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  • Physics  (486)
  • 1970-1974  (486)
  • 1974  (486)
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 317-333 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphological features of random block copolymers of tetramethyl-p-silphenylene (TMPS) and dimethylsiloxane (DMS) have been studied as a function of copolymer composition. Wide-angle and small-angle x-ray diffraction coupled with several electron diffraction and microscopy studies were used to investigate these materials. The results of this work clearly indicate that the amorphous segments do not enter into the crystalline lattice of the crystallizable component which is varied in content from 90% to 30%. Over the entire range of compositions the block copolymers are crystallizable. Spherulites can be grown from the melt, and single crystals and/or spherulites may be obtained from solution. Single crystals can be obtained over the entire range of compositions provided ample time is allowed for crystallization. The crystalline TMPS component exhibits tetragonal symmetry at all compositions. The amorphous phase manifests itself as a diffuse halo in patterns obtained by electron and x-ray diffraction.
    Additional Material: 12 Ill.
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  • 2
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of isothermal crystallization from the glassy state at low temperatures and the morphology of poly(ethylene terephthalate) (PET) filled with additives are reported. Talc, kaolin, silicon oxide, and titanium oxide have been used as fillers; they act as effective nucleating agents for PET. The overall rate of crystallization depends on the volume concentration, the size distribution, and the nucleating ability of the additives. An electron microscopic study reveals a transcrystalline morphology at the surface of the filler particles. The occurrence of transcrystallinity is attributed to extensive heterogeneous nucleation induced at the filler surface. From the shape of the crystallization isotherms, it can be concluded that the crystallization mechanism depends on the type of filler.
    Additional Material: 9 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 399-406 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The nonlinear integral equations governing phase transition kinetics with homogeneous nucleation and growth site impingement are developed and solved to the first order for the two-dimensional case. It is shown that the fractional transformed area at time t is given approximately by a(t) = Kt3/(1 + Kt3). The iteration method used to get the solution is applicable to certain other nonlinear differential and integral equations. It is shown that the theory predicts the total number of growth sites formed, and that the nucleation rate and growth constants can be deduced from this and the gross kinetic data. The extension of the method of three-dimensional growth is indicated.
    Additional Material: 1 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 417-429 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study of the effect of excluded volume on the mean-square optical anisotropy 〈γ2〉 and the mean-square end-to-end distance 〈R2〉 has been carried out for polymer chains of up to 2000 bonds. The calculations have been made for models assuming (a) equiprobability of internal rotations and (b) interdependence of short-range intramolecular interactions. All the results indicate that 〈γ2〉 is practically insensitive to the excluded-volume effect. Concomitantly the behavior of 〈R2〉 has been analyzed.
    Additional Material: 5 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 655-664 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The 100-MHz proton NMR spectra of commercial and laboratory-prepared poly(vinyl chloride) (PVC) have been measured in various solvents at high temperature (80-150°C). Tacticity in PVC was determined by the analysis of the β-proton spectrum. The spectrum was calculated assuming that the PVC chain consists of tetrad sequences of monomer units and that their distribution in the chain is described by a simple Bernoulli-sequence statistics with a Pm (the probability of isotactic placement) of 0.45 for commercial PVC polymerized at 50°C. Tacticity calibration curves based on measurements made for the polymer in pentachloroethane and β-dichlorobenzene were established, and they provide a simple method for the measurement of tacticity in PVC directly from the observed spectra. Excluding samples prepared in butyraldehyde solution, the formation of syndiotactic structures in PVC (prepared by free-radical polymerization) was found to be favored by lowering the polymerization temperature. This preference is due to an increase in the activation enthalpy of 510 cal/mole which is required for forming an isotactic placement in the chain during the propagation step.
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 695-702 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Band assignments of phase-I PVF2 have been Revised by using additional data obtained by laser Raman spectra of oriented samples. A set of least-squares refined force constants was obtained which reproduce the experimental data to an average error in frequencies of 1.3 cm-1. In order to determine the effect of electrical polarization on the spectra, a Gaussian distribution of the dipole axis was assumed. The calculation shows that polarizations of less than 60% will not significantly affect the Raman spectra.
    Additional Material: 4 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 713-733 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Brillouin scattering of laser light has been used to study the temperature dependence of phonon velocity in a variety of amorphous polymeric systems, particularly internally and externally plasticized methacrylates. Discontinuities in the temperature coefficient of the hypersound velocities are observed at the glass transition temperatures (Tg). This phenomenon is related to changes in the temperature behavior of the specific volume accompanied by corresponding discontinuities in certain second-order thermodynamic quantities. This method was also used to examine the temperature dependence of the Landau-Placzek ratio.This ratio is relatively large in polymer systems and appears to be independent of temperature in the region of the glass transition, provided that there are no internal strains in the sample at the temperature of measurement. Evidence is presented which suggests that the abrupt changes in this ratio at Tg reported by earlier workers were due to kinetic effects related to the relaxation of internal strains above Tg, and the results of recent studies by other investigators, both corroborating and supplementing the present work, are reviewed.
    Additional Material: 11 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 785-793 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Analysis of the solution fractionation of ethylene-propylene copolymers was carried out by assuming a bivariate normal distribution function for the distribution of molecular weight and chemical composition. It was found that the variation of the molecular weight and composition distributions in fractions was complicated, because two distribution characteristics of the original copolymer affect fractionation to differing extents. The hypothetical cumulative weight distribution curves thus obtained agreed essentially with those obtained experimentally.
    Additional Material: 11 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 815-818 
    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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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 871-890 
    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 polystyrenes with weight-average molecular weight M̄w up to 1.3 × 107 was prepared by anionic polymerization in tetrahydrofuran (THF). Each sample was characterized by gel-permeation chromatography, light scattering, and viscometry. It was found that each sample had an almost symmetrical and very narrow molecular weight distribution (M̄w/M̄n 〈 1.07). The mean-square unperturbed radius of gyration 〈S2〉0 was determined in trans-decalin at 20.4°C as 〈S2〉0 = 7.86 × 10-18M̄w (cm2). The particle scattering factor was well represented by the Debye equation irrespective of solvent in the range of M̄w 〈 4 × 106, and only a small deviation was observed in benzene at higher molecular weights. The penetration function Ψ ≡ A2M2/4π3/2NA〈S〉23/2 was found to approach a relatively low asymptotic value of 0.21-0.23 at molecular weights above 2 × 106 in benzene at 30°C, where A2 is the second virial coefficient and NA is Avogrado's number. It was also found that the theta temperature in trans-decalin was affected by the nature of polymer samples. A difference of about 3°C in the theta temperature was observed between two series of anionic polystyrenes, one prepared in THF and the other in benzene, but there was practically no difference in unperturbed chain dimension.
    Additional Material: 15 Ill.
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