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  • 11
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    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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  • 12
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2551-2562 
    ISSN: 0887-6266
    Keywords: polytetrafluoroethylene ; virgin powder ; two-stage draw ; morphology ; tensile properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polytetrafluoroethylene (PTFE) virgin powder was ultradrawn uniaxially by a two-stage draw. A film, compression molded from powder below the melting temperature (Tm), was initially solid-state coextruded to an extrudate draw ratio (EDR) of 6-20 at an established optimum extrusion temperature of 325°C, near the Tm of 335°C. These extrudates from first draw were found to exhibit the highest ductility at 45-100°C for the second-stage tensile draw, depending on the initial EDR and draw rate. The maximum achievable total draw ratio (DRt, max) was 36-48. Such high ductility of PTFE, far below the Tg (125°C) and Tm, is in sharp contrast to other crystalline polymers that generally exhibit the highest ductility above their Tg and near Tm. The unusual draw characteristics of PTFE was ascribed to the existence of the reversible crystal/crystal transitions around room temperature and the low intermolecular force of this polymer, which leads to a rapid decrease in tensile strength with temperature. The structure and tensile properties of drawn products were sensitive to the initial EDR, although this had no significant influence on DRt,max. The most efficient and highest draw was achieved by the second-stage tensile draw of an extrudate with the highest EDR 20 at 100°C, as evaluated by the morphological and tensile properties as a function of DRt. The efficiency of draw for the cold tensile draw at 100°C was a little lower than that for solid-state coextrusion near the Tm. However, significantly higher tensile modulus and strength along the fiber axis at 24°C of 60 ± 2 GPa and 380 ± 20 MPa, respectively, were achieved by the two-stage draw, because the DRt,max was remarkably higher for this technique than for solid-state coextrusion (DRt,max = 48 vs. 25). The increase in the crystallite size along the fiber axis (D0015), determined by X-ray diffraction, is found to be a useful measure for the development of the morphological continuity along the fiber axis of drawn products.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2551-2562, 1998
    Additional Material: 13 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 635-643 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Semicrystalline polymers generally exhibit moduli well below their theoretical limit due to chain folding and to lack of crystal alignment. Modulus increases attainable through standard drawing procedures are limited by sample fracture before large draw ratios are reached. Using an Instron capillary rheometer which allowed a draw ratio of 〉 300, transparent polyethylene strands of unusually high c-axis orientation have been produced by a combination of pressure and shear. The virtually perfect crystalline orientation and evidence for extended chains confirm that a significant improvement in modulus can be realized by this technique. The dynamic tensile storage modulus was measured by Vibron over the temperature range -160°C to +120°C. Room-temperature moduli were 7 × 1011 dyne/cm2, higher than any reported values for drawn polyethylene. Values also remained above 1011 dyne/cm2 even at 120°C. The moduli and morphological data have been related by a model consisting of an extended-chain component in paralled with a conventional drawn morphology. Experimental and calculated moduli are compared and related to available theory.
    Additional Material: 3 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1177-1186 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High-density polyethylene filaments prepared by a solid-state deformation in an Instron capillary rheometer show unusually high crystal orientation, chain extension, axial modulus, and ultimate tensile strength. The Young's modulus and ultimate tensile strength have been determined from stress-strain curves. Gripping of this high modulus polyethylene has been a problem heretofore, but the measurement of ultimate tensile strength has now been made feasible by a special gripping procedure. Tensile moduli show an increase with sample preparation temperature and pressure. Values as high as 6.7 × 1011 dyne/cm2 are obtained from samples extruded at 134°C and 2400 atm and tested at a strain rate of 3.3 × 10-4 sec-1. The effect of strain rate and frequency on modulus has also been evaluated by a combination of stress-strain data and dynamic tension plus sonic measurements over nine decades of time.
    Additional Material: 5 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2031-2048 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transparent strands of high-density polyethylene of unusually high c-axis orientation have been produced by a solid-state extrusion, involving pressure, temperature, and deformation, in an Instron capillary rheometer. Measured values for tensile modulus are higher than previously reported for any polyolefin. Previous modulus and electron microscopic data are consistent with a strand morphology comprised (≤20%) of of extended chain crystals. The remainder resembles an oriented fibrillar morphology such as found in highly drawn polyethylene. In the present study, fuming nitric acid etching of the ultraoriented strands, in combination with gel permeation chromatography (GPC), has provided incisive structural information. The strands exhibit ≥3X the resistance to acid degradation shown by conventionally drawn polyethylene. GPC molecular weight distributions (MWD) of etched samples show a single broad peak with a prominent high molecular weight tail. The crystal size, represented by the MWD, is in agreement with the crystal long period determined by small-angle x-ray scattering. The absence of multiple peaks in the etched MWD's is evidence of limited chain folding. The extended chain content, determined from the etched MWD's, is a strong function of strand formation temperature and is in agreement with the fraction of extended chains calculated from modulus measurements.
    Additional Material: 9 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1427-1434 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of ultradrawn high density polyethylene were studied by thermomechanical analysis. The purpose was to study the dimensional changes in polyethylene morphologies of extreme orientation. Dimensional changes were measured from -140 to +70°C with a precision of better than 1%. A negative thermal expansion coefficient was observed along the length (c axis) of the fibers containing the polyethylene morphologies of extreme orientation. A change in negative coefficient is observed between -35 and -45°C. The sign and magnitude of the expansion coefficient confirm, along with other evidence, the existence of extended chain structures in these morphologies. A series-parallel model has been developed for the ultradrawn polyethylenes to describe the dimensional changes with temperature.
    Additional Material: 3 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1709-1719 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The steady-state and dynamic melt rheology for a series of poly(1-olefins) has been investigated. The series includes poly(1-butene), poly(1-hexene), poly(1-heptene), poly(1-octene), Poly(1-undecene), poly(1-tridecene), poly(1-hexadecene), and poly(1-octadecene). The flow behavior was investigated by use of a Weissenberg rheogoniometer. Measurements on poly(1-butene) were also made using an Instron capillary rheometer. The empirical relationship developed by Cox and Merz was obeyed for the entire series of poly(1-olefins) at all temperatures investigated. Graessley's theory was used to calculate the flow curves for the poly(1-olefins) from the measured molecular weight distributions. The purpose was to investigate the effect of polymer composition on the shear rate dependence of viscosity. It was found that all experimental flow curves except those for poly(1-hexene) can be fitted with the calculated curves from the individual molecular weight distributions. The conclusion is made that flow curves of poly(1-olefins) depend predominately on molecular weight distribution and are essentially independent of side-chain length even for poly(1-olefins) with pendant groups as long as 16 carbon atoms. The low-shear limiting Newtonian viscosity η0 for all poly(1-olefins) was expressed by, η0 = KM̄w3.4 or by η0 = K′P̄w3.4 where M̄w is the weight-average molecular weight and P̄w is the weight-average degree of polymerization. The K and K′ values obtained decrease systematically as the side chain is increased.
    Additional Material: 10 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1721-1728 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solid-state extrusion of high-density polyethylene (HDPE) has received considerable attention. It has been shown that extrudate may have high values of optical clarity, tensile modulus (∼70 GPa = 7 × 1011 dyn/cm2), and c-axis orientation. The effects of extrusion conditions on the properties of the resultant fibers have, however, not yet been clarified. A systematic study has thus been made here to evaluate extrusion pressure, temperature, and extrusion (draw) ratio, and the molecular weight of extruded HDPE. The effects of extrusion ratio on the degree of crystallinity, melting behavior, crystal orientation, and dimensional change along the extrusion direction are reported.
    Additional Material: 5 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1729-1737 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The tensile properties have been evaluated for high-density solid-state polyethylene extruded to different extrusion (draw) ratios. The results are compared with measured and theoretical values on this and other polymers. An extrusion (draw) ratio and a deformation gradient are defined and discussed. The content of extended tie molecules in extruded high-density polyethylene was calculated from a model and modulus data.
    Additional Material: 4 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2049-2065 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A transparent, ultraoriented, high-density polyethylene morphology has been produced by solid-state (ultradraw) extrusion in a capillary rheometer. From the perspective of modulus and nitric acid etching behavior, the uniquely high draw ratios (〈325) experienced by the polyethylene during extrusion result in a morphology with a high level of chain extension. The effect of nitric acid etching on strand thermal behavior has been determined by DSC. The observed melting points of unetched strands were sensitive to the thermal contact between sample and sample pan. Under conditions ensuring improved contact, strand superheating is reduced to one-third of previously reported values. The negligible shrinkage evidenced by these strands up to 130° is consistent with the presence of a thermally stable component such as extended chain crystals or crystallized tie chains. The single, high-melting peak is gradually replaced by a nonsuperheating, lower melting peak during the initial stages of acid etch. The resultant peak melting temperature is consistent with the value predicted for the peak crystal thickness of the etched polymer. No evidence is found for a higher melting peak attributable to the extended chain crystalline component. A highly constrained morphology produced by the large tie chain content is believed responsible for strand melting behavior. The melting point of the extended chain crystalline component is reduced by defects and a large ratio of lateral to basal surface area.
    Additional Material: 10 Ill.
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