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  • Physics  (487)
  • 2015-2019
  • 1975-1979  (487)
  • 1977  (487)
  • 1
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 109-125 
    ISSN: 0098-1273
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The Flory-Huggins formulation of the combinatorial entropy, supplemented with residual free energy, is applied locally to obtain the interfacial free energy and the concentration profile of polymer in the interface between two demixed polymer solution phases. Two choices were investigated for the residual free energy: a “regular solution” formulation and an empirical formulation of Koningsveld for polystyrene in cyclohexane. Asymptotic, analytical solutions of the equations near the critical solution point and solutions obtained by numerical calculations are given as a function of temperature for several molecular weights. At temperatures farther below the critical temperature the equations have no solutions. The reason for this is not entirely clear. The local formulation of the free energy used here is an improved version of a previous one, which gave wrong results for asymmetric systems (polymer in a low molecular weight solvent). This newer version is consistent with our theory of critical opalescence and gives a relation between the interface “thickness” and the correlation range of the concentration fluctuations. The calculated correlation ranges were in good accord with those found experimentally by Debye, Chu, and Woerman. That the newer version of our equations for an interface gives no acceptable solutions at lower temperatures could be caused by a “collapse” of a diffuse to a sharp interface as suggested by Nose.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 173-191 
    ISSN: 0098-1273
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The four-center photopolymerization of five diolefinic compounds has been investigated by x-ray crystal analysis. A common packing feature is found for the photopolymerizable crystals and all polymers are three-dimensionally oriented. Topotaxies observed are classified according to the coincidence of space group and the three crystal axes, between monomer and polymer. The polymerization mechanism is discussed on the basis of the topotaxies and it is concluded that the polymerization is lattice controlled over the whole reaction process.
    Zusätzliches Material: 15 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 199-210 
    ISSN: 0098-1273
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: It is well known that polycarbonate annealed at 80-130°C undergoes gradual changes in mechanical properties. Annealing below Tg (ca. 150°C) results in a decrease in impact resistance and an increase in strength. Polycarbonate has three single relaxation processes and some distributed relaxation processes in the temperature range between 100 and 250°K (the β transition region). The effect of thermal pretreatment on the relaxation has been investigated by the thermally stimulated discharge current technique. Partial heating, peak cleaning, and theoretical fitting have also been performed and the activation parameters associated with the relaxation processes have also been calculated to assist in the analysis of the relationship between effects of annealing and structural motions in polycarbonate.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 211-226 
    ISSN: 0098-1273
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Oriented gels, obtained by high supercoolings of isotactic polystyrene solutions, exhibit unexpected “fiber-type” x-ray diffraction patterns. In particular a pronounced meridional reflection at a spacing of 0.51 nm, together with its successive orders, requires an extended, or nearly extended, chain conformation which appears irreconcilable with the stereochemistry of isotactic polystyrene. Furthermore, the value of 0.51 nm correlates directly with the axial projected repeat expected for two styrene monomer units. Two possible stereosequences merit atention: syndiotactic and syncephalic (head-to-head, tail-to-tail). In addition to the 0.51 nm meridional reflection, layer lines are observed with spacing 3.06 nm (6 × 0.51) which equate with 24 carbon-carbon bonds in the backbone. Cylindrically averaged Fourier transform calculations for the various models are compared with the observed x-ray results and the best fit is obtained for a 24/11 helix of isolactic polystyrene with the syncephalic stereosequence. This conclusion, however, clashes with the 13CNMR evidence which indicates that the polymer is essentially isotactic. The implications of these novel results in relation to gel crystallization are discussed.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 239-245 
    ISSN: 0098-1273
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The dynamic mechanical properties of four aromatic polyesters were measured at temperatures in the 78-540°K region at 103-104 cps. The polymers studied were: poly(1,3 phenylene isophthalate), poly(1,4 phenylene terephthalate), poly(4,4′ diphenylene isophthalate), and poly(4,4′ diphenylene terephthalate). All four polymers had β loss peaks at about 280°K. Distinct β* mechanical processes were found for the two terephthalate esters. Broad-line nuclear magnetic resonance measurements were carried out in the 150-440°K temperature range on the four polyesters mentioned above in addition to poly(4,4′ diphenylene 4,4′ biphenyl dicarboxylate). A change in NMR second moment takes place in the 190-330°K region, the magnitude of which is dependent on the polymer structure. The results are compared with those found for a series of aromatic polyamides and are discussed in terms of possible motional processes.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 6
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 247-253 
    ISSN: 0098-1273
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The melting point of the 1:1 copolymer of ethylene and CO is 244°C. It falls rapidly as the percent CO is reduced indicating that the heat and entropy of fusion are 0.60 kcal and 1.15 e.u./mol of chain atoms, respectively. These are lower than the values for polyethylene. Dynamic mechanical measurements showed loss peaks at -100° and 25°C. The low temperature γ-relaxation which is also seen in dielectric data appears to be a local mode relaxation with an activation energy of about 12 kcal/mol. The room temperature relaxation is associated with a large decrease in the modulus and a large increase in the dielectric constant. It is probable that the low entropy of fusion is due in part to extensive motion in the crystal.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 7
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 283-289 
    ISSN: 0098-1273
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The kinetics of the quaternization of poly(4-vinyl pyridine) with 1-bromopropane in sulfolane has been studied in the temperature range 308-348°K with data points covering the whole conversion range. The results have been analyzed according to the neighbouring-group model with rate constants k0, k1, and k2 for reaction of pyridyl groups with zero, one, and two already reacted neighbors. Allowing for limiting reaction at about 95%, the experimental results substantiate the model with K = k1/k0 = 0.80 ± 0.03, and L = k2/k0 = 0.37 ± 0.03, which are independent of temperature. The temperature dependence of k0 values gives an activation energy of 66.22 ± 4.20 kJ mol-1. It is still not possible to decide whether steric or electrostatic factors are responsible for K and L values less than unity. Other systems are mentioned where side reactions occur.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 8
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 303-320 
    ISSN: 0098-1273
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The design and operation of an automated light-scattering apparatus for studying structures in polymer films are described. The apparatus has angular resolution of 0.02 and 1.0° in radial and azimuthal angles, respectively. The radial scan can be made over the range of 0.5 (or less) to 90° and the azimuthal scan covers 180°. Time resolution is in the order of milliseconds. The operation, data collection, and reduction are fully automatic. Illustrative data on the crystallization of a low density polyethylene are described.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 9
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 321-331 
    ISSN: 0098-1273
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Periodate oxidation of polysaccharides shows inhibitory neighbor effects due to hemiacetal formations. A second periodate oxidation may be performed after removal of all protecting hemiacetals formed in the first oxidation.We give the theoretical analysis of the kinetics of such repeated oxidations. For complete protection the oxidation limit of the second reaction, as function of the extent of the first oxidation, lies between 41.1 and 43.2%, in good agreement with experiments on alginate. For general protection effects we calculate the degree of oxidation and the mean sequence lengths of the three types of monomer units. Second-oxidation data, in contradistinction to first-oxidation results, allow separate determination of left-and right-hand inhibitory effects.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 10
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 333-353 
    ISSN: 0098-1273
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Deformation bands formed at the yield point in tensile tests on oriented high-density polyethylene have been studied by optical microscopy and wide-angle x-ray (WAXS) diffraction. The observations of the rotation of the optical extinction direction are shown to obey a simple scheme proposed previously by us: the principal directions of the refractive index ellipsoid within the deformation bands are everywhere parallel to the principal axes of the plastic strain ellipsoid, zero strain referring to the isotropic state. This result is similar to that obtained previously for polyethylene terephthalate (PET) and polypropylene despite the much higher crystallinity obtained with polyethylene. Independent measurements of the molecular reorientation in the deformation bands made using wide-angle x-ray scattering broadly confirm the optical measurements. The results taken together suggest that the material within the band, whether crystalline or not, becomes realigned about the new direction of maximum elongation as if controlled by the deformation of an effective molecular network.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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