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  • ZIB Catalog
  • Articles: DFG German National Licenses  (470)
  • 1980-1984
  • 1975-1979  (470)
  • 1935-1939
  • 1890-1899
  • 1975  (470)
  • Physics  (470)
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  • ZIB Catalog
  • Articles: DFG German National Licenses  (470)
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  • 1980-1984
  • 1975-1979  (470)
  • 1935-1939
  • 1890-1899
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  • 101
    Electronic Resource
    Electronic Resource
    Statistical mechanics of two-dimensional wormlike chains (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 871-871 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130421
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  • 102
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 17 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130504
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  • 103
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130507
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  • 104
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130511
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  • 105
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130602
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  • 106
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130605
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  • 107
    Electronic Resource
    Electronic Resource
    Tensile properties of ultradrawn polyethylene (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1177-1186 
    Details
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130610
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  • 108
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130614
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  • 109
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130702
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  • 110
    Electronic Resource
    Electronic Resource
    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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  • 111
    Electronic Resource
    Electronic Resource
    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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  • 112
    Electronic Resource
    Electronic Resource
    “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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  • 113
    Electronic Resource
    Electronic Resource
    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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  • 114
    Electronic Resource
    Electronic Resource
    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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  • 115
    Electronic Resource
    Electronic Resource
    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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  • 116
    Electronic Resource
    Electronic Resource
    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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  • 117
    Electronic Resource
    Electronic Resource
    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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  • 118
    Electronic Resource
    Electronic Resource
    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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  • 119
    Electronic Resource
    Electronic Resource
    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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  • 120
    Electronic Resource
    Electronic Resource
    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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  • 121
    Electronic Resource
    Electronic Resource
    Molecular orbital calculation of the electronic structure of poly(N-vinylcarbazole) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1863-1869 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Energy levels and molecular orbital wave functions of π-electrons in a carbazole ring are calculated by the ω-method. The result agrees well with observed optical absorption spectra of carbazole and poly(N-vinylcarbazole) (PVCA). Molecular orbital wave functions are obtained for a PVCA chain in a 3/1 helix. The overlap integral between adjacent carbazole rings is evaluated for each molecular orbital of the ring. The result affords evidence for hole conduction in PVCA and explains the photoconductivity spectrum under high de field.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180131001
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  • 122
    Electronic Resource
    Electronic Resource
    Threshold fracture energies for elastomers (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1903-1911 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fracture energies have been measured for two types of polybutadiene elastomer, crosslinked to various extents and torn under various conditions. Threshold values, ranging from 40 to 80 jm-2, were observed for samples torn at extremely low rates of tearing, at high temperatures, and in the swollen state. These values were found to be independent of temperature and rate of tearing, and also of the degree of swelling and the nature of the swelling liquid, provided a correction is made for the reduced areal concentration of molecular chains. They decreased somewhat with increased crosslinking, in good agreement with theoretical predictions of Lake and Thomas.6 The results for the two elastomers were substantially the same.These observations are strikingly different from those made at normal temperatures and rates of tearing, when large differences in fracture energy were observed between the elastomers, and between samples crosslinked to different extents, due to energy losses from nonequilibrium deformation processes in addition to the energy required for fracture.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131005
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    Carbon-13 nuclear magnetic resonance quantitative measurements of monomer sequence distributions in hydrogenated polybutadienes (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1975-1990 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The 1,4-1,2 additions in three hydrogenated polybutadienes are described in terms of triads of monomer units, average sequence lengths, and branches per 1000 carbon atoms. A test for conformity with Markov statistical behavior shows that the measured triad distributions can be closely reproduced assuming a first-order model. Transition probabilities from the statistical analysis can be used to calculate the relative concentration of any desired sequence. Steric factors during polymerization may lead to the first-order bias in the monomer distribution.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131011
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  • 124
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    Elastic behavior of simple model networks (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2069-2077 
    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 behaviors of simple networks consisting of but a few chains have been calculated on the basis of the James and Guth theory of elasticity. The calculations show that the number of elastically effective chains in a network is less than the actual number of network chains, and that the total number of chain backbone links distribute themselves equally (approximately) among the effective chains. It is also demonstrated that a chain molecular weight distribution could be of consequence in non-Gaussian elasticity. Extrapolation of the findings to a macroscopic network suggests that the number of effective chains is one half the number of network chains, and that each effective chain behaves as if it contained twice as many of backbone links as a network chain.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131101
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  • 125
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    The morphology of ultradrawn polyethylene. I. Nitric acid etching plus gel permeation chromatography (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2031-2048 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transparent strands of high-density polyethylene of unusually high c-axis orientation have been produced by a solid-state extrusion, involving pressure, temperature, and deformation, in an Instron capillary rheometer. Measured values for tensile modulus are higher than previously reported for any polyolefin. Previous modulus and electron microscopic data are consistent with a strand morphology comprised (≤20%) of of extended chain crystals. The remainder resembles an oriented fibrillar morphology such as found in highly drawn polyethylene. In the present study, fuming nitric acid etching of the ultraoriented strands, in combination with gel permeation chromatography (GPC), has provided incisive structural information. The strands exhibit ≥3X the resistance to acid degradation shown by conventionally drawn polyethylene. GPC molecular weight distributions (MWD) of etched samples show a single broad peak with a prominent high molecular weight tail. The crystal size, represented by the MWD, is in agreement with the crystal long period determined by small-angle x-ray scattering. The absence of multiple peaks in the etched MWD's is evidence of limited chain folding. The extended chain content, determined from the etched MWD's, is a strong function of strand formation temperature and is in agreement with the fraction of extended chains calculated from modulus measurements.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131013
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  • 126
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    Dynamic mechanical properties of some novel ionene polymers (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2091-2102 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Novel ionic polymers of the type x,y-oxyethylene ionenes (x,y-OEI), have been synthesized, for x and y varying from 2 to 5. The 2,2-, 2,3-, 2,4-, and 3,3-OEI are crystalline; the 3,4-, 4,4-, 4,5-, and 5,5-OEI are amorphous. The temperature dependence of the dynamic mechanical properties of these polymers, studied by torsional braid analysis over a temperature range from -170° to +150°C, shows two types of dispersion in each polymer. The dispersions lying between -6° and +90°C appear to be primary dispersions due to the amorphous phase. The dispersions between -110° and 0°C, on the other hand, are attributed to local modes. The temperature of the primary dispersion depends linearly on the charge density along the main chains of the polymer. However, the dependence of the local mode dispersion temperature on the charge density shows no regular pattern. Both dispersions are greatly influenced by the presence of absorbed water. Measurements of Tg at various water contents reveal the existence of abnormal plasticizing effects by water.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131103
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  • 127
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    Computer simulation of brownian motion of a polyelectrolyte molecule (charged bead-spring model) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2135-2153 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A Langevin equation of motion for a charged bead-spring statistical chain is written in difference form and the relaxation and equilibrium behavior of the chain is studied by computer simulation. Results are presented for the behavior of end-to-end length h, principal axes of the polymer ellipsoid L1, L2, L3, and chain contour length c in terms of their averages, root mean square values, root mean square fluctuations, orientations, and relaxation strengths and times. The simulation was made with various sets of parameters, bead number N, charge on the bead q, and radius of ion atmosphere around the bead k-1. It is found that 〈h2〉1/2 and 〈L12〉1/2 increase more strongly with increasing q and decreasing κ than 〈L22〉1/2, 〈L32〉1/2, and 〈c12〉1/2, indicating that the chain is expanded in three dimensions and at the same time is extended along the end-to-end direction. The relaxation time τrot of rotation of the end-to-end vector, which is proportional to N2 at q = 0, increases with increasing q and tends to be proportional to N3 for an extended chain, while the relaxation time τconf of the magnitude of h is almost independent of q and is always proportional to N2. It is concluded that the extended chain possesses a well-defined end-to-end axis and the chain rotates as a whole with a relaxation time τrot which is much longer than τconf. The complex viscosity of the chain is calculated from the Fourier transform of the time-correlation function of momentum flux and is found to have a frequency spectrum similar to that observed for aqueous solutions of poly(acrylic acid). The dominant mode appearing in the low-frequency range is evidenced to arise from the rotation of the extended chain.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131107
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  • 128
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    Transcrystalline region of polycaprolactam filament (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2237-2240 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180131113
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  • 129
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    Optical studies of the crystallization of trans 1,4-polybutadiene in stretched networks (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2195-2219 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The stress-induced crystallization of trans 1,4-polybutadiene was studied by observing changes in birefringence, stress, x-ray diffraction, and low angle light scattering during the course of crystallization. From these data, the degree of crystallinity was determined as a function of time, temperature, and elongation. Data were fitted to the Avrami equation, leading to an exponent of the order of unity. Light-scattering patterns suggested the simultaneous existence of two stretched forms: a rod-like structure oriented preferentially parallel to the stretching direction and a deformed spherulitelike growth with its greatest extension perpendicular to the stretching direction.
    Additional Material: 18 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131111
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  • 130
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    Long-time orientation relaxation for an internal bond of a chain (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2251-2251 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180131116
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  • 131
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    An investigation on the chain-folding structure of an ethylene-propylene copolymer by selective degradation (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2281-2288 
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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 renewed explanatory study is reported on the fold structure and branch location in single crystals of an ethylene-propylene copolymer by means of the ozone degradation method. By analogy with concurrent studies on linear polyethylenes a distribution of fold lengths is inferred, this distribution being broader, more uniform, and spreading deeper into the crystal interior in the case of the copolymer than for the linear polyethylene. Perhaps the most salient points of the work is that in contrast to nitric acid the oxidation by ozone does not obscure then characteristic CH3 infrared absorption band enabling the branch content to be followed during degradation. The single exploratory experiment of the present work reveals that while there is a certain amount of preference for the branches to accumulate near the fold surface, a substantial portion of them can still be located in the crystal interior. The potential of the present method for a more systematic study is indicated.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131203
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  • 132
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    Dynamic mechanical properties of poly(2-hydroxyethyl methacrylate) hydrogels (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2299-2311 
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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: Homogeneous and heterogeneous poly(2-hydroxyethyl methacrylate) hydrogels were prepared by copolymerization of 2-hydroxyethyl methacrylate and small amounts of ethylene glycol dimethacrylate in the presence of water; concentrations of water (V1) in the polymerization mixture and the volume fractions of water (v1) of the gels swollen to equilibrium were 40, 50, 60, 70% by volume, and 0.475, 0.541, 0.669, 0.778, respectively. From the homogeneous (clear) hydrogel (V1 = 40%) preparation, four hydrogels were prepared with v1 = 0.434, 0.418, 0.378, 0.326. Tensile dynamic moduli were measured in the frequency range from 0.006 to 0.6 cps and the temperature range from 0 to 40°C. In these cases, the influence of swelling on the shape of the relaxation spectra and on the monomeric unit friction coefficient was studied. The dependence of the friction coefficient on water concentration was interpreted in terms of free volume. In the heterogeneous (opaque) gel preparations (V1 = 50, 60, 70%), the effect of the aqueous phase in the system on the mechanical behavior was described by a modification of the blending law of Ninomiya. For the systems with V1 = 60% and 70% the shapes of the storage and loss moduli in the main transition region and the friction coefficient were similar to those of the homogeneous gel with V1 = 40%, except for the decrease in absolute value of the storage moduli. For the system with V1 = 50% the shape of the relaxation spectrum changes appreciably and the wedge distribution does not hold.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180131205
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  • 133
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    Heterogeneous nucleation of crystallization of high polymers from the melt. I. Substrate-induced morphologies (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2369-2383 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melt crystallization of isotactic polypropylene (iPP), poly(ethylene oxide), poly(butene-1), and polycaprolactone in contact with various substrates (mostly polymeric) has been studied by hot stage polarizing microscopy. Nucleating abilities of surfaces have been characterized qualitatively by examining the substrate-induced morphologies of the crystallizing polymer. These morphologies have been classified into three groups, depending on whether the substrate is very active (transcrystallinity), moderately active, or inactive as a nucleating agent. The morphologies observed are temperature-dependent, changing from transcrystalline to spherulitic upon increase of the crystallization temperature. At intermediate temperatures, mixed surface morphologies (transcrystalline plus spherulitic) are observed.The concentration of titanium and aluminum catalytic residues in isotactic polystyrene (iPS) samples can be reduced by two methods, i.e., (a) fractionating the polymer and (b) chelating Ti and Al with acetylacetone. The high nucleating ability of iPS samples in the crystallization of iPP has been shown to be due to the polymer (iPS) itself, and not to Ti and Al residues. Apart from iPS, other polymers (low energy surfaces) have also been found to induce transcrystallinity.From a survey of 43 substrate-crystallizing polymer pairs, conclusions have been drawn which are relevant to the following potential factors in heterogeneous nucleation processes: (a) chemical structure, (b) crystallographic unit cell type, (c) lattice parameters, (d) crystallinity of substrate, and (e) surface energy of substrate.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131211
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    The optical interference pattern in a polystyrene craze layer (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2429-2434 
    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 interference pattern seen in monochromatic light reflected from a craze layer in polystyrene, the bright fringes are of alternating intensity. The phenomenon is explained in terms of a four-beam interference. Apart from the two reflections from the outer surfaces of the craze layer others arise from a thin layer of approximately constant thickness within the craze layer at its median plane. The phenomenon provides independent evidence to support the electron microscopic observations of the microstructure of crazes in polystyrene.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131216
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  • 135
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    Electrical conductivity of small ions in polyacrylonitrile in the glass-transition region (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 9-18 
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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 electrical conductivity process in a new class of ion-containing polymers - highly concentrated solid solutions of hydrated perchlorate salts in polyacrylonitrile (PAN) - is described (σdc = 10-7-10-2Ω-1cm-1). A low-ac instrument (70 cps) is used to measure electrical conductivity. We present a cryogenic system in which the temperature dependence of the conductivity is studied (78-340°K). The ionic character of the conductivity process is established. The conductivity both above and below the glass-transition (Tg) point is thermally activated with an activation energy of 0.7-0.9 e V for the glassy state (∊g) and 0.12-0.6 eV for the rubber-like state (∊r). The systems described exhibit a compensation effect between the pre-exponential factor for the conductivity in the glassy state σ0g and the difference in activation energy ∊g - ∊r \documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{\varepsilon _{\rm g} - \varepsilon _{\rm r} }}{{KT_{\rm g} }} - \ln \sigma _{0{\rm g}} = {\rm const}.$$\end{document}
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130102
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  • 136
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    An X-ray study of atactic poly(p-biphenyl acrylate) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 87-93 
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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: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130108
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  • 137
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    Characterization of macromolecules in liquid solutions by thermal diffusion. I. Dependence of the soret coefficient on the nature of the dispersing medium (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 177-202 
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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 have been carried out on thermal diffusion of macromolecular particles dispersed in various liquids, with the object of checking some predictions of the radiation-pressure theory of Soret effect in liquids and of establishing a method of physical characterization of macromolecules in liquid solutions. The experimental results confirm the importance of the ratio G between thermal conductivity K and (phase) velocity v of high-frequency elastic waves of the materials composing the mixture in determining the thermodiffusive behavior of a liquid solution. We have shown that the migration of the macromolecular component takes place in the same direction in which thermal energy is flowing or opposite to it, depending on whether G of the dispersed particles is smaller or larger relative to the G of the liquid.Another aspect of the same phenomenon may be observed when macroscopic pieces of nonmetallic materials are suspended in a liquid, and heat is made to flow through this solid plunger and the surrounding liquid. The experiments performed with molecular solutions and with macroscopic plungers mutually complement and confirm each other.Anomalous results obtained in the case of solutions of polyvinylpyrrolidone in methanol are also discussed, and the possibility that this might be the consequence of the existence of a marked velocity dispersion in the high-frequency region of the spectrum of thermal waves in both water and methyl alcohol is indicated.Finally the possibility is hinted that thermal diffusion might have been responsible for the phenomena of molecular selection and evolution which ultimately led to the origin of life on our planet.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130115
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  • 138
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    Deformational, swelling, and potentiometric behavior of ionized poly(methacrylic acid) gels. I. Theory (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 253-262 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By using the model of a randomly coiled chain, a relation is derived describing the equilibrium stress-strain behavior of variously ionized polyelectrolyte gels swollen in solutions of a uni-univalent salt. The effect of the concentration of bound counterions calculated on the basis of the cylindrical model and the effect of the change of length of the statistical chain segment with the change in ionization of the gel on stress-strain, swelling, and potentiometric equilibria is discussed.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130203
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  • 139
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    Measurement of the Grüneisen number in polystyrene by brillouin light scattering (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 295-301 
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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: Brillouin light scattering has been used to measure the sound velocities in polystyrene of two different molecular weights. The variation of sound velocity with temperature is related to volumetric expansion of the polymer. Using the thermal expansion data of Fox and Flory we have determined the Grüneisen number, γ, below the glass transition to be 4.4 and 4.3 for low- and high-molecular-weight polystyrenes, respectively, and 5.1 and 5.6 above the glass transition. These numbers compare reasonably well with the value of 3.9 determined by Wada et al. Our measured values are in good agreement with Barker's “bundle of chains” model.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130207
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  • 140
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    Transient and steady-state water vapor permeation through polymer films (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 493-507 
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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: Water vapor transport properties for the polymers Kapton HReference to a company or product name does not imply approval or recommendation of the product by the University of California or the U.S. Atomic Energy Commission to the exclusion of others that may be suitable. and Parylene C were determined over a temperature range of 20 to 55°C. Activation energies and entropies for permeation as well as partial molar free energies, heats, and entropies of dilution were calculated for water vapor concentrations ranging from 3 × 10-6 to 1 × 10-3 mole H2O per cm3 of polymer. Mylar A was tested to extend the available data for partial molar heats and entropies of dilution and to compare permeation and diffusion results with the corresponding values in the literature. Diffusion coefficients were measured using the time-lag technique of Barrer but employing a modified test apparatus. Equilibrium sorption isotherms at 30°C were obtained for Mylar A and Kapton H with a Cahn microbalance. The ratios of the permeability to diffusion coefficients as measured from time-lag experiments agreed with solubility coefficients within 3% for Mylar A and within 12% for Kapton H. Both polymers obeyed Henry's law. The results were interpreted in light of polymer polarity and morphology.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130304
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  • 141
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    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 
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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 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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  • 142
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    Crystallization during polymerization of diazomethane. II. Studies of model compounds and chain extension of etched polyethylene single crystals by chemical reaction (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 607-618 
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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 order to study the mechanism of crystallization during polymerization, a method to produce living oligomer crystal nuclei was developed. The living oligomers are diazoketones prepared from their carboxylic acids or acid chlorides. These diazoketones were proved to be reactive toward boron trifluoride etherate. The complex could be further chain-extended through a living polymerization mechanism with diazomethane. The optimal conditions for the reactions were worked out using model compounds. These reactions were then applied to chain extension of etched polyethylene single crystals. The reactions were confirmed by a combination of time-dependent differential thermal analysis, molecular weight determination, nuclear magnetic resonance and infrared analysis. The importance and potential application of such reactions for the study of nucleation and crystallization, and final properties of the resulting polymers are discussed.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130311
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  • 143
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    Crystallization and melting of polyethylene under high pressure. II. Effect of pressure on melting behavior of various types of crystals (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 637-651 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of pressure on the melting point and volume of fusion of polyethylene was studied by high-pressure dilatometry. Starting materials were crystallized slowly from the melt under pressures of 1500, 3500, 5130 kg/cm2, and 1 atm. It has been shown that the unusual behavior observed at pressures above 4000 kg/cm2 is due to crystallization and melting of two kinds of extended-chain crystals differing in thermal stability. These are designated as ordinary extended-chain and highly extended-chain crystals, respectively. The relation between pressure P and melting temperature Tm of folded-chain, ordinary extended-chain, and highly extended-chain polyethylene was determined precisely. At pressures up to about 3000 kg/cm2, plots of P against Tm for the crystal forms have almost the same curvature and then become parallel. But at pressures above 4000 kg/cm2, ordinary extended-chain crystals show a linear increase of Tm with a constant slope of about 70 atm/deg. Curve for the highly extended-chain crystals changes in slope from 70 to 50 atm/deg at pressures between 3500 and 4300 kg/cm2, and then show a sharp increase of Tm with increasing pressure. Experiments show that the meltingpoint curve of the highly extended-chain crystals overlaps that of the ordinary extended-chain crystals at pressures below 4000 kg/cm2. Annealing experiments with folded-chain and ordinary extended-chain crystals have been made under high pressure. It is suggested that the formation of highly extended-chain crystals occurs stepwise through the formation and reorganization of ordinary extended-chain crystals from the original folded-chain crystals by a mechanism of partial melting and recrystallization at pressures above 4000 kg/cm2.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130313
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    Determination of the coefficients of selective sorption in the system polymer-ternary solvent by the density and refractive index increments method (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 715-725 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The method of density and refractive index increments was used for the determination of the coefficients of selective sorption of acetophenone and bromoform on polymer in the system poly(methyl methacrylate)-isopropanol-acetophenone-bromoform as a function of the composition of the ternary solvent. In systems containing more than 80% by volume of bromoform the precipitant - isopropanol - is selectively sorbed. The conditions under which the method gives satisfactory results and some methodological problems of densitometry have been discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130405
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  • 145
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    The role of dislocations in the solid-state polymerization of monomers having conjugated triple bonds: A study of 2,4-hexadiyne-1,6-diol bis(p-toluene sulfonate) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 753-763 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal structure of the monomer bis(p-toluene sulfonate) ester of 2,4-hexadiyne-1,6-diol (pT) is conducive from the viewpoint of both the separation distances and molecular configuration, to polymerization, irrespective of whether initiation is thermal, photochemical, or mechanical. The dislocations present in the monomer and polymer structures have been characterized by employing optical microscopic techniques. The slip system (102)[010] is found to be present in both monomer and polymer crystals but the (010)[001] system is found only in the monomer. On this basis a crystal structure for the monomer is proposed based on existing crystallographic information relating to the structure of the polymer. Dislocations are thought, on energetic grounds, to facilitate nucleation of product in the thermal polymerization but have no observable influence on the photoinduced reaction which proceeds homogeneously through the bulk.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130408
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  • 146
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    Theory of the epitaxial crystallization of polymers on alkali halide substrates. II. Polyoxymethylene and polythiomethylene (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 787-798 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The epitactic behavior of a single chain of polyoxymethylene and of polythiomethylene on alkali halide substrates has been simulated by computing the coulombic, induced dipolar, and dispersion-repulsive potential energies as a function of polymer-substrate geometry. Inspection of the total potential energy surface for a polyoxymethylene chain in a 9/5 helix reveals a favorable alignment in which the chain is parallel to the substrate surface ((001) cleavage plane) with specific positioning along rows of positive charge. This preferential orientation has been found to be independent of lattice matching between the substrate and deposited phase. An identical mode of orientation is predicted for a polyoxymethylene chain and a polythiomethylene chain, both in the 2/1 cis-planar conformation. The theoretical results for polyoxymethylene are in agreement with available experimental evidence, whereas the outcomes of the calculations performed on polythiomethylene should be considered predictive study to be complemented by a future experimental investigation.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130411
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  • 147
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    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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  • 148
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    Persistent polarization in poly(vinylidene fluoride). II. Piezoelectricity of poly(vinylidene fluoride) thermoelectretsPaper presented in part before Microsymposium on Electrical Properties of Polymers, Tokyo (Jan. 1972). (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1033-1047 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The piezoelectricity of PVDF thermoelect rets formed with vacuum-coated aluminum electrodes has been investigated in detail. The piezoelectricity depends on the β-form crystal structure of PVDF homopolymer and copolymers. However, the piezoelectricity is not attributed to the stress dependence of the spontaneous polarization of β-form crystals, but rather to the persistent polarization arising from trapped charges. The trapping mechanism is discussed.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130515
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  • 149
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    Orientation of crystallites in lightly crosslinked isotactic polypropylene crystallized from the melt under uniaxial compression (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1085-1095 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A lightly crosslinked polymer film was made from isotactic polypropylene by gammaray irradiation in an acetylene atmosphere. When the crosslinked polymer film was crystallized from the melt under uniaxial compression, a unique alignment of crystallites is found. The (040) crystal plane is preferentially oriented parallel to the film surface at relatively low degrees of compression, and the (110) and (130) crystal planes are oriented parallel to the film surface at higher degrees of compression. The origin of these orientations, analogous to that previously found in a lightly crosslinked polyethylene, is discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130603
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  • 150
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    Infrared spectroscopic evidence of structural defects in the crystalline regions of trans-1,4-polychloroprene (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1145-1158 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared spectra have been obtained for the crystalline regions of samples of predominantly trans-1,4-polychloroprenes polymerized at -20, 0, and 40°C. Spectral differences among the polychloroprenes are interpreted in terms of the increase in structural irregularities that occur as the polymerization temperature is increased. Results of this study indicate that crystallization occurs with random inclusion of these structural irregularities into the crystalline domains. The conclusion is supported by the spectra of the crystalline regions of a chloroprene copolymer containing known impurities in the form of 2,3-dichloro-2-butenylene units in addition to the normal 2-chloro-2-butenylene units.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130607
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  • 151
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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 
    Details
    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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  • 152
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    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 
    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 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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  • 153
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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 
    Details
    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.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130513
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  • 154
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    Crosslinking of elastomers by coordination bonding. Study of clustering of the coordination complexes by Mössbauer spectroscopy (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1057-1061 
    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.1975.180130517
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  • 155
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    Dielectric study of low-temperature relaxations in poly(isobutyl methacrylate), poly(n-butyl methacrylate), poly(isopropyl methacrylate), and poly(4-methylpentene-1) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1959-1974 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isochronal measurements of dielectric constant and loss are made for poly(isobutyl methacrylate) (PiBMA), poly(n-butyl methacrylate) (PnBMA), poly(isopropyl methacrylate) (PiBMA), and poly(4-methylpentene-1) (P4MP1) at temperatures ranging from 4°K to 250°K. Loss peaks are found around 120°K (10-100 Hz) for PiBMA, PnBMA, and P4MP1. By comparing the activation energy with the calculated potential barrier for the internal rotation of alkyl group in the side chain, the motion responsible for the 120°K peak is concluded to be essentially the rotation of the isopropyl group as a whole for PiBMA and P4MP1 but, for PnBMA, the rotation of n-propyl group accompanied by the rotation of the end ethyl group. Multiple paths of internal rotation are involved with the 120°K peaks of PiBMA and, in particular, PnBMA, which explain differences between PiBMA and PnBMA in the broadness and the temperature location of the 120°K peak. The 120°K peak is in general assigned to a side chain including a sequence—O—C—C—C or —C—C—C—C. PiPMA without this sequence in the side chain does not show the 120°K peak, but it exhibits the 50°K peak (1 kHz) like poly(ethyl methacrylate). The 50°K peak is assigned to the rotation of ethyl or isopropyl group attached to COO group. Poly-L-valine in which the isopropyl group is directly attached to carbon does not have the 50°K peak. An additional loss peak at 20°K (1 kHz) for P4MP1 is also discussed on the basis of the calculated potential.
    Additional Material: 17 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131010
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  • 156
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    Morphology of ultradrawn polyethylene strands. II. Nitric acid etching and melting behavior (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2049-2065 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A transparent, ultraoriented, high-density polyethylene morphology has been produced by solid-state (ultradraw) extrusion in a capillary rheometer. From the perspective of modulus and nitric acid etching behavior, the uniquely high draw ratios (〈325) experienced by the polyethylene during extrusion result in a morphology with a high level of chain extension. The effect of nitric acid etching on strand thermal behavior has been determined by DSC. The observed melting points of unetched strands were sensitive to the thermal contact between sample and sample pan. Under conditions ensuring improved contact, strand superheating is reduced to one-third of previously reported values. The negligible shrinkage evidenced by these strands up to 130° is consistent with the presence of a thermally stable component such as extended chain crystals or crystallized tie chains. The single, high-melting peak is gradually replaced by a nonsuperheating, lower melting peak during the initial stages of acid etch. The resultant peak melting temperature is consistent with the value predicted for the peak crystal thickness of the etched polymer. No evidence is found for a higher melting peak attributable to the extended chain crystalline component. A highly constrained morphology produced by the large tie chain content is believed responsible for strand melting behavior. The melting point of the extended chain crystalline component is reduced by defects and a large ratio of lateral to basal surface area.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180131014
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  • 157
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    High-pressure phases in polymers. II. Spherulitic growth morphology in cis-polyisoprene (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2117-2127 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphological details of the nucleation and growth of spherulites in cis-polyisoprene at elevated pressures are discussed on the basis of transmission electron microscopy of films stained in situ by osmium tetroxide and cold-stage electron diffraction of unstained films. The crystalline structure is unchanged but growth habits are modified. Spherulites begin, as in crystallization at atmospheric pressure, with a single lamella. The formation of a spherulite proceeds primarily through “spawning” and is unaffected by the imposition of pressure. Lamellae tend to propagate as plates or hedrites at supercoolings in excess of 50-60°C (e.g., 1 kbar at 0°C) unlike at atmospheric pressure where only ribbonlike lamellae are observed. Propagation is invariably as sheafs since nucleation of lamellae which grow perpendicular to the primary lamella is suppressed. The nucleation density varies considerably with pressure, a maximum being observed in the pressure plane at constant temperature (e.g., 0.70 kbar at 0°C). It is difficult to resolve clearly the morphological details in the diffusion controlled region because of fine texture. Although much more difficult to achieve experimentally, the effects of pre-orienting the melt are similar to those occurring at atmospheric pressure.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180131105
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  • 158
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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 
    Details
    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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  • 159
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    Dielectric relaxations in polymers with pendent phenyl or pyridine groups at temperatures from 4°K to 80°K (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2357-2368 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isochronal measurements of dielectric loss are made for polystyrene (PS), poly(4-vinyl pyridine) (P4VP), poly(2-vinyl pyridine) (P2VP), poly(L-phenylalanine) (PLPA), and poly(γ-benzyl-L-glutamate) (PBLG) at temperatures ranging from 4°K to 80°K and at frequencies from 10 Hz to 100 kHz. PS, P4VP, and PLPA show loss peaks around 50°K (10 kHz) while P2VP exhibits a loss peak around 20°K (10 kHz). PBLG has no detectable peak in this temperature range. The 50°K and 20°K peaks are ascribed to wagging and rotation, respectively, of phenyl or pyridine groups between two energy minima. The barrier height and energy difference between the minima evaluated from the experimental data are reasonably explained by assuming that the double minima are caused by interaction between a pair of phenyl or pyridine groups, each belonging to adjacent chains which pack irregularly.
    Additional Material: 11 Ill.
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  • 160
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    Current reversal in the thermally stimulated current spectra of polyethylene (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2401-2410 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyethylene thermoelectrets were prepared under static electric fields ranging from 70 to 750 kV/cm at various polarization temperatures. Thermally stimulated current (TSC) spectra were observed for those samples in the high-temperature region above room temperature. The TSC spectra of polyethylene were complex and were composed of two current peaks, of opposite polarity and dependent on the applied voltage and temperature. This result suggests that there are two trapping mechanisms which result in different charge injection modes. In addition, TSC spectra were obtained on polyethylenes of various morphologies to examine the relationship between the mechanical relaxations and the trapping mechanisms.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180131214
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  • 161
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    The solid-state thermal polymerization of bis(p-toluene sulphonate) of 2,4-hexadiyne-1,6-diol. III. An ESR study (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2411-2427 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electron spin resonance (ESR) observations of the solid-state thermal polymerization of bis(p-toluene sulphonate) of 2,4-hexadiyne-1, 6-diol at 60°C, 70°C, and 80°C are reported. The weak paramagnetism observed in polycrystalline samples is interpreted in terms of departures of the polymer chain from an equilibrium conformation. Decomposition occurs at 70°C and 80°C during the final phase of polymerization producing additional paramagnetic centers. Lineshape parameters measured during polymerization show changes which we attribute to changes in the delocalization and mobility of the paramagnetic center. We conclude that the nature of paramagnetism in crystalline conjugated diacetylene polymers is a chain defect property characteristic of interband electronic states close to the valence band.
    Additional Material: 12 Ill.
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  • 162
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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 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier transform infrared 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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130413
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  • 163
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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 
    Details
    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.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130707
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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 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of 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.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130708
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  • 165
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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 
    Details
    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.
    Additional Material: 18 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130711
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  • 166
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    The gaussian chain with excluded volume (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1655-1658 
    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.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130817
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  • 167
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    High-resolution preparative-scale gel-permeation chromatography (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1695-1703 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sharp polymer fractions have been obtained in preparative-scale gel-permeation chromatography by use of a column set packed with polystyrene gel particles of about 10 μ diameter. When 0.13 g of standard polystyrene NBS 706 was fractionated per injection, fractions with polydispersities of about 1.02-1.03 were obtained over the molecular weight range 104-106. Effects of a injection volume, solution concentration, and fraction volume on fractionation efficiency were also investigated. Polydispersities of fractions increased appreciably with increasing amounts of polymer injected.
    Additional Material: 8 Ill.
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    Pressure dependence of dielectric properties of chlorinated polyethylene vulcanizate. I. α relaxation and shift factors (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1737-1746 
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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 complex dielectric constant was measured under elevated pressure for the α relaxation of vulcanized chlorinated polyethylene. Both temperature and pressure effects on the static dielectric constants, the activation enthalpy, and volume, and the pressure dependence of the glass-transition temperature were obtained. The dependence of shift factors on temperature was expressed by the Vogel-Fulcher-Tamman-Hesse (VFTH) equation: -log aT = A - B/(T - T0). The parameters A, B, and T0 for each pressure applied were calculated by minimizing the standard deviation between log aT and experiments. The values of the parameters in the Williams-Landel-Ferry (WLF) equation: -log aT = C1(T - Tg)/[C2 + (T - Tg)], were also estimated from the resulting values of the VFTH parameters. All these parameters depended on pressure. The activation volume plotted against T - Tg decreased with increasing pressure.
    Additional Material: 6 Ill.
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  • 169
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    ESR study of pressure dependence of free-radical decay in irradiated polystyrene (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1789-1794 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Radicals giving the usual triplet ESR spectrum have been generated in polystyrene by γ-irradiation at room temperature. The decay of the radicals has been investigated in the temperature interval between 90° and 200° and pressures ranging from 1 to 8000 atm. The effect of pressure on the mechanism of the free-radical decay is discussed. There are two regions of free-radical decay showing different activation volumes: VI = 11.5 cm3/mole and VII = 66 cm3/mole. The correlation between molecular motion in the α-relaxation region and radical decay is pointed out.
    Additional Material: 4 Ill.
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  • 170
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    Piezoelectricity of α-chitin (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1845-1847 
    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.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130916
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  • 171
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    Crystallinity and the effect of ionizing radiation in polyethylene. IV. Effect of segregation of low molecular weight chains on determination of main-chain scission in linear polyethylene (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 339-350 
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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: Different single crystal preparations of polyethylene with (unfractionated) and without (partially fractionated) low molecular weight chains were irradiated at room temperature. G(crosslink) was determined from the gel point. It is shown that in addition to the molecular weight and molecular weight distribution of polymers, G(crosslink) is determined by three more parameters: thickness of crystalline core, amount of amorphous surface layer, and degree of interlamellar contact. Unlike unfractionated polyethylene, partially fractionated polyethylene showed almost 100% gel at about 250 Mrad. To obtain the same amount of gel, unfractionated polyethylene required a much higher dose than that required by partially fractionated polyethylene. Molecular weight distribution of sol fractions of unfractionated and partially fractionated polyethylene was studied by gel permeation chromatography (GPC) and the solubility data analyzed by Charlesby-Pinner plots. It has been shown that the unattainability of 100% gel from unfractionated polyethylene is due to segregation of low molecular weight chains during crystallization which need very high doses for complete gelation.
    Additional Material: 8 Ill.
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  • 172
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    Pressure and temperature effects on the vibrational frequencies of crystalline polymethylenes. II. Lattice anharmonicity and the equation of state (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 387-399 
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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 lattice anharmonicity of crystalline polymethylene is interpreted from the observed pressure and temperature dependence of Raman active interchain lattice frequencies of the n-paraffins C23H48 and C44H90. The temperature dependence of the Lc′ interchain lattice frequency is separated into quasiharmonic and self-energy shifts. The former is due to the volume dependence of the force constant of the oscillator. The latter is due to the anharmonicity of the dynamic potential, and is obtained as a function of volume and phonon population. The setting angle of the carbon skeleton is predicted to be temperature-sensitive. While the potential surface of the crystal is asymmetric along the Lc′ normal coordinate, it is essentially symmetrical along the Tb′ coordinate.The well-known Mie-Gruneisen equation of state is generalized to include anharmonicities of oscillators through the temperature dependence of their vibrational frequencies.
    Additional Material: 8 Ill.
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  • 173
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    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 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130218
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  • 174
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    Lactone polymers. VI. Glass-transition temperatures of methyl-substituted ∊-caprolactones and polymer blends (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 851-856 
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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.1975.180130416
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  • 175
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    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 
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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 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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  • 176
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    Pressure quenching and chain-extended crystallization of polyethylene (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1501-1509 
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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: Recent work has shown that so-called chain-extended crystallization of polyethylene is crystallization of the newly discovered hexagonal phase. This hypothesis is supported by experiments on the pressure quenching of molten polyethylene.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130804
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    On the structure of glassy polymers. I. Small-angle X-ray scattering from polycarbonate (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1247-1262 
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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 small-angle x-ray scattering (SAXS) from glassy bisphenol-A polycarbonate 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 vertical beam divergence, they 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, 0.44 (electrons)2 Å-3, is well represented by the thermodynamic 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 this material (50-200 Å), but can be well represented by a small concentration of heterogeneities (0.04% by volume or less), several thousand angstrom units in size, superimposed on the thermal density fluctuations frozen in at the glass transition.It is suggested that the nodular features reported for this material are not representative of bulk material but should be associated with surface effects. The bulk structure can - as far as the SAXS is concerned - be well described as a random amorphous solid, containing simple thermal fluctuations and a small concentration of relatively large heterogeneities.
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  • 178
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    NMR measurements on cis-1,4-polybutadiene as a function of pressure (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1301-1314 
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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 are reported of the nuclear spin - lattice relaxation time T1 in cis-1,4-polybutadiene at room temperature up to a pressure of 3,500 bar. Up to 2,000 bar the relaxation curves are described by a single T1, the pressure variation of which indicates, in the Arrhenius model, an activation volume of 14.5 cm3 mole-1. Above 2,000 bar the effects of strain due to partial crystallization become evident, and multiple relaxation is observed. By measuring the compressibility of this material up to 10 kbar an estimate of the free volume is made, giving \documentclass{article}\pagestyle{empty}\begin{document}$$V_{\rm f} = 1.58\left( {10 - P} \right){\rm cm}^3 {\rm mole}^{ - 1}$$\end{document} with P in kbar. This measurement is applied in turn to two models of the glassy state, that of Cohen and Turnbull1 which yields an activation volume of 84 cm3 mole-1, and that of Adam and Gibbs,2 which leads to a critical configurational entropy of 7.7 kB.In the liquid state the transverse nuclear relaxation, measured by the spin-echo technique, appears to be governed by the same process as T1.
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  • 179
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    On the transition from paraffinic to polymeric behavior: Mechanical properties (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1407-1416 
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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 attempt has been made to determine what influence chain folds may have on the α and γ mechanical loss peaks in linear polyethylene. In so doing, one long-chain n-paraffin (C94H190) and two low molecular weight polyethylene fractions have been examined with mechanical relaxation, differential scanning calorimetry (DSC), and low-angle x-ray diffraction techniques. The data suggest that chain folds play a prominent role in both the α and γ processes but that other factors such as polydispersity and/or branching are also important.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130712
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  • 180
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    Effect of internal field on the birefringence of polyethylene crystals and on the anisotropy of polymer chains. I. Birefringence effects (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1447-1459 
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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: Values of the anisotropy of polarizability of methylene groups deduced from the refractive indexes of n-paraffin crystals differ appreciably from those obtained from gas- or liquid-phase measurements. The differences is attributed to the erroneous application of the Lorenz - Lorentz internal field to the anisotropic n-paraffin crystal. A more detailed calculation of the internal field is carried out by detailed summation of the dipolar field over an idealized n-paraffin crystal in which the molecular chains are replaced by anisotropic rods. With reasonable values of parameters and assumed crystal shape, the discrepancy in polarizability anisotropy is resolved.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1975.180130714
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    Morphology and physical properties of triblock copolymers with crystalline end blocks (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1543-1561 
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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 morphology of crystalline end-block copolymers of poly(thiacyclobutane-b-isoprene-b-thiacyclobutane) (TCB-I-TCB) was studied by optical microscopy, electron microscopy, and small-angle x-ray scattering (SAXS). A spherulitic texture was observed for both the TCB homopolymer and the TCB-I-TCB block copolymers. Well-defined phases arranged in an ordered structure exist when the films are cast above the melting temperature of the crystalline end blocks. The dimensions and the arrangements of the domains have been derived from both SAXS and electron microscope measurements. The deformation mechanism of the 41% end-block copolymer sample was also examined by a combination of SAXS and stress-strain studies. It was found that the interdomain spacing increased along the stretching direction as the extension ratio was increased. The morphology changes from hexagonally packed cylinders to rowtype cylinders upon the application of stress.
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  • 182
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    Light scattering from polymer films having optically anisotropic rodlike texture. A quantitative test of theoriesPublished in part in Rept. Progr. Polym. Phys. Japan, 17, 1974. (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1613-1631 
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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 light scattering intensity distribution from rodlike crystalline superstructures is quantitatively investigated theoretically and experimentally. The arithmetic average of theoretical Hv scattered intensities at azimuthal angle μ = 0° and μ = 45° is shown to decrease with increasing scattering angle θ in proportion to W-1 at high scattering angles for a system composed of a random assembly of rodlike superstructure having very small lateral dimensions relative to the length. The quantity W is defined as 2π(L/λ) sin θ where L is the length of the rod, and λ is the wavelength of light in the medium. A method is proposed to estimate the length L by using the W-1 dependence. Effects of internal heterogenity, polydispersity in rod length, and finite lateral dimensions of the rodlike superstructure are considered to account for experimental deviation of the scattered intensity distributions from the W-1 dependence. The effect of finite lateral dimensions turns out to be the most important.
    Additional Material: 19 Ill.
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  • 183
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    Orientation effects in rolled and annealed polyethylene plates (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1659-1662 
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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.1975.180130818
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  • 184
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    Crystal structure of optically active poly(isopropylethylene oxide) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 285-294 
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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 crystal structure of optically active poly(isopropylethylene oxide) was analyzed by x-ray diffraction. Two molecular chains having twofold screw symmetry pass through an orthorhombic unit cell with parameters a = 12.85 Å, b = 7.52 Å, and c (fiber period) = 5.55 Å and space group P212121-D24. The crystal structure was refined by the constrained least-squares method. The molecular structure consists mainly of ḠTG sequences and is very similar to the (9/4) helical structure in poly(tert-butylethylene oxide).
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    URL: http://dx.doi.org/10.1002/pol.1975.180130206
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  • 185
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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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    URL: http://dx.doi.org/10.1002/pol.1975.180130417
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  • 186
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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 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130420
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  • 187
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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 
    Details
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130501
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  • 188
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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 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130508
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  • 189
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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 
    Details
    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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130512
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  • 190
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    Electronic Resource
    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 
    Details
    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.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130516
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  • 191
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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 
    Details
    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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130601
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  • 192
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    Rheology of dispersions of swollen gel particlesPresented at the 45th Annual Meeting of the Society of Rheology, University of Massachusetts, Amherst, October 21-24, 1974. (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1133-1144 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A centrifugal technique was used to determine the swelling, Q (g swollen gel/g dry polymer), of crosslinked polyacrylate gel particles in water. Both centrifugal force and time of centrifugation affected the magnitude of Q but under constant centrifuge conditions it was found that Q-1 was proportional to μ1/2, μ being the ionic strength. The viscoelastic properties of water dispersions of these gel particles were measured as functions of concentration and ionic strength. Viscosity data were reducible to a normalized master curve by plotting (ηsp/cr) versus cr, where cr is a reduced concentration defined as cQ. Values of shear modulus, G, computed from the first normal stress difference measured at various concentrations and ionic strengths also fell on a single curve when plotted against the reduced concentration, cQ. Comparison of these results with those obtained earlier on a similar polyacrylate dispersion, but one in which as much as 20% of the polyacrylate is in a soluble, uncrosslinked form, shows that the soluble fraction has little effect on the magnitude of the viscosity and, moreover, that the presence or absence of the soluble fraction does not affect the transient stress overshoot phenomenon. As in the earlier work, high absolute values of viscosity occur when cQ ≧ 1, that is when the dispersion consists of close-packed deformable gel particles in intimate contact with little or no interstitial solvent present.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130606
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  • 193
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    Electronic Resource
    Photoconduction in polyolefins and in poly(ethylene-carbon monoxide) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1187-1199 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ultraviolet photoconductivity of high-density polyethylene, polypropylene, and poly(ethylene-carbon monoxide) has been studied in the range 360-180 nm. The response of the polyolefins is similar to that found in low-density polyethylene both in spectral distribution and in time behavior, with hole injection setting in at 3.7 eV. There is evidence also of electron injection in polypropylene at 4.5 eV and higher energies. A copolymer containing 0.5% CO is similar except that the hole threshold is at 4.2 eV, but a 1% CO copolymer shows marked differences, with electron injection being dominant. It is suggested that the change is due to a shift in the Fermi level rather than direct excitation of electrons from carbonyl groups, but some inconsistencies remain in this model.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130611
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  • 194
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    Electronic Resource
    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 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130616
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  • 195
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    Electronic Resource
    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 
    Details
    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.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130703
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  • 196
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    Electronic Resource
    Fibrous mercerization of Valonia cellulose (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1859-1862 
    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.1975.180130919
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  • 197
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    Pressure dependence of dielectric properties of chlorinated polyethylene vulcanizate. III. β relaxation (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1893-1901 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of temperature and pressure on the shift factor and the dielectric increment of the β relaxation process were measured for vulcanized chlorinated polyethylene. The isobaric and isochoric activation enthalpies, H*P and H*V, the activation volume V*, the pressure dependence of the glass-glass transition temperature, Tgβ/dP, and the apparent extinction temperature T0β were obtained. The pressure dependences of both V* and the dielectric increment would reach very small values near the liquid-glass transition temperature Tg, and the β process seems to be affected by the transition near Tg. The value of H*v/H*p for the β process is larger than that for the α process, and it is suggested that the molecular motions pertaining to the β process are more strongly restricted than those pertaining to the α process. The ratio T0β/T0, where T0 is the characteristic temperature in the Vogel-Fulcher-Tammann-Hesse equation for the α process, follows the empirical relation of Matsuoka and Ishida, Tgβ/Tg ∼0.75. The value of dTgβ/dP estimated from Tg and T0β/T0 is consistent with the experimental value.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180131004
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  • 198
    Electronic Resource
    Electronic Resource
    Crystallization during polymerization of poly-p-xylylene. III. Crystal structure and molecular orientation as a function of temperature (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1925-1938 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymerization of p-xylylene was carried out from the gas phase with monomer produced by the pyrolysis of [2,2]-p-cyclophane. The crystalline form and preferred orientation of as-polymerized polymer deposited at various temperatures (-196 to 80°C) were investigated by x-ray diffraction methods. The melting behavior and other thermal transitions were studied by DSC. At 80°C the polymer film deposit is a mixture of the α and β forms, while between 60 and 0°C the deposit is of the α form. At lower temperature the polymer deposit is mainly of the β form, which shows diffuse reflections. At liquid nitrogen temperature it is of the β form with sharp reflections, contaminated with a small amount of oligomer. It was also found that at low temperatures, fibrillar crystals grow from the substrate in a direction 45° against the gas flow, and at even lower temperature, well-oriented filmlike crystals grow perpendicular to the substrate surface.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180131007
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  • 199
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    Electronic Resource
    The orientation of amorphous chains in spherulites (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1991-2029 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theory for amorphous orientation in spherulitic polymers is presented based upon a consideration of conformational changes in the chains, loops, and cilia located between crystalline lamellae within a spherulite which is assumed to undergo an affine deformation. Chain statistics are worked out on the basis of (a) an analytical method involving random walks on a cubic lattice between barriers following a technique proposed by DiMarzio and Rubin and (b) a Monte Carlo computer simulation on a tetrahedral lattice. The latter method is considered more appropriate in view of the chain constraints such that lattice geometry becomes important. Values of the amorphous orientation are calculated as a function of the degree of crystallinity, initial lamellar separation, mole fraction of bonds in amorphous chains of each type, and chain lengths of each type of amorphous chain. It is found that tie chains are the principal contributor to amorphous orientation and the amount increases with increasing fraction and decreasing length of these. Results are compared with measurements of amorphous orientation by the birefringence x-ray and the infrared dichroism technique. It is concluded that the tie chains must be initially quite highly elongated and that the assumed affineness of spherulite deformation is not closely obeyed.
    Additional Material: 24 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180131012
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  • 200
    Electronic Resource
    Electronic Resource
    Dipole moments in oriented poly(ethylene terephthalate) (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2079-2090 
    Details
    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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180131102
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