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  • Physics  (974)
  • 1985-1989
  • 1980-1984
  • 1975-1979  (974)
  • 1925-1929
  • 1978  (504)
  • 1975  (470)
  • 1
    Electronic Resource
    Electronic Resource
    Relationship between dielectric side-group relaxation and conformations of poly(alkyl acrylates) in the glassy state (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 431-436 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130218
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  • 2
    Electronic Resource
    Electronic Resource
    Partial molar excess free enthalpies of n-alkenes in apiezon M and alkanes in squalane and polydimethylsiloxane, and the solution theories of prigogine and flory: An investigation by gas chromatography (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 401-417 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Partial molar excess free enthalpies (or excess chemical potentials) at infinite dilution were obtained over a large temperature range by gas chromatography. Data on n-alkenes in Apiezon M are interpreted by the Prigogine-Patterson theory; data on normal and branched alkanes in squalane and polydimethylsiloxane (PDMS) are discussed in terms of the Prigogine-Patterson theory and the solution theory of Flory, Orwoll, and Vrij. For the alkane-PDMS systems heats of dilution and partial excess heat capacity data are given.The aim of this work is to get some insight in the applicability of these solution theories to mixtures of fluids, the properties of which may slightly violate the basic assumptions of these theories. It is shown that orientational order in and a large cross-sectional chain diameter of the polymer solvent do not affect their applicability to the partical molar excess free enthalpies of apolar mixtures, whereas large dissimilarities between the force fields around the segments of the mixture components and/or dissimilar chain flexibilities detract from the applicability of these theories (alkanes in PDMS).Special attention has been paid to the effects of dissimilar size and shape of the segments of the mixture compounds on the magnitude of the interchange interaction parameter. It is shown that the multiple-connected segment model after Lichtenthaler et al. does not warrant a reliable combinatorial contribution. Comparison of the interaction parameters obtained for n-alkanes in n-alkanes, Apiezon, squalane, and polyisobutylene and for branched alkanes in squalane reveals that the magnitude of this parameter is affected by small end-effects due to the relative weakness of methyl-methylene interactions.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130216
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  • 3
    Electronic Resource
    Electronic Resource
    Estimation of molecular structure in amorphous poly(4,4′-dioxydiphenyl-2,2′-propane carbonate) by dielectric measurements and Monte Carlo calculations (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 437-441 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130219
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  • 4
    Electronic Resource
    Electronic Resource
    Mechanical behavior of SBR-glass bead compositesPresented in part at the 4th National Colloidal Symposium, Madison, Wisconsin, June 1966. (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 579-597 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanical properties of crosslinked SBR containing varying amounts of a glass bead filler have been studied. It is shown that the stress-strain response at a given test rate and temperature can be rationalized provided dewetting around the glass bead filler is taken into account. Direct measurements of the volume dilatation as a function of both strain and filler content have been obtained. This information in conjunction with the model proposed herein has been used to satisfactorily reproduce the stress-strain curves to strains up to about 200%. It is also shown that at the break point complete dewetting has occurred so that the rupture properties of the filled are the same as that of the unfilled gum. This was found to be true for all temperatures and rates studied.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130309
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  • 5
    Electronic Resource
    Electronic Resource
    The dielectric permittivity response of rodlike polymer solutions to high electric field pulses (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 599-605 
    Details
    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.1975.180130310
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  • 6
    Electronic Resource
    Electronic Resource
    Micelle formation in butanone solutions of styrene-butadiene-styrene triblock copolymer (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 663-666 
    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 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130315
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  • 7
    Electronic Resource
    Electronic Resource
    Dynamics of macromolecular chains. II. Orientation relaxation generated by elementary three-bond motions and notion of an independent kinetic segment (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), 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: In the preceding paper, general equations were established for the motions of chains confined to a tetrahedral lattice. In the present paper, bond orientation correlation and autocorrelation functions are explicitly calculated for the case where only three-bond elementary motions are considered. Effects due to the chain end are analyzed and the relaxation time distribution function is established. The expressions obtained reflect the influence of the chain structure. Finally, to characterize the dynamic behavior of chains in orientation relaxation experiments, the notion of an independent kinetic segment is proposed.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130402
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  • 8
    Electronic Resource
    Electronic Resource
    The elastic free energy and the elastic equation of state: Elongation and swelling of polydimethylsiloxane networks (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 683-702 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The elastic free energy for a tetrafunctional network is here expressed as \documentclass{article}\pagestyle{empty}\begin{document}$$ G_{{\rm el}} = C_1 \left( {\lambda _1 ^2 + \lambda _2 ^2 + \lambda _3 ^2 - 3} \right) + C_2 \left[ {\left( {\lambda _1 \lambda _2 \lambda _3 } \right)^m \left( {\lambda _1 ^{ - 2} + \lambda _2 ^{ - 2} + \lambda _3 ^{ - 2} } \right) - 3} \right] - \left( {{{C_1 } \mathord{\left/ {\vphantom {{C_1 } {C_2 }}} \right. \kern-\nulldelimiterspace} {C_2 }}} \right){\rm }\ln {\rm }\left( {\lambda _1 \lambda _2 \lambda _3 } \right) $$\end{document} where λ1, etc., are the principal extension ratios relative to the state of reference (wherein 〈r2〉 = 〈r2〉0), and C1, C2, and m are arbitrary parameters. The free energy of a swollen system is taken to be the sum G = Gmix + Gel of Gel and the free energy of mixing \documentclass{article}\pagestyle{empty}\begin{document}$ G_{{\rm mix}} = RT\left[ {n_1 \ln v_1 + n_2 \ln v_2 + \bar \chi n_1 v_2 } \right] $\end{document}. Stress-strain relations and the chemical potential μ1 are derived from G as functions of the elasticity parameters C1, C2, and m, and of the thermodynamic interaction parameter χ or of \documentclass{article}\pagestyle{empty}\begin{document}$\chi = \bar \chi + n_1 v_2^{ - 1} \partial \bar \chi /\partial n_1 $\end{document}. The dilation of the semi-open system subject to deformation when exposed to diluent at fixed activity is derived as the sum of the dilation at fixed composition and the dilation due to absorption of diluent. Experiments are reported on the dependence of the equilibrium retractive force on elongation for cross-linked polydimethylsiloxanes (PDMS) exposed to benzene or hexamethyldisiloxane vapor at regulated activities. Volume fractions of samples covered the range v2 = 1.00 to v2 ≈ 0.30. With the choice of m = ½ the elastic behavior of a given polymer is well represented by one combination of values for C1 and C2 at all dilutions by either diluent. The dependence of the Mooney-Rivlin (C2) term on volume is thus established, at least for PDMS, and the scope of the semi-empirical free energy expression and its consequents is greatly enlarged. Values of χ deduced from the equilibrium swelling of the unstrained networks exposed to benzene at various activities are in excellent agreement with those obtained previously from vapor pressures and osmotic pressures on linear PDMS. The results of Allen, Kirkham, Padget, and Price on the elastic behavior of natural rubber are discussed, with particular reference to the coefficients of dilation with elongation which they determined at fixed composition. The present results lend strong support to the principle of additivity of the free energies attributable to the network and to the bulk liquid system, respectively. This principle is fundamental to the analysis of rubber elasticity.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130403
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  • 9
    Electronic Resource
    Electronic Resource
    Relaxation spectra of concentrated polystyrene solutions (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 775-786 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relaxation modulus G(t) and the stress decay after cessation of steady shear flow were measured on concentrated solutions of polystyrenes in diethyl phthalate. Ranges of concentration c and molecular weight M of the polymer were from 0.112 to 0.329 g/ml and from 1.23 × 106 to 7.62 × 106, respectively. The relaxation spectrum H(τ) as calculated from G(t) for the solution of very high M was found to be composed of two parts. One, at relatively short times, was a broad distribution (plateau zone) with height proportional to c2. The second, at the long-time end, was very sensitive to concentration and gave rise to a maximum in H(τ) for very high concentrations. The behavior of H(τ) at long times was examined quantitatively by evaluating the longest relaxation time τ10 and the corresponding relaxation strength G10 from G(t) and from the stress decay function, on the assumption of a discrete distribution of relaxation times at long times. The longest relaxation time was approximately proportional to M3.5, even at relatively low concentrations where the zero-shear viscosity was not proportional to M3.5. The strengths of relaxation modes with the longest few relaxation times are proportional to the third power of concentration.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130410
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  • 10
    Electronic Resource
    Electronic Resource
    Matrix ENDOR of polyenyl radicals in polymers (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 825-834 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: EPR and matrix ENDOR spectra have been examined for polyenyl radicals in γ-irradiated PVF, PVF2, PVC, and PMMA polymers. Proton matrix ENDOR is observed for all four polymers, and fluorine matrix ENDOR for PVF and PVF2. By line shape analysis of the ENDOR spectra obtained under comparable conditions, delocalization diameters for the unpaired electron of the polyenyl radical in each polymer are obtained. These diameters indicate extensive delocalization over 5-7 carbon double bonds for the polyenyl radicals investigated. It is suggested that these conjugated and crosslinked radiation products account for the observed nondevelopment of electron beam resist PMMA material at high radiation charge densities.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130414
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  • 11
    Electronic Resource
    Electronic Resource
    On the refractive indexes and birefringence of nylon 6 yarns as a function of draw ratio and strain (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 835-850 
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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 systematic study of the dispersion curves of the refractive indexes of nylon 6 yarns was made. The parameters were the draw ratio and strain. The measurements show that the dispersions of the refractive indexes n∥ and n⊥, parallel and perpendicular to the fiber axis, are equal, independently of draw ratio and strain. The average dispersion equals nF - nC = 109 × 10-4. Consequently, the birefringence is, within experimental accuracy, independent of the wavelength. The refractive indexes and the birefringence show a change in trend at 10-12% strain. This point corresponds to the yield strain in the stress-strain diagrams. The inference is that beyond the yield point the overall molecular orientation must increase less strongly with strain than before. An analysis shows that the Lorentz-Lorenz relation holds for the average refractive index n̄ = ⅓ (n∥ + 2n⊥). So the change in n̄ versus draw ratio is mainly due to the change in density. By applying the Lorentz-Lorenz relation to the change of n̄ on straining, a value of Poisson's ratio (μ) could be derived. The average value found for nylon 6 yarns was μ = 0.48, which means that the density hardly changes with strain.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130415
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  • 12
    Electronic Resource
    Electronic Resource
    Temperature dependence among the grant and Paul parameters as derived from 13C NMR polymer spectra (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 901-908 
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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: Improvements in the 13C NMR Grant and Paul parameters as applied to polymers have been obtained by noting that the “corrective terms” can be temperature-sensitive. A corresponding temperature sensitivity was not observed for the primary parameters, α through ∊. Results are given for a hydrogenated polybutadiene and six different ethylene-1-olefin copolymers where the standard deviation between calculated and observed chemical shifts has been improved from 1.04 to 0.30 ppm. Since the “corrective terms” in the Grant and Paul empirical analyses of chemical shifts reflect the conformational character of polymers, it is shown that values for these terms can best be obtained directly from the system under study.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130503
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  • 13
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    Persistent polarization in poly(vinylidene fluoride). I. Surface charges and piezoelectricity of poly(vinylidene fluoride) thermoelectrets (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 929-946 
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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: Persistent polarization in poly(vinylidene fluoride) (PVDF) thermoelectrets prepared under high electric field strengths has been studied by measurements of surface charge and piezoelectricity. An anomalous heterocharge appears after the normal homocharge disappears. A model is proposed to explain the surface charge phenomena; the anomalous heterocharge is expressed as a sum of a hidden homocharge and a hidden heterocharge. It is concluded that the anomalous heterocharge as well as the apparent homocharge are not responsible for the piezoelectricity of PVDF electrets. The piezoelectricity is shown to depend on the structure of the original PVDF films or the amount of β-form crystals. However, the piezoelectricity is not attributed to stress dependence of the spontaneous polarization in the β-form crystal of PVDF, but to the hidden polarization which bring about the anomalous heterocharge. The hidden polarizations are attributed to trapped charges.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130505
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  • 14
    Electronic Resource
    Electronic Resource
    Dielectric study of relaxations and polymorphism in poly(diethyl siloxane) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 977-983 
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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 behavior of poly(diethyl siloxane) supports the adiabatic calorimetric findings of Beatty and Karasz. In particular, a sub-Tg transition is observed near -180°C at 100 Hz, the glass transition near -135°C at 100 Hz, and a first-order transition near -70°C (crystal-crystal transformation). This glass-transition temperature is the lowest reported polymeric glass transition for polymers.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130510
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  • 15
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    A theoretical analysis of the effect of solvent on the Kerr constant of dilute polymer solutions (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1011-1021 
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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 new model in which solvent molecules are regarded as discrete particles is used for investigating the influence of solvent orientation near a polymer chain and of the anisotropy of the internal electric field on the Kerr effect in a polymer solution. The relation derived for the Kerr constant consists of two parts containing nine terms each in the general case (the physical meaning of the terms is briefly discussed). Relations for the above effect in a nonpolar isotropic solvent, and explicit calculations of the Kerr constant for a simple model of a rigid polymer molecule are given.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130513
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  • 16
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    Mechanics of peeling of rubbery materials. I. Peel strength and energy dissipation (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2129-2134 
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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 peel strength found in the trousers-type peeling process is treated for the case in which the adherends, assumed to be flexible but inextensible are bonded by rubbery viscoelastic adhesives.Taking into consideration energy dissipation during deformation of the adhesive, Griffith's criterion is extended to the peeling of viscoelastic materials. For the peeling force per unit width f it is deduced that 2f = Γ + u′h, where T is twice the surface energy, u' is the energy dissipation per unit volume of adhesive, and h is the thickness of the adhesive layer. Values of u' obtained from peeling tests for various thicknesses are compared with those from the tensile tests and found to agree with the above relation. The deduction that the peel strength is independent of the thickness for adhesives with no energy dissipation is also verified experimentally.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131106
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  • 17
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    Effect of molecular weight on the crystalline structure of polytetrafluoroethylene as-polymerized (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2183-2194 
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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: Melting and crystallization behavior of polytetrafluoroethylene as polymerized in emulsion and suspension is shown to depend on molecular weight. DSC heating curves for virgin PTFE with low molecular weight below 3 × 105 have a single peak, whereas curves for higher molecular weight samples have double peaks. With increasing heating rate the areas of higher melting peaks become larger than the lower melting peaks. The morphology of polymer exhibiting double melting peaks is mainly folded ribbons or granular particles. The phenomenon of double melting is explained on the basis of two different crystalline states which correspond to the “fold regions” and the “linear segments” in a folded ribbon.The melting temperature of virgin PTFE is almost constant at ca. 330°C for molecular weights below 1 × 106, and rises as the molecular weight increases above 1 × 106. The heat of melting of virgin PTFE is nearly independent of molecular weight.On the basis of these results, we propose a model for melting and crystallization of low and high molecular weight PTFE and for the crystal structure.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131110
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  • 18
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    Excluded volume of linear macromolecules in gel permeation chromatography: The one-dimensional case (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2253-2257 
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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.1975.180131117
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  • 19
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    Low-frequency dynamic mechanical behavior of lightly crosslinked 1,5-trans-polypentenamer in the rubberlike region (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2289-2298 
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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 low-frequency (10-3 to 5 × 10-1 Hz) dynamic mechanical properties were obtained over the temperature range of 25 to 96°C for 1,5-trans-polypentenamer networks prepared in the presence of 0,0.01, 0.02, 0.04, 0.1, 0.2, and 0.4% dicumyl peroxide. For comparison, similar properties of 1,4-polybutadiene crosslinked with 0.02% dicumyl peroxide were also measured. Superimposed curves for the components of the dynamic compliance, Jp′ and Jp″, reduced to 25°C were obtained and the retardation spectra L were calculated over a range of four logarithmic decades deep in the rubberlike region. It was found that networks containing 0.04 and 0.1% DCP have a small loss maximum Jp″ in the reduced frequency region log ωaT between -2 and 0 which can be assigned to relaxations of untrapped entanglements. The values of (Jp′ - 1/ωη) for very lightly crosslinked polypentenamer networks approached equilibrium very slowly compared to 1,4-polybutadiene crosslinked to the same degree, which suggests the participation of very long retardation times of this polymer which is also probably reflected in the comparatively high values of C2 of the Mooney-Rivlin equation.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131204
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  • 20
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    The dynamic mechanical behavior of ultra-high modulus linear polyethylenes (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2331-2343 
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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 dynamic mechanical properties of a number of ultra-highly drawn polyethylenes have been studied over a wide range of temperature. It is shown that the materials possess low temperature Young's moduli as high as 1.6 Mbar, a figure which approaches the theoretical and experimental values for the c-axis crystalline modulus of this polymer.The α and γ relaxation processes are still clearly discernible even at highest drawn ratios (ca. 35) and a quantitative analysis of the results, using structural data obtained from broad line nuclear magnetic resonance (NMR) measurements, suggests that the data are consistent with a modified series model.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131208
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  • 21
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    Heterogeneous nucleation of crystallization of high polymers from the melt. II. Aspects of transcrystallinity and nucleation density (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2385-2390 
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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 the initial stage of the development of transcrystallinity, nuclei appear sporadically on the substrate. The growth rate and melting temperature of the transcrystalline region are found to be the same as those of spherulites nucleated in the bulk of the polymer. Nucleation densities ns at the interface, and nb in bulk, for the crystallization of isotactic polypropylene, poly(ethylene oxide), and poly(butene-1) in contact with various substrates, have been measured by counting the number of spherulites generated. Despite variations in the results from various causes, the quantities ns and ns/nb are useful parameters for characterizing the nucleating ability of various substrates.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131212
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  • 22
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    Heterogeneous nucleation of crystallization of high polymers from the melt. III. Nucleation kinetics and interfacial energies (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2391-2400 
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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 the melt crystallization of isotactic polypropylene, poly(ethylene oxide) and poly(butene-1) in contact with substrates, the existence of a fixed number of nucleating sites on the substrate surfaces has been established. When these sites become active successively (the transient in the number of nuclei is long) during crystallization, pseudohomogeneous nucleation on the substrate occurs. Nucleation rates for poly(butene-1) and poly(ethylene oxide) on substrates and in bulk have been measured. These data can be used for comparing the nucleating ability of substrates. Estimates of the variation of bulk nucleation rates from one volume element to another as well as for repeated crystallization within a given volume element have been included. Finally, the temperature coefficients of heterogeneous nucleation rates have been combined with the temperature coefficient of spherulitic growth rate of poly(butene-1), to yield values of the interfacial energy parameters appearing in the theory of heterogeneous nucleation. The quantitative characterization of the nucleating ability of substrates by this method is an improvement over the mere use of nucleation densities or nucleation rates.
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    Thermal activation parameters for large strain deformation of polyethylene and polycarbonateSupported by the U.S. Army Research Office, Durham. (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 19-34 
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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: Experiments were performed to determine the effects of strain rate, temperature, and pressure on the flow stress of polyethylene and Lexan polycarbonate deformed in shear. The results were analyzed to determine the activation enthalpy and the shear and dilatation activation volumes of the rate-limiting mechanism of the deformation process. Results show that the activation event involves a volume containing several monomer units and that this volume must dilate by as much as 7% during the activation event. The activation enthalpy was approximately 2.5 × 10-12 erg for polyethylene and 1.1 × 10-12 erg for polycarbonate. The rate-limiting mechanism for polyethylene seemed to be unchanged by plastic strains of up to 250%.
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    Viscoelastic behavior of glass-bead filled crosslinked polymers in the dry and swollen states (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 703-714 
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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: Stress relaxation and moduli of elasticity of the composite system crosslinked poly(2-hydroxyethyl methacrylate) (PHEMA)-glass beads were studied dry and swollen in water to equilibrium state over the temperature range 5-170°C. The moduli of the composites in the dry state increased with increasing filler concentration, while those of the composites measured in the swollen state up to the volume concentration of the filler vf′ ≅ 0.15 decreased. In this respect the composites behaved as porous systems, i.e., as polymers with macroscopic defects. This effect was explained as a consequence of weak filler-matrix interaction. The results were compared with the existing theories of moduli of the composite materials.
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    Dielectric relaxation in concentrated solutions of poly(γ-benzyl-L-glutamate) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 737-752 
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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: Measurements of dielectric constant and loss, broad-line nuclear magnetic resonance, and differential thermal analysis of concentrated solutions of poly(γ-benzyl-L-glutamate) (PBLG) were carried out to determine the effects of intermolecular interactions on the mobility of the side group and the solvent (dichloromethane or dioxane). Only one dielectric loss peak due to the cooperative motion of the side group and the solvent was found. The activation energy of this relaxation process varied from 3 to 47 kcal/mole with increasing concentration of PBLG from 20 to 100% by weight accompanied with steep increases at about 40 and 80%. This result is explained as due to entanglement of neighboring side groups. In NMR, narrowing of the line was observed near the temperature where the dielectric loss was observed. The glass transition was also observed by differential thermal analysis. From these results it was concluded that the relaxation observed in PBLG solution and in pure PBLG have the nature of primary or α relaxations.
    Additional Material: 18 Ill.
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    Fourier transform infrared study of the effects of irradiation on polyethylene (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 815-824 
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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: Fourier transform infrared spectra have been obtained for polyethylene irradiated in oxygen and nitrogen atmospheres. The spectra before and after irradiation have been compared by digital subtraction. The difference spectra are indicative of changes caused by irradiation. Crosslinking and chain scission reactions produce the observed changes.
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    On the thermoelastic behavior of polymer networks (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 857-858 
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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 Tab.
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    Relaxations in the transition region of crosslinked polyesters. I. The β relaxation (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 871-871 
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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
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    Laser light scattering studies of poly(L-lysine HBr) in aqueous solutionsPartly presented at the 1974 March Meeting of the American Physical Society, Philadelphia, Pa. (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 873-888 
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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 simple theory for the relaxation of concentration fluctuations in polyelectrolyte solutions is presented, and particular results for the high-salt and no-salt limiting cases are discussed.Autocorrelation functions for the fluctuating intensity of scattered light from dilute aqueous solutions of poly(L-lysine HBr) (PLL-HBr) with and without added salt have been observed over a wide range of pH. The observed autocorrelation functions are in general very satisfactorily represented by single exponentials except at high pH (〉10.5), where considerable aggregation is manifested. Solutions of PLL HBr without added salt exhibit extraordinary behavior, evident at low pH, involving a species with a very slowly decaying autocorrelation function. Though this species is readily annealed to a more ordinary individual free-molecule form by cycling the pH to 9.5 or higher and back, the resulting molecules are found to require unusually long times to reach internal configuration equilibrium under low pH conditions. Solutions of PLL-HBr in 0.2M NaBr and 0.1M NaCl are apparently free of similar extraordinary effects and show the normal isothermal helix-coil transition accompanied by a 15-30% rise in the diffusion coefficient to a maximum at pH 10.5, which is interpreted in terms of a change in molecular dimension of an interrupted helix.The predicted K2 dependence of the reciprocal relaxation time and enhancement of the apparent diffusion coefficient of the polyelectrolyte in the absence of salt is confirmed.
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    Degrees of order from X-ray diffraction in highly crystalline poly(vinyl chloride) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 961-970 
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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: Convenient x-ray diffraction instrumentation for assessing PVC order is described. A reflectance diffractometer, copper radiation, a monochromator, and a proportional detector are used to make measurements on low molecular weight, highly crystalline PVC prepared using chain-transfer agents. Interpretation includes a correction for air scattering, employment of a trimodal noncrystalline pattern, and the calculation of crystallinity from the ratio of the crystalline to the total integrated intensity. The results are reasonably insensitive to the assumptions made. The noncrystalline pattern used is taken to indicate a single, partially ordered mesomorphous phase. A whole polymer prepared in the presence of butyraldehyde, a fraction therefrom prepared by precipitation, and a similar fraction terminated by butyl mercaptan have similar molecular weights (M̄n ca. 1600) and crystallinities of 30, 44, and 44%, respectively. Fractionation apparently effects a separation with respect to syndiotactic content, and the resultant crystallinity appears to be the highest valid x-ray value reported to date for a PVC polymer, irrespective of polymerization variables, fractionation procedure, or molecular weight. The order in these polymers is due in part to their greater syndiotacticity (about 64% for the fractions by 13C NMR spectroscopy), although a more favorable tactic placement distribution may be involved in addition to a possible effect of molecular weight itself.
    Additional Material: 4 Ill.
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    Conformation of poly(dimethyl siloxane) and polystyrene in solution measured by polarized Raman scattering (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 997-1009 
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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: Depolarization ratios ρ have been measured over ranges of temperature T and molecular weight M for polystyrene (PS) dissolved in cyclohexane (1002 cm-1 Raman band) and for poly(dimethyl siloxane) (PDMS) dissolved in benzene (2907 cm-1 Raman band). The ranges in the case of PS are 15 〈 T 〈 65°C and 2 × 103 〈 M 〈 4 × 105 and in the case of PDMS are -3 〈 T 〈 60°C and M = 104. Measurements were also made of PDMS radii of gyration using conventional light scattering. The results are interpreted in terms of a theory connecting rotational isomeric populations with polymer extension. In the case of PDMS, an experimental value of the proportionality constant for trans isomers (D2 = -3.9 ± 0.9) is deduced. This is closer to the theoretical value than previous estimates but there is still some discrepancy. In the case of PS the isomeric changes resulting from extension are independent of M for M 〉 104. Deviations are observed for lower M.
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    Low-temperature relaxations in styrene-crosslinked polyester networks (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1049-1056 
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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 low-temperature dynamic mechanical relaxations have been observed in networks formed by copolymerization of poly(1,2-propylene fumarate) and poly(1,2-propylene phthalate fumarate) with styrene. The γ relaxation which occurs around -100°C (1 Hz) is induced by small amounts of water, while the broad γ′ relaxation is reduced in height by the presence of water. Neither xylene nor 1,2-propylene glycol induced a γ relaxation. The γ relaxation was ascribed to motions involving a fumarate ester group-water complex.
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    Polymerization mechanisms and molecular weight distribution. I. Mathematical treatment (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1063-1070 
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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 novel method for determining the polymerization mechanism and the kinetic rate constants from the molecular weight distribution is proposed. The particular criterion function used as basis for parameter adjustment is \documentclass{article}\pagestyle{empty}\begin{document}$$ \mathop {{\rm Min}}\limits_\theta \int_0^\infty {\left[ {y\left( {r,\theta } \right) - y_{\rm E} \left( r \right)} \right]^2 dr} $$\end{document} where θ is the vector of dependent variables, y(r, θ) is the theoretical molecular weight distribution for the assumed polymerization mechanism, and yE(r) is the experimental molecular weight distribution which is a function of the chain length r. A form of the gradient method of optimization was used to solve the criterion function. The proposed method is particularly powerful since the whole molecular weight distribution is utilized.
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    The heat capacity difference Cp - Cv for polymers (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1263-1267 
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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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    Effect of interfacial bonding on the strength of adhesion (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1285-1300 
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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 strength of adhesion has been determined experimentally for an elastomer layer coupled to a rigid substrate by interfacial chemical bonds of varying surface density. Sites for interfacial bonding were obtained by treating glass plates with mixtures of vinyl-and ethylsilanes in varying proportions. A layer of polybutadiene was then applied and cross-linked in situ by a free-radical process. Formation of interfacial bonds to vinyl groups (when present) on the glass substrate is inferred from the proportional increase in strength of adhesion under near-equilibrium conditions, i.e., at low rates of detachment and at high temperatures. A 35-fold increase in strength was found for vinylsilane, relative to ethylsilane, in rough agreement with the relative magnitudes of the strengths of covalent and dispersion bonds. However, the absolute magnitudes were much greater than predicted, by a factor of about 25 in both cases. This is attributed to the polymeric character of the elastomer: many molecular bonds must be stressed in order to detach or rupture one.4 In agreement with this hypothesis, the strength of adhesion decreased with increasing crosslinking. Anomalously high adhesion was found with clean glass. It presumably reflects a specific bonding mechanism of unknown type.
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    Physical properties and structure of silk. II. Dynamic mechanical and dielectric properties of silk fibroin (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1347-1351 
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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: Dynamic mechanical and dielectric properties of amorphous regenerated films of silk fibroin were studied as a function of temperature. A mechanical loss tangent peak at about 175°C may be due to the segmental motion of the main chains in the amorphous silk fibroin film. The dynamic modulus of the amorphous silk fibroin increased at 185°C due to the crystallization of the silk fibroin. Dielectric loss tangent peaks were observed at about -40°C and 175°C at 1 kHz. The former is ascribed to the local motion of the amorphous silk fibroin with absorbed water, while the latter seems to originate from the segmental motion of the main chains and the crystallization of silk fibroin.
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    Crystalline isomeric polyester block copolymers. Scanning calorimetry and density measurements (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1353-1363 
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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 series of isomeric polyester block copolymers were synthesized by coupling hydroxyl-terminated poly(hexamethylenesebacate) (HMS) and poly(2-methyl-2-ethyl-1,3-propylene sebacate) (MEPS) with hexamethylene diisocyanate. Poly(HMS) is crystalline, whereas poly(MEPS) is amorphous. All of the block copolymers, including one containing only 28% HMS were found to crystallize. DSC, density, and optical microscopy were used to measure the thermal transition temperatures and the degree of crystallinity. The data indicate that block copolymerization causes a small depression in the melting point and that the degree of crystallinity of the HMS block in the copolymer is more a function of molecular weight than it is of copolymer composition. Crystallization appears to be the major driving force for phase separation in this isomeric copolymer system.
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    The nature of multiple melting transitions in cis-polyisoprene (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1387-1405 
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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 multiple melting transitions previously reported for cis-polyisoprene have been related to different morphological species observed in thin films using transmission electron microscopy. Two distinct types of spherulitic lamellar crystal have been identified which have characteristic growth rates, lamellar thicknesses, and fold planes.In addition to the α-lamellar crystals, which grow in prestrained films with the a axis perpendicular to the stretch direction, a second type of lamellar crystal was identified with the b axis perpendicular to the stretch direction: β-lamellae. From an analysis of the kinetics of growth and the variation of lamellar thicknesses with crystallization temperature, values of the side and surface free energies of the two types of lamellar crystal have been calculated.
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    A method for experimental determination of the temperature dependence of relaxation times in dielectrics (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1467-1479 
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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 new method is suggested for the experimental determination of the dependence of the relaxation times on the temperature in dielectrics for which the time-temperature superposition principle is valid. The method makes possible the determination of this dependence for a separate relaxation process (for instance, for the β-relaxation process) over a wide temperature range by means of comparatively simple mathematical operations which are only slightly sensitive to experimental errors. Two or more discharge-current curves, measured with temperatures increasing in an arbitrary way with time, are used for this purpose.
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    Calorimetric study of mixtures of butyl methacrylate oligomers with methanolCommunication VII in the series “Specific Interactions in Solutions of Polymers”; Part VI, Coll. Czech. Chem. Commun. 39, 3677 (1974). (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1511-1514 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Heats of mixing of methanol with butyl isobutyrate and with oligomers of butyl methacrylate (monomer to tetramer) having a butoxyl group on one chain end have been measured. To discuss the effect of hydrogen bonding on the heat values, it is appropriate to correlate the heat per mole of binding sites with the binding site fraction. This dependence can be described by a single curve for all oligomers studied, in contrast to the results obtained in a previous paper for the same oligomers with chloroform. This fact suggests that the binding parameters for methanol are not influenced by the degree of polymerization.
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    Electro-osmosis of water through a cellulose acetate membrane (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1603-1611 
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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: Experiments on electro-osmosis of water through a cellulose acetate membrane have been reported and the data analyzed in the light of nonequilibrium thermodynamics. The linear phenomenological equations have been found to be valid. Study of the directional dependence of phenomenological coefficients has revealed the anisotropic character of the membrane. Efficiency of energy conversion for both electro-osmosis and streaming potential has been calculated and the results have been analyzed in the light of thermodynamic theories.
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    Dipole moments in oriented poly(ethylene terephthalate) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2079-2090 
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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: Dielectric experiments were performed in the β temperature region on poly(ethylene terephthalate) films of different draw ratios. The proportion of various conformations, crystallinity, and orientation were estimated from infrared, density, and birefringence measurements. The dielectric relaxation strength was determined from the Cole-Cole plot of the dielectric constants over a wide frequency range. An attempt was made to modify the Fröhlich equation, originally for isotropic systems, for application to systems of oriented dipoles. When the experimental data are analyzed through this modified equation, it is evident that the changes in the dielectric constants of PET with stretching could not be accounted for by improvement in the alignment of chain molecules alone. The relative abundance of the trans conformation, both crystalline and amorphous, and gauche conformation appears to be a factor which cannot be ignored. The calculation indicates that the dipole moment seems to be greater in the trans conformation than in the gauche conformation.
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    The crystal structure of poly(tetramethylene terephthalate) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2173-2181 
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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 unit cell of poly(tetramethylene terephthalate) is triclinic with parameters a = 5.96 Å, b = 4.83 Å, c (fiber axis) = 11.62 Å, α = 115.2. β = 99.9, and γ = 111.3°; space group P1, calculated crystalline density 1.41 g/cc. The plane of the benzene ring is found to be inclined by about 15° from the fiber axis, contributing to a shortening of the fiber period as compared to the period expected on the basis of analogy with other members of the terephthalate ester series. The remaining shortening of the fiber period occurs in the —O—°CH2—°CH2—segment of the chain. No abnormally short distances among neighboring chain atoms were observed. A typical texture pattern was found in specimens of this polymer that were cold rolled and subsequently annealed. In this texture the c axis of the unit cell is highly oriented in the rolling direction; the a and b axes of the unit cell are oriented preferentially so that the terephthalate residue lies as close as possible to the plane of rolling.
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    Morphology of as-polymerized polyacrylonitrile prepared by radiation-induced heterogeneous polymerization in bulk (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2241-2245 
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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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    Dynamic mechanical and dielectric properties of phosphonylated polypentenamers and their hydrogenated derivatives (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 59-80 
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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: Dynamic mechanical and dielectric properties of substituted polypentenamers with phosphonate side groups and their hydrogenated derivatives have been studied. Methyl esters, acids, and salts were investigated at two concentrations, 6.5 and 11.1 mole percent. In the unhydrogenated derivatives, one principal relaxation, labeled β, is observed mechanically in the temperature range from -160 to 100°C. This β relaxation arises from micro-Brownian segmental motion accompanying the glass transition. Its temperature is substantially affected by the substituent concentration while its breadth is affected by the chemical nature of the substituent. An extended “rubbery plateau” region exists in the acid and salt derivatives. The dielectric results generally reinforce the mechanical assignments. In the hydrogenated derivatives, three relaxations labeled α, β, and γ in order of decreasing temperature occur mechanically in this temperature range. The temperatures at which the α and β relaxations occur depend greatly on the chemical nature of the substituents, the substituent concentration, and the thermal history of the sample; while the γ relaxation appears to be independent of these variables. Suggested assignments for the relaxations observed in these polymers, based on the dual glass transition theory of Boyer for semicrystalline polymers, have been proposed. The dielectric results are consistent with the proposed assignments.
    Additional Material: 10 Ill.
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    Intrinsic viscosity and friction coefficient of polymer molecules in solution: Porous sphere model (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 245-263 
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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 intrinsic viscosity [η] and the translational friction coefficient f of polymer molecules in solution are calculated on the basis of the porous sphere model. The only information needed to predict [η] and f is the polymer molecular weight, the radius of gyration in the solvent, and the permeability as a function of position in the “porous sphere.” For systems for which this information is available there is satisfactory agreement between predicated and directly measured values of [η] and f. No adjustment of parameters is required. The influence of solvent quality is more complex than is suggested by the experimentally verified Flory-Fox relation for [η]; the simple form of this relation stems from the fact that two quite large effects of solvent quality approximately compensate each other. The complete flow pattern of the solvent around and through the polymer coil can be calculated. Contrary to what is usually believed the solvent flow in the polymer coil is not “effectively blocked”, even at the center. The connection between the present treatment and the microscopic theory of Kirkwood and Riseman is investigated.
    Additional Material: 8 Ill.
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    Nonstationary diffusion of polystyrenes through a cellophane membrane (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 297-318 
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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: Diffusion of five polystyrene fractions at various concentrations in toluene through cellophane membranes has been observed. The results have been used to calculate friction coefficients between solvent and solute, and between solute and membrane. The calculation requires measurement of the diffusion coefficient and the reflection coefficient of the solute, of the permeability for the solvent, of the pore volume of the membrane, and of the partition coefficient of the solute between membrane and solvent. By comparing the friction coefficient between solvent and solute in the membrane with this coefficient in free solution, the tortuosity factor and the pore diameter of the membrane can be estimated. The dependence of the friction coefficients on molecular weight M2 of the solute is determined. For large values of M2, the friction between solute and solvent is the determining factor. The friction coefficient between solute and solvent increases more strongly with M2 in the membrane than in free solution owing to an entrance effect for the permeating solute at the interface.
    Additional Material: 9 Ill.
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    Chain folding and cross-sectional area per chain (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 371-374 
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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.1978.180160216
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    Chain rupture and tensile deformation of polymers (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 485-500 
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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: Macromolecular chain rupture occurring during tensile deformation of semicrystalline polymers has been investigated by measuring changes in the viscosity-average molecular weight. When interpreted in terms of a random-scission scheme, the observed changes in molecular weight correspond to chain rupture concentrations β ≈ 1018/cm3 for high strength nylon and poly(ethylene terephthalate) fibers. Polypropylene fibers and isotropic samples of polyethylene, polypropylene, and nylon 6 had β ≈ 1016/cm3. The effects of stretching environment and thermal and mechanical history were noted. In all cases, the present study indicated bond rupture concentrations about 10 times larger than those obtained from electron spin resonance (ESR) experiments. The relation between viscometry, ESR, and infrared (IR) estimates of bond rupture and their relevance to mechanical properties are considered.
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    Importance of the metal-polymer interface for the piezoelectricity of polyvinylidene fluoride (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 529-543 
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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 piezoelectric effect in films of polyvinylidene fluoride (PVF2) is investigated using optical and ultrasonic detection techniques. From the analysis of the vibrational resonance frequencies of a freely suspended film we conclude that the polarization induced in PVF2 is inhomogeneous across the volume of the sample. Poling the foils in a sandwich configuration or using blocking electrodes, we can clearly demonstrate that the piezoelectric effect in PVF2 originates from the positive metal electrode. Monitoring the time dependence of the piezoelectric effect during the poling process, a fast and slow component are observed. Using a blocking electrode, however, the same dynamical poling behavior is found only if the contacting metal electrode is positive. In view of these observations, which clearly demonstrate the importance of the metal-polymer interface for the strong piezoelectricity of PVF2, the existing theoretical models, based on the bulk properties of the polymer, are critically reviewed.
    Additional Material: 10 Ill.
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    Properties of aqueous salt solutions of poly(ethylene oxide): Thermodynamic quantities based on viscosity and other measurements (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 501-511 
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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 previous study of poly(ethylene oxide) (PEO) in aqueous salt solutions has been extended to incorporate cloud-point measurements in potassium thiocyanate solutions (salt concentration range 3.3-3.8M where salting out occurs) and, particularly, viscosity measurements. A few osmoticpressure measurements were made and molecular weights (∼2 × 104) from gel-permeation chromatography (GPC) compared. The theta temperature for PEO in water from cloud points was found to be 369 ± 3°K. An empirical linear relation has been found for sodium and potassium salts between the finite change of theta temperatures with change in ionic strength, δθ/δI, and (v3 - v̄3), the difference between the molar van der Waals volume and the partial molar volume of the salt. Values of the Huggins constant k′ are less than 0.5 for PEO in pure water at 303.2°K, indicating a good solvent, whereas in salt solutions they vary from 0.59 to 1.14 in nontheta solvents. They and other findings are attributed to binding of salt to the polymer and to water structure breaking. Kraemer's constants k″ were also determined: k′ - k″ = 0.5 for PEO in pure water, and for aqueous salt solutions of PEO, k′ - k″ = 0.666 at 298°K. Values of K0(= M-1/2[η]θ) with M = 2 × 104 were found to very with salt type (valence) - mean values of 103 K0/dlg-1 with number of observations in brackets are 1:1, 1.19 (2); 1:2, 1.45 (3); 2:2, 1.75 (3). Unperturbed dimensions 〈r2〉01/2 vary from 11.0 to 12.6 nm from 1:1 to 2:2 salts. Values of the characteristic ratio Cn, the steric parameter σ, and the enthalpy and entropy of dilution parameters χH and χS have also been calculated.
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    Ion clustering in a butadiene, styrene, 4-vinylpyridine terpolymer crosslinked by coordination with iron(III) chloride (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 569-581 
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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 butadiene, styrene, 4-vinylpyridine terpolymer has been crosslinked by coordination of the pyridine groups with iron chloride. The distribution and structure of the iron complexes have been studied. Electron microscopy has given evidence of clustering of the iron complexes. The size distribution of these clusters has been evaluated by small-angle x-ray and neutron scattering. Mössbauer spectroscopy and magnetization measurements have shown the presence of three different kinds of iron complexes: (a) complexes with a speromagnetic structure in the clusters previously found, (b) dimers with antiferromagnetic coupling, and (c) quasi-isolated complexes with weak ferromagnetic coupling. The percentages of these different iron complexes have been measured.
    Additional Material: 10 Ill.
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    Dielectric properties of maleic acid-ethylene copolymer in salt-free aqueous solutions (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 641-651 
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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 behavior of maleic acid-ethylene copolymer solutions has been investigated at different polymer concentrations and two degrees of neutralization α′. It is shown that this behavior is analogous to that of ordinary polyacids. Also the experimental data can be explained in terms of the van der Touw-Mandel theory, but at low α′ a possible contribution from motion of negative charges (in turn related to bound proton fluctuations) has to be taken into account. The dielectric results suggest that the formation of intramolecular hydrogen bonds has an influence on the change of the average dimensions of the chain with increasing α′. This seems to be confirmed by viscosity data.
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    Influence of pressure and chemical structure on the thermal conductivity of vitreous poly(alkyl methacrylates). II. Relation to free volume (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 689-694 
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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 quantitative model for the pressure dependence of the thermal conductivity K in glassy polymers is presented. By extending the hole theory of liquids to temperatures below the glass transition temperature, an equation of state is obtained and an expression for the pressure dependence of the thermal conductivity is then formulated from a consideration of the anharmonicity associated with the segmental vibrations. The resulting equation ΔK/K = γGf0[1-exp(-p/B*)], where γG is the Grüneisen parameter, f0 is the fractional free volume, and B* = kTg/V0, is compared with experimental results for the poly(alkyl methacrylates).
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    Electrically conductive elastomeric TCNQ complexes (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 717-723 
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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: New elastomeric ionene polymers containing poly(tetramethylene oxide) chain units were synthesized. The electrical conductivities of the salts of these polymers with (the anion radical of tetracyanoquinodimethane) (simple salt) and with neutral TCNQ added (doped salt) were investigated. Each cationic site in the polycationic polymer chain is separated by a long elastic chain unit, and consequently, moieties in the simple salt are expected to be well separated. Unexpectedly, doping with neutral TCNQ caused a marked decrease in the specific resistivity and the activation energy. Although the simple salt is elastic, doping with neutral TCNQ increased the stiffness of the material. The room-temperature specific resistivity of the doped salts was in the range of 103 to 104 Ω cm. The marked change of electrical and mechanical properties brought about by doping with neutral TCNQ is discussed in terms of a structural model in which phase separation of the ionic part from the nonionic elastic units has been assumed.
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    Thermodynamic properties of phenol-formaldehyde resin (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 759-766 
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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: Characterization measurements of a commercial phenol-formaldehyde resin prepared from constituents including phenol and formaldehyde in the molar ratio 1:1.33 are reported. The measurements consist of (1) the linear thermal expansion coefficient between approximately 85 and 270°K; (2) the specific heat capacity between approximately 6 and 100°K; (3) the Young's modulus at room temperature. A critical examination of the data reveals that: (1) the vibrational behavior is predominantly that of a three-dimensional assembly; (2) as far as data available from other sources permit an assessment to be made, the principle of additivity appears to be applicable to the specific heat capacity between approximately 50 and 100°K; and (3) the data lie near the limit of an empirical relationship observed between the Young's modulus and linear thermal expansion coefficient of other polymers.
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    Effect of ozone on creep of vulcanizates (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 813-820 
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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-service secondary creep rates of natural rubber (NR) vulcanizates at ambient temperature are known to be low. However, in tests on thin strips of NR vulcanizates in tension, secondary creep at rates of up to 120%/week were observed. From an examination of the effect of antioxidants, antiozonants, waxes, and specimen thickness it was shown that the anomalous creep was due to ozone attack on the vulcanizate, which only becomes serious in tests on thin strips in tension.
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    Solubility of carbon dioxide in cellulose acetate at elevated pressures (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 735-751 
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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 solubility of carbon dioxide in symmetric (dense) cellulose 2.4-acetate has been measured at temperatures from 0 to 70°C and pressures up to 45 atm. The polymer samples were prepared by slowly drying asymmetric reverse osmosis membranes. The solubility isotherms can be described satisfactorily up to 60°C by the “dual-sorption” model for glassy polymers. The model cannot represent the experimental data above 60°C, possibly because of a second-order transition in the polymer between 60 and 70°C. An analysis of the dual-sorption parameters and of the heats of solution and “hole filling” suggests that the polymer samples contained a relatively large volume of microcavities. Gas solution appears to occur predominantly in microcavities, a large fraction of the penetrant moleculers being immobilized or partially immobilized. The solubilities obtained in this work are compared with similar data computed from time-lag measurements of other investigators, and the validity of the dual-sorption model is examined for the present case.
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    An upper limit to the glass temperature of linear polyethylene as determined by high-field carbon-13 fourier transform nuclear magnetic resonance (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1135-1138 
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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: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1978.180160618
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    Raman spectroscopic method for determining the crystallinity of polyethylene (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1181-1193 
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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 Raman spectrum of partially crystalline polyethylene can be described as a superposition of three components, which originate from the orthorhombic crystalline phase, a meltlike amorphous phase, and a disordered phase of anisotropic nature, where chains are stretched but have lost their lateral order. The mass fractions involved in the three phases can be derived directly from the integral intensities of characteristic bands without an additional calibration procedure. A comparison of the results obtained for a variety of samples shows agreement with the crystallinities derived from the density, and the small-angle and wide-angle x-ray diagrams. Data indicate that the disordered anisotropic phase is located at a transition zone between crystalline and amorphous layers. Application of the method in a temperature-dependence experiment permits a detailed examination of partial melting.
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    Effect of polymorphism on the C—H stretching region of the infrared spectrum of polyethylene (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1253-1260 
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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 complex fine structure in the C—H stretching region of the infrared spectrum of deformed polyethylene single crystals is reported. The deformed crystals are shown to be transformed from the orthorhombic crystal form to a monoclinic structure. The previously deduced C2/m monoclinic structure does not account for the appearance of the new bands. An alternative but similar monoclinic structure is proposed. The symmetry of this structure is consistent with the Fermi resonance interactions required for the observation of these bands.
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    The thermoelastic effect in glassy polymers (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1277-1290 
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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 thermoelastic effect has been measured in compression on four glassy polymers; namely, polystyrene, poly(methyl methacrylate), polycarbonate, and epoxy resin. Quantitative results have been obtained for the first time on three of these polymers. It has been shown that by paying attention to specimen geometry and instrumentation results can be obtained to a high degree of accuracy (better than ±1.5% on a given set of measurements). The polymers are shown to obey the classical Thompson equation for thermoelasticity in solids over the temperature range studied (ca. 220-350°K). By inference such materials can be expected to behave classically in general. The results have been used, as first suggested by Trainor and Haward, to obtain values for the linear thermal expansion coefficient and the values so obtained are shown to be in excellent agreement, in general, with literature values obtained by more conventional methods. Results are given for a range of stress from 5 MN m-2 to between 25 and 50 MN m-2 according to ambient temperature. The method affords a measurement of parameters, in particular, linear thermal expansion coefficient. Values of specific heat for the four plastics have been measured by differential scanning calorimetry and the results compared with published data.
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    The statistics of chain sectioning experiments on cellulose fibers (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1-7 
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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 has been suggested that transverse sectioning of natural cellulose fibers can be used to test ideas about microfibril structure. This proposal has been examined theoretically and numerical calculations of the weight-distribution curve of sectioned chains are given for several different models. These calculations illustrate the effects that different types of chain folding have on the sectioned size distribution. The difficulties involved in the practical execution of this type of experiment are discussed and it is concluded that fiber-sectioning experiments described in the literature do not disprove the folded-chain hypothesis.
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    Non-Newtonian behavior in steady flow over the range from the lower to the upper Newtonian region for polystyrene solution (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 35-41 
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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: Graessley's entanglement theory of viscosity modified by a frictional viscosity parameter ηfric is applied to data on solutions of polystyrene in diethyl phthalate at various concentrations and different temperatures. All the data modified give a single master curve over the entire rates of shear, as obtained previously with polydimethyl-siloxanes of various molecular weights and their solutions of various concentrations. The zero-shear viscosity η0, the upper Newtonian viscosity η∞, and ηfric are compared. Three activation energies for flow are estimated from η0, η∞ and ηfric, and are compared. The result suggests that the flow behavior in the upper Newtonian region is much more dependent on ηfric than on the entanglement viscosity term ηent. The ratio of zero-shear entanglement viscosity ηent,0 to ηfric can be used as a measure of the non-Newtonian behavior of the present solutions. Non-Newtonian behavior of the investigated polymer solution becomes appreciable at about ηent,0/ηfric = 2.5. These results are in agreement with previous conclusions based on comparison between η0, η∞ and ηfric for polydimethyl-siloxanes and their solutions.
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    Rheological effects of structure formation in polymer meltsPresented in part as a short communication at the International Symposium on Macromolecules, Aberdeen, 1973. (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 95-112 
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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 viscosity of a number of molten polystyrenes and polypropylenes obtained in various ways from solutions is found to be very strongly dependent on the history of dissolution of the polymer (the concentration of the solution and the “goodness” of the solvent), and on the presence of certain organic oligomeric compounds in very small amounts. The viscosity of the melt may be orders of magnitude less than that of the original samples. The present discussion of these effects is based on the concept of structure formation in amorphous polymers. The structure formed on the solution appears to be very stable with respect to heating and prolonged standing at elevated temperature, although it (and hence the viscosity) strongly depends on the initial concentration of the solution and the nature of the solvent. The role played by additives, present in amounts of small fractions of a percent, is accounted for by the fact that the melt retains the microheterogeneity of the medium. The material moves without its micromosaic structure being disturbed, and the role of the additives is reduced to surface (with respect to structural elements) phenomena.
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    Effect of hydrogen bonding and ionic aggregation on the melt rheology of an ethylene-methacrylic acid copolymer and its sodium salt (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 143-157 
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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 study has been made of the dynamic and steady shear melt theology of an ethylene-methacrylic acid copolymer, its methyl ester, and 70% neutralized sodium salt. Measurements were made with a Rheometrics mechanical spectrometer using the eccentric rotating disks and cone-and-plate geometries over a temperature range of 120-180°C and frequency range of 10-3 to 102 rad/sec. Correspondence was found between steady shear viscosity and the complex dynamic viscosity for the ester and acid materials. Over the temperature and frequency range studied the time-temperature superposition principle was applicable to G′ data for each of the derivatives and a supermaster curve could be constructed from the three individual master curves. Time-temperature superposition was found not applicable to G″ data for the sodium salt. Differences in rheological response between the ester and acid copolymers are explained by differences in Tg. It is suggested that differences in temperature shifts ΔT required to produce G′ superposition between the three derivatives reflect differences in ΔH for interchain interactions. A mechanism for flow of clustered ionomers is consisting of an initiation and a propagation step.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1978.180160113
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    Theory of second-order Raman scattering from a zigzag chain with application to polyethylene (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 189-200 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The extinction coefficient for acoustic branch, second-order (two-phonon) Raman scattering from a zigzag chain, using force constants and polarizabilities appropriate to polyethylene is computed. As a consequence of the computation, we propose identification of a line at 890 cm-1 in the published Raman spectrum of polyethylene as a second-order Raman line.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1978.180160201
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    Intramolecular excimer formation in macromolecules. I. Energy migration and excimer formation in copolymers exhibiting nearest-neighbor excimer interactions (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 231-244 
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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: Energy migration and intramolecular excimer formation have been studied in a series of copolymers comprising 1-vinylnaphthalene, 2-vinylnaphthalene, and styrene with methyl methacrylate. The technique of fluorescence depolarization was used to characterize energy migration in glassy solutions of the copolymers. The extent of energy migration in these copolymers is determined by the mean sequence length of aromatic species l̄a. Assuming that excimer formation occurs as a result of nearest-neighbor interactions, the concentration of excimer sites in the macromolecule will be proportional to the fraction of links between aromatic species faa. It is proposed that these sites are populated via energy migration from the site of absorption. Proportionality between the ratio of excimer to monomer emission intensities and the function l̄a·faa was predicted. Good agreement with this relationship was obtained in each of the copolymer systems studied. Reactivity ratios of methyl methacrylate (rm) in copolymerization at 70°C with the aromatic monomers (ra) were determined as: 1-vinylnaphthalene - rm = 0.43, ra = 1.71: 2-vinylnaphthalene - rm = 0.37, ra = 4.46; styrene-rm = 0.45, ra = 0.58.
    Additional Material: 6 Ill.
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    Crystal and amorphous orientation behavior of poly(chlorotrifluoroethylene) films in relation to crystalline superstructure (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 271-288 
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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 relationship between the crystalline superstructure of polymer films and molecular orientation was studied in cold-drawn poly(chlorotrifluoroethylene) films by wide-angle x-ray diffraction, birefringence, and depolarized light scattering. By changing crystallization conditions, specimens with almost identical crystallinity but different crystalline superstructures were obtained; i.e., (1) a structure having a random array of crystallites, (2) a superstructure having a rod-like orientation correlation of the chains (a prespherulitic and sheaf-like superstructure), and (3) spherulitic superstructure. Upon stretching of specimens, crystallites initially randomly arranged orient with their chain axes along the stretching direction in accord with simple affine deformation. The amorphous chains also orient along the stretching direction. The orientation behavior of the specimens having the rod-like superstructure is similar to that of the specimens with a random array of crystallites, indicating that the interaction between the crystallites in the superstructure is relatively weak. The molecular orientation behavior of the spherulitic specimens, however, strongly deviates from simple affine deformation owing to strong interaction of the crystallites in the spherulites. The deviation can be interpreted in terms of spherulite deformation and of internal reorientation of chains within deformed spherulites.
    Additional Material: 16 Ill.
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    Proton NMR study of molecular motion in polydimethylsiloxane (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 341-347 
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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 spin-lattice relaxation times T1 were measured for two samples of polydimethylsiloxane (PDMS), one with weight-average molecular weight Mw = 77,400 and the other with Mw = 609,000. Two T1 minima and a T1 discontinuity were observed for each compound. The high-temperature T1 minima were attributed to a stretching and flexing motion of the PDMS chain. Quantitative comparison of the relaxation data with a theoretical model developed for this motion allowed the activation energy, 2.3 kcal/mole, and the maximum angular displacement of the methyl group symmetry axis to be determined. The latter was found to be 31°, independent of sample molecular weight. The low-temperature minima were ascribed to methyl reorientation with an activation energy of 1.6 kcal/mole. The T1 discontinuities were attributed to melting and allowed the degree of crystallinity to be estimated.
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    On the location of chain ends in polyethylene single crystals (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 375-377 
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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: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1978.180160217
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    Collapse of pyramidal polyethylene crystals (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 395-405 
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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: An assessment of the possible collapse mechanisms for solution-grown pyramidal polymer crystals is made, taking into account electron microscope observations and the mechanics of the loading situation. That comprehensive collapse always occurs is shown not to be as self-evident as is normally assumed, even though the more exacting criteria for its establishment are indeed usually met. Bending of lamellar crystals is found to account for many observations, although an alternative means of tilting molecular chains, the “differential shear tilt model” is also considered.
    Additional Material: 9 Ill.
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    Orientation and molecular dynamics in uniaxial polymers. I. Theory of fluorescence polarization (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 443-455 
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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 theory of polarized fluorescence is developed for uniaxial physical systems in which micro-Brownian motion is not negligible. All experimental information is shown to reduce, with reasonable assumptions, to four quantities characterizing molecular orientation and reorientational molecular mobility. The geometrical properties of the mobility in uniaxial systems are studied and methods are given for correcting for the effects of the birefringence and for a possible delocalization of the fluorescence transition moments.
    Additional Material: 5 Ill.
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    Radiation chemistry of polyethylene. XIV. Allyl radical decay kinetics in different types of polyethyleneFor Part XIII of this series see ref. 1. (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 467-484 
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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 decay kinetics of the chain allyl free radical has been studied in the following morphological forms of polyethylene (PE): Marlex bulk film, hydrogenated PE, and extended-chain PE. Coupled with previous work on single-crystalline PE it can be seen that the decay rate is greater the more amorphous the sample. In the Marlex bulk film and hydrogenated PE the decay can be interpreted in terms of a simultaneous fast and slow decay process by means of our Q-function equation, but with rising temperature the decay approximates a single rate process. With extended-chain PE the allyl decay rate does not become appreciable until the melting range is approached. The fraction of allyl radicals decaying by the slow process is 2 to 10 times greater than the fraction of fast decaying radicals. The ratio of the fast decay rate constant to that of the slow rate constant is greater for the bulk Marlex film than for the hydrogenated PE. All ratios decrease with rising temperature. For times up to about 150 min the allyl decay in the extended-chain PE accurately follows a single second-order decay law with a time-independent diffusion controlled reaction rate constant.
    Additional Material: 14 Ill.
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    Stress-induced diffusion of macromolecules (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 565-565 
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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
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    URL: http://dx.doi.org/10.1002/pol.1978.180160318
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    Dynamics of macromolecular chains. I. Theory of motions on a tetrahedral lattice (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 667-674 
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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 bond correlation function for a macromolecular model chain on a tetrahedral lattice is derived by considering elementary three-bond and four-bond motions. The method of calculation allows the conformational structure of the chain to be involved in the final equations. Moreover, when the three-bond motions are considered alone, no linearization assumption is required; hence, the theory is valid at short times.
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    Incompatibility in polymer solutions: Light scattering of two polymers in a single solvent (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 727-736 
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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 fluctuation theory of light scattering for moderately concentrated polymer solutions is extended in a phenomenological fashion to include angle-dependent terms up to sin2 (θ/2). The treatment is based on an uncoupling of the center of mass and segment contributions to the free enthalpy. In particular, equations are derived for three-component mixtures containing two polymer and one solvent component. These are applied near the region of incompatibility. The results are compared with Debye's theory of critical opalescence. It is found that the Debye l parameter should be of the order of magnitude of the radii of gyration of the polymer molecules. This is confirmed by some experiments.
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    Characterization of selectively degraded poly(ethylene terephthalate) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 765-774 
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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: To investigate the morphology of unoriented poly(ethylene terephthalate) (PET) films and the selective character of the aminolysis of PET, 67% crystalline polymer samples were degraded with 40% aqueous methylamine at room temperature. The aminolyzed PET samples were subjected to gel permeation chromatography (GPC), viscometry, electron microscopy, and small-angle x-ray diffraction (SAXD). Weight loss and density crystallinity measurements were also made.After 24 hr of aminolysis, the amorphous regions and chain folds were completely removed. The long molecular chains in the semi-crystalline polymer were reduced to monodisperse rods having a molecular weight of 1,800. The corresponding lamellar thickness was calculated to be 101 Å, consistent with the x-ray diffraction and electron microscope (EM) measurements. The EM photographs of “stripped” crystals show the lamellar structure previously found for other selectively degraded polymeric materials. The weight of crystalline debris remaining was consistent with the initial crystallinity. After degradation the crystallinity as determined by density was 96%.
    Additional Material: 5 Ill.
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    Crystal deformation in aromatic polyesters (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 799-813 
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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 study has been carried out of the changes in the x-ray diffraction patterns which occur when oriented fibers or tapes of poly(trimethylene terephthalate) (3GT) and poly-(tetramethylene terephthalate) (4GT) are subjected to mechanical tensile stress. Although the polymers show very different behavior in detail, in both cases comparatively large reversible lattice strains are observed (∼ several %). The diffraction pattern of 3GT changes monotonically with increasing macroscopic strain, suggesting that the lattice responds immediately to the applied stress, and deforms as though it were a coiled spring. In 4GT, on the other hand, there is no detectable change in the x-ray diffraction pattern at low macroscopic strains, i.e., low values of the applied stress. At higher stresses, changes in the pattern occur which suggest a definite change in the crystal structure. Finally at the highest values of applied stress, the lattice deformations cease to increase. A preliminary discussion is presented of the relationship of these x-ray diffraction results to the mechanical stress-strain behavior.
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    Gas diffusion in glassy polymers (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 859-861 
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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
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    URL: http://dx.doi.org/10.1002/pol.1975.180130418
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    Statistical mechanics of two-dimensional wormlike chains (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 871-871 
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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
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130421
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    Basic modes of three-dimensional polymer crystal associations: Interlocked single crystals and crystal halves (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 909-927 
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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: Tridimensional associations of lamellar polymer single crystals, grown from dilute solutions, are described as derived from their sedimentation patterns. These associations include interlocked crystals and decorating crystal halves. The origin of these crystals and their mutual orientation are discussed and tentatively interpreted by specific interactions between the fold surface and the crystallizing chains.
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    Mechanochemical reaction of polymers by ultrasonic irradiation. I. Mechanochemical reaction in mixtures of polystyrene, styrene, and cyclohexanone (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 953-960 
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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: Mechanical degradation and mechanochemical polymerization in polystyrene-styrene-cyclohexanone mixtures have been studied by ultrasonic irradiation at 60°C. The number of fresh polymer chains after the degradation is 2 × 10-5 mole l-1 hr-1. The rate equations for mechanical scission and mechanochemical polymerization have been deduced. The rate equation for mechanical scission was found to be in agreement with the expression of a previous paper. In addition, the rate equation for mechanochemical polymerization is not essentially different from that for the general radical polymerization in the presence of solvents. The kinetic chain length for polymeric free radicals in the polymerization process has been calculated. The mechanochemical polymerization of styrene was initiated by only one of the two kinds of end radicals after mechanical scission of polystyrene. The molecular weight distributions of the samples after the degradation and the polymerization have been compared and discussed.
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    Electrospray mass spectroscopy of macromolecule degradation in the electrospray (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 985-995 
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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: As previously shown, by electrospraying dilute polystyrene (PS) solutions gas phase macroions can be produced. Degradation of the PS in the electrospray was tested by collecting the electrosprayed PS and measuring its number-average molecular weight osmotically. About 10% degradation was observed when using negative voltages, but the degradation was considerably reduced when the electrospray occurred in the presence of SF6 gas. No degradation was apparent in the case of positive sprays. A quantitative analysis of the results was made difficult by a small less of PS in the nitrogen gas stream and by diffusion of lighter ions to the vertical wall of the spray chamber. The latter effect did not occur at the highest spray voltage used, -24 kV.
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    Effects of annealing and isothermal crystallization upon crystalline forms of poly(vinylidene fluoride) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1071-1083 
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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(vinylidene fluoride) exists in three crystalline forms. Optimum conditions for preparing form III were established by infrared spectroscopy, differential scanning calorimetry, and x-ray diffraction measurements. Form III is easily obtained by annealing mats of solution-grown crystals of form II at 175-185°C and is also preferentially formed by isothermal crystallization from the melt between 165 and 175°C. Below 165° crystallization of form II is favored. The melting point of form III is higher than that of form II.
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    Measured and calculated solubility of polymers in mixed solvents: Monotony and cosolvencyDedicated to Professor G. V. Schulz in honor of his 70th birthday. (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1115-1132 
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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 a study of two ternary systems, 4-heptanon-1-chlorobutane-poly(methyl methacrylate) and 2-butanol-1-chlorobutane-poly(methyl methacrylate), differing only in one component of the mixed solvent, two types of demixing behavior are demonstrated: i.e., a monotone change with composition of the mixed solvent (monotony), of which the first system is a good example, and the synergistic behavior (cosolvency) exhibited by the second system. The situation can be seen most clearly from the binodal edges (precipitation thresholds as a function of solvent composition) which were constructed from various types of sections through the binodal surface of the systems.In order to compare experimental results with theoretical calculations, we first characterized the binary subsystems. The polymer solutions, representing conventional (endothermal) theta systems, were investigated by light scattering and cloud point measurements. For the cosolvent 2-butanol-1-chlorobutane the necessary thermodynamic information was accessible from vapor pressure measurements. Applying the Prigogine-Patterson theory to the polymer solutions and using the single-liquid approximation of Scott for the ternary systems yielded theoretical binodal edges in good agreement with experiment except for the branch belonging to mixed solvents rich in 2-butanol. This finding is explained by an abnormal amplification of preferential solvation effects due to the existence of an association equilibrium of the alcohol via hydrogen bonds.
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    Tensile properties of ultradrawn polyethylene (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1177-1186 
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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: High-density polyethylene filaments prepared by a solid-state deformation in an Instron capillary rheometer show unusually high crystal orientation, chain extension, axial modulus, and ultimate tensile strength. The Young's modulus and ultimate tensile strength have been determined from stress-strain curves. Gripping of this high modulus polyethylene has been a problem heretofore, but the measurement of ultimate tensile strength has now been made feasible by a special gripping procedure. Tensile moduli show an increase with sample preparation temperature and pressure. Values as high as 6.7 × 1011 dyne/cm2 are obtained from samples extruded at 134°C and 2400 atm and tested at a strain rate of 3.3 × 10-4 sec-1. The effect of strain rate and frequency on modulus has also been evaluated by a combination of stress-strain data and dynamic tension plus sonic measurements over nine decades of time.
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    ESR evidence for main-chain scission produced by mechanical fracture of polymers at low temperature (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1233-1245 
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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: ESR spectra have been observed from several polymers (polyethylene, polypropylene, polymethylmethacrylate, polytetrafluoroethylene, and polybutadiene) which were mechanically fractured in vacuum at 77°K. The spectra permit identification of the free radicals produced in chain scission. It has been demonstrated for the polymers of the type such as polypropylene and poly(methyl methacrylate), that the mechanical fracture produces two different scission radicals in pairs, namely, The results indicate convincingly that microscopic scission of polymer chains is caused by macroscopic destruction of polymeric material. The critical molecular size for mechanical rupture of polyethylene chains was experimentally determined to be a degree of polymerization between 70 and 100. This size agrees fairly well with the value predicted from a theoretical model.
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    Photoinduced charge transfer at the poly(N-vinylcarbazole) - tin oxide interface (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1275-1284 
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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: An investigation of steady state and transient photoconductivity in films of poly-(N-vinylcarbazole) equipped with SnO2 and metal electrodes is described. The studies have shown that photoinduced charge transfer, leading to hole injection into the polymer film, takes place with photons of energy greater than 1.8-1.9 eV. Dark conductivity studies on samples equipped with grounded guard rings have shown that carriers originating in the bulk of the polymer film dominate the dark current when the metal electrode is at negative bias. Thermionic hole emission from the SnO2 electrode is not observed.
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    Nucleation and growth of crazes in amorphous polychlorotrifluoroethylene in liquid nitrogen (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1315-1331 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The density of mature crazes initially increases linearly with stress and then more rapidly at higher stresses. Once the crazes become observable then density was independent of time. The lowest stress at which an appreciable density of crazes was produced corresponds to the proportional limit. The average velocity of mature crazes was constant for a given stress and varied exponentially with the stress. The velocity depended on stress in the same way that the post-yield point stress depended on strain rate, whereas the yield point varied differently being a nonlinear function of the logarithm of the strain rate.The density of crazes was quantitatively related to the concentration of surface defects at which the crazes nucleate. The craze velocity was directly related to the diffusion coefficient of N2 into the polymer. The analysis indicates that bulk diffusion of the N2 governs the craze velocity and that plasticization of the tip of the craze is most important for the nucleation and growth of a craze in PCTFE.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130705
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    Dielectric relaxation studies in poly(hexamethylenesebacate) (HMS), poly(2-methyl-2-ethyl propylenesebacate) (MEPS), poly(2,5-dimethylbutylene sebacate) (DBS), and block copolymers of HMS and MEPS (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1365-1376 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The α and β dielectric relaxations of poly(hexamethylenesebacate) (HMS), poly(2-methyl-2-ethyl propylenesebacate) (MEPS), poly(1,4- dimethylbutylene sebacate) (DBS) and block copolymers of HMS and MEPS have been studied. The α relaxation is amenable to a W.L.F. analysis and is associated with the glass transition of the polymers. This relaxation moves to higher temperatures with increasing HMS content in HMS/MEPS block copolymers. All the polymers studied exhibit psuedo-activation energies of ∼32 kcal/mole at the glass transition. It is concluded that because the superposition principle is operative in the block copolymers, the glass transition must be very similar in both polymers and morphology and degree of crystallinity do not greatly affect this transition. The β relaxation which has been associated with segmental relaxation of polymethylene segments in polymers is also shown to be a function of HMS/MEPS block copolymer composition and chemical structure. This relaxation takes place at lower temperatures with increased HMS content in the blocks and also shifts to lower temperatures with side chain substitution adjacent to the carbonyl group in the polymer. It is concluded that the β relaxation takes place in the amorphous and crystalline regions of the polymer.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130709
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  • 92
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    “Shish kebab” structures formed on needle-like polyoxymethylene crystals (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1461-1465 
    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.1975.180130715
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  • 93
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    Phase transition in dilute solution of poly(γ-benzyl-L-glutamate) in dichloromethane at a low temperature (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1491-1499 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric constant of solutions of poly(γ-benzyl-L-glutamate) (PBLG) in dichloromethane shows a jump near 195°K, irrespective of frequency. Therefore, the discontinuity is not a dispersion phenomenon but a phase transition in the thermodynamic sense. The transition temperature is independent of the concentration in the range from 0.01 to 10% by weight, but it increases linearly with the logarithm of the molecular weight of PBLG. The height of the jump depends strongly on frequency, concentration, and molecular weight. The viscosity also changes abruptly at 195°K. These results suggest that the PBLG molecule forms a cluster like a liquid crystal or is in a random coil state below the transition point.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130803
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  • 94
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    On the structure of glassy polymers. II. Small-angle x-ray scattering from poly(methyl methacrylate) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1481-1490 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The small-angle x-ray scattering (SAXS) from glassy poly(methyl methacrylate) has been measured using a Bonse-Hart system. The data cover the angular range (2θ) between 20 sec and 2 deg. After correcting for absorption, background, and beam divergence, the data have been placed on an absolute basis by comparison with the scattering from a standard silica suspension. The corrected absolute intensity decreases strongly with increasing angle over the range between 20 sec and 30 min, and is nearly constant between 30 min and 2 deg. The magnitude of the scattering in the constant range, 0.6 (electrons)2 Å-3, is within a factor of 1.5 of the value predicted by the thermodynamic fluctuation theory for fluids applied at the glass transition temperature. The increase in intensity at smaller angles cannot be described by structures on the scale of the nodules reported in highly isotactic PMMA (150-200 Å), but can be well represented by small concentrations of heterogeneities, several thousand angstrom units in size, superimposed on the thermal density fluctuations frozen-in at the glass transition. The bulk structure of this material is well described as a random amorphous solid, containing simple thermal fluctuations and a small concentration of relatively large heterogeneities.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130802
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  • 95
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    Radical formation during tensile deformation of highly drawn crystalline poly[p-(2-hydroxyethoxy)benzoic acid] fibers (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1515-1532 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The micromechanism of tensile deformation of poly[p-(2-hydroxyethoxy)benzoic acid] fibers is discussed on the basis of a detailed esr study of radical formation. The concentration of primary phenoxy radicals, which were detected during deformation at room temperature as a direct indicator of main-chain rupture, was determined by extrapolating the radical decay curves at various strains to zero time. The relation between the initial radical concentration and the strain is well expressed by the cumulative normal distribution curve. By use of this relation and a model of fiber structure, the distribution of the contour length of tie chains was determined. No radicals were detected during a second stretching cycle until the maximum strain in the first run was exceeded. The deformation model which includes alternating crystalline and amorphous regions connected by tie chains, a distribution of contour lengths of tie chains, and a phase transformation of molecular chains in the crystalline region accounted fairly well for the observed stress-strain behavior of monofilaments in first and second stretching cycles. The comparison between the observed and the calculated radical concentration suggests that statistical factors and other deformation mechanisms have to be taken into account.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130806
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  • 96
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    A comparison of two techniques for inducing fibrous crystallization from solution (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1643-1649 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental results are presented and discussed comparing two techniques for inducing fibrous growth of polyethylene crystals from flowing solutions: a plunging cone device and a standard rotating cylinder (Couette) device. Comparison of crystal “overgrowth” diameter to spacing ratios for the several experiments with predictions based on an earlier postulated model lead to conclusions regarding the model inadequacy. A detailed comparison is made of the melting behavior of crystals produced by both flow fields and those results are discussed in light of a modified model for the growth process presented elsewhere. The conclusion is reached that differences in melting behavior may be attributed to differences in extension of the high molecular weight chains involved in the growth processes occurring in the two different flow fields.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130815
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  • 97
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    Investigation of the dual mode sorption of ammonia in polystyrene by NMRThis work supported by the U.S. Energy Research and Development Administration. (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1665-1673 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The sorption of ammonia by polystyrene was investigated by pulsed nuclear magnetic resonance (NMR) relaxation techniques. The concentration of sorbed gas was determined from the intensity of the gas signal and analyzed by the dual mode sorption model. The relaxation data were used to examine the validity of assuming that the molecules exchange rapidly between sites and that the adsorbed species is relatively immobile. Both assumptions were found to be substantially correct although the possibility that the adsorbed species may have some small mobility (no more than 5% that of the faster moving molecules) could not be eliminated.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130901
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  • 98
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    A rotational rheometer with a drag-cup torque transducer (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1761-1781 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A rotational cone-and-plate rheometer incorporating a drag-cup torque transducer and a frictionless, wire suspension has been designed and constructed. The instrument design provides for a controlled atmosphere for the sample, including anhydrous conditions necessary for studies on solutions of polymers in strong acids. The rheometer can be used to determine the shear deformation in response to an applied stress, including creep, recovery, and the shear stress in response to an applied steady shear. Both transient and steady-state measurements are possible. Illustrative examples of the instrument performance are given.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130909
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  • 99
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    Mechanisms of frequency shifting in the infrared spectrum of stressed polymer (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1795-1808 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the vibrational spectrum of a polymer obtained under tensile stress loading conditions, several modes of molecular deformation can lead to different mechanisms of frequency shifting and asymmetric band deformation. Theoretically and experimentally it has been observed that quasielastic deformations (reduction of force constants due to bond weakening under stress), pure elastic bond stretching and angle bending, conformational variations, and several types of chain defects can cause linear shifts in frequency and infrared band distortion. A detailed study of the deformation spectra of isotactic polypropylene and polyphenyl-p-sulfide indicated that quasielastic and elastic mechanisms are the major contributors to frequency shifting, principally affecting stretching and bending vibrational modes. Conformational mechanisms can affect torsional modes whereas the defect mechanism, when present, can cause random distortion of an infrared band. The latter mechanism is difficult to quantize. The extent to which each mechanism contributes to the total spectral deformation can be a function of morphology, macroscopic loading conditions, thermal and strain histories.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130912
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  • 100
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    Thermal analyses of polymers. XIII. Crystalline character of the 70°c transition of poly(ethylene terephthalate) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1831-1844 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The abrupt changes in the linear expansion and dilatometric measurements of poly-(ethylene terephthalate) near 70°C indicate that the transition may be first order. DTA and DSC data show the normal heat capacity change at 70°C, while annealing for for 30 min. at 110°C induces further molecular order. Rapid quenching of PET after heating to 120°C yields an amorphous sample and measurement by depolarized light transmission as the sample is reheated shows rapid crystallization occurring near 80°C. With the occurrence of shrinkage near 68°C and apparent recrystallization at slow heating rates by depolarized light analyses, further support is added to the first-order character of this phase transition. Isothermal annealing for short times at temperatures between 50°C and 80°C produces further increases in molecular order. Cyclic and linear PET oligomers do not contribute to the occurrence of the 70°C transition.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130915
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