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  • 1985-1989  (480)
  • 1975-1979  (2,541)
  • 1860-1869
  • Physics  (3,021)
  • 1
    Electronic Resource
    Electronic Resource
    Atoms to astronomy: Computer graphics at the Jet Propulsion Laboratory (1986)
    Springer
    The visual computer 2 (1986), S. 159-163 
    Details
    ISSN: 1432-2315
    Keywords: Education ; Animation ; Computer graphics ; Physics ; Solar system
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract Within the Jet Propulsion Laboratory in Pasadena, California, state of the art computer graphics animation is done in the Computer Graphics Laboratory. The topics of the animations cover many scientific disciplines. Specific features of the system developed there, both hardware and software, are discussed. The prime mover of the effort is Dr. James F. Blinn of Pasadena; his role and experiences are elaborated. Their current largest project is The Mechanical Universe; the system is used for its production.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01900326
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  • 2
    Electronic Resource
    Electronic Resource
    Quantum yield for poly(methyl methacrylate) chain scission by 214-229 nm wavelength light (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1749-1758 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The quantum yield for poly(methyl methacrylate)chain scission by ultraviolet light in the 214-229 nm wavelength region was found to be φd = 0.03 scissions per absorbed photon. Samples were 1.65-μm films spun cast on silicon wafers and irradiated under flowing nitrogen by a cadmium vapor lamp. Gel permeation chromatography was used for molecular weight determination. Heating (postbaking) the irradiated films at 150°C for one hour under reduced-pressure flowing nitrogen increased the observed scissions per absorbed photon to 0.04. Glass transition temperatures by DSC are well-represented by Tg (K) = 393.3 - 2.0 × 105/Mn for the postbaked samples (139,000 〉 Mn 〉 6500).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230902
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  • 3
    Electronic Resource
    Electronic Resource
    Evidence for sorption-desorption phenomena during thermal cycling in highly hydrated perfluorinated membranes (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2009-2020 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Perfluorinated ionomer membranes can absorb large amounts of water. DSC experiments show the existence of exothermic or endothermic peaks for water contents larger than 8 wt % at room temperature in Nafion 1200 EW in the acid form. Changes in the number of mobile protons versus temperature have been measured by NMR spectroscopy. A desorption process with an activation energy of 6 kcal/mol is proposed during the sample cooling. Such an explanation quantitatively explains both the DSC and NMR results and is also consistent with the other results obtained from mechanical experiments, low-temperature sorption isotherms, and ESR spectroscopy.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231003
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  • 4
    Electronic Resource
    Electronic Resource
    Conformational analysis of substituted polyacetylenes (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2021-2030 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A conformational analysis of isolated chains of polymethylacetylene (PMA), polypentylacetylene (PPA), and poly(t-butylacetylene) (PTA) was carried out taking into account interactions between nonbonded atoms and torsional potentials. It was found that the trans configuration of all three polymers is more stable than the cis configuration, the difference in potential energy between the trans and the cis isomers however being very small for PTA, leading to the possibility of observing a trans→ cis isomerization in some solvents. The calculations show that the substituted polyacetylenes are not found in a planar conformation, the larger deviations from planarity being found with the bulkier substituents: PTA 〉 PPA 〉 PMA. A correlation could be established between the UV absorption limit of the samples and the minimum torsional angle of the potential-energy functions. This relation predicts that the absorption limit is shifted to long wavelengths on increasing the planarity of the molecule. Moreover, UV spectra could be calculated from the potential-energy functions, and it is shown that the potential-energy functions of other substituted polyacetylenes can be calculated from their experimental UV spectra.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231004
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  • 5
    Electronic Resource
    Electronic Resource
    Determination of the geometric structure of three substituted polyacetylenes: Polymethylacetylene, polypentylacetylene, and poly(tbutylacetylene) (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2031-2041 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The geometric structure of polymethylacetylene (PMA), polypentylacetylene (PPA), and poly(t-butylacetylene) (PTA) was investigated by 1H NMR, 13C NMR, and IR spectroscopies. It was shown that both NMR techniques can be used to determine the trans isomer content of PPA and PTA, whereas the 1H NMR and IR methods can be used for PMA. A calibration curve was constructed by using the 965- and 720-cm-1 bands of the IR spectrum of PPA, and could be used in future work for the same purpose if the samples had molecular weights similar to that of the one used in this study. The isomerization kinetics of PTA was investigated and cis→ trans activation energies of 88 and 121 kJ/mol were calculated in solution and in the solid state, respectively. Heat treatment of the PMA and PPA samples always leads to a cis→ trans isomerization with a 100% trans content under extreme conditions. Moreover, a cis→ trans isomerization of PTA was induced in CCl4, CDCl3, toluene, and benzene, but a trans→ cis isomerization was induced in decalin. The reversible isomerization of PTA covered a trans isomer concentration ranging form 25 to 60%.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231005
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  • 6
    Electronic Resource
    Electronic Resource
    Spectroscopic study of α- and β-phase isotactic polypropylene and of atactic polypropylene in solution (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2043-2057 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman spectroscopy is used to investigate the conformation and packing of isotactic crystalline α-phase polypropylene compared with lower-order β-phase isotactic polypropylene and to study the solution behavior of atactic polypropylene. The high-frequency region of the spectrum is analyzed in light of a normal-mode calculation that takes into account the methyl-group vibrations. This region is sensitive to both chain conformation and packing, and because of the high intensity of the methyl and methylene high-frequency stretching modes, it can be used to probe small changes in intermolecular or intramolecular order. Differences in the thermal behavior between the two solid isotactic polypropylene samples are explained interms of packing defects which exist in the β-phase form. In the solution study, we demonstrate that, for molecules in which bands sensitive to intermolecular interactions exist, as is the case of the methyl and methylene vibrations of polypropylene, spectroscopic techniques can be used to estimate the minimum overlap concentration.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231006
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  • 7
    Electronic Resource
    Electronic Resource
    Analysis of stress-induced crystallization in high-cis-1,4-polybutadiene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2109-2118 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stress-induced crystallization of a crosslinked polybutadiene with a high 1,4-cis content is investigated, at room temperature. The change in the fraction of crystallinity with deformation is evaluated by two different methods. The first is based on simultaneous measurement of birefringence and stress. The second is based on calorimetric analysis. The data on crystallinity obtained by these two methods are in good agreement in the range of low deformations, while, in the range of higher deformation (λ 〉 5), the degree of crystallinity obtained by calorimetry is higher than that obtained by the optical method. Qualitative information on the crystallization was also obtained by optical analysis of the hysteresis behavior. The hysteresis data show the presence of ordering phenomena at deformations at which there seems to be no crystallinity according to both quantitative methods.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231009
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  • 8
    Electronic Resource
    Electronic Resource
    Coherent elastic scattering of a reptating chain in a melt during transient relaxation (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 833-844 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We calculate the elastic scattering of a long chain in a polymer melt during the process of relaxation after a sudden deformation, i.e., the return to equilibrium with time, while the deformed shape is maintained. The scattering thus depends on the duration t of the relaxation, as well as on the scattering vector, and is a physical quantity characteristic of the dynamics of long chains. The reptation model of de Gennes is used as developed for deformed melts by Doi and Edwards: the chain is confined by other chains in a tube, from which disengagement by the ends is the only way of renewing its configuration. The tube diameter is taken as a parameter. We give both an analytic form and numerical evaluations. On comparison with calculations based on the Rouse model, in which the chain is assumed to be free in a viscous medium, it is seen that the experimental data (given elsewhere) should enable one to distinguish between the two models.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230501
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  • 9
    Electronic Resource
    Electronic Resource
    Spectroscopic characterization of acetylene-terminated sulfone resin (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 845-859 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier-transform infrared spectroscopy was used to characterize the thermal polymerization of the acetylene-terminated (AT) resin, bis[4-(3-ethynylphenoxy)phenyl]sulfone. Spectral processing techniques (including the method of factor analysis) were utilized in the analysis of the infrared data. The degree of cure was quantitatively monitored as the resin was thermally polymerized. Factor analysis indicated that only one reaction product is spectroscopically distinguishable. Further band analysis indicated the formation of predominantly trans conjugated polyene structures. No evidence for cyclotrimerization was found.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230502
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  • 10
    Electronic Resource
    Electronic Resource
    Quantitative aspects of internal reflection spectroscopy: Polymer surface composition measurementThis paper was presented in part at the FACSS XI meeting, Philadelphia, Pennsylvania, 1984. (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 861-871 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The use of band-ratioing techniques in internal reflection spectroscopy (IRS) for a wide variety of polymer surface composition and orientation measurements is discussed. It is shown that quantitative data can be obtained under a wide range of experimental conditions. The effects of variations in sample contact, internal reflection element, and angle of incidence are considered in detail. The applicability and limitations of calibration procedures for the determination of surface composition under various experimental conditions are considered. The requirements for obtaining quantitative results by IRS are shown to be far more lenient than is typically assumed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230503
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  • 11
    Electronic Resource
    Electronic Resource
    Percolation and effective-medium theories for perfluorinated ionomers and polymer composites (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 933-953 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Percolation and effective-medium theories are applied to model the transport and elastic properties of perfluorinated ionomers. The composite nature of these polymers is emphasized. The effective-medium theory is generalized to track continuously the evolution from lamellar to fibrillar morphology. The predicted dramatic difference in ion selectivity between lamellar and spherical morphology is verified quantitatively in perfluorinated ionomer blends. The limitations and potential improvements of the effective-medium theory and its relationship to percolation theory are discussed. Applications of these theories to other multiphase polymer systems are also discussed.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230508
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  • 12
    Electronic Resource
    Electronic Resource
    Effect of molecular weight on the refractive index increments of polystyrene, poly(ethylene glycol), poly(propylene glycol), and poly(dichlorophenylene oxide) in solution (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 925-931 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The variation of refractive index increments with molecular weight has been studied using solutions of polystyrene (2.2 × 103 〈 Mw 〈 1.8 × 106), poly(ethylene glycol) (1.0 × 103 〈 Mw 〈 2.0 × 104), and poly(dichlorophenylene oxide) (3.3 × 103 〈 Mw 〈 4.8 × 105) in toluene and poly(propylene glycol) (1.2 × 103 〈 Mw 〈 4.0 × 103) in benzene. The refractive index increments of polyglycols containing aliphatic ether moieties are negative in these solvents. However, poly(dichlorophenylene oxide) polymers, which contain aromatic ether moieties, give positive values. Linear and branched halogenated poly(phenylene oxide)s show an asymptotic approach of the refractive index increment to the same limiting value, but the approach is more rapid for the branched polymer.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230507
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  • 13
    Electronic Resource
    Electronic Resource
    Influence of the interphase on block copolymer thermodynamics: Extension of the leary model (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1001-1029 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Leary-Williams model for the microphase thermodynamics of triblock ABA copolymers has been modified to accommodate deviations from homogeneous random-coil configurations in the B-chain dimensions as well as in those of the A chains, and has also been extended to cover the case of diblock AB copolymers. Only planar morphology is considered, but qualitative conclusions reported herein are expected to hold for other morphologies as well. The focus is on interphase thickness ΔT, with predictions made also for separation temperature Ts and planar repeat distance D. Results are presented as systematic functions of copolymer composition (0 ≤ φA ≤ 1), total molar volume (25,000 ≤ Ṽ ≤ 4 × 106 cm3/g mol), block architecture (AB vs. ABA), temperature (298, 373 K), and for five different interphase composition profiles. In most cases, A represents a polystyrene block and B a butadiene block in these calculations. Predictions for ΔT increase with temperature and depend on architecture, profile, and Ṽ; comparisons with data are close, in the range 15-30Å. It is shown that Ts depends strongly on profile choice and φA, reaching a maximum in the φA midrange but always with φA 〉 0.5. The major parameter influencing D (at constant Ṽ) is architecture, with D(SB) ≈ 2D(SBS), and D(Ṽ) varies from D ∝ Ṽ0.75 at low Ṽ to D ∝ Ṽ0.5 at high Ṽ.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230512
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  • 14
    Electronic Resource
    Electronic Resource
    Morphological studies of liquid-crystalline cellulose derivatives. I. Liquid-crystalline characteristics of hydroxypropyl cellulose in 2-hydroxyethyl methacrylate solutions and in polymer composites prepared by bulk polymerization (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1043-1052 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The formation of liquid-crystalline structure in hydroxypropyl cellulose (HPC) in the solvent 2-hydroxyethyl methacrylate (HEMA) is described. In addition, an attempt is made to preserve the ordered structure of HPC in a composite by polymerizing the solvent. Optical evidence, including refractive index, absorption spectra, polarized-light microscopy, and x-ray diffraction, indicates that HPC-HEMA solutions exhibit the cholesteric nature of the mesophase over limited concentration and temperature ranges. The polymer composite (HPC-PHEMA) prepared from the liquid-crystalline solution by polymerization of HEMA is endowed with anisotropic organization reflecting liquid-crystalline character. Detailed morphological observations of the composite by electron microscopy show many round particles composed of parallel-stacked, disklike lamellae, and aggregate bodies developed by coalescence of neighboring particles.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230514
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  • 15
    Electronic Resource
    Electronic Resource
    Time dependence of mechanical and transport properties of drawn and annealed linear polyethylene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1217-1234 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Linear polyethylene both as drawn, or drawn and subsequently annealed with free ends, changes its length, density, crystallinity, elastic modulus, sorption, and diffusivity as the sample stands completely unrestrained at room temperature. Most of these changes occur during the first few hours. But they are important on a molecular scale since they suggest strongly that drawn, and drawn and annealed samples are far from equilibrium. As a consequence of the tendency of each mobile tie molecule in the amorphous conformation to retract and to crystallize, the specimen approaches but does not reach complete equilibrium. The transient seems to be caused by slow crystallization of tie molecules which creates crystalline bridges across the amorphous layers.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230613
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  • 16
    Electronic Resource
    Electronic Resource
    Random-coil configurations of aromatic polyesters: Birefringence of poly(triethylene glycol terephthalate) networks in elongation (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1235-1245 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydroxyl-terminatd poly(triethylene glycol terephthalate) was crosslinked with an aromatic triisocyanate. Birefringence-stress-strain experiments, performed on the networks at 70°C, showed an anomalous increase in the modulus and a downturn in the birefringence-strain isotherms at high elongations. These results suggest that crystallinity is not responsible for the non-Gaussian behavior of the chains at high extension. The same kind of experiments were performed over the range 20-70°C. Values of the optical configuration parameter Δa of the order of 13.3 × 10-24 cm3 with negligible temperature coefficient were found for these networks. The quantities Δa and d In Δa/dT were calculated by means of the rotational isomeric state model. Better agreement between the theoretical and experimental values of these parameters was found for poly(triethylene glycol terephthalate) than for poly(diethylene glycol terephthalate). Since the polarities of the two chains are similar, intermolecular interactions involving terephthaloyl residues may be responsible for the discrepancies observed between theory and experiment for Δa in aromatic polyesters.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230614
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  • 17
    Electronic Resource
    Electronic Resource
    Dilute-solution properties of trans-1,4-polyisoprene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1255-1262 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Trans-1,4-polyisoprene was fractionated by both fractional precipitation and preparative gel permeation chromatography to obtain possibly sharp fractions of narrow molecular weight distribution. Selected fractions were characterized by light scattering, viscosity, and gel permeation chromatography. Necessary corrections for molecular heterogeneity were applied. Some of the characteristic relations between [η] and Mw are [η] = 1.81 × 10-4 Mw0.722 in benzene at 30°C, [η] = 1.38 × 10-4 Mw0.711 in n-hexane at 30°C, which are found to be in good agreement with literature data when corrected for molecular heterogeneity.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230616
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  • 18
    Electronic Resource
    Electronic Resource
    Picosecond relaxations in hydrated polyamide-6 observed by millimeter-wave spectroscopy (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1247-1254 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Absorption measurements at millimeter-wave frequencies (50-151 GHz) are reported for dried and hydrated polyamide-6. The measurements were extended over the temperature range from liquid helium to room temperature using the oversized-cavity technique. For dried polyamide-6 (water content ≤ 0.5% w/w), a nearly linear increase with frequency and an exponential increase with temperature of the absorption coefficient is found between 50 and 300 K. This frequency and temperature dependence is described by relaxation processes in asymmetric double-well potentials. The observed relaxation times are on a picosecond time scale, thus suggesting an assignment to the NH…OC hydrogen bonds and the adjacent peptide unit (O=C—N—H). Hydration results in an increase of the absorption over the whole temperature and frequency range. This is attributed to the fact that the water of hydration is adsorbed in the neighborhood of the hydrogen bonds and changes their dynamical properties. This interpretation is supported by IR-spectroscopic measurements of the shift of amide I and amide II after hydration.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230615
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  • 19
    Electronic Resource
    Electronic Resource
    An experimental test of the relationship between creep and dynamic linear viscoelastic data (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1263-1265 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230617
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  • 20
    Electronic Resource
    Electronic Resource
    Effects of a magnetic field applied during the curing of a polymer loaded with magnetic filler (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1267-1269 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230618
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  • 21
    Electronic Resource
    Electronic Resource
    Dilute solutions of poly(vinyl alcohol) derived from vinyl trifluoroacetate (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1703-1712 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dilute-solution behavior of poly(vinyl alcohol) (PVAVTFA), derived from vinyl trifluoroacetate, in water-dimethylsulfoxide (DMSO) mixtures was investigated. With solvent mixtures ranging from 10 to 20 vol % DMSO, the relation between the reduced viscosity ηsp/C and the polymer concentration C was linear for polymer concentrations above 0.2 g/dL, whereas in solutions in mixed solvents of other compositions the dependence was linear for polymer concentrations above 0.1 g/dL. The relation between the intrinsic viscosity [η] obtained for aqueous solutions of PVAVTFA and the molecular weight M estimated from viscosity measurements in solutions of poly(vinyl acetate) (PVAVTFA), obtained by acetylation of PVAVTFA, was given by [η]30°Cwater = 7.34 × 10-4 M0.63. The value of [η] was greatest for the solvent mixture with 10 vol % DMSO and smallest for about 50 vol % DMSO, and Huggins constants k were smallest and greatest for these two cases, respectively. The turbidity of the solutions of low-molecular-weight PVAVTFA, was higher than that of high-molecular-weight PVAVTFA up to 30 vol % DMSO, and the reverse relation held for 40-70 vol % DMSO.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230821
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  • 22
    Electronic Resource
    Electronic Resource
    Polydimethylsiloxane-polyurethane elastomers: Synthesis and properties of segmented copolymers and related zwitterionomers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2319-2338 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of polyurethane block polymers based on hydroxybutyl-terminated polydimethyl-siloxane soft segments of molecular weight 2000 were synthesized. The hard segments consisted of 4,4′-methylenediphenylene diisocyanate (MDI) which was chain extended with either 1,4-butanediol (BD) or N-methyldiethanolamine (MDEA). The MDEA-extended materials were ionized by using 1,3-propane sultone. The weight fraction of hard segments was in the range 0.13-0.39. The morphology and properties of these polyurethane elastomers were studied by a variety of techniques. All of these short-segment block copolymers showed nearly complete phase separation. The zwitterionomer materials exhibited ionic aggregation within the hard domains. Hard-segment crystallinity or ionic aggregation did not affect the morphology. Hard-domain cohesion was found to be a more important factor than hard-domain volume fraction in determining the tensile and viscoelastic properties of these elastomers.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231106
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    Polyethylene fiber formation in tubular flow. II. Discussion of precursor formation and nucleation time analysis (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2359-2368 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This is a continuation of the preceeding paper, Part I, and presents a discussion of the nature of the precursor structure formation process observed in the flow-induced crystallization experiments described in I. A discussion of stress-induced crystallization theory as applied to these experiments is also given and a first-order analysis of crystal nucleation rates is presented. Conclusions regarding the nature of flow-induced crystallization and our current ability to quantitatively model the overall process are also presented.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231108
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    Polyethylene fiber formation in tubular flow. I. Observations of growth pattern and fiber properties (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2339-2358 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The process of seeded growth of fibrillar polyethylene crystals has been studied in a tubular flow geometry for 0.01-wt % solutions of a high-molecular-weight polyethylene in xylene. The transformation sequence has been followed visually by using polarized-light illumination in conjunction with a video camera. Data are presented to show that transformation is initiated by the formation of a concentrated, unoriented, amorphous precursor fiber within which oriented birefringent crystals subsequently grow in consequence of the stresses transmitted by the flowing solution. Time constants for the precursor formation, birefringence initiation, and completion of birefringence were measured as functions of temperature and flow rate over a range of growth conditions. Wide-angle x-ray diffraction, overall birefringence, and optical hot-stage melting data were also obtained on the grown fibers. The net result of these observations is to conclude that fibrillar crystal growth during flow is always preceded by the formation of a liquidlike phase transformation which produces the concentrated, unoriented precursor. Subsequent orientation is in consequence of stress-induced crystallization with overall fiber orientation showing an increase with solution flow rate at a fixed temperature and a decrease with temperature at a fixed flow rate. At higher temperatures and lower flow rates, birefringence develops in an oscillatory fashion, indicating a remelting process possibly due to slippage of trapped chain entanglements formed by flow. A discussion is given of the implications of these observations for the understanding of flow-induced structure development, phase transformation, and oriented crystallization; this is expanded upon in a companion paper, Part II.
    Additional Material: 10 Ill.
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    Structure of iodide ion arrays in iodinated nylon 6 and the chain orientation induced by iodine in nylon 6 filmsPresented at the XIII Congress and General Assembly of the International Union of Crystallography, August 1984, Hamburg, Federal Republic of Germany. (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2369-2376 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two species of iodide ions (I3- and I5-) are found in iodine - nylon 6 complexes. Orientation of I5- arrays (most likely I2/I3- complex) along the polymer chain and I3- ions perpendicular to the chain axis in uniaxially drawn films and in films with planar orientation suggests that there is and intrinsic relation between the direction of iodide ion arrays and nylon 6 chains. When an unoriented film of nylon 6 in the amorphous or the α crystalline form is treated with an aqueous solution of iodine - potassium iodide, the I3- species in the resulting iodine - nylon complex lie in planes parallel to the surface of the film, and I2/I3- units are oriented normal to the surface of the film. The γ form obtained by desorbing the iodine from this complex shows considerable uniaxial rientation with the nylon chains oriented perpendicular to the plane of the film; this orientation is maintained during the γ to α transition. It is proposed that the iodine-induced orientation of the nylon 6 chains is due to the nucleating effects of the iodide ion species as the iodine diffuses unidirectionally into the film.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231109
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  • 26
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    Estimation of the equilibrium modulus of rubber networks by nonlinear regression analysis (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2377-2385 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A nonlinear regression analysis is presented to estimate the equilibrium modulus of relaxing rubber networks from G'(ω) or G(t) data. Various semiempirical curve-fitting equations are tested with two-function minimization algorithms.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231110
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    Tube relaxation: A quantitative molecular model for the viscoelastic plateau of entangled polymeric mediaThis paper is dedicated to Dr. Pierre Thirion on the occasion of his retirement. (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2423-2442 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relaxation of an entangled polymeric medium in the viscoelastic plateau is investigated theoretically by using the slip-link representation of topological constraints. In addition to the chain retraction process introduced by Daoudi and investigated theoretically by Doi, we show that two processes contribute significantly to the relaxation: The first, “equilibration across slip-links,” is a longitudinal reequilibration between parts of the chain which have been differently extended or compressed, depending on their initial orientation relatively to the strain tensor. The second, “tube relaxation,” is a mean-field representation of the loss of topological constraints on one chain due to the retraction of the others. Closed analytical expressions for the stress accounting for these three processes are derived and compared with previous theories: the relaxation should be much more progressive than previously predicted, and the terminal time for retraction is reduced significantly by tube relaxation.
    Additional Material: 4 Ill.
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  • 28
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    Evaluation of theories for diffusion in polymer-solvent systems (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2469-2475 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is proposed for examining differences in the predictive capabilities of three versions of the free-volume theory of polymer - solvent diffusion using only a small amount of diffusivity data. The utility of the method is illustrated using a limited diffusivity data set for the methanol-poly(vinyl acetate) system.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231205
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  • 29
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    Temperature dependence of the crystal structures of nylon 11 (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2477-2482 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Careful examination of x-ray diffraction patterns from melt-crystallized nylon 11 films show significant discrepancies with the proposed α-form structure. These discrepancies do not disappear after the samples have been annealed. The temperature dependence of the d spacings of the two strongest peaks show further evidence that the melt-crystallized and solution-cast films (α form) possess different crystal structures. These results suggest a different crystal structure for the melt-crystallized films; this would help explain the rather low piezoelectric response of these films and also the failure to observe a rapid decrease in polarization at the transition temperature.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231206
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    Kinetics of wetting of a glass surface by molten polyethylene: An empirical approach (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2499-2504 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The spreading kinetics of molten polyethylene was studied on a flat type A glass surface. Empirical equations are known in the literature which fit the experimental data only at short times. We present a relationship between the surface free energy and the shape of the melt drop interpreted by the θ contact angle. Relating the experimental θ values obtained at different times with the surface free energy (F), we obtain curves F,t. Using isothermal data at 150°C, we could fit them with a linear relationship between In (F-F∞)/(F0-F∞) and In t/t0, where o and ∞ are related to initial and equilibrium conditions.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231208
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    The influence of morphology on the dielectric and dynamic mechanical behavior of a linear low-density polyethylene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2483-2498 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric and viscoelastic relaxation behavior of linear low-density polyethylene has been investigated. All three usual relaxation regions occur; however, the α process is more dominant than in conventional low-density polyethylene made dielectrically active through the introduction of carbonyl groups. The observed behavior is very sensitive to orientation and morphology. There are significant differences between oriented samples (stretching or extrusion) and a single-crystal texture specimen. Effects are caused by dipolar orientation and dipolar immobilization, the relative importance of each effect varying with specimen preparation. Active dipolar groups are not carbonyls, or any common organic species, but appear to be due to chain ends having residual dipoles caused by the catalyst used in synthesis.
    Additional Material: 15 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231207
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    Kink motion in poly(vinylidene fluoride) form I (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2505-2515 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffuse-streak x-ray scattering intensity from poly(vinylidene fluoride) form I, which is caused by kink bands with GTnḠ (n odd) conformation contained in the crystallite, decreases with increasing temperature, while the intensity of the 001 reflection does not change. This is attributed to the disappearance of the kink bands in the crystallite, not to partial melting of crystallites containing kink bands. The disappearance of the kink bands suggests that kink motion takes place in the crystallite. Plots of the intensity of diffuse-streak scattering, estimated from the asymmetric part of the 001 reflection, against 1/T roughly give ΔHv = -4.6 kcal/mol. This suggests that the kink band is energetically more stable than the regular structure of form I.
    Additional Material: 10 Ill.
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    An x-ray diffraction study of nonlinear polyethylene. I. Room-temperature observations (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2517-2537 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this investigation on samples of high- and low-density polyethylene and ethylene-vinyl acetate copolymers, crystallinities φW and crystalline densities ρcW were obtained with the aid of wide-angle x-ray scattering (WAXS) methods. From small-angle x-ray scattering (SAXS) the following characteristics were obtained either directly or by combination with the WAXS data: values, or limiting values, of the crystallinity φS; crystal densities ρcS; thicknesses of the diffuse boundary layer; number-average thicknesses of the crystalline and amorphous layers; and both number and weight averages of the long periods. It was shown that a discrepancy between φS and φW cannot be attributed to the occurrence of large amorphous regions outside the regular stacks of lamellae; the data were reconciled by assuming that the WAXS crystallinities pertain to the cores of the crystalline lamellae, whereas part of the diffuse boundary layers is comprised in the values of φS. The ρcW and ρcS data of the nonlinear samples show systematic differences, which were attributed to partial incorporation of side groups in the crystalline regions at a concentration estimated to be of the order of 20-40% of the overall concentration. With increasing side-group concentration, the thickness of the core of the crystalline lamellae was found to approach the average length of the linear chain segments between side groups. On the basis of these observations a scheme for the crystallization of nonlinear polyethylene is proposed according to which a number of side groups is encapsulated by the growing crystal. The data can be explained by assuming that all chains, offered at a crystal face where growth takes place, crystallize directly, irrespective of whether the crystallizing stem carries a side group. Further crystallization would then proceed by chain folding at both ends of the first stem, until a noncrystallizable unit is met. In this scheme, allowance is made for about half the stems in the crystals to be connected by folds; this is required in view of the “overcrowding” effect. Finally, the effect of cooling rate and molecular weight on the thicknesses of the crystalline and amorphous layers is discussed, and differences between the amorphous densities of high-and low-density polyethylene are noted.
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    Stability of the γ form and the development of the α form in nylon 6 (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2549-2565 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of nylon 6 fibers is analyzed by x-ray diffraction. Our results suggest that only two forms of nylon 6, α and γ, along with lattice distortion and crystallite size, are sufficient to explain the whole range of crystalline structures observed in nylon 6. The γ phase is the preferred initial form in a number of nylon 6 samples. The lattice distortion of the γ form along the chain axis varies from 0.8 to 2.4%, depending on the processing conditions. Upon annealing nylon 6 fibers, the α form is produced primarily by γ-to-α conversion in high-orientation fibers, while additional α form can also crystallize from the amorphous phase in low-orientation fibers. Finally, we show that α crystallites are favored during conditioning of poorly crystallized fibers in a humid atmosphere, and therefore fibers with α as the major crystalline form are produced upon drawing these conditioned fibers. Fibers drawn without lag time contain primarily the γ phase.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231212
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    An x-ray diffraction study of nonlinear polyethylene. II. Small-angle scattering observations near the melting point (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2539-2548 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is presented for obtaining from the zeroth-order peak in small-angle x-ray scattering (SAXS) patterns the weight average of the thickness C of crystalline lamellae in polymers close to the melting point. The method fails if a first-order peak can be discerned to be superimposed on the zeroth-order peak. The method was applied, together with the one described in Part I of this series for obtaining the number average of C, to three polyethylene samples of different side-group content which were heated to temperatures close to the melting point. While heating always causes an increasing number of lamellae to melt, a linear sample also shows pronounced thickening of the remaining lamellae. This effect, however, decreases with increasing side-group content, and is virtually absent in a vinyl acetate copolymer containing 53 side groups per 1000 C atoms. A qualitative explanation for the role of the side groups in limiting the crystal thickening processes is put forward. By comparing results obtained after isothermal annealing and during isothermal crystallization from the melt it is concluded that at temperatures close to the melting point the polymers approach a final state which no longer depends on the thermal history of the sample.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231211
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    Crazing as quasifracture in an oriented viscoelastic medium (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2579-2597 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crazes of different types occur in polymeric systems. Long, sparse crazes develop in less oriented molecular systems, while fine, short, dense crazes occur in highly oriented molecular systems. Different crazing mechanisms and different models may have to be studied for a better understanding of these differences. However, in this report, using one model and one theory, an analysis has been made of the differences in the geometry of craze development. By emphasizing the mechanism of molecular orientation, it is found that the basic differences are essentially attributable to the variation of the anisotropy of the material system as a result of large deformation rather than to any fundamental differences in the crazing mechanism.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231214
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    Light-scattering characterization of poly(ethylene terephthalate) (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2567-2578 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By using a closed-circuit filtration system, we have succeeded in clarifying poly(ethylene terephthalate) (PET) dissolved in hexafluoroisopropanol (HFIP). Such static properties as the radius of gyration Rg, the weight-average molecular weight Mw, and the second virial coefficient A2 and such dynamic properties as the translational diffusion coefficient D, or its equivalent hydrodynamic radius Rh, and the second (diffusion) virial coefficient kd were determined for several PET samples of different molecular weights by using light-scattering intensity and linewidth measurements. An empirical relation between Do (or Rh) and Mw was established: Rh = (1.77±0.15)X10-2 Mw+0.58±0.01 with Rh and Mw expressed in units of nanometers and grams per mole, respectively. The empirical exponent αD(ca. 0.58±0.01) is in good agreement with the less precisely determined intrinsic viscosity/molecular weight exponent αη (ca. 0.71±0.02). Several intensity correlation functions were measured very precisely using long accumulation times. A Laplace inversion was performed using the singular-value decomposition technique. The approximate molecular weight distribution (MWD) determined by light-scattering spectroscopy was in reasonable agreement with a completely independent determination of MWD using gel permeation chromatography (GPC). It was interesting to note, though not surprising, that GPC showed emphasis on lower-molecular-weight fractions, while light-scattering emphasized higher-molecular-weight fractions. The agreement further strengthens some complementary aspects of the two techniques.
    Additional Material: 7 Ill.
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    Epitaxial crystallization of polyethylene and paraffin on oriented polypropylene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2623-2627 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231217
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    Studies on comblike polymers. X. Characterization of comblike polyesters by 13C NMR spectroscopy (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2611-2621 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The 13C NMR spectra of aromatic comblike polyesters obtained from 1,2-icosanediol and isomeric phthalic acids are reported and discussed. The analysis shows that the most informative spectral regions are those of the carbonyl and quaternary carbon resonances, whose peak multiplicities have been interpreted in terms of dyad and triad sequences. The results indicate that the extent of structural characterization possible for the polymers examined is dependent on the type of isomerism of the aromatic acid involved.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231216
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    Monte carlo simulations relevant to the upturns in modulus observed for natural rubber at high elongations (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2629-2632 
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    ISSN: 0098-1273
    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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    URL: http://dx.doi.org/10.1002/pol.1985.180231218
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  • 41
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    Improvement in polypropylene thermal oxidative stability by annealing under an inert atmosphere (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2633-2634 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231219
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  • 42
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    Estimation of the equilibrium modulus of rubber networks by nonlinear regression analysis (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2635-2635 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231220
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    Rebuttal to “comments on ‘some evidence against the existence of the liquid-liquid transition. III. The evaluation of the TLL event by differential scanning calorimetry’ ” (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 13-19 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is proposed here that readily observable viscous deformation is the common underlying phenomenon which is reflected in several kinds of evidence advanced for the existence of a liquid-liquid transition TLL. These include flow temperature Tf measurements, microscope hotstage coalescence, and differential scanning calorimetry (DSC) measurements. A DSC peak observed at Tg in high-molecular-weight bulk-polymerized poly(methyl methacrylate) is discussed in terms of the presence of conformations of low entropy.
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    URL: http://dx.doi.org/10.1002/pol.1985.180230102
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    Comments on “some evidence against the existence of the liquid-liquid transition. III. The evaluation of the TLL event by differential scanning calorimetry”This paper is in two parts, using a common set of references. Part A was submitted in January 1983 with the same title and purpose implied by that title, but with minor modifications suggested by referees. Part B responds to the rebuttal to Part A by Chen et al. in the following paper and adds pertinent new material in response to their rebuttal. (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1-12 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The volatile-component evaporation mechanism proposed by Chen et al. to explain molecular-weight-dependent endothermic peaks found at temperatures above Tg in anionically prepared polystyrenes (PSs) on first heating in open DSC pans is inconsistent with several bodies of literature data which were overlooked, including similar data with closed DSC pans. Moreover, this mechanism appears deficient in explaining details of the dependence of the endothermic peak temperature on M̄n both below and above the entanglement molecular weight Mc, with a sharp increase in slope at Mc. The original fusion-flow mechanism of Stadnicki et al. is compatible with all other known literature data including results on thermal PS and PMMA fractions. Hot-stage microscope examination of powdered anionic PSs supports the Stadnicki mechanism from M̄n = 1900 to at least M̄n = 350,000. Addition of small amounts (ca. 1 wt %) of benzene or ethylbenzene to PS results in open-pan DSC traces without endothermic peaks but with an endothermic slope change indicating gradual loss of diluent at decreasing rate as the temperature is increased from below Tg up through the TLL region.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230101
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  • 45
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    Electronic Resource
    Carbon-13 NMR relaxation and transitions in polymers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 367-385 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High-resolution proton-decoupled carbon-13 nuclear magnetic resonance relaxation parameters have been obtained as a function of temperature for a set of completely amorphous polymers, semicrystalline polymers, and a series of ethylene-vinyl acetate copolymers. With these samples the nature of the glass temperature, other postulated amorphous transitions, and the β transition were investigated. For the completely amorphous polymers, the average correlation times depend on temperature according to the Williams-Landel-Ferry relation. Spectral collapse occurs at temperatures whose ratio to Tg is in the range 1.2-1.4 and corresponds to a correlation time of about 10-7s. The loss of resolvable spectra is demonstrated to be a consequence of experimental methods and is not due to the occurrence of another amorphous transition. Both the methylene and methine carbons can be resolved for the ethylenevinyl acetate copolymers. Although the correlation time for the methylene carbon is continuous and resolvable through the β transition region, the methine branch-point resonance is lost. The implication of these results to the molecular nature of the β transition is discussed.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230211
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  • 46
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    Electronic Resource
    Phase transitions in mesophase macromolecules. V. Transitions in poly(oxy-1,4-phenylene carbonyl-co-oxy-2,6-naphthaloyl) (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 521-535 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The copolymer system HBA (4-hydroxybenzoic acid) and HNA (2,6-hydroxyhaphthoic acid) has been studied mainly by means of differential scanning calorimetry. Heat capacities for the two homopolymers and three copolymers are reported from 175 to 650 K. The heat capacities are additive with composition. The whole copolymer system represents an example of a mesophase intermediate between the liquid-crystalline and the condis-crystalline state with a small amount of crystallinity. The disordering transitions (520-620 K) have a eutecticlike phase diagram. The transitions to the isotropic states occur above the decomposition temperatures (600-700 K). The glass transitions (377-434 K) show normal changes in heat capacity (31-34 J/K mol), but are broadened to as much as 200 K.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230309
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  • 47
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    Electronic Resource
    Rheo-optical studies of concentrated polystyrene solutions subjected to transient simple shear flow (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 575-589 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Concentrated polystyrene solutions were investigated on the inception and cessation of simple shear flow by means of the technique of two-color flow birefringence. Both monodisperse solutions of various molecular weights and bimodal mixtures were studied. The molecular weight affected both the amount of overshoot in the birefringence and the response time on the inception of shear flow. Large overshoots in birefringence, up to 250%, and undershoot in the orientation angle were observed. The shear stress and the first normal stress difference were calculated by using the stress-optical rule. The amount of strain at the peaks in the stress growth curves are presented along with the steady-state viscosity and primary normal stress coefficient. The experimental results are compared qualitatively with theoretical predictions of various molecular models.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230313
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  • 48
    Electronic Resource
    Electronic Resource
    Macromolecular pair correlation functions from fluorescence depolarization experiments (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 591-599 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Depolarization of fluorescence resulting from the transport of electronic excitations in chromophore-containing polymers is investigated as a technique for detecting deviations from ideal-chain statistics. An approximate expression for the fluorescence anisotropy that depends only on the pair correlation function of chromophore labels is presented. This approximation is shown to be accurate for particular cases of long-range correlations, short-range correlations, and no correlations among chromophore positions. The formalism allows fluorescence depolarization experiments to be used as a probe of macromolecular pair correlation functions.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230314
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  • 49
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    Electronic Resource
    Low-frequency excitations in amorphous poly(vinyl acetate) (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 609-614 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman-active modes have been detected in amorphous poly(vinyl acetate) in the frequency region 20-160 cm-1. The low-frequency spectrum appears as a broad band for all three molecular weights examined. Spectra were recorded at two temperatures, 293 and 77 K, and found to show similar characteristics at both temperatures. The presence in solid amorphous polymers of broad structureless bands in general and their significance are discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230401
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  • 50
    Electronic Resource
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    Crystallization in oriented poly(ethylene terephthalate) fibers. I. Fundamental aspects (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 653-674 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The nature of crystallization- and mobility-induced changes during annealing of melt-spun poly(ethylene terephthalate) precursor fibers of a range of orientations has been examined. The kinetics of crystallization and the accompanying orientational changes have been studied under conditions of constant, low tensile stress, with the accompanying dimensional changes and under a constraint against shrinkage in length, with the stress developed being monitored. The effects of precursor orientation and externally imposed constraints on the course of the fundamental crystallization and orientational relaxation processes are revealed. Oriented crystallization has been shown to have a significant effect on the stress developed and on the dimensions of oriented precursor fibers, with a strong tendency to spontaneously extend as a consequence of the reorientation of crystallizing segments predominantly along the preferred fiber direction. The sequence in which crystallization and major orientational relaxation, if any, occur is found to have a profound effect on the structure and thus the deformability of oriented fibers after annealing above the glass transition temperature.
    Additional Material: 20 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230404
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    Relaxation of chemical potential and a generalized diffusion equation (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 675-682 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of slow structural relaxation in a solvent of high viscosity on the chemical potential driving the diffusion of penetrant molecules is described by a generalized diffusion equation with a memory term. The linearized version of this equation is solved for some special cases, and the correlation function of concentration fluctuations in thermodynamic equilibrium is calculated. As a result of the memory term, for very slow relaxation two different stages of the diffusion process can be distinguished.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180230405
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  • 52
    Electronic Resource
    Electronic Resource
    Energy absorption in polymer crazing (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 683-693 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The total energy absorbed by a craze during its development in creep is analyzed and calculated on the basis of a time-dependent theory of crazing. Experimental measurements of the craze length have been utilized in the energy calculations. For polystyrene the initial energy absorption in the craze region is found to be several hundred times that in the uncrazed medium. This ratio decreases sharply in a short period of time to about 50 to 1 and less and remains low afterward. For polycarbonate, somewhat similar behavior has been found. The initial strain energy absorption by crazing is about 200 times that in the uncrazed region. The energy ratio reduces rapidly to about 55 to 1 and tends to level off thereafter. However, in general, the amount of strain energy absorbed does increase as a function of time, as it should.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230406
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  • 53
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    Electronic Resource
    Bead-spring model for adsorbed polymer chains in shear flow: Hydrodynamic interaction (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 695-707 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We consider the hydrodynamic interaction between two absorbed polymer chains in a simple shear flow, each modeled by a bead connected to the wall by a linear spring. It is concluded that hydrodynamic interaction between the beads or between the beads and the wall cannot be responsible for the experimentally observed increase in hydrodynamic thickness.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230407
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  • 54
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    Rheological and DSC changes in poly(vinyl alcohol) gels induced by immersion in water (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1803-1811 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(vinyl alcohol) (PVA) gels were prepared by freezing and thawing aqueous solutions at temperatures from -20 to 15°C. The temperature was varied periodically by use of a computer. The endothermic DSC peak was observed for the PVA gels at about 60°C for five specimens of different degrees of saponification (DS). Another endothermic peak was also observed in the range 67-80°C, and this peak shifted to higher temperature with increasing DS. These endothermic peaks shifted to lower temperature on immersion of the PVA gels in water. The dynamic Young's modulus E′ at room temperature was also decreased by immersion of PVA gels in water; E′ decreased monotonically with increasing temperature for PVA gels without immersion in water, while it increased up to a certain temperature and then decreased with increasing temperature for PVA gels in water. The X-ray diffraction showed a characteristic crystalline pattern for PVA gels of higher DS, and this peak was intensified by stretching the gel.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230906
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  • 55
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    Study of spin-lattice relaxation and local motion in dissolved poly[2,2-propanediylbis(3,5-dimethyl-4, hydroxyphenyl)carbonate] (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1793-1802 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Proton and carbon-13 spin-lattice relaxation times are reported for 10-wt % solutions of tetramethyl bisphenol-A polycarbonate. The relaxation times for both nuclei were measured at two Larmor frequencies and as a function of temperature. These relaxation times are interpreted in terms of three motions: segmental motion, restricted rotational diffusion, and backbone methyl-group rotation. The Hall-Helfand correlation function is used to describe the segmental motion. Internal rotation is described by the usual Woessner approach and restricted anisotropic rotational diffusion by the Gronski approach. As demonstrated by its higher activation energy, correlated segmental motion appears to be slower than the unsubstituted polycarbonate of BPA. In addition, the single-transition processes seem to be still less important than correlated backbone transitions. Phenylene-group rotation is described in terms of restricted rotational diffusion instead of complete anisotropic rotation. The time scale for backbone methyl-group rotation is comparable to that in BPA, a fact indicative of weaker cooperativity between this motion and the other motions. Rotation of the methyl group attached to the phenylene ring is too fast to significantly contribute to relaxation except by partially averaging the dipole-dipole interactions. The higher activation energies for segmental motion observed in solution for this methyl-substituted polycarbonate relative to the unsubstituted polycarbonate parallel a significant increase in the glass transition temperature observed for the substituted material. The restricted pheylene-group rotation in solution is also parallelled by a large upward shift of the low-temperature loss peak in the glassy polymer.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230905
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  • 56
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    The role of molecular diffusion in the adhesion of EPDM and EPR elastomers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1823-1830 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Adhesion of lightly crosslinked sheets of EPDM (ethylene-propylene-diene terpolymer) to themselves and to a Mylar substrate has been investigated over wide ranges of peel rate and test temperature. The effect of incorporating ethylene-propylene copolymer (EPR) before crosslinking, to yield a loose macromolecular network containing dissolved linear EPR macromolecules, was also studied. The self-adhesion of these materials was found to be much greater than their adhesion to Mylar, over a wide range of effective peel rates. This is attributed to interdiffusion of EPR and EPDM molecular strands. At extremely low peel rates the enhancement of adhesion was smaller, probably because of back-diffusion, and at high rates, the strength of adhesion became high in all cases. These results are compared to those obtained previously for polyisobutylene-co- isoprene networks containing linear polyisobutylene molecules. The enhancement of self-adhesion at intermediate rates of peel was considerably greater for the EPDM-based materials, probably because of a lower degree of crosslinking and a greater tendency to form molecular entanglements.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230908
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  • 57
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    Differential sorption in viscoelastic fluids (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1831-1855 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffusion of organic solvents in concentrated polymer solutions often deviates from the predictions of Fick's second law, especially when the solution is in the glassy state; such behavior is called anomalous or non-Fickian. This paper analyzes the one-dimensional sorption of a solvent into a concentrated polymer solution under a small driving force. The treatment includes the effect of an entanglement network on the process as postulated by Thomas and Windle. The deformation of the entanglement network during sorption creates a normal stress on the solvent equivalent to an osmotic pressure. Including the osmotic pressure gradient in the driving force for solvent diffusion leads to a linear, third-order partial differential equation for solvent concentration distributions. By evaluating the physical constants in the theory for the system methyl acetate/poly(methyl methacrylate) at 30°C the treatment is shown to predict the anomalous characteristics found experimentally.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230909
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  • 58
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    A SAXS study of a single crack and craze in plasticized polystyrene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1857-1867 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle x-ray scattering (SAXS) was used to study the structure along a single craze that had broken down to form a crack along part of its length. This study was made possible by use of radiation from the synchrotron source CHESS which is sufficiently intense to permit examination of just a single craze. The total scattering from the craze was in excellent agreement with that expected from a knowledge of its dimensions and fibril volume fraction and width. This fact adds confidence to the interpretation of the scattering pattern of the craze as part diffraction, part reflection, and demonstrates that SAXS is a technique that may be used to measure craze volume within a sample. The craze was shown to grow in width by surface drawing with a constant structure, and then the fibrils broke to form a crack. The broken fibrils contracted and their diameters increased but they appeared to stay parallel with a constant fibril-axis radial distribution function.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230910
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  • 59
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    Far-infrared studies of microphase separation in sulfonated ionomers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1869-1881 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Far-infrared spectra of a series of un-neutralized and neutralized lightly sulfonated polystyrenes with varying sulfonation levels have been investigated to seek spectroscopic evidence for microphase separation known to control the physical properties of these polymers. Broad, strong absorbance bands, not found in the spectrum of unmodified polystyrene, are observed in the spectra of the sulfonated analogs. The effects on the far-infrared spectra both of sulfonation level and of the mass and charge of the neutralizing cation are discussed in terms of cation motion and the formation of ion-rich domains.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230911
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  • 60
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    Small-angle scattering analysis of hard-microdomain structure and microphase mixing in polyurethane elastomers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1883-1913 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The microdomain structure of a series of segmented polyurethane block copolymers is characterized by small-angle x-ray and neutron scattering analyses. The materials contain hard segments formed from 4,4′- diphenylmethane diisocyanate (MDI) and butanediol (BD), and range in hard-segment content from 20 to 80% by weight. The results provide evidence for a transition from discrete to continuous hard-microdomain morphology as the hard-segment content is increased above ca. 50%. The measured concentration dependences of the interdomain spacing, specific interfacial area, diffuse microphase boundary thickness, and scattering invariants are used to examine the validity of present models for hard-microdomain structure. The observed behavior corresponds well with the general predictions of a lamellar model wherein partially coiled hard-segment sequence configurations are allowed. The thickness of the hard microdomains extracted from the model corresponds to approximately four hard-segment repeat units. Scattering invariant calculations are used together with determinations of the soft-microphase glass transition temperatures to examine possible models for microdomain mixing. These calculations suggest that both the hard and soft microphases are phase mixed.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230912
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  • 61
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    The structure of MDI/BDO-based polyurethanes: Diffraction studies on model compounds and oriented thin films (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1915-1932 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyurethanes based on MDI/BDO are known to crystallize in three distinct forms. Two of these crystal structures, type II and type III, have been characterized by electron and x-ray diffraction experiments on model compounds and oriented thin films of a 77% hard-segment polyurethane elastomer. The model compounds were of the form BDO(MDI/BDO)n with n = 1, 2, 3. Results from the model compounds indicate that the MDI/BDO repeat crystallizes in the type-II structure, which has a contracted conformation with a monomer repeat length of 1.70 nm. MDI/BDO-based polyurethanes also exhibit the type-II structure under quiescent crystallization conditions. Studies of oriented thin films of an MDI/BDO-based polyurethane indicate that a change in crystal form occurs on stretching to the fully extended monomer conformation. This crystal form is termed type III and has a monomer repeat length of 1.92 nm.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230913
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  • 62
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    Extraction and sorption studies using linear polymer chains and model networks (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1933-1940 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Model networks have been prepared by tetrafunctionally endlinking linear polydimethylsiloxane (PDMS) chains having molecular weights Mn in the range 2000-15,000 g mole-1. The first series of networks were prepared from mixtures containing known amounts of unreactive linear PDMS chains with molecular weights Md between 1000 and 16,000 g mole-1. Rates of extraction were used to estimate diffusion coefficients; as expected, they were found to increase with increase in molecular weight Mc = Mn between crosslinks, but to decrease with increase in Md. The ease with which all of such a diluent could be removed showed the same dependence on Mc and Md. A second series of networks was prepared from the same reactive PDMS chains without diluents. Sorption and extraction studies using the same diluents were then carried out. The diffusion coefficients for sorption were found to be in the range (1.7-15.0) × 10-12 m2 s-1 and depended on both Mc and Md. The amount of diluent absorbed at equilibrium was between 10 and 70%, which is in good agreement with predictions from the Flory equation for dilation in networks, with account of constraints on crosslink fluctuations.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230914
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    Phase separation phenomena in solutions of poly(2,6-dimethyl-1,4-phenyleneoxide) in mixtures of trichloroethylene, 1-octanol, and methanol: Relationship to membrane formationA part of this work was presented at the First Europe-Japan Congress on Membranes and Membrane Processes, Stresa, Italy, June 18-22, 1984. (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1941-1955 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phase boundaries in the quaternary system consisting of the polymer poly(2,6-dimethyl-1,4-phenyleneoxide) (PPOPPO is a registered trademark of the General Electric Company.), the solvent trichloroethylene (TCE), and the nonsolvents 1-octanol (OcOH) and methanol (MeOH) are determined. The kinetics of crystallization are investigated by pulse-induced critical scattering. The formation and properties of PPO membranes are discussed in relation to the phase separation phenomena.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230915
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  • 64
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    Short-branch formation via the roedel mechanism in copolymers of ethylene and vinyl acetate (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1957-1965 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A realistic rotational isomeric state model has been used to estimate the relative probabilities of the formation of various types of short branches in ethylene-vinyl acetate copolymers that are rich in ethylene. Butyl is predicted to be the most common short branch in all of the copolymers examined, although it is less common in the copolymers than in low-density polyethylene. The major factor responsible for the suppression of the R04 backbiting intrachain radical transfer is the increased preference for trans states at the mainchain bonds flanking the attachment site for an isolated acetoxy side chain.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230916
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  • 65
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    The local structure of blends of polystyrene and poly(2,6-dimethylphenylene oxide) (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1967-1974 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polystyrene (PS) and poly(2,6-dimethylphenylene oxide) (PPO) are miscible over the complete composition range. The addition of 30-40% PPO to PS changes the mechanical behavior of the material from brittle to tough and ductile. The x-ray scattering curves from unoriented and oriented samples of PS and of PPO are compared with those from a 50/50 blend. The introduction of PPO into PS disrupts microsegregation of phenyl groups into stacks which are a feature of the pure polymer and which may be responsible for formation of sharp shear bands and brittle behavior of PS. The local structure of the blend is significantly different from both PS and PPO.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230917
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    Dynamic behavior of flexible polymers at a solid/liquid interface (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1997-2008 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mean time spent by a macromolecule at a solid/liquid interface is analyzed in the region of adsorption saturation. The method consists of carrying out preliminary adsorption with radioactively labeled high-molecular-weight polyacrylamide and subsequently exposing the surface to a solution of unlabeled polyacrylamide. It was found that, apart from a small fraction of polymers “loosely” attached, the exchange between labeled and unlabeled polymers takes place at the interface at a very slow rate. Furthermore, desorption of surface molecules occurs only in the presence of a solution, and then the rate of desorption increases proportionally to the number of molecules in the solution. A mechanism based on a bimolecular chemical exchange process is proposed.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231002
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  • 67
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    Miscibility and deformation behavior in some thermoplastic polymer blends containing poly(styrene-co-acrylonitrile) (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1975-1995 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Miscibility in blends of poly(styrene-co-acrylonitrile) (PSAN) with several other polymeric components has been investigated over a range of compositions by means of thermal analysis and transmission electron microscopy. Systems in vestigated were (i) PSAN/polycarbonate (PC), (ii) PSAN/styrene-maleic anhydride-methyl methacrylate terpolymer (S/MA/MM), (iii) PSAN/polynorbornene nitrile (PNN), and (iv) PSAN//S/MA/MM//PC. PSAN/PC was demonstrated to be partially miscible in all proportions over the PSAN copolymer composition range 23-70 wt % AN, while the miscibility or lack thereof of PSAN//S/MA/MM depended on the relative AN and MA contents of the PSAN and S/MA/MM, respectively. In contrast, PSAN/PNN was found to be immiscible in all proporations, while the system PSAN//S/MA/MM//PC was shown to be partially miscible. Deformation studies performed on rubber-modified versions of these blends defined deformation mode and microstructural deformation behavior. Dual extensometer tensile testing yielded relative contributions of crazing and of plastic flow, which correlated both with blend composition and with toughness. TEM observations of deformed specimens indicated a deformation process in the multiphase matrix blends consisting of craze initiation and propagation in the rubber-containing phase, craze arresting in the ductile second matrix phase, and coordinated extensive deformation of the matrix phases and of the rubber particles, where the ability to support the latter coordinated forms of deformation were observed to increase with increasing proportion of plastically deforming phase.
    Additional Material: 23 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231001
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  • 68
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    The effect of spherulitic truncation on small-angle light scattering (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2059-2084 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of spherulitic truncation on the Hv small-angle light-scattering (SALS) patterns are determined by computer simulation of spherulite nucleation and growth. The simulation is carried out for simultaneous and sporadic nucleation of two-dimensional spherulites and simultaneous nucleation of three-dimensional spherulites. The scattered intensity differences between truncated spherulites and round spherulites are determined as functions of the type of growth and the volume (or area) fraction of spherulites. Methods for the determination of certain geometrical characteristics of spherulites systems by SALS are developed. These characteristics include the volume (or area). fraction of spherulites, the average spherulite radius, and the average spherulite volume (or area). The results of this study are essential in the quantitative analysis of Hv SALS from spherulitic systems. The simulation process is readily extendable to the examination of other morphological phenomena by SALS.
    Additional Material: 19 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231007
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  • 69
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    Quantitative small-angle light scattering studies of the melting of poly(ethylene terephthalate) (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2085-2107 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Quantitative Hv small-angle light-scattering (SALS) studies of the melting of poly(ethylene terephthalate) (PET) have been performed. The results are compared with those from differential scanning calorimetry (DSC). It is found that fully grown spherulites melt over a temperature range of about 20°C without change in spherulite size, number, or internal disorder. The decrease in Hv SALS intensity is due to a decrease in spherulitic crystallinity over the melting range. The corrected experimental intensities are lower than, but in reasonable agreement with, the theoretically predicted intensities based on the DSC results. Procedures are presented for the quantitative analysis of Hv SALS intensities from spherulitic systems, including the corrections for the experimental, external disorder, and internal disorder effects.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231008
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  • 70
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    Monte Carlo simulation of the crystal structure of the low-temperature phase of polytetrafluoroethylene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 771-786 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An energy analysis based on molecular field theory and Monte Carlo simulation is carried out for the crystal structure of the low-temperature phase of polytetrafluoroethylene (PTFE). PTFE molecules in right-handed and left-handed 13/6 helical conformation are assumed to be packed in a hexagonal array, with each molecule having 13 possible orientations around the chain axis. Interactions between nearest-neighbor chains are calculated from van der Waals interactions between nonbonded C-C, C-F, and F-F atom pairs. First, an approximate molecular field calculation is made of the critical fluctuation of the chain orientation at the order-disorder transition point. This suggests that the low-temperature phase has two chain stems in the unit cell. The Monte Carlo calculation, similar to that used for spin systems, is then applied to the equilibrium packing mode in the low-temperature phase. A crystal structure containing two chain stems in the unit cell is again obtained. A large amount of disorder in the chain orientation is indicated and is believed to be essential in the PTFE crystal.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230412
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  • 71
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    Fracto-emission from filled and unfilled polybutadiene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 873-888 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We further examine the mechanisms involved in the emission of electrons and positive ions from polybutadiene accompanying fracture. Experimental evidence is given in support of a previously presented model involving a microdischarge accompanying fracture which excites the fracture surfaces by particle bombardment. Calculations of the time dependence for the emission from such excitations for both isothermal and thermal stimulation from a simple trap model are presented. We conclude that both filled and unfilled polybutadiene are experiencing the same excitations except at a considerably reduced intensity for the unfilled material.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230504
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  • 72
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    Effect of polydispersity on the cloud-point curves of polymer mixtures (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 917-924 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is presented for the calculation of cloud-point curves of polymer-polymer mixtures when the polymers involved are polydisperse. The method is based on the Flory-Huggins free energy of mixing with a concentration-independent χ parameter. Numerical results are given for cases in which the molecular weight distributions are represented by the Schulz-Flory type. When the two polymers have similar average molecular weights and polydispersities, the cloud-point curves become flatter as the polydispersity increases. When the two polymers have similar average molecular weights but differ in polydispersity, the cloud-point curves become more skewed as the difference in the polydispersity increases. The results point out that, if the polydispersity effect is not properly accounted for, the value of χ deduced from experimental cloud points is liable to be in error, especially with regard to its temperature coefficient and its concentration dependence.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230506
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  • 73
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    Influence of tacticity on Tβ, Tg, and TLL in poly(methyl methacrylate)s by the method of thermally stimulated current (TSC) (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 889-916 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermally stimulated-current method (TSC) has been employed to determine the temperatures and intensities of Tβ, Tg, and T 〉 Tg for pure isotactic, pure syndiotactic, and five atactic specimens with syndiotactic triad content from 49.5 to 75%; Tg was found to increase linearly with syndiotactic triad content as Tg (°C) = 48.0 + 0.856 (% syn), with R2 = 0.970 standard error 5.6°C; Tg for the syndiotactic specimen is 136.6°C measured, 133.6°C calculated. Several atactic specimens exhibit a second glass temperature 15 to 35 K above the regression line ascribed to some pure syndio content, and/or some isotactic-syndiotactic stereocomplexes. All specimens exhibited the liquid-liquid or TLL transition (relaxation) which increases linearly with 100-% isotactic triad content. Isotactic PMMA shows a T′LL relaxation 50 K above TLL. The Tg and TLL values obtained correlate extremely well with values from differential scanning calorimetry (DSC) determined in a separate study, as well as with most literature data. Intensities of Tg and TLL by TSC are greatest for isotactic, next for syndiotactic, with a broad, low minimum for atactic materials. The intensity of a β relaxation increases slowly from isotactic to syndiotactic. The TLL found by TSC compares well with literature values for isotactic PMMA obtained by several methods, and TLL in the atactic region compares well with literature values for atactic material. The ratio TLL/Tg ranges from 1.09 to 1.20 with no dependence on tacticity. Tg follows simple Arrhenius behavior with enthalpies of activation about one-half of the values normally calculated from dielectric and mechanical loss. The frequency dependences of TLL and T′LL follow a Vogel-WLF relationship with temperature. The origin of TLL is discussed in terms of the Frenkel hypothesis of segment-segment interaction. Evidence for TLL and TLL from a variety of methods indicates that these two temperatures are not artifacts of the TSC method.
    Additional Material: 20 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230505
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  • 74
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    Polymer migration in newtonian fluids (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 955-971 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theory of Freed and Edwards is used to investigate polymer migration in nonhomogeneous flow fields with confined geometry. Polymer migration from the main flow originates in three effects: (i) nonhomogeneous flow-field effect, (ii) the confined-geometry effect, and (iii) the concentration effect. General correlation function formulas for these three effects are explicitly derived. Some specific examples are illustrated and solved by using the harmonic dumbbell and Rouse-Zimm models.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230509
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  • 75
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    Conformational behavior of styrene-dymethylsiloxane block copolymers in dilute solution (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 991-1000 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To determine the behavior of a copolymer is dilute solution, a viscosity study has been performed on a polystyrene-polydimethylsiloxane block copolymer in three solvents presenting different thermodynamic conditions. The results are discussed in relation to a mixture of homopolymers and a segregated model. The unperturbed dimensions, obtained by the Stock-mayer-Fixman method, are intermediate between those of the parent homopolymers. The intrinsic viscosity measured in a good solvent, toluene, was close to the weighted averages of those of the corresponding homopolymers of equal molecular weight, but higher in decalin and in butanone, θ solvents for PS and PDMS, respectively. According to the low value obtained for the interaction parameter, the chain is slightly expanded as a result of the interactions between the unlike monomer units. Both segregation and random conformation would probably occur, depending on the quality of the solvent.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230511
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    Sorption and diffusion of toluene in isotropic and oriented linear polyethylene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 973-989 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption and diffusion of toluene vapor in linear polyethylene with mass-fraction crystallinity between 0.48 and 0.82 and draw ratios λ up to 10 have been studied at 30°C. The sorbed concentration in the amorphous phase Ca is little affected by crystallinity, indicating that the free-volume fraction is roughly the same for all isotropic samples. However, the diffusion path becomes more tortuous with increasing crystalline content, thereby leading to a sixfold drop in the zero-concentration diffusion coefficient D0. Drawing has more drastic effects, reducing Ca and D0 by factors of 4 and 60, respectively, as λ increases to 10. These large changes result from the transformation of the initially spherulitic material into a fibrous structure, which is composed of aligned microfibrils with taut tie molecules lying on the outer boundaries. The effects of crystallinity and orientation on the concentration dependence of the diffusion coefficient are also discussed.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180230510
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    Stress-optical behavior of poly(cis/trans-1, 4-cyclohexane dimethanol-alt-formaldehyde) (PCDO) networks (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1031-1041 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two samples of poly(cis/trans-1,4-cyclohexane dimethanol-alt-formaldehyde), having fractions of trans configuration of cyclohexylene rings Ft = 0.1 and 0.7, were synthesized by polycondensation of the appropriate mixtures of glycols with paraformaldehyde. These two samples were crosslinked by a chemical reaction using 2,4-bis(p-isocyanatebenzyl) phenylisocyanate as the crosslinking agent. The stress-optical behavior of the resulting networks was studied at several temperatures in the range 10-80°C. The values of the optical configuration parameter Δα were 9.9 and 7.2 in units of 10-24 cm3 for Ft = 0.7 and 0.1, respectively. The temperature coefficient of this quantity was roughly zero. Theoretical analysis, performed using the rotational isomeric state model, proved that the only parameters that have an appreciable effect on the calculated values of Δα are those concerning the cyclohexane ring (i.e., Ft and the optical parameter ΓCC = ΔαCC - 2ΔαCH). Conformational energies, geometrical parameters, and contributions to the optical anisotropies from the oxymethylene oxide have no noticeable effect on the value of Δα calculated for the polymer. In fact, values of Δα calculated for the polymer at Ft = 0 and 1 are very close to those obtained, respectively, for cis and trans cyclohexane dimethylene. The theoretical values of Δα are roughly one order of magnitude lower than the experimental results; however, the theory reproduces satisfactorily both the variation of Δα with Ft and its temperature coefficient.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180230513
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    An investigation of the effect of sample preparation on the thermal behavior and the small-angle x-ray scattering of a polyurethane block copolymer (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1065-1077 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of varying sample preparation parameters on the thermal behavior and on the small-angle x-ray scattering (SAXS) properties of a polyether polyurethane were investigated. The polyurethane studied was a methylene bis(p-phenyl isocyanate) (MDI)/butanediol/poly(tetramethylene oxide) (PTMO) system synthesized in a 6/5/1 mole ratio by a two-step solution polymerization. The PTMO had a nominal molecular weight of 2000. The samples were compression molded under different conditions for the SAXS experiments. The preparation parameters studied included molding time and temperature, sample thickness, and quenching rate from the molding temperature. The molding temperature has the greatest effect on the SAXS data. In this case the domain size was observed to increase as the molding temperature increased from 130 to 200°C. The thermal properties were also found to be strongly dependent on the molding temperature, as measured by differential scanning calorimetry (DSC). An endotherm related to the annealing that occurs during the molding process appears in each sample near the molding temperature. The other preparation parameters have little or no effect on the SAXS and thermal properties of this sample.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230516
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    Morphological studies of liquid-crystalline cellulose derivatives. II. Hydroxypropyl cellulose films prepared from liquid-crystalline aqueous solutions (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1053-1064 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A morphological study of hydroxypropyl cellulose (HPC) was performed on solid films prepared by casting from a liquid-crystalline aqueous solution at rest or under shear. Electron microscopic observations reveal that many round particles composed of stacked disks are densely packed in the interior of a quiescently cast HPC film, while on the film surface formation of fibrous textures is also noted. Shear-deformed HPC films exhibit some interesting morphological features according to the shearing conditions. It is found by electron microscopy that the originally round particles become more and more elongated as shear stress increases. The resulting rodlike fibrillar entities are considerably aligned in the shear direction (SD), but form a banded structure with periodic discontinuities of molecular orientation distribution along the SD. A new mechanism of structural transformation is proposed in order to interpret these results.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230515
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  • 80
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    Dynamic structure factor of a dilute solution of dumbbells in simple shear flow (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1079-1083 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230517
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    The diffusion equations for polymer membrane formation in ternary systems (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1271-1274 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230619
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    Crystallographic changes in cryogenically pulverized polymers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1449-1466 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cryogenic pulverization of polymers in liquid nitrogen results in a variety of physical and chemical changes, of which crystallographic transformations are among the earliest. These have been investigated in detail for isotactic polystyrene using x-ray and calorimetric techniques. Amorphization was found to occur rapidly, but with concomitant decreases in crystallite sizes of only a limited extent. These changes can to a large degree be reversed upon annealing at high temperature. Similar behavior is seen also in other polymers possessing stronger intermolecular cohesion, such as polyesters and polyamides. In polymers susceptible to mechanically induced phase transformations, cryogenic pulverization causes polymorphic changes en route to amorphization: these include formation of the monoclinic phase in polyethylene and of the β phase in poly(vinylidene fluoride). Based on these results, a model is proposed for the mechanism of pulverization that incorporates both thermal and mechanical effects; this model suggests a two-phase structure of the pulverized, particles, consisting of an amorphous skin that surrounds a damaged crystalline core.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180230708
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  • 83
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    Corrections to calculations of the radius of gyration of polydisperse gaussian coils when scattering measurements at low angle are missing (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1477-1484 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The initial slopes and intercepts of Zimm plots of scattering experiments yield the centroidal radius of gyration of the scattering particle. In many cases, it is not possible to measure at sufficiently low angle to obtain accurate initial slopes and intercepts. Errors for missing data can be corrected by using calculated scattering functions as models. Such corrections are given here for polydisperse Gaussian coils.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230801
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    Concentration distribution of elements in heterogeneous polymer systems determined by electron microprobe analysis (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1485-1494 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A technique for analysis of composition variations in heterogeneous polymer systems permits investigation of materials with both uniform and nonuniform distribution of heterostructural components. To illustrate the method, determinations have been made of concentration profiles of dibromo-diallyl-phthalate formed in porous PVC in two different ways.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230802
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  • 85
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    Application of the method of brather for the determination of complex dielectric permittivity from measurements of isothermal polarization current (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1505-1511 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some years ago, Brather proposed a method for calculation of the real and imaginary parts of the complex dielectric permittivity starting from measurements of isothermal polarization current. This method shows some advantages over the Hamon method, which is normally used. Both methods are applied in this work to the β relaxation of poly(butyl methacrylate). It is concluded that, with the usual accuracy of measurement, a combination of the two methods is advisable; Hamon's method is taken to be a first approximation to that of Brather. Results following the two procedures are compared, and their respective advantages and disadvantages are discussed.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180230804
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    Model calculation of the thermal conductivity of polymer crystals (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1495-1504 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A linear lattice model without adjustable parameters provides an accurate description of the magnitude and temperature dependence of the thermal conductivity of Kc of polyethylene crystals parallel (∥) and perpendicular (⊥) to the chain direction. The model shows that heat is transported principally by phonons polarized transverse (T) to the chain direction. Phonons polarized longitudinal (L) to the chain direction contribute about 20% to the heat transport along the chain direction, and negligibly to heat transport perpendicular to the chain direction. Thermal resistance is caused by LTT three-phonon umklapp scattering in the parallel direction, and by TTT scattering in the perpendicular direction. The calculated values for large crystals are Kc∥ = 465 W m-1 K-1, Kc∥ = 0.16 W m-1 K-1 at 300 K, in agreement with experimental estimates and implying an anisotropy ratio of Kc∥/Kc⊥ ≈ 3000. The axial thermal conductivity of polyethylene crystals is extremely high and comparable to that of copper. Comparison with experimental data on semicrystalline samples at lower temperature yields a crude value of mean free path for boundary scattering of about 50 nm, agreeing in order of magnitude with the size of crystalline blocks.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230803
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  • 87
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    Analysis of the effect of electrical conductance of ferroelectric polymers on D-E hysteresis curves measured by the sawyer-tower method (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1513-1521 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The D-E (electric displacement vs. field) hysteresis curve of a ferroelectric polymer is conventionally measured by the Sawyer-Tower method. The effect of the electrical conductance of the polymer on the measured hysteresis curve is theoretically analyzed and a new method is proposed for elimination of the error arising from the conductance. Examples of original and corrected hysteresis curves of vinylidene fluoride-trifluoroethylene copolymer are presented.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230805
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  • 88
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    Study of poly[bis(p-toluene sulfonate) diacetylene] films prepared by a modification of the Langmuir-Blodgett technique (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1523-1532 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Coherent this films of poly[bis(p-toluene sulfonate) diacetylene] were successfully formed by modified Langmuir-Blodgett techniques using two methods: (i) Photopolymerization of the monomer film at the gas/liquid interface and then transfer to a solid substrate, and (ii) transfer of the monomer film to the solid substrate and subsequent photopolymerization on the substrate itself. The films thus obtained were characterized by traditional force-area isotherms while on pure water subphases. Segments were transferred at either 1 or 10 dyn/cm surface pressure, in different stages of photopolymerization, to glass or germanium substrates. The films on the substrate were characterized by the methods of multiple attenuated-internal-reflection infrared spectroscopy, ellipsometry, contact-potential measurement, and laser Raman spectroscopy. Our results show that the films are multimolecular and about 100 Å thick. Of special interest were the observation of significant anisotropy of oriented dipoles and the ability to obtain excellent spectral data for these very thin oriented films. Raman spectroscopic features are similar to those observed for the bulk polymer, even in the low-frequency region. Polarized Raman spectroscopy confirmed the presence of local anisotropy in these films.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230806
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  • 89
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    Electronic Resource
    Application of a new structural theory to polymers. I. Uniaxial stress in crosslinked rubbers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2243-2271 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A continuum rheological theory, endowed with generalized structural significance, has recently been developed. Based on nonequilibrium thermodynamics, it relates stress σ, strain rate \documentclass{article}\pagestyle{empty}\begin{document}$\dot \varepsilon$\end{document} and temperature in terms of material evolution through a series of structural states. The theory has previously had success in dealing with crystalline metals and surface physics, and here it is applied to crosslinked rubbery polymers in the nominally amorphous condition. Structure is believed to be related to interchain associations, chain entanglements, chain ends, and other defects in the hypothetical ideal network which by itself would lead to neo-Hookean predictions in uniaxial deformation, σnH ∝ λ2  -  λ-1, where λ is the stretch ratio. Predictions are made for σ(λ) in both tension and compression and shown to be more compatible with data than either σnH(λ) or the Mooney - Rivlin expression σMR(λ). Only two parameters are required, moduli Go (reflecting initial structure) and Gs (the steady-state condition), and rate effects are incorporated through Go(\documentclass{article}\pagestyle{empty}\begin{document}$\dot \varepsilon$\end{document}) and Gs(\documentclass{article}\pagestyle{empty}\begin{document}$\dot \varepsilon$\end{document}). The phenomena of yielding and stress softening in cyclic tensile loading are also predicted, suggesting advantages to this approach relative to conventional viscoelastic continuum models.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231102
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  • 90
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    Electronic Resource
    Spectroscopic analysis of poly(p-phenylene benzobisthiazole) films (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2307-2317 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared spectroscopy has been used to determine the relative amount, location, and orientation of residual water and acid molecules in poly(p-phenylene benzobisthiazole) films. By analyzing the relative absorbance of reflected polarized infrared radiation from highly oriented films, the indices of refraction parallel and perpendicular to the chain axis were also obtained.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231105
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  • 91
    Electronic Resource
    Electronic Resource
    Electron-beam-induced fracture of polymers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2273-2293 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When a notched polymeric material is stressed, the notch opens into a wide crack tip, exposing a region of high stress concentration. The consequences of electron bombardment of the tip of such a stressed material under vacuum are explored here for the first time. Evidence is presented for electron-induced crack growth at stress far below that needed for crack growth due to stress alone. The electron current densities used in these experiments are sufficiently small that thermal heating of the zone near the crack tip is minimal. To provide information on the phenomena involved, we present simultaneous measurements of electron current, gas pressure, and sample load in response to periodic bombardment of the sample. Experiments involving the bombardment of un-notched polymers under stress are also described. Fractography of the unique structures obtained by fracture due to the combination of electron bombardment and stress are presented and interpreted in terms of a crosslinking mechanism.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231103
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  • 92
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    The application of gas barrier and thermal expansion techniques to study structural changes on annealing (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2295-2306 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Changes occur in the structure of drawn polyethylene when it is annealed at temperatures close to that of the drawing process. Measurements have been made of the oxygen barrier properties and of the thermal expansion coefficient in the draw direction on samples over a wide draw ratio range both before and after annealing at various temperatures. The results are augmented by density, creep modulus, and shrinkage observations. All samples show a drop in the barrier properties and an increase in the thermal expansion after annealing. However, whereas high-draw-ratio samples show relatively small effects, the changes observed at low draw ratios are very large, with some barrier properties even lower than those of the isotropic feedstock. The effects are larger at the higher annealing temperatures. The diffusion and expansion measurements are greatly influenced by the amorphous regions in the polymer; these results are interpreted as a relaxation of internal stresses giving rise to greater accessibility of the intercrystalline regions. Further experimental work is required to exploit these techniques.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231104
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  • 93
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    Studies on the morphology and structure of aromatic polyester films (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2387-2393 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Oriented films of an aromatic polyester containing a triad ester mesogenic group and a decamethylene flexible spacer were studied by polarized light microscopy, small-angle light scattering, and polarized infrared spectroscopy to determine the nature of the alignment of the polymer chains, induced by shearing, which is responsible for the banded or striped morphology observed. The stripes are apparently composed of fibrils arranged in a zigzag manner containing polymer chains packed in a highly ordered, parallel alignment at an angle of ±26° to the shearing direction.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231111
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  • 94
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    Electronic Resource
    A model for radiation-induced changes in ultrahigh-molecular-weight polyethylene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2407-2409 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231113
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  • 95
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    On the mechanical preconditioning of ultrahigh-molecular-weight polyethylene at small uniaxial deformations (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2599-2610 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The results of creep and recovery experiments are reported for a sample of ultrahigh-molecular-weight polyethylene at three different temperatures and creep times in the range from 10 s to 1.47 X 106s. In order to approximate constant-true-stress conditions all the experiments were carried out at the same value of applied stress (4 MPa) and the change in strain during creep was never more than about 2%. It was found that within the range of conditions used the creep and recovery data could be described quite well by a one-dimensional constitutive equation consisting of two terms, one a single integral hereditary term and the other a plasticity term. Further, it was shown that to a very good approximation the idea of time-temperature superposition can be applied to the description of the hereditary term Ĵ (σ, T, t). We believe that the results described here provide greater insight into what constitutes “mechanical preconditioning” of semicrystalline polymers and further provide a relatively simple method for describing the uniaxial creep and recovery behavior of such materials.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231215
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  • 96
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    Electronic Resource
    Spectroscopic study of α- and β-phase isotactic polypropylene and of atactic polypropylene in solution (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2635-2636 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231221
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  • 97
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    Electronic Resource
    Crystallization of poly(m-xylylene adipamide) induced by sorption of water (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 743-750 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption of water in quenched amorphous poly(m-xylylene adipamide) has been studied at 50°C. The sorption process is nearly Fickian at low humidity. At relative humidities higher than about 58%, however, extremely abnormal behavior, such as a decrease in moisture uptake and a change in appearance from transparent to opaque, is found. From x-ray diffraction analysis, these changes can be attributed to crystallization. Thermal analysis of moistened samples confirmed that the crystallization is due to a drop in crystallization temperature caused by sorption of water. From the relation between the reduction in moisture uptake and the increase in volumetric crystallinity, it is proposed that the change in moisture uptake is caused by the exclusion of water from the crystalline phase.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230410
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  • 98
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    Electronic Resource
    A study of the gas barrier properties of highly oriented polyethylene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 709-731 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of permeability and diffusivity have been undertaken for the gases helium and oxygen in a range of highly oriented polyethylene films. The solubilities deduced for both gases are proportional to the amorphous volume fraction, showing that the noncrystalline regions are the transport medium in all instances. The changes in diffusion coefficient are more complex. A large reduction in diffusion coefficient is observed with increasing draw ratio, and this is particularly marked in the case of the larger oxygen molecule, where significant differences are also observed for different grades of polymer and different drawing conditions. These changes in diffusion coefficient are discussed in the light of previous studies of diffusion in polymers and present knowledge of the changes in structure produced by drawing.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230408
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  • 99
    Electronic Resource
    Electronic Resource
    Structural studies on the polymorphism of nylon 3 (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 733-742 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure and morphology of crystalline nylon 3 [poly(β-alanine)] have been studied by electron microscopy and x-ray diffraction. Two clearly defined forms are detected. Form I appears as spherulites made up of ribbonlike lamellae upon crystallization at high temperature from a solution in phenol-butanediol-1,4. They have monoclinic unit cell with a = 9.60 Å, c = 8.96 Å, and β = 122.5°. The hydrogen-bonded planes run parallel to the long dimension of the crystals. Form II is observed when the samples are prepared from formic acid solution at room temperature. A second type of spherulite with a microfibrillar structure is formed in this case. The isolated crystalline structures obtained from Form II appear to grow along the intersheet direction rather than along the hydrogen bond direction, which constitutes anomalous behaviour. Our results for this second form are consistent with an orthorhombic lattice with a = 9.56 Å and c = 7.56 Å. No clear information is obtained on the b dimension of the unit cell (chain axis) in either case. We assume a value of 4.78 Å, which corresponds to fully extended chains. The two forms coexist in films prepared from a formic acid-water solution as well as in samples recovered immediately after polymerization.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230409
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  • 100
    Electronic Resource
    Electronic Resource
    Elastic moduli of ultradrawn polyethylene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1759-1780 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The five independent elastic moduli C11, C12, C13, C33, and C44 of oriented high-density polyethylene with draw ratio λ from 1 to 27 have been determined from -60 to 100°C by an ultrasonic method at 10 MHz. At low temperature the sharp rise in the axial extensional modulus C33 with increasing λ and the slight changes in the other moduli result from chain alignment and the increase in the number of intercrystalline bridges connecting the crystalline blocks. At high temperature (say, 100°C) the transverse extensional modulus C11, as well as the axial (C44) and transverse (C66) shear moduli, also show substantial increases, reflecting the prominent reinforcing effect of stiff crystalline bridges in this temperature region where the amorphous matrix is rubbery. If the crystalline bridges are regarded as the fiber phase, the mechanical behavior can be understood in terms of the Halpin-Tsai equation for aligned short-fiber composites.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230903
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