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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 76 (1979), S. 191-208 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Anwachsen von Zugspannung und Scherung zu Beginn einer konstanten Scherung wurde an Lösungen linearer Makromoleküle untersucht, um Aussagen über nichtlineare Viskoelastizität zu machen. Die Polyacrylamide (PAAm)…wurden in Wasser, Formamid und Ethylenglycol gelöst. Die Polymeren wurden in diesem Labor hergestellt. Sie waren unverzweight und initiatorfrei. Die Polystyrolproben (PS) von der Pressure Chemical Company wurden in Dekalinlösung untersucht. PAAm zeigt mit steigendem Molekulargewicht und steigender Konzetration zunehmend typischen Gelcharaketer in allen drei Lösungsmitteln. für homogene Systeme wurde Gelbruch und ein „undershoot“ beob-achtet. Zum ersten Ma1 konnten „overshoot“ aufgrund von verhakten Ketten und auf-grund von energetisch assoziierten Ketten voneinander unterschieden werden. Dies Ver-halten zeigt einen grol3en Gegensatz gegenuber dem PS/Dekalin-System und zeigt die Starke der Nebenvalenzbindungen in den PAAm-Systemen.
    Notes: The growth of stress (shear stress and normal stress) at the onset of steady shear flow was investigated for linear chain macromolecular fluids to determine nonlinear viscoelasticity. The polyacrylamides (PAAm) were dissolved in H2O, formamide and ethyleneglycol. The polymers were prepared in this laboratory. They were unbranched and free of initiator. The polystyrene (PS) samples from Pressure Chemical Company were studied in decalin solutions. PAAm shows increasingly typical gel character - in all 3 solvents - with increasing molecular weight and polymer concentration. For homogeneous systems gel fracture and undershoot were observed. Further for the first time overshoot due to entangled molecules and overshoot due to energetically associated chains have been distinguished. This behaviour is a strong contrast to the PS/decalin system and demonstrates the strength of the second valence bondings in the PAAm-systems.
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  • 12
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 26 (1988), S. 981-988 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Studied here are miscible binary cosolvents for polystyrene, for which polystyrene is insoluble in either of the individual solvents. Polymer-solvent interactions in solutions of atactic polystyrene in acetone/diethyl ether and in methylcyclopentane (MCP)/acetone binary cosolvents have been investigated using nuclear magnetic resonance (NMR) spectroscopy. Polystyrene 13C chemical shifts were measured as a function of miscible binary solvent compositions and temperature. The NMR data were used to calculate “association constants” as a measure of specific interactions of the solvent components with all sites on the polymer. In mixtures of acetone and diethyl ether, 13C-NMR indicates a weak interaction between the polystyrene phenyl ring and the diethylether solvent component. In the polystyrene/MCP/acetone system, present NMR data reveal no preferential interactions. Additional NMR measurements were performed on polystyrene in mixtures of CCl4/acetone. From these results, it is concluded that although preferential polymer-solvent interactions are present in some cosolvent systems, they are not a prerequisite for such behavior.
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  • 13
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 27 (1989), S. 2587-2603 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solid-state coextrusion has been used to prepare uniaxially drawn films from isotropic poly(ethylene 2,6-naphthalate) (PEN) of a minimum degree of crystallinity (ca. 5%) both below and above its glass transition temperature Tg. The onset of cold crystallization (Tc) of the drawn films has been studied as a function of the extrusion temperature (ET) and the draw ratio (EDR). It has been shown that Tc decreases markedly on draw, as much as 95°C, and, at constant draw ratio Tc goes through a minimum in the Tg region. For undrawn PEN, annealing below 153°C has no significant effect on Tc. To evaluate the crystallization rate constant (k) and the activation energy (Ea) of the drawn specimens, a nonisothermal DSC procedure has been used. With increasing EDR, k increases markedly and Ea goes down over threefold compared with the undrawn polymer. At high ET, strain-induced crystallization has also been shown to play an important role in lowering Ea for cold crystallization. Thermal shrinkage above Tm indicates a high elastic recovery, underlining the efficiency of deformation, ca. 93%, achieved by solid-state coextrusion.
    Additional Material: 16 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 26 (1988), S. 83-90 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal-nematic phase transition of a copolyester consisting of 20 mol% poly(ethylene terephthalate) and 80 mol% p-hydroxybenzoic acid (PHB) was characterized by depression of the crystal-nematic transition by the addition of a liquid crystal diluent. This copolyester contains blocks of crystalline PHB. Its transition behavior was compared with thatrandom copolyester with diluent of the same composition. From the extrapolated transition temperature depression data, the heat of transition per mole of p-oxybenzoate was calculated as about 1.3 kcal/mol, with an entropy of about 2 cal/deg mol. This assumes that only the p-oxybenzoate unit crystallized from the nematic state. The validity of the Flory-Huggins model for this transition point depression was confirmed graphically by comparison with two different thermotropic-liquid crystal polyesters. These results may represent the first reported crystal-nematic temperatures and heats generated by the dilution method for liquid crystal copolyesters of this type.
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  • 15
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 24 (1986), S. 2459-2472 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polycarbonate is known to crystallize thermally, but only slowly and to a limited (25%) extent. The melting points reported exhibit a wide variation. We have found that the melting temperature of polycarbonate may be drastically increased by employing a sequence of vapor-induced crystallization and annealing treatments. The crystals formed by the treatment with organic vapor act as a nucleation or precursor state for further crystallization into larger, more perfect lamellae. An initial peak melting temperature of 195°C has been annealed up to 239°C, and then to 295°C by a double-heat treatment. This sample is 60% crystalline, based on heat-of-fusion calculations. An equilibrium melting point of 335°C has been obtained for PC from an extrapolation of reciprocal lamellar thickness.
    Additional Material: 8 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 26 (1988), S. 795-805 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(aryl-ether-ether-ketone) (PEEK) films and rods have been solid-state extruded at 154 and 310°C, respectively. The crystal orientation functions, melting behavior, density, and tensile properties of the drawn PEEK films (EDR ≤ 3.7) and rods (EDR ≤ 5.5) have been measured. As extrusion draw ratio (EDR) was increased, the c-axis orientation function, melting temperature, and tensile modulus and strength increased. Moduli up to 6.5 GPa and the strengths up to 600 MPa, 3 and 6 times the values of undrawn films, respectively, were obtained for the drawn films. The thermal expansivities along (α‖) and perpendicular (α⊥) to the draw direction of PEEK rods were measured from -40 to +10°C. As EDR was increased, α⊥ increased, but α‖ decreased. At EDRs of 3.8 and 5.5, α‖ even exhibited negative values (about -5 × 10-6°C-1), probably due to reversible contraction of elongated tie-molecules.
    Additional Material: 8 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 32 (1994), S. 535-540 
    ISSN: 0887-6266
    Keywords: poly (4-methyl-1-pentene) ; isotactic polypropylene ; biaxial deformation ; stress-strain behavior ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(4-methyl-1-pentene) (PMP) has been uniaxially compressed by a forging (equibiaxial) process. The rheology of the process has been examined for this semicrystalline polyolefin, melting point about 235°C. The yield energy, area under the compressive stress-strain curve up to the yield point, as a function of temperature was found to consist of two linear components of different slope. These two linear relations arise from the glassy and crystalline phases of PMP. The intercept temperature (Ti) at zero yield energy for the glassy phase has been evaluated. The attainable maximum compression ratio without sample rupture (CRmax) increased steadily on increasing forging temperature above Ti, and below Tm. In this range, the crystalline relaxation temperature (Tc), evaluated from an Arrhenius plot of yield stress was 160°C. Above Tc, a CRmax of 240 was reached. This value is five times higher than that attained for isotactic polypropylene (i-PP). However, the draw efficiency evaluated by elastic recovery in the plane direction of PMP (0.76) is lower than for i-PP (0.97). Differential scanning calorimetry analyses showed that the melting peak became a complex doublet on increasing compression ratio ( 〉 100). The drawing and stress-strain behavior of PMP are compared with i-PP. © 1994 John Wiley & Sons, Inc.
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  • 18
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 33 (1995), S. 785-790 
    ISSN: 0887-6266
    Keywords: nylon ; nylon 13,13 ; cast film ; thin films ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Substrate-free thin film of Nylon 13,13 has been prepared continuously by casting the polymer on a water surface from m-cresol solution. The uniform thickness of film is ca. 500 A, as measured with a Profilometer. Film morphology and properties have been characterized by transmission electronic microscopy (TEM), x-ray photoelectron spectroscopy, wide-angle x-ray scattering, differential scanning calorimetry and by contact angle measurements. Results show that there is no preferential accumulation of the amide group toward the water surface. A spherulite structure exists in this film with a crystallinity of 26% by DSC. Fibers were drawn from the films which had a tensile modulus of 5 GPa, stiffer than reported for this nylon as prepared by other means. Other members of the nylon series, such as Nylon 6, Nylon 12, have also been prepared in films by the same casting method under modified conditions. © 1995 John Wiley & Sons, Inc.
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  • 19
    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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  • 20
    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
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