growth rates at 290 and 300°C suggest that when the melt of PEEK has been equilibrated for 15 min at 400°C, the subsequent crystallization behavior was nearly independent of the prior thermal history. Linear growth rates of crystallization of PEEK have been measuredin the temperature range of 260-325°C for melt-pressed films and solvent cast films. Detailed kinetic analysis indicated that PEEK exhibited an unmistakable regime II → III transition at 296 ± 1°C. The II → III transition was clearly present irrespective of the rather drastic changes in U*. It is interesting that the branching and crosslinking retarded the growth rate of PEEK, but a transition from regime II to regime III still existed. For melt-pressed films after equilibration at 400°C for 15 min, values of σ and q suggest that U* should be taken nearer to 1500 cal/mol in the case of T∞ = Tg - 30 K and 2000 cal/mol in the case of T∞ = Tg - 51.6 K. The Kg(III)/Kg(II) ratio (1.32) was not as close to the predicted value of 2 as was Hoffman's ratio. For PEEK, the Thomas-Staveley constant (β) should be closer to 0.25 or 0.3 instead of 0.1. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1335-1348, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1383-1392 
    ISSN: 0887-6266
    Keywords: BPFCB ; PFCB ; crosslinking ; thermal and mechanical properties ; low dielectric constant ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As the minimum features in semiconductor devices decrease, it is a new trend to incorporate copper and polymers with dielectric constant less than 3.0 to enhance the performance of the devices. Two fluorinated polymers, poly(biphenyl perfluorocyclobutyl ether) (BPFCB) and poly(1,1,1-triphenyl ethane perfluorocyclobutyl ether) (PFCB), are newly developed polymers with dielectric constants below 3.0. These two polymers have a similar backbone structure, but PFCB has the capability of crosslinking. To know the implications of these two polymers in the semiconductor industry, properties that are important for the integral reliability of Integral Circuits (IC), such as thermal and mechanical properties, should be understood. This comparative study shows that the crosslinking in perfluorocyclobutane aromatic ether polymer can reduce vertical thermal expansion and increase glass transition temperature (Tg) while water absorption, crystalline-like phase, and dielectric constant are slightly increased. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1383-1392, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1423-1432 
    ISSN: 0887-6266
    Keywords: recycling ; polyolefine modification ; mechanical properties ; SAXS ; disorder ; compatibilizer ; blend ; block copolymers ; polyethylene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Blends from polyethylene (PE) and polystyrene-b-polybutadiene-b-polystyrene star block copolymers (SBS) (thermoplastic elastomers) are studied with polyolefine recycling in view. Each component, dispersed in a heterogeneous blend, exhibits a two-phase morphology. This structure is investigated by small angle X-ray scattering (SAXS) and compared to mechanical properties as a function of SBS grade and content. Increasing the SBS content one observes a vanishing PE-related long period reflection, while an SBS-related peak emerges. Best mechanical properties are obtained at concentrations, where the width of the observed long period reflection is broadest. For a quantitative analysis of the SAXS, the interface distribution function (IDF) analysis is employed. Data are fitted with a function modeling arrangement as well as disorder of domains inside the two different kinds of dispersed grains. The analysis yields that the observed broadening of the long spacing peak is caused only by an increased fluctuation of the thicknesses of amorphous layers in the PE stacks. This fluctuation again decreases for SBS concentrations beyond 15 wt %. The effect is strongest for blends containing the SBS grade with the lowest molecular weight and is discussed in terms of its compatibilization effect. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1423-1432, 1998
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 198
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1465-1481 
    ISSN: 0887-6266
    Keywords: poly(phenylene) ; dielectric ; dynamic mechanical ; relaxation ; free volume ; positron annihilation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The free volume and related mobility properties of substituted poly(p-phenylene) polymers are examined. The techniques used range from positron annihilation, dielectric relaxation, and dynamic mechanical spectroscopy to thermally stimulated currents. Fractional free volume is determined for the samples with different substituted side groups and related to the glass transition temperature. Bulkier groups lead to a greater fractional free volume and lower glass transition temperatures. Comparison of molecular relaxation times using the different characterization techniques demonstrates that there is strong coupling between motion of the main chain and the side groups, on which the dipoles reside. Intermolecular coupling between the main chains at the primary relaxation is shown in this work to be related to the nature of the side chains and resultant free volume, as are the temperature locations of local, secondary relaxations. A qualitative model describing the effect of regiochemistry on the motions and packing of these materials is also proposed. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1465-1481, 1998
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 199
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1539-1546 
    ISSN: 0887-6266
    Keywords: nucleophilic substitution ; polyurethane metal complexes (PUC) ; coordination interaction ; phase separation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: N-Picolyl polyurethanes (PUPY) were synthesized by nucleophilic substitution. The blends of these polyurethanes with various of transition metal chlorides [cobalt(II), nickel(II), and copper(II)] were studied by spectroscopic and thermal analysis. Ultraviolet-visible and infrared spectroscopic evidence indicates that a tetrahedral cobalt(II) complex with two pendent picolyl groups in the first-shell coordination sphere of Co2+ is formed in a series of blends with different molar ratio (from 10/1 to 2/1) of picolyl groups to cobalt(II) ions. According to the result of Small-Angle X-ray Scattering (SAXS), Differential Scanning Calorimetry (DSC), and Dynamic Mechanical Thermal Analysis (DMTA), coordination interaction between ligands in hard segments and metal ions provides a driving force for phase separation. The coordination strength of pyridine with Ni2+ is stronger than Co2+ and Cu2+. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1539-1546, 1998
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 200
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1591-1594 
    ISSN: 0887-6266
    Keywords: polypyrrole film ; contraction ; electric field ; desorption ; actuator ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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