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  • 2000-2004
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  • 1980  (558)
  • 101
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1005-1020 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The primitive chain model of Doi and Edwards is generalized to include the short-time relaxation process. Stress relaxation after a sudden imposition of strain is studied in detail. It is shown that in the linear region (small strain) stress relaxation occurs in two steps, the relaxation of chain segments between the fixed entanglement points, and the relaxation of the entanglement points, in accordance with the conventional picture, whereas in the nonlinear region (large strain) there appears a new relaxation process between the above two. The characteristic time of this process is the Rouse relaxation time which the entire chain would have if there were no entanglements, and increases with the square of the molecular weight. This result is consistent with experimental observations.
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  • 102
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1035-1045 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Preliminary small-angle neutron scattering (SANS) studies have been made of different ionomers in the dry state and after saturation with water. Scattering from the dry samples arises from differences in the neutron scattering cross sections of the ionic and nonionic units in the polymer. The SANS technique is complementary to previous small-angle x-ray scattering (SAXS) studies since the SANS contrast differences are generally quite different than those for SAXS. A quantitative comparison is made of SANS and SAXS intensities for a dry cesium salt of an ethylene-methacrylic acid (E-MAA) copolymer. For water-saturated samples the technique of isotopic replacement can be used in conjunction with SANS since saturation can be effected with either H2O or D2O. In this case information about the chemical composition of the phases is obtained from an analysis of the intensity ratio ID2O/IH2O. Results are consistent with the presence of a separate phase containing water molecules and ions in a matrix of the nonionic units. A Guinier analysis gives a radius of gyration of 17 Å for a water-saturated cesium salt of an E-MAA copolymer.
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  • 103
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1047-1052 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The chain repeat distance in the α-phase crystal of nylon-6 was measured from -150 to 150°C. The distance increases with decreasing temperature, indicating that the chain is not a complete planar zigzag but is twisted at room temperature. The relation between the distance and temperature changes at about -110°C and again near 40°C. Both changes seem to be related to the mechanical dispersions of the material. Young's modulus in the chain direction is 270 GN/m2 at -150°C, or 14% less than the theoretical value given by Tashiro and Tadokoro for the planar zig-zag structure. It is not possible to determine from the (0k0) diffraction intensities whether the amide or methylene moieties are the more important in the chain twisting.
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  • 104
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1021-1034 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Phosphorescence depolarization measurements, under steady state polarized excitation, have been used to examine the relaxation behavior of bulk poly(methyl methacrylate) (PMMA). Poly(methyl methacrylate) bearing phosphorescent labels has been synthesized by copolymerization of small quantities of acenaphthylene (I), 1-vinylnaphthalene (II), 2-vinylnaphthalene (III), 1-naphthyl methacrylate (IV), and 2-naphthyl methacrylate (V), respectively, with methyl methacrylate. In no case was depolarization of emission due to probe rotation apparent below the onset of the β-relaxation of the polymer. Rotation of label V was characterized by an activation energy of 94 kJ mole-1 in excellent agreement with that of the β relaxation measured by conventional relaxation techniques. This result clearly implicates ester motion in the β relaxation. No motion of label I, which cannot move independently of the polymer backbone, was evident in the vicinity of the β relaxation. Above 378 K the activation energy for rotational relaxation of label I of 460 kJ mole-1 is in excellent agreement with published data for the α transition in PMMA. This result is in accord with the general assumption that backbone segmental motion is involved in the α relaxation. However, backbone motion of lesser temperature dependence (Ea = 115 kJ mole-1) is apparent from depolarization behavior of probe I between 343 and 378 K. Label II shows three regions of relaxation behavior. In the temperature range above the β transition motion of the label independent of the polymer is evident (Ea = 44 kJ mole-1). At temperatures in excess of 343 K this motion becomes cooperative with that of the backbone yielding activation energies comparable to those obtained in system I. Label III, while exhibiting depolarization characteristics similar to those of label II in the vicinity of the β relaxation, emitted insufficient intensity to permit estimation of an energy of activation for the motion. The phosphorescence of label IV was completely depolarized over the entire temperature range studied. While phosphorescence intensity and lifetime data may be used to detect the existence of polymeric transitions, the photophysical behavior of the naphthalene species studied is independent of the attachment to the polymer and does not primarily yield information regarding the polymer relaxations.
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  • 105
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1103-1124 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model of simple molecule sorption in polymers is proposed which embraces both the glassy and rubbery regions, and incorporates the successful dual-mode model below the glass-transition temperature. Hole filling is shown to be an important sorption mechanism both above and below Tg, although saturation effects do not occur in the rubbery polymer. The model interprets the “dual-mode” Langmuir and Henry's law parameters at the molecular level, and a simple statistical mechanical analysis allows estimation of the parameter values, as well as specifying certain interrelationships between the parameters. Applications of the model to gas solubility data in five polymers are considered [polyethylene (PE), poly(ethylene terephthalate) (PET), polystyrene (PS), polymethacrylate (PMA), poly(vinyl acetate) (PVAc)] and semiquantitative agreement is obtained for PE, PET, and to a lesser extent, PS. For PMA and PVAc, the agreement is qualitative only.
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  • 106
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1175-1186 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The flexibility of some polyimide chains has been studied theoretically as a function of the chemical structure of the repeat unit. It has been shown that the thermodynamic flexibility can be varied over a wide range by the choice of the unit structure. For three polyimides, as an example, the flexibility of cyclochain structures approximates that for free rotation.
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  • 107
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1209-1217 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Lamellar single crystals of cellulose were obtained from dilute solutions of low-DP cellulose triacetate, by deacetylation followed by precipitation. At temperatures between 150 and 160°C, pure cellulose IVII crystals were obtained whereas at temperatures between 90 and 150°C, hybrid crystals, having cellulose II and cellulose IVII domains cocrystallized in syntaxy were obtained. In both cases, the crystals were identified and characterized by electron diffraction. When the solutions leading to cellulose IVII were seeded with native cellulose microfibrils, a shish-kebab structure resulted with the microfibrils decorated by cellulose II lamellae.
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  • 108
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1271-1283 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermal, dynamic mechanical, and dielectric relaxation techniques were used to determine the relaxation behavior of isotactic and syndiotactic poly(2-hydroxyethyl methacrylate) (pHEMA). Activation energies Ea were determined for the dielectric γ relaxation and compared with those of poly(2-methoxyethyl methacrylate) (pMEMA) to determine the influence of hydrogen bonding on side-chain relaxation processes. No difference in Ea was observed between syndiotactic pHEMA and atactic (predominantly syndiotactic) pMEMA. Isotactic pHEMA, however, had Ea + 1 kcal/mole higher than that of syndiotactic pHEMA. This was attributed to improved side-chain packing in the isotactic polymer.
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  • 109
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1303-1310 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data obtained by hot-stage cross-polarized light microscopy and thermogravimetric analysis were used to plot a transition map for the poly(n-alkylisocyanate) homologous family. Most members had a low-temperature transition (or relaxation). The middle members of the family, with side-chain length of 4 ≤ n 〈 13 carbon atoms, exhibit a mesomorphic range of temperatures. Members with sidechains of n ≥ 13 in length, go directly from the low-temperature transition to the melting point without passage through a liquid crystalline state. A transition map for two homopolymers and a series of their copolymers, poly[x mol% n-butyl + (100-x)mol% p-anisole-3-propyl]isocyanate, was also prepared. The range of mesomorphicity as a function of composition and temperature is clearly indicated.
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  • 110
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2077-2082 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We study the effect of the memory function on the coherent scattering function of a dilute polymer solution, taking into account hydrodynamic interactions among the polymer segments. The line shape, given by a sum of two exponentials, is very accurate numerically for ka ≳ 3 (with a the length of a polymer segment) and for times such that ω0(k)t ≲ 1.5 [with ω0(k) the initial slope]. However, this approximation to the scattering function is not nearly so accurate at the smaller values of ka encountered in light scattering experiments. The amplitudes and relaxation times associated with the two exponentials are found to be markedly dependent on the strength of the hydrodynamic interactions.
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  • 111
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2097-2121 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The infrared and Raman spectra of the two polymorphic forms of trans-1,4-poly(isoprene) (TPI) and trans-1,4-poly(2,3-dimethyl butadiene) (TPDMB) are presented. Infrared spectra of the alpha and beta forms of TPI were obtained by digitally subtracting the amorphous contribution from the corresponding spectra of semicrystalline TPI polymers. Normal coordinate calculations are presented for both polymorphic forms of TPI and TPDMB, and the assignments of the normal modes are discussed.
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  • 112
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2243-2256 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: PCILO conformational calculations have been carried out on several model compounds of aromatic polyamide oxamides and polyamide hydrazides. The comparison of the entropy of the equilibrium conformations allows a classification of the various constitutive units into “rigid” segments, and “flexible” ones having respectively low or high entropies. From the results, it is possible to predict the mesogenic nature of solutions of a large number of aromatic polyamides, polyamide hydrazides, and polyamide oxamides.
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  • 113
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 27-34 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Doi and Edwards have recently proposed a molecular theory for the dynamics of entangled polymer liquids based on a tube model to represent the mutual constraints on configurational rearrangement of the chains. Expressions for diffusion coefficient, plateau modulus, zero-shear viscosity, steady-state recoverable compliance, and terminal relaxation time can be devloped, and relations among these properties that depend only upon observable quantities can be obtained. Several such relations are derived and are compared with experimental observations.
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  • 114
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 35-50 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization kinetics has been studied for a polydioxolan (PDOL) sample, over a wide temperature range, by dilatometry and microscopy. The dilatometry results can be analyzed using the Avrami equation. At temperatures higher than 22°C, the crystallization data must be analyzed in two steps: the first part of the curve corresponds to PDOL with a very disordered morphology (Phase I) while the second part of the crystallization curve is related to a spherulitic morphology (Phase II). The passage from the low to the high crystallization temperature region is associated with a change in the Avrami exponent from 3 to 4. The crystal surface free-energy product σσe was found to be 18 × 102 erg2/cm4, very close to that of polyoxymethylene. The crystallization kinetics was studied by microscopy over the temperature range-18 to 35°C. Growth and nucleation rates were recorded. Two phases are found only at temperatures higher than 22°C. The appearance of Phase II is related to a decrease in the growth rate of the sample. From the growth rates, the crystal surface free-energy product σσe was found equal to 17 × 102 erg2/cm4. The detailed analysis of the crystallization of the two phases reveals a complicated process which can be divided into four different steps: (a) growth of a disordered phase, Phase I; (b) nucleation of a higher birefringence structure; (c) propagation of a high birefringence phase; and (d) spherulitic growth, Phase II. The analysis of PDOL crystallization strongly suggests the presence of a hedrite → oval → spherulite transition: the hedrite formation corresponds to step (a), the oval formation to steps (b) and (c), and the spherulite formation to step (d).
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  • 115
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 83-93 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The isothermal crystallization of isotactic polypropylene at different temperatures in the presence of fibrous substrates has been investigated. It is shown that preferential transcrystalline growth occurs at the fiber surface and that changes in nucleation density in the bulk material adjacent to the fibers also occur, the extent of which is dependent on temperature and fiber volume fraction. The effects are discussed in terms of the diffusion of heterogeneities in the bulk due to interaction and the adsorption on the fibers.
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  • 116
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 51-69 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The initial stage of the suspension polymerization of poly(vinyl chloride) (PVC) is characterized by the formation of colloidally stable micron-sized grains of PVC inside the polymerizing ca. 150 μm vinyl chloride droplets. The fate of these micron-sized PVC grains depends upon the agitation conditions. If no agitation is employed, they serve as growth centers for further polymerization to give a final particle possessing a uniform internal bead morphology. In agitated systems, these grains coagulate early in the conversion to give a more irregular structure in the interior of the PVC particle. The formation of these stable growth centers appears to be unique to PVC. The polymerization of acrylonitrile, also insoluble in its monomer, is characterized by rapid agglomeration of the precipitated polymer throughout the polymerization. In PVC, the colloidal stability of the polymerizing grains is demonstrated to be electrical in nature. A pericellular membrane or skin formed by polymerization in both the water and vinyl phase completely surrounds the polymerizing droplet after about (1-2)% conversion. This skin is responsible for the charge retention of the PVC grains inside the polymerizing monomer droplets.
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  • 117
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 71-82 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In light of novel and problematic diffraction patterns arising through the thermoreversible gelation of isotactic polystyrene, the conformational possibilities were examined with particular reference to other conformational works published recently on this polymer. The specific objective was to ascertain whether highly extended, helical backbone geometries such as are required by the new x-ray patterns are possible or not with a purely isotactic arrangement of side groups. The first realization was that the recently announced low-energy, near-trans conformations are not relevant to the present issue as they do not provide the required extended geometry. Further, specific sampling of the conformational energy map revealed that the required high chain extension may be energetically feasible, contrary to traditional conceptions and to recent conformational calculations elsewhere. The divergences as regards the latter were traced to the specific choice of nonbonded atomic radii - all within generally accepted limits - which accordingly has a crucial effect even to the extent whether specific conformation types are forbidden or energetically stable. The implications this has for conformational analysis in general are being pointed out. While the novel crystal structure has not been solved, the present study at least eliminates the previously believed categoric objections to it being associated with isotactic chains and, beyond this, opens up new perspectives as regards conformational possibilities in polyolefins. The more general problems concerning the nature and origin of the gelation phenomenon nevertheless remain.
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  • 118
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 111-120 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Normal coordinate calculations have been performed for poly(vinylidene chloride) employing a TXTX′ conformational model (X and X′ denote torsional angles of equal value but opposite sign). A valence force field previously determined from the model compounds 2,2-dichloropropane and 2,2-dichlorobutane was directly transferred to the chain conformation of the polymer. The results are in excellent agreement with the observed vibrational spectra and we have been able to satisfactorily assign all the major normal modes.
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  • 119
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 121-126 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that the partial molal volumes (pmv) of the repeat units of nonionic polymers in aqueous solutions calculated from pmv group contributions, obtained from pmv data for small molecules and salts in aqueous solutions, agree in most instances to within ± 1 cm3/mole with the experimental values. The pmv of ionic polymers calculated from pmv group contributions have been found to be always larger than the experimental values. The difference gives a lower bound of the cooperative electrostrictive effect of neighboring charged sites of the polymer chain on surrounding water molecules.
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  • 120
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 127-156 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ericksen's theory incorporates in the constitutive equations a vector ni that characterizes the anisotropy of a fluid particle arising from flow induced orientation. The present study is an appraisal of the potential of such an approach in studying orientable polymeric fluids. The behavior of a normalized version of ni (ni → 0 at rest and ni → 1 when fully stretched) is studied in simple shear, elongational, and converging flow fields. Following a discussion of the merits and the problems with this approach, a modification is proposed where directional anisotropy and stretching of a fluid particle are separated. Empirical extensions include the incorporation of a simple structure parameter in viscoelastic fluid theories.
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  • 121
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 95-110 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polymer chain conformation of crystalline poly(vinylidene chloride) (PVDC) has been the subject of controversy for the past three decades. In this study, a combination of techniques has been employed in an attempt to elucidate the preferred conformation of PVDC. Conformational models containing two monomers per translational repeat distance have been considered. Calculations of the translational repeat distance and the nonbonded Cl⃛Cl contact distance between two adjacent CCl2 groups have been performed for each of the models. By comparing these results with those derived from x-ray analysis and a theoretical estimation of the minimum nonbonded Cl⃛Cl contact distance, an initial judgment of the structural feasibility of the models has been gained. A symmetry analysis has been performed for each conformational model and theoretical estimations of the polarization and intensity of the C—Cl and C—H stretching vibrations have been obtained. These results have been compared with experimental infrared and Raman spectra. It is concluded that a TXTX′ (where X and X′ are torsional angles of equal value but opposite sign) chain-conformational model for PVDC is favored.
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  • 122
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 157-160 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 123
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 161-164 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 124
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 165-167 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 125
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An extension of Hartel's theory for multiple scattering has been applied to the case of small-angle light scattering from polymer films with random two-phase morphology. The scattering is treated in terms of Debye-Bueche theory from which values of the correlation length, an average phase size, and mean-square fluctuation in polarizability are determined. It is shown that multiple scattering leads to a reduction in the angular dependence of scattering due to an enhancement of scattering at high angles. This leads to an underestimate of the correlation length and an overestimate of the magnitude of the mean-square polarizability fluctuation.
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  • 126
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 207-216 
    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 linear polyethylene of Mw/Mn 1.19 crystallized isothermally from the melt has been investigated. Electron microscopy (EM) of stained thin sections gave exceptionally well-defined images. There were no qualitative differences between Regime I and Regime II crystallization, but the lamellae grown at lower supercooling were thicker, larger, and had fewer spiral growths per unit area of fold surface. Small-angle x-ray scattering indicated a much sharper distribution of lamellar thicknesses than EM and Raman LAM did. This is evidence of the complementary nature of the techniques and not a contradiction. EM also revealed nonrepresentative features in detail. There were extremely thin lamellae formed on cooling, indicating molecular weight segregation even in this fractionated material, and there were extremely thick lamellae, attributed to isothermal thickening. As the representative lamellae are also supposed to have thickened isothermally, this raises the issue of when and how the lamellae which are the primary products of crystallization can be identified.
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  • 127
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 217-226 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal expansion of epoxy-resin (Epikote 828)/particle composites has been measured in the range 77 to 450 K. The fillers used were Cu spheres (seven sizes from 5 to 150 μm diameter) and glass ballotini spheres (three sizes from 3.5 to 200 μm diameter). The volume concentrations used were 0.3 and 0.5 for Cu and 0.3 for glass. The experiments show that the addition of filler raises the glass transition temperature Tg, especially for fine particles. Below the normal value of Tg the thermal expansion is independent of particle size while above Tg the expansion is considerably smaller for samples containing the smaller particles. The effect is more pronounced for Cu than for glass filler. In addition a rapid heating rate reduces the expansion for specimens containing smaller particles but it does not effect the expansion for those containing large particles. The results, which are discussed in the light of the work of other authors, suggest that the addition of particles increases Tg by changing the nature of the polymer not only immediately at the particle surface but also for a considerable distance into the polymer itself. This probably occurs because the epoxy bonds strongly to the particles and this inhibits segmental rotations of the polymer even at considerable distances from the particle surface.
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  • 128
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 227-232 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Quantitative comparison of previously published NMR spin-relaxation data for polydiethylsiloxane with theoretical predictions for a variety of motional processes allowed both the nature and time scale of molecular motions to be identified. At the lowest temperatures, methyl reorientation produced a T1 minimum and was found to proceed with an activation energy of 2.4 kcal/mole in both amorphous and crystalline phases. Reorientation of the ethyl groups in the amorphous phase was observed at a higher temperature with an activation energy of 9.3 kcal/mole. Relaxation in the melting region was influenced by flexing and stretching of the helical polymer chain. The maximum angular displacement of the chain was estimated to be 24°, with an activation energy for this process of 2.6 kcal/mole.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 233-237 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular structural changes of a vinyl functional silane coupling agent on E-glass fibers, induced during the immersion test in hot water, have been studied using Fourier transform infrared spectroscopy. The amount of the coupling agent on the glass fibers is reduced by hydrolytic degradation. Silanol groups formed by the hydrolysis of the siloxane groups have been detected in the FT-IR difference spectrum in the range 930-840 cm-1 due to the SiO stretching mode of the SiOH groups. Heat treatment produces partial reformation of the siloxane bonds.
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  • 130
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 239-245 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The course of melting of melt-crystallized polyethylene fractions and of a poly(ethylene oxide)-polystyrene-poly(ethylene oxide) triblock copolymer has been followed by small-angle x-ray scattering (SAXS). Changes in the intensity and shape of the SAXS curves indicated that both surface melting and melting over the full crystallite thickness (full-strand melting) take place. Full strand melting is the final, irreversible process. Comparison with an analytical model indicates that in the earlier stages of the irreversible, full-strand process the crystallites melt out randomly throughout the bulk. Later stages may occur by the simultaneous melting of a larger stack of crystallites.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 265-275 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Double-exposure speckle patterns created by scattered light were used to study tensile deformation of isotactic polypropylene film. The method makes possible a quantitative investigation of the deformation process (relative magnitude and orientation of the displacement vector, Poisson's ratio μ) by means of a simple optical analysis of stepwise deformations covering the desired range. The displacement vector and Poisson's ratio have been determined with an accuuracy of ± 5% in the range of small deformations (up to 18% relative deformation); and the role of stress relaxation has been examined. Limitations of the method, such as the range of measurable displacements, effect of prestressing, and stability of the system, etc., are discussed. Among advantages of the method are comparative simplicity and accuracy, and the possibility of its application to other systems studied by the small-angle light scattering method.
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  • 132
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 683-695 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric absorption measurements are made on three ethylene-carbon monoxide copolymers containing 2.3, 8.7, and 18 C=O per 1000 CH2 at frequencies ranging from 1 kHz to 1 MHz throughout the 90-373°K temperature range. Mean values of the activation energies of the γ, β, and α relaxations are found to be, respectively, 11.5, 41.5, and 31 kcal/mole from measurements done at fixed frequency by varying the temperature and 27 kcal/mole for the α relaxation as obtained from measurements at steady temperatures with drifting frequencies. The interaction energy of the CH2 unit in the crystalline polyethylene chain with its neighbors is calculated on the basis of the chain rotation model as well as of the rotation-translation model proposed by Hoffman et al. It seems that their αc models accounting for the molecular origin of the α relaxation have to be rejected. It is further shown that the sharp decrease of permittivity for high temperature (above 330°K at 1 kHz) is only due to the marked decrease of the density of polyethylene with increasing temperature.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 723-729 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared spectra of isotactic polystyrene gel films are observed to be significantly different from those of amorphous and crystalline polymer, indicating that the gel form is in a different conformation than the usual 31 helical crystal structure. Computer-assisted subtraction indicates that approximately 35% of the chains participate in the gel component, effectively ruling out structural defects as the origin of the ordered gel component.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 829-852 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The lamellar growth kinetics and lamellar thickness of poly(ethylene terephthalate) crystallized from the glassy state have been determined as a function of crystallization temperature. Values of end and side surface free energies have been estimated as well as the residual lamellar thickness. Analyses carried out using secondary nucleation approaches indicate that the width of a critical nucleus is comparable to the effective substrate length for multiple nucleation in this and other slowly crystallizing polymers at high supercoolings. A “universal” critical value of Tm2/T2ΔT below which the strip completion process ceases was found to exist. All crystallization must, therefore, occur through the deposition of critical nuclei. Models are proposed for this process which appear to be consistent with both neutron scattering and infrared experiments on quenched polyethylenes. Comparison of crystallization rates, expressed as “jump” rates, with relaxation frequencies suggest that in order for crystallization to occur at any given temperature the relaxation frequency must be at least two decades faster than the crystal “jump” rate.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 891-896 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 136
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 877-890 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photoconductivity has been measured in well-dried poly(vinyl alcohol) (PVAl) films containing Cu2+ complexes prepared by treatment with Cu(NO3)2, CuSO4, CuCl2, and CuBr2. When the ratio [Cu2+]/[MU] ([MU] denoting the concentration of PVAl monomer residues) is greater than 0.015, illumination at the charge-transfer (UV) band produces a strong photocurrent in PVAl-CuCl2 and PVAl-CuBr2, but not in PVAl-Cu(NO3)2 or PVAl-CuSO4. Optical absorption spectra suggest that two halide ions enter the first coordination sphere in the cis configuration. The temperature dependence of ESR indicates the existence of antiferromagnetic superexchange interaction via intervening halide ions. Hence, there exists a network structure of the PVAl-CuCl2 or PVAl-CuBr2 complex. The dependence of the photocurrent on the polarity of the illuminated electrode shows that the majority of carriers are holes. Holes in the network structure produced by charge transfer from halogen to Cu2+ ions are concluded to be responsible for the photoconduction.
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  • 137
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 909-913 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 138
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 927-942 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle x-ray scattering has been used to characterize a variety of polyethylene fibers of the so-called shish-kebab type. These fibers are aggregates of elementary fibrils each consisting of a backbone with a lamellar overgrowth. Intense scattering is due to voids between the lamellae giving rise to a “Bragg maximum” reflecting the ordering of lamellae along the backbones. It can be described by rather broad distributions for both the interlamellar spacings and the lamellar thicknesses. This is shown by comparing experimental scattering curves with SAXS patterns calculated on the basis of the theory for one-dimensional scattering of linearly ordered lamellar systems, using the general paracrystalline model. A negative exponential distribution for the center-to-center distance of the lamellae, characteristic of a random nucleation process, apparently cannot be employed for the description of these shish-kebab morphologies. From a discussion on the discrepancies between experimental and theoretical scattering curves it is concluded that the fibers may be inhomogeneous with respect to the statistics of lamellar ordering. This may be due to the nonisothermal character of the crystallization process.
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  • 139
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1125-1136 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric relaxation of polyacrylonitrile (PAN) samples, in which the presence of an amorphous phase is evidenced by x-ray diffraction, has been studied over the temperature range 30-150°C and frequency range 102-105 Hz. These data as well as those reported by other authors, reveal several points useful to the understanding of the dielectric relaxations of PAN in relation to its structure. A glass transition in PAN is evidenced by at least two of the four data sets investigated; the third shows combined effect of two relaxations, whereas the fourth clearly shows a relaxation process different from the glass transition. The glass-transition behavior of the dielectric relaxation data is confirmed by Williams-Landel-Ferry theory and a recent theory of Phillips, both of which lead to consistent conclusions.
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    Notes: Normal and abnormal spherulites of polybutylene terephthalate cast from solution in HFIP were investigated by electron microscopy (CTEM and STEM). Both spherulite types crystallize in the α form. The crystallite is biaxial with its greatest polarizability directions Z and Y oriented along the molecular chain and perpendicular to it in the plane of the terephthalate residue. In the normal spherulites, the [210]* direction is parallel to the radius direction, so that both Z and Y directions are oriented tangentially (negative spherulites). In the abnormal spherulites, the [111]* direction is parallel to the radius, and this explains the observed abnormal light scattering pattern.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1137-1144 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cellulose mesophases were obtained by preparing concentrated solutions of cellulose (20-55%) in a mixture of N-methyl-morpholine N-oxide (MMNO) and water. The anisotropy depends on four interconnected parameters: the temperature of the solution which, in general, must be lower than 90°C; the concentration of cellulose which must exceed 20%; a water content such that the mole ratio water/anhydrous MMNO is smaller than unity; and the degree of polymerization of the dissolved cellulose. The anisotropic cellulose solutions can readily be oriented during extrusion or casting thus giving fibers or films which upon regeneration exhibit high orientation.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1169-1173 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Results from two types of experiments, both on polyethylene, which allow, respectively, direct and indirect estimates of the magnitude of simple penetrant diffusion jump lengths are examined. In both cases the jump lengths inferred, for several small penetrants, are consistent with the values suggested by a recently proposed theory of diffusion in polymers.
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  • 143
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1159-1165 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Unit cell expansion data for (a) melt-crystallized polyethylene (PE) containing known amounts of methyl, ethyl, and butyl branches and for (b) plastically deformed samples, are examined in the light of a model which takes into account the penetration of constitutional defects (branches) at interstitial crystal sites by means of a generation of 2g1 step chain defects (kink isomers). The present analysis complements previous results obtained for melt-crystallized PE samples with a widely varying number concentration ∊ of butyl or longer branches. An estimation of the concentration of chain defects incorporated into the crystal lattice is carried out. The results reveal that the fraction χc of defects which are accomodated within the lattice depends on both the amount and size of the chain defects and on the mechanical deformation of the sample. For PE chains with methyl and ethyl groups, χc ≈ 50%, whereas for butyl and longer branches, χc does not exceed 20% of the total concentration of defects. In addition, after cold drawing, PE with low amounts (∊ 〈 1%) of butyl or longer chain branching, χc turns out to be zero; i.e., during deformation single molecular chain rearrangements leading to a chain segregation of defects into the amorphous phase must occur.
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  • 144
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1187-1207 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermal conductivities of six oriented semicrystalline polymers which range from 0.37 to 0.63 in crystallinity and 1 to 5 in draw ratio λ (up to about 15 for two polymers) have been measured between 100 and 340 K. It was found that for increasing λ the conductivity K∥ (along the draw direction n̂) increases rapidly while K⊥ (normal to n̂) decreases slightly; K∥ also increases with temperature, but K⊥ shows no simple pattern in temperature dependence. These general features can be reproduced reasonably well at low draw ratio (λ 〈 5) by the modified Maxwell model, and the discrepancy in details may be attributed to the fact that the model does not take into account the possible anisotropy of the amorphous phase of the oriented polymers. At high draw ratio the intercrystalline bridge effect becomes important, and one must resort to the Takayanagi model, but the lack of corroborating x-ray data has rendered a detailed comparison impossible.
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  • 145
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1439-1453 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using combined results of isothermal viscosity measurements and cross-polarized light microscopy on four polyisocyanate/solvent systems, the following were demonstrated: (a) an anisotropic phase appears, associated with a shoulder in the viscosity curve, at a concentration v2* lower than the peak viscosity at v2p; (b) the inversion from anisotropic inclusions in an isotropic matrix to isotropic inclusions in an anisotropic matrix, occurs at concentrations v20 〉 v2p and (c) the attainment of a single phase, microscopically anisotropic, occurs at v20 〉 v2p; where the viscosity is decreasing but has not yet reached its minimum. When the experiments were repeated with changes in temperature, the following were observed: (a) within each single phase the viscosity drops with increased temperature; (b) in the biphasic range, the total viscosity η0 remains about constant in the concentration range 20 ≤ 2p and increases with temperature in the range v20 〉 v2p; (c) in the interval v 20 〉 v2p of the biphasic range, at constant temperature an increase in concentration decreases η0, and at constant concentration, a decrease in temperature lowers η0. Qualitative explanations of the observations are proposed.
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  • 146
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1497-1512 
    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) pattern from a cesium salt of a 6.1 mole % ethylenemethacrylic acid (E-MAA) copolymer is shown to become azimuthally dependent on sample elongation. SAXS was measured using the Oak Ridge National Laboratory (ORNL) spectrometer with pinhole collimation and a two-dimensional position-sensitive detector. The sample was quenched prior to deformation to avoid crystallization of the ethylene unit which would complicate the interpretation of scattering. The observed SAXS patterns are interpreted in terms of several proposed models for the structure of ionomers. A model in which ionic aggregates are arranged on a paracrystalline lattice is found to be largely in disagreement with the results for undeformed and deformed samples. Spherical and lamellar models incorporating local structure around a central ionic core are capable of predicting the observed SAXS for the undeformed sample. A model of ellipsoidal deformation of the spherical shell-core model fails to predict the correct azimuthal dependence of scattering. However, a deformation scheme involving rotation of the lamellar model is more satisfactory.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1599-1607 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The stepwise growth and emergence of spherulitic structures as isolated entities from lyotropic solutions of polybenzylglutamate liquid crystals is described. Spherulites that form ringed internal structures indicative of a cholesteric organization of macromolecules have large optical rotatory powers. The sense of the rotation is solvent dependent. The morphology of the spherulite is distorted in the presence of a magnetic field. The pitch of the cumulative twist of “onion-shell” molecular layers was measured as a function of field strength and found to follow the theoretical form shown previously to hold for continuous-phase polypeptide liquid crystals.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1891-1905 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The stress relaxation of concentrated polymer solutions after double-step strain is analyzed by the model of Doi and Edwards (DE model). The theory explains the experiments of Osaki et al., who showed that the Bernstein-Kearsley-Zapas (BKZ) constitutive equation works reasonably well when the successive deformations are applied in the same direction, but that it fails when the direction of the second deformation is reversed. This experimental result has been considered contrary to the DE model, since the previous theory of Doi and Edwards provides a BKZ-type constitutive equation. In the present paper the discrepancy is reconciled by showing that (i) the source of the discrepancy is a mathematical approximation used in the previous DE theory, and that (ii) if this approximation is removed, the agreement between the theory and experiment becomes fairly good.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1993-1996 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1997-2014 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crosslinking chemistry and network formation in hydroxy and carboxy functional acrylic copolymer resins cured with representative melamine-formaldehyde crosslinking agents have been studied by infrared spectroscopy. Network formation in these systems is dominated by two reactions, the condensation of the hydroxy (or carboxy) functionality of the acrylic resin with melamine alkoxy groups to form acrylic-melamine crosslinks, and the condensation of melamine hydroxy groups to form melamine-melamine crosslinks. The extents of these reactions have been studied as functions of acrylic resin composition, melamine type and concentration, and cure time and temperature. For melamines with just methoxy functionality, the extent of formation of acrylic-melamine crosslinks increased steadily with cure temperature. For melamines with substantial hydroxy functionality, the extent of formation of acrylic-melamine crosslinks increased rapidly then leveled off with increasing cure temperature. The formation of melamine-melamine crosslinks increased slowly with increasing cure temperature. From these data and a statistical model, effective crosslink densities were calculated. The crosslink densities correlated well with solvent resistance.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2037-2053 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phase diagram of poly(p-benzamide) (PBA) in N,N-dimethylacetamide/LiCl solutions was determined for two PBA samples having weight-average molecular weights of about 10,000. The various equilibria were studied using analytical, viscometric, and optical microscope measurements. The phase diagram at 25°C, taking as variables the concentration of polymer (Cp) and LiCl (Cs), involves several equilibria which can be summarized as follows: solid ↔ isotropic solution when 0.75 ≤ Cs ≤ 2 g/dl, solid ↔ anisotropic solution when 2 ≤ Cs ≤ 4 g/dl, isotropic solution ↔ anisotropic solution when 2 ≤ Cs ≤ 4 g/dl, and Cp 〉 6 g/dl, and dilute isotropic solution ↔ gel when Cs 〉 4 g/dl. In the Cp range in which the isotropic and anisotropic phases coexist, enrichment of the high-molecular-weight component of the polymer in the anisotropic phase becomes more marked as the volume fraction of the latter phase is decreased. The two PBA samples exhibit noticeable differences in solubility, absolute viscosity, and in their viscosity-concentration behavior. The location of the maximum in the latter dependence does not necessarily coincide with the first appearance of the anisotropic phase. In the absence of a flow field, anisotropic solutions exhibit an irreversible increase in viscosity. Inclusion of the equilibria involving the crystalline state furnishes insight into some of the common observations for extended-chain polymers. A diagram illustrates the superposition of the solubility curves for a crystalline polymer and the liquid-crystal regions. This indicates that, for the high melting crystalline polymers, the crystalline phase should be stable relative to the concentrated anisotropic phase of the wide biphasic region.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2069-2076 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adsorption of linear polystyrenes from cyclohexane solutions onto a chrome plate of 35 (the theta temperature), 40, and 45°C was studied by ellipsometry. The adsorbance decreases with increasing temperature, while the extension of the adsorbed polymer layer increases. The adsorbance is almost independent of the molecular weight at these temperatures. The slope of a double logarithmic plot of extension versus molecular weight is 0.5 at the theta temperature, whereas at the higher temperatures the slope is a little larger. Both the adsorbance and the extension of the adsorbed layer change reversibly over a cycle of temperature change, indicating that a reversible conformational change has occurred. The expansion factor αt of the adsorbed layer is compared with the theoretical predictions of Hoeve and of Jones and Richmond. The expansion factor αt according to Hoeve's theory, was smaller than the measured value, whereas the expansion calculated by the Jones-Richmond theory is much larger than the measured value. It is concluded that the tail portions of adsorbed chains predominantly govern the extension of the adsorbed layer.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2271-2276 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have examined the poling time dependence of the field-induced phase transition (from phase II to polar phase II) of biaxially oriented poly(vinylidene fluoride) films by x-ray methods. These results were compared with the poling-time dependence of the piezoelectric response (d31 and e31) determined using a piezotron Model U (Toyo Seiki, Tokyo). The piezoelectric response shows an initial rapid increase with poling time followed by a slow increase as the poling time increases. The x-ray results show that the field-induced phase transition is time dependent, and occurs first for those crystallites with their a axes perpendicular to the film surface. Crystallites with a in the plane of the film transform at a much slower rate. The data indicate that the poling time dependence of d31 and e31 (and, presumably, film polarization) are dependent on the transition rates.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2263-2270 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Model networks were prepared by selective crosslinking through vinyl groups occurring as either chain ends or as side-groups on a poly(dimethylsiloxane) backbone. Iodometric titrations were used to determine the number of unreacted groups, thereby providing detailed information on the completeness of the reactions and the structure of the resulting networks. The end-linking reaction of the vinyl-terminated chains was generally found to be at least 95% complete. In the case of very high junction functionality, however, the extent of reaction was significantly lower, presumably because of steric interferences in the vicinity of the junctions, as was concluded in a previous investigation. Lower extents of reaction were also found in the case of vinyl groups located along the chains, probably because such groups are constrained by two chain sequences instead of one. The equilibrium elastomeric properties of both types of networks were interpreted using the structural information thus obtained and were found to be in good agreement with previous experimental results. They are also in satisfactory agreement with theory, without introduction of the highly questionable assumption of large contributions from interchain entanglements.
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  • 155
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2303-2305 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 156
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2369-2377 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A general equation for light scattering in multicomponent solutions is derived and applied to some important systems. The equation is compared with one published earlier by Casassa and Eisenberg [Adv. Protein Chem., 19, 287 (1964)], and the difference between them is explained.
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  • 157
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2391-2400 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Surface and interfacial activities of A(B)2 star-shaped block copolymers, where B is a polyoxirane block and A a polydiene or polyvinyl block, have been measured at 20°C. The surface tension of organic solvents is only slightly lowered by these copolymers, whereas a significant surface activity is noted in water. Interfacial tensions are dependent on both the nature of the organic solvent (aliphatic or aromatic hydrocarbons) and the molecular parameters of the copolymers; 50% polyoxirane seems to be the composition of maximum surface activity. The role played by the molecular architecture [A-B or A(B)2] of the copolymers is demonstrated. The same limiting interfacial tension is obtained on increasing the concentration of diblock [A-B] or star-shaped block [A(B)2] copolymer. The limiting value is, however, attained at significantly lower concentration with the star-shaped copolymers. Their ability to fill the interface is accordingly higher.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2415-2416 
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    Keywords: Physics ; Polymer and Materials Science
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  • 159
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1343-1359 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: A discussion of the general properties of the one-dimensional electron density correlation function K(z) of a partially crystalline polymer with lamellar structure shows that application of a graphical extrapolation procedure permits direct determination of the crystallinity, the specific inner surface, and the electron density difference ηc - ηa. The procedure is based upon the occurrence of a straight section in the “self-correlation” range of K(z). Curved and nonparallel lamellae do not invalidate the concept. In the case of heterogeneous samples composed of partially crystalline and totally amorphous regions, some of the parameters of the experimentally obtained correlation function, as for example the invariant K(0), are affected and may lose their definiteness. Use of the method is demonstrated in a detailed discussion of the correlation functions measured for a sample of lowdensity polyethylene at 25 and 100°C.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1403-1412 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier-transform infrared (FTIR) studies of the poly(β-propiolactone) (PPL)-poly(vinyl chloride) (PVC) blend system are presented. PPL-PVC blends are observed to be incompatible in the molten (80°C) and solid (25°C) states, over the entire range of compositions. This is in marked contrast to our previous results of the poly(∊-caprolactone)-PVC blend system which was shown to be compatible in the amorphous state. The results of both studies are compared and discussed with particular reference to the detection of intermolecular interactions by FTIR and correlation with compatibility in polyester-PVC blends. The role of the chemical interactions in the compatibilization of polymer blends is discussed in terms of thermodynamic considerations. Finally, it is well known that changes in refractive index of polymer blend compositions can cause frequency shifts of infrared bands, which are particularly relevant to the interpretation of residual peaks obtained by difference spectroscopy. The FTIR results of the PPL-PVC blends are germane to this subject and are discussed.
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  • 161
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1455-1468 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The addition of small amounts of polyfunctional agents can substantially alter the melt and the solid-state properties of polymers. A practical characterization scheme is necessary for control of polymer preparation and for process analysis. Trifunctionally branched samples of poly(2,2′-oxydiethylene trans-1,4-cyclohexanedicarboxylate) have been prepared as representative of polycondensation polymers. The Drott-Mendelson procedure was applied to the dilute solution data from gel permeation chromatography and intrinsic viscosity to yield the true molecular weight distributions and the average branching frequency. The melt zero-shear-rate viscosity of a branched sample was less than that of a linear sample of equal weight-average molecular weight, in good agreement with Bueche's theory. The melt elasticity, as measured by the terminal relaxation time, was equal to that of the equivalent linear polymer at constant weight-average molecular weight.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1485-1495 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics and equilibria of SO2 sorption in Kapton polyimide film have been measured at 25°C for pressures up to 58 cm Hg using a quartz spring balance. The observed equilibria are described well by the dual-mode model for sorption of penetrants in glassy polymers. Observed hysteresis in sorption-desorption cycling indicates that the diffusivity of SO2 increases markedly with increasing local penetrant concentration in the polymer. The concentration dependence of the effective average diffusion coefficient is described well by an expression from dual-mode theory. The Langmuir component of the sorption population has an extremely low mobility compared to that of the Henry's law component; in fact, the so-called “total immobilization” limiting case, which assigns a zero diffusion coefficient to this component, appears to be satisfactory under the conditions studied. These results, coupled with published results for other penetrants, suggest that the degree of immobilization of the Langmuir population depends to a great extent on the condensability and/or the molecular size of the penetrant. Predictions of the SO2 diffusion time lag and permeability in Kapton as functions of the upstream SO2 pressure are presented and discussed in terms of the dual-mode theory.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1561-1572 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: T1, T2, and T1ρ measurements are reported for a blended fiber of polyethylene and polypropylene prepared by the “surface growth” technique. The data support the view that the fiber contains mixed crystalline regions of each pure component that may weakly interact via spin diffusion. A tentative model is proposed for the blended fiber.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1609-1619 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Complex elastic, dielectric, and piezoelectric properties were measured on amylose films as a function of temperature and moisture content at 10 Hz. The real part of the complex Young's modulus of films containing a small amount of moisture was larger than that of a dry film. Peaks in the imaginary parts of these complex response functions were observed at about -80°C. The height of these peaks decreased when the specimen absorbed a little moisture. The activation energy for this peak as determined from an Arrhenius plot of the dielectric frequency dispersion was about 9.5 kcal/mole. This peak was ascribed to methylol rotation. The real part of piezoelectric e constant was shifted downwards when the specimen absorbed moisture. This was attributed to the instantaneous response in the case of a step function excitation. The structure of amylose was thought to be stabilized by moisture absorption, probably due to hydrogen bonding. The mechanism of methylol rotation was examined by dielectric measurements.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1651-1653 
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    Keywords: Physics ; Polymer and Materials Science
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1659-1661 
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    Keywords: Physics ; Polymer and Materials Science
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1697-1706 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Piezoelectric relaxation has been studied on elongated poly(γ-methyl-L-glutamate) films with the α-helical molecular conformation. Relaxation processes are observed near 0 and 100°C. Each process has a dual character composed of relaxational and retardational frequency dependences. The low-temperature process is ascribed to thermal motion of side chains. The high-temperature process, discussed in relation to the dielectric relaxation, is attributed to the ionic dc conduction connected with the two-phase structure of crystalline regions and the electrode polarization.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1685-1695 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: A purified, well characterized sample of polybenzimidazole (PBI) has been studied by fluorescence spectroscopy in order to obtain information concerning molecular aggregation in solution. Fluorescence and excitation spectra of PBI and a model compound have been measured in N,N-dimethylacetamide (DMA) and in formic acid (FA). The major emission band for PBI solutions is attributed an excited 1Lb state, which consists of 0-0 and 0-1 vibrational energy bands. Concentration quenching is attributed to reabsorption of the emitted light, and self-quenching due to the formation of molecular aggregates. Therefore, the extent of molecular aggregation in solution is estimated from the self-quenching constant. In the course of the investigation, a new fluorescence band was found for the PBI-DMA solution; its intensity increased markedly due to overlapping of polymer coils. The formation of polyelectrolytes in PBI-FA solutions was confirmed by viscometry. The major fluorescence band was found to originate from the excited 1Lb state and to shift to longer wavelengths upon addition of lithium bromide.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1753-1769 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental results of vibrational spectroscopic studies on the orthorhombic modification of poly(trans-pentenylene) and poly(trans-heptenylene) are discussed on the basis of a normal coordinate analysis for an isolated chain model.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1781-1790 
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    Notes: The porous-sphere model of Debye-Brinkman-Bueche is applied to predict the limiting frictional coefficient f0 and intrinsic viscosity [η] of polystyrene fractions in tetrahydrofuran and random protein coils in 6M guanidine hydrochloride. Following the formulation of Wiegel and Mijnlieff, the molecular permeability is modeled to increase exponentially as the square of the distance from the center of the molecule. A method is developed to obtain this permeability from the translational diffusion coefficient. The experimental values of f0 and [η] are in satisfactory agreement with the calculated values. Also, this analysis predicts values of the Mandelkern-Flory-Scheraga parameter for flexible coils which are significantly smaller than the minimum values permitted by the Kirkwood-Riseman theory. This is in accord with the experimental evidence.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1811-1820 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Analytical expressions are derived which relate the degree of orientation caused by a biaxial nonorthogonal pseudoaffine deformation to the conditions and parameters of drawing. They contain relations previously given by Kuhn et al. and Sasaguri et al. as special cases and can be evaluated in a way which allows a proper analysis of experimental data. The plastic and elastic components of the deformation can be estimated on the basis of these equations. The equations are useful for analysis of biaxial drawing, including technical drawing of polymer films and of the phenomenon of “bowing.”
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1821-1836 
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    Notes: The solution behavior of metal sulfonate-containing ionomers has been investigated in various mixed solvent systems. Ionomers, such as lightly sulfonated polystyrene (sodium salt) and sulfonated ethylene-propylene-diene terpolymer (metal salts) are generally insoluble in typical hydrocarbon solvents, but readily dissolve when small amounts of alcohols or other polar cosolvents are present. At relatively low polymer concentration these ionomers display unusually high thickening behavior in nonpolar solvents when compared with nonionic polymers because of association of the metal sulfonate groups. The addition of modest levels of polar cosolvent markedly decreases the solution viscosity and gives rise to viscosity-temperature relationships different from those of conventional polymer solutions. For example, such solutions can display vicosities which increase, are relatively constant, or display maxima or minima over broad temperature ranges. These observations are interpreted as arising from a temperature-dependent preferential interaction of the cosolvent with the sulfonate groups. While these ionomers can be regarded as polyelectrolytes of low charge density, they do not display the typical “polyelectrolyte” behavior often observed in aqueous solutions. This anomalous behavior is attributed to the fact that the metal sulfonate groups are largely un-ionized in solvents of low dielectric constant. Therefore, the solution behavior is dominated by ion pair interactions rather than free ions.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1853-1858 
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    Keywords: Physics ; Polymer and Materials Science
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1863-1878 
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    Notes: Three crystal modifications of poly(3,3-dimethyloxacyclobutane) [—CH2C(CH3)2CH2O—]n were found and their structures were analyzed by x-ray diffraction. Modification I is obtained only under tension and disappears on relaxing the tension. From the fiber period of 4.83 Å, the molecular structure seems to be planar zigzag. In modification II, two chains in T3GT3Ḡ conformation pass through a monoclinic cell with parameters a = 8.93 Å, b = 7.48 Å, c (fiber axis) = 8.35 Å, β = 97.9°, and the space group P21/c-C52h. In modification III, two (T2G2)2 chains pass through an orthorhombic cell with parameters a = 15.60 Å, b = 5.74 Å, c (fiber axis) = 6.51 Å, and the space group, C2221-D52. Molecular conformations of the three crystal modifications correspond to those of polyoxacyclobutane.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1919-1929 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Wide-angle and small-angle x-ray diffraction patterns of 11 poly(N-(10-n-alkyloxycarbonyl-n-decyl)maleimides) (PEMI) (including only even members of the series) have been obtained on unoriented samples. They show major maxima at two diffraction angles. The one at the larger angles is due to the interaction of neighboring n-alkyl side-chains. The smaller one (which shows second and third orders of diffraction in higher members of the series, n = 14 to n = 22, where n is the number of methylene groups in the external n-alkyl sequence in the side chain) is related to the distance between lamellar planes formed by the main chains. In all cases, the measured layer separation di is higher than the structural unit length L of the side-chain in the most extended conformation, and lower than the length corresponding to two side-chains. On the basis of the experimental results reported here, a model is proposed for the packing of these comblike polymers in the solid state. The mode of packing is also supported by infrared spectra in the 720 cm-1 region for the —CH2— rocking mode of vibration of the n-alkyl side-chain.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2337-2345 
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Homogeneous films comprised of mixtures of polystyrene and poly(vinyl methyl ether) can be obtained by evaporation from a ternary solution containing toluene as the solvent. Heterogeneous films result when the solvent is trichloroethylene. The possibility that a heterogeneous film cast from trichloroethylene can be transformed to a homogeneous one by physical means is a logical expectation when the polymer-polymer interaction is favorable, though as yet no comprehensive report has appeared in the literature. We have accomplished the transformation by increasing the temperature. Optical microscopy and glass transition experiments were employed to observe the effects.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2379-2389 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The high-pressure crystallization of polyethylene in a diamond cell has been studied by infrared spectroscopy. The splitting of the CH2 rocking band at 720-730 cm-1 as a function of pressure was analyzed. It was found that pressure alone up to 3 kbar will not change the distance between methylene groups in the unit cell. However, this distance can be shortened by crystallization at this pressure. Intensities of selected crystalline (1176 and 1050 cm-1) and amorphous (1303, 1352, and 1368 cm-1) bands were measured on samples before and after high-pressure crystallization, and also on samples of various densities crystallized under atmospheric pressure. The increase in the intensities of crystalline bands and concomitant decrease in amorphous bands, together with density changes, indicate that the crystallinity can be enhanced by crystallization under high pressure. Nevertheless, the crystallinity of polyethylene crystallized at high pressure is comparable with that of polyethylene crystallized at atmospheric pressure at low undercooling for long periods of time.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2417-2420 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 169-172 
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    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 173-174 
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 175-176 
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 177-179 
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 181-185 
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 189-198 
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    Notes: Temperature dependences of diffusion and permeation coefficients of hydrogen and deuterium in glassy and rubbery polymer films have been measured. The size of the free volume element in rubbery polymers has been calculated according to the theory of Frisch and Rogers for the quantum isotope effect, but the free volume is too large for precise calculation below the glass-transition temperature. The cooperative movement of segments is also discussed using the ratio of preexponential factors for diffusion mechanisms above and below the glass-transition temperature.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 301-309 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The drawing behavior of linear polyethylene homopolymers with weight-average molecular weights (M̄w) from 101,450 to ca. 3,500,000 has been studied over the temperature range 75°C to the melting point. In all cases 1-cm gauge length samples were drawn in an Instron tensile testing machine at a constant cross-head speed of 10 cm/min. With the exception of the lowest molecular weight polymer, it was found that increasing the draw temperature led to substantial increases in the maximum draw ratio which could be achieved, and that this increased monotonically with increasing draw temperature. Measurements of the Young's modulus of the drawn materials showed, however, that the unique relationship between modulus and draw ratio previously established for drawing at 75°C was not maintained to the highest draw temperatures. The highest draw temperature at which this relation held was found to be strongly molecular weight dependent, increasing from ca. 80 to ca. 125°C when M̄w increased from 101,450 to 800,000. In all cases conditions could be found for drawing samples to draw ratios of 20 or more with correspondingly large values of the Young's modulus.
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 311-325 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: A thermodynamic analysis of the thermally activated yielding of glassy atactic poly(methyl methacrylate) has been carried out. Samples were deformed in compression at a constant strain rate in the temperature range 150-330 K. Two different deformation modes are rate controlling below and above a critical temperature Tc of the order of 200 K. The low-temperature mode is characterized by a purely exponential stress dependence of the strain-rate, and thus defines a true stress-activation volume. The higher-temperature mode reveals a stress dependence of the strain rate in the form of a power law with a constant activation energy.
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  • 187
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 389-391 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 188
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 429-441 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The tensile properties of both cis- and trans-polyacetylene, (CH)x, were investigated in order to determine the variables that influence that ultimate extension ratio (l/l0) of polyacetylene films. It was found that when cis-films of polyacetylene were extended in an inert (argon) atmosphere, ultimate extension ratios as high as 3.3 were obtained and with subsequent isomerization at 160-200°C under stress, a final l/l0, of about 4 was obtained. The extension ratio is extremely sensitive to exposure to oxygen and decreases markedly after periods as short as 1 min. It appears as though crosslinking may occur in the polymer when it is exposed to air and this produces brittleness in the specimen. When (CH)x was isomerized from cis to trans, it became brittle, even in the absence of air.
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  • 189
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 449-456 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Heat capacities of liquid selenium have been measured by computer interfaced differential scanning calorimetry in the metastable region with an accuracy of ± 1% from 330 to 520°K. To avoid crystallization, the measurements were done on cooling. A semiquantitative fitting of the heat capacity to vibrational energy contributions, free volume (hole) effects, and heats of reaction from the changes in the ring-chain and depolymerization equilibria was possible to within ±5% of the newly measured and literature data between the glass transition temperature (ca. 303°K) and 1000°K. It could be established that the shift in the ring-chain equilibrium is not the major reason for the overall decrease in heat capacity above the glass transition temperature. The floor temperature, which was earlier placed at about 356°K, is possibly below the glass transition temperature. The increase in heat capacity beyond 800°K has been linked with the depolymerization reaction.
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  • 190
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Needlelike crystals of a phenylsilicon compound synthesized on crystallization during polymerization in a transport reaction in a temperature gradient, which were thought earlier to be polymeric diphenylsilylene, are shown to be actually tetraphenylsilane. Similarly produced crystals of the germanium analog led, in contrast, to polydiphenylgermylene. An overall reaction scheme uniting both reactions is suggested.
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  • 191
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 457-467 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Excimer formation has been studied in a series of ancenaphthylene - methyl methacrylate copolymers of content varying over the total composition range. In accord with a previous model [Reid and Soutar, J. Polym. Sci. Polym. Lett. Ed., 15, 153 (1977)], the excimer formation has been described by a composite function representative of energy migration and excimer site concentration. In tramolecular energy migration in glassy solutions of the polymers was characterized by use of fluorescence depolarization measurements. The extent of energy migration in the acenaphthylene copolymers is determined by the mole fraction of aromatic chromophore fa. A function Σ descriptive of the excimer site concentration has been generated on the assumption that excimer formation results predominantly from next- to nearest-neighbor interactions. Σ is based upon the pentad distribution of aromatic chromophores in the chain and contains pentad fractions appropriately weighted according to the frequency and relative importance of their potential excimer sites. Reactivity ratios of acenaphthylene and methyl methacrylate in copolymerization at 70°C were ra = 0.80 and rm = 0.57.
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  • 192
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 469-478 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Proton spin-lattice relaxation experiments on the bis-(p-toluenesulfonate) of 2,4-hexadiyne-1,6-diol (TSHD) as a function of temperature (25 to 353 K), of frequency (22 and 44 MHz), and of conversion to polymer were performed to determine the molecular motions in this crystal and to follow the conversion via the changes in the relaxation time T1. It was found that T1 is dominated below 125 K by weakly hindered (ΔE = 2.8 kJ/mole) tunneling (Λ = 220 MHz) CH3 groups, at about 160 K by order-disorder fluctuations around the phase-transition temperature ϑc which depends strongly on the conversion, and above 200 K by the motion of the whole side group. T1 can be used as sensitive probe for the conversion: The change in T1 at about 44 K is directly proportional to the conversion, whereas the change at high temperatures (e.g., 353 K) occurs essentially at low conversions (≤10%). This is explained by distorted (stressed) areas around the isolated polymer chains, which are estimated to be about 16 times the size of the chains. After an induction period the stresses are relieved by further polymerization.
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  • 193
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 479-492 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ethyl acrylate ionomers were studied by stress relaxation. The results are compared with those for the styrene ionomers studied previously. The behaviour of the two systems is qualitatively similar, although significant quantitative differences exist. Specifically, the onset of thermorheological complexity is found here at 12-16 mole% of ions, while in styrene it is observed at ca. 6 mole%. Furthermore, the modulus-temperature plots show great similarity if the present samples are compared with the styrenes containing about half as many ions. Other properties show similar trends. The increased dielectric constant of the acrylates is believed to be responsible for the observed differences in the two systems. The effect of a change in counterions was also studied to some extent. The onset of thermorheological complexity is seen to be qualitatively related to the size and charge of the cation.
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  • 194
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 493-509 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of molecular weight and temperature on the tensile drawing behavior of polypropylene has been studied, with particular reference to the production of ultra-high-modulus oriented materials. It has been shown that the optimum draw temperature is molecular weight independent to a good approximation, and that high-modulus products can be obtained for M̄w in the range 180,000-400,000, the highest modulus being achieved for polymer with M̄w = 181,000. As in the case of linear polyethylene, under optimum drawing conditions the Young's modulus relates only to the draw ratio. Low-temperature moduli as high as 25-27 GPa were recorded, which compare favorably with a previously reported value of 42 GPa for the crystal-lattice modulus. Although the drawing behaviour of the samples studied appeared comparatively insensitive to molecular weight, some of the properties of the draw materials, notably melting point and shrinkage at high temperature, showed a wide range of behavior.
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  • 195
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 511-521 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When certain substances, notably waxes, are incorporated into rubber during vulcanization, the surface of the vulcanized rubber may subsequently become covered by a film of the substance diffusing out. This phenomenon, known as blooming, depends on the substance being soluble at the vulcanization temperature but only partially soluble at the temperature of blooming. A study has been made using pure waxes in natural rubber vulcanizates with a range of crosslink densities. The mass of bloomed material has been determined as a function of time, and the expected dependence on the square root of the time has been found to hold over the anticipated range. It has been shown that the kinetics of the process cannot be explained simply in terms of the degree of supersaturation of the wax in the rubber, the observed rates being much too low. This appears to be related to the precipitation of the wax in the body of the material. A theory has been developed based on a calculation of the stresses set up around such a precipitated particle and the effect of the consequent free-energy gradient on the rate of diffusion. Comparison with experiment shows satisfactory agreement with the theory.
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  • 196
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 523-527 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photocurrents induced by pulsed ultraviolet light in polyhexamethylene adipamide (nylon-66) have been studied. Two transient photocurrents are observed for light wavelenghts shorter than 3000 Å;. The first one is weakly field and temperature dependent and has been ascribed to electron photoinjection. On the whole, the time dependence of the two photoresponses suggests the possible formation of a space charge in the material.
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  • 197
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 529-536 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The continued fraction formalism of Mori is adapted to study the coherent scattering law of dilute polymer solutions. Calculations are carried out for the Rouse chain to see the effects of the memory function. We find such effects to be significant.
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  • 198
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 537-546 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoelasticity studies of poly(vinyl alcohol) networks swollen in aqueous glycol indicate that the effects of specific polymer-diluent interactions diminish at high swelling, much as in the situation of poly(vinyl alcohol) in pure water reported earlier. In 20% glycol, the ratio of the energy component fe of the force to the total force f was found to be -0.59 at high swelling. Swelling was controlled by the degree of network crosslinking. Evidence that fe/f could be determined under the condition of a null thermal expansion coefficient was not obtained; in fact, the contrary was indicated.
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  • 199
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 547-558 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: From sedimentation equilibrium, light scattering, and viscosity measurements on a series of native and sonicated samples of schizophyllan, and extracellular β-1,3-D-glucan, the following results were obtained: (i) weight-average and z-average molecular weights (M̄w and M̄z) in water are about three times as large as those in dimethylsulfoxide (DMSO); (ii) the exponent in the Houwink-Mark-Sakurada intrinsic viscosity relation in water is close to 1.7, whereas in DMSO it is 0.68; (iii) intrinsic viscosities of samples with M̄w below 5 × 105 in water at 25°C can be fitted by Yamakawa's theory for along rigid rod if the pitch (1.836 nm) of the triple helix of Atkins et al. and the diameter (3 nm) estimated from the model triple helix are used; (iv) intrinsic viscosities in water-DMSO mixtures at 25°C undergo and almost discontinuous decrease when the weight fraction of DMSO in the mixture increases to about 87%. These results combined lead to the conclusion that schizophyllan dissolves in water as a triple helix similar to that proposed by Atkins et al. and that the triple helix in aqueous DMSO solution “melts” abruptly to single chains when the DMSO coposition reaches about 87 wt%. It was also found that the triple helix is not recoverable once it is broken in DMSO.
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  • 200
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    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 559-573 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In many cases, polymer adsorption is studied by measuring adsorption isotherms. Quite often it is found that the results are at variance with theoretical predictions. However, usually these adsorption isotherms are interpreted in terms of a single polymeric solute. Most polymers used in experimental studies are polydisperse and should be treated as mixtures. It is well established that the larger molecules in such mixtures adsorb preferentially over the smaller ones. In this paper we show that many discrepancies between polymer adsorption theory and experiment (e.g., the rounded shape of isotherms, the dependence of the adsorbance on adsorbent concentration, and the lack of desorption upon dilution) can be attributed to polydispersity. A quantitative analysis enables us to calculate isotherms for a polymer of arbitrary molecular weight distribution, provided the dependency of the plateau adsorbance on molecular weight is known. Experiments supporting the theory are reported. The fact that polymers do not desorb upon dilution with solvent is often regarded as a proof that polymer adsorption is irreversible. We show that, if a polydisperse sample is in equilibrium with an adsorbing surface, no detectable desorption may take place upon dilution. Therefore, the adsorption of polymers might well be reversible, even if desorption experiments would indicate apparent irreversibility.
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