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  • 1
    Electronic Resource
    Electronic Resource
    Dynamics of macromolecular chains. III. Time-dependent fluorescence polarization studies of local motions of polystyrene in solution (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 11-27 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fluorescence anisotropy decay experiments are described for polystyrene in various ethylacetate-tripropionin mixtures. Decay curve trends agree with the proposed theoretical autocorrelation function. Study of the effects of viscosity shows that the mean relaxation time varies according to a nonlinear law for low viscosities and that the relaxation time θ, reflecting the effects of the possible departures from the motions permitted by an ideal tetrahedral lattice, obeys a law of the type: θ = α + bη. Furthermore, the effects of the direction of the fluorophore transition moment are examined.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140102
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  • 2
    Electronic Resource
    Electronic Resource
    Quasielastic scattering by dilute polymer solutionsA summary of this work was presented at the IUPAP International Conference on Statistical Physics, August 25-29, 1975. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1-10 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The scattering law S(k,w) for dilute polymer solutions is obtained from Kirkwood's diffusion equation via the projection operator technique. The width Ω(k) of S(k,w) is obtained for all k without replacing the Oseen tensor by its average (as is done in the Rouse-Zimm model) using the “spring-bead” model ignoring memory effects. For small (ka\documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt N $ \end{document} ≪ 1) and large (ka ≫ 1) values of k we find Ω = 0.195 k2/β α η0 \documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt N $ \end{document} and Ω = k2/βξ, respectively, indicating that the width is governed mainly by the viscosity η0 for small k values and by the friction coefficient ξ for large k values. For intermediate k values which are of importance in neutron scattering we find that in the Rouse limit Ω = k4a2/12βξ. When the hydrodynamic effects are included, Ω(k) becomes 0.055 k3/βη0. Using the Rouse-Zimm model, it is seen that the effect of pre-averaging the Oseen tensor is to underestimate the half-width Ω(k). The implications of the theoretical predictions for scattering experiments are discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140101
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  • 3
    Electronic Resource
    Electronic Resource
    Ion recombination luminescence in polymer glasses induced by electron irradiation. I. High-vinyl polybutadiene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 437-449 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The luminescence of 1,2-polybutadiene was measured during and following irradiation with 1.4-MeV electrons at 90 °K. Measured under isothermal conditions, the light intensity at first increases sharply on start-up of irradiation, and then reaches a plateau after several seconds. The equilibrium value was found to be linearly dependent on the dose rate employed. The postirradiation luminescence decay measured at 90°K follows second-order kinetics.The light emitted by the irradiated sample during warm-up to room temperature is characterized by the appearance of four intensity maxima at 118, 168, 223, and 261 °K. The first three peaks are attributable to the onset of local motion, whereas the peak at 223 °K is caused by the long-range motion occurring at the glass-to-rubber transition. A preirradiation of the polymer in vacuo causes an increase in these four peaks as well as the formation of a new maximum at 143 °K.Intermittent exposure of the irradiated sample to light of wavelengths λ 〉 450 nm causes the isothermal luminescence decay to be interrupted by a burst of light emitted by the sample during and shortly following the light exposure. This treatment also results in considerably reduced intensity maxima during warm-up to room temperature. An interpretation of the findings reported is given on the basis of reactions involving primary and secondary transient species produced during irradiation and on the molecular parameters of the polybutadiene.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140306
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  • 4
    Electronic Resource
    Electronic Resource
    Piezoelectric properties of oriented films of poly(γ-methyl D-glutamate) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 401-414 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic piezoelectric stress constant e*25 of drawn films of poly(γ-methyl D-glutamate) (PMDG) cast from solutions in α-helix-promoting solvents 1,2-dichloroethane (DCE) and chloroform and from the nonhelicogenic solvent dichloroacetic acid (DCA) was measured from -180°C to 200°C at 110 Hz. The drawn and annealed films cast from chloroform show a small peak for the real part of piezoelectric stress constant -e′25 in the temperature range of the mechanical α2-crystalline relaxation, which is caused by the distortion motion of the backbone chain of the α-helix. On the other hand, drawn films cast from DCE show the peak of the real part of the piezoelectric stress constant, whose magnitude decreases in the range of the mechanical α1-crystalline relaxation or the β-relaxation processes, which were previously ascribed, respectively, to mutual slipping of α-helices and to the micro-Brownian motion of disordered regions. Also, -e′25 becomes virtually zero near 180°C where the α2-relaxation is located. These results suggest that the polarization change induced by applied strain is caused by distortion of the backbone chains in the α-helix. Near 0°C, the temperature range of the side-chain mechanical relaxation, -e′25 exhibits a marked peak both for films cast from chloroform and from DCE. The maximum value of -e′25 and the orientation function of the α-helix axis are linearly related and extrapolation of -e′25,max to unit orientation function gives 1.3 × 104 cgs esu which corresponds to 2.4 Debye per residue. This value corresponds reasonably to the value of 3.71 Debye for the permanent dipole moment of NHCO bond if the correction for crystallinity is made. This result also indicates the piezoelectric properties of PMDG arise from distortion of the backbone chain of the α-helix induced by applied strain.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140303
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  • 5
    Electronic Resource
    Electronic Resource
    An anomalous transition to a lower activation energy for dc electrical conduction above the glass-transition temperature (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 955-957 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140516
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  • 6
    Electronic Resource
    Electronic Resource
    Quantitative information from x-ray diffraction of nylon-6 yarns. II. Physical aspects of some quantitative parameters (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 941-954 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A mathematical model developed in an earlier paper describes the experimental x-ray profiles of equatorial nylon-6 reflections in terms of Pearson VII functions. The present paper deals with the physical aspects and interpretations of the interrelations of the parameters obtained and the relation between these parameters and the results of other types of measurements. It was found that the growth of the crystallites perpendicular to the chain axis is not isotropic, the strongest growth being in the direction of the hydrogen bonds. Growth and perfection of the crystallites are found to be highly correlated. Large crystals are related to short distances between the planes containing the hydrogen bonds and so to densely packed, i.e., perfect unit cells. This correlation forms the basis for the observed similarity between our quantification technique and the method of the crystal perfection index introduced by Statton. Curve resolution, however, makes the method better applicable for poorly crystallized samples. Comparison of the results with those of small-angle x-ray scattering gave a high degree of consistency with respect to the determined crystal size. In the literature mention is made of a relation between the dimensions and the melting point of the crystals; this relation is confirmed by comparing the appropriate x-ray parameters with DTA results of methoxymethylated nylon 6-yarns.Information about the γ-phase can be obtained from equatorial and meridional reflections. The expected relationship between the relevant peak areas was established. This reported evidence shows the physical validity of the parameters obtained using the Pearson VII model for the analytical description of x-ray reflections of nylon-6 yarns.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140515
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  • 7
    Electronic Resource
    Electronic Resource
    Glass transitions of ethyl acrylate-based ionomers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1201-1209 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The glass-transition temperatures of a series of copolymers of ethyl acrylate and acrylic acid neutralized with various cations were investigated. It was found that a plot of Tg as a function of ion content, for every type of ion investigated here, gives an unusual sigmoidal curve, which can be correlated with the onset of the failure of time-temperature superposition in viscoelastic studies, as will be shown in a future publication. Also, all of the Tg versus concentration curves for the various counterions can be superposed if the plots are made against cq/a, where c is the metal acrylate content, q the cation charge, and a the distance between centers of charge. Furthermore, in one region of water content, a linear relation is obtained between the glass transition and the water content (in weight-%) independent of the ion concentration over wide ranges of ion content. Finally, above an ion concentration of 12 mole-%, the rate of change in Tg per water molecule per ion pair at constant ion content, (∂Tg/∂n)c is linear but with different slopes above and below two water molecules per ion pair.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140705
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  • 8
    Electronic Resource
    Electronic Resource
    Enthalpy relaxation of rigid poly(vinyl chloride) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1087-1095 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The changes which take place on annealing rigid PVC in the vicinity of the glass transition have been followed by differential scanning calorimetry. The changes appear as an increase in the glass-transition temperature and a decrease in the enthalpy with time of annealing. For annealing at 75°C, the enthalpy after 50-100 hr approaches the value characteristic of the equilibrium liquid state. The results obtained for annealing at 65°C and 75°C are in accord with those expected for the relaxation of an amorphous material, and are at variance with those expected on the basis of crystallization taking place on annealing. The enthalpy relaxation process is characterized by a distribution of activation energies centered about 18.8 kcal mole-1, and seems to reflect a multiplicity of molecular processes.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140611
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  • 9
    Electronic Resource
    Electronic Resource
    Newtonian behavior of a styrene-butadiene-styrene block copolymer (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1149-1156 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melt rheological behavior of an anionically polymerized styrene-butadiene-styrene (SBS) block copolymer sample (S: 7 × 103 and B: 43 × 103) was studied using a Weissenberg rheogoniometer. Highly non-Newtonian behavior, high viscosity and high elasticity, which are characteristics of ABA type block copolymers, were observed at 125°C, 140°C, and 150°C. The data at these temperatures superimposed well onto a master curve giving a constant flow activation energy. However, the data at 175°C indicated a marked change in the flow mechanism between 150°C and 175°C. At 175°C, the sample showed Newtonian behavior, negligible elasticity, and deviation from the master curve. These findings may be considered as an indication that the SBS block copolymer sample undergoes a structural change from a multiphase structure at low temperatures into a homogeneous structure at some temperature between 150°C and 175°C.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140616
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  • 10
    Electronic Resource
    Electronic Resource
    Isotactic poly(pentene-1): Form III (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1161-1167 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new crystalline form of isotactic poly(pentene-1) was obtained from dilute solution in amyl acetate. We have designated it as form III. The morphology and structure of isothermally crystallized samples were investigated by electron microscopy and electron and x-ray diffraction. This crystalline modification can be indexed on an orthorhombic unit cell (cell dimensions: a = 21.20 ± 0.05 Å, b = 11.48 ± 0.05 Å, c = 14.39 ± 0.05 Å (fiber axis) and probable space group P212121).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140701
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  • 11
    Electronic Resource
    Electronic Resource
    Phase equilibrium and glass-transition temperatures in plasticized amorphous bisphenol-A polycarbonate (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1187-1199 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Glass-transition temperatures and phase separation have been studied in amorphous bisphenol-A polycarbonate plasticized with pentaerythritol tetranonanoate (PETN), trimellitic acid, tridecyloctyl ester (TMDO), and tritolyl phosphate. (TTP). Phase separations occur with partially compatible plasticizers like PETN or TMDO. With PETN, for compositions situated in the miscibility gap, the system is composed of a pure plasticizer phase and of a plasticized polymeric phase characterized by a transition temperature of 110°C. In the case of TMDO and additional phase separation occurs below 55°C and two plasticized polycarbonate phases are observed. In compositions falling in the region where the could point curve crosses the glass-transition diagram the phase separation may be delayed by quick cooling. TTP is completely compatible with polycarbonate and the variation of the glass-transition temperature follows a Gordon and Taylor equation.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140704
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  • 12
    Electronic Resource
    Electronic Resource
    Thermal expansion and compressibility in the chain direction of a polydiacetylene single crystal (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1235-1240 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An x-ray back-reflection rotating camera has been used to measure the lattice constant, thermal expansion, and compressibility in the polymer chain direction of a polydiacetylene, poly[bis(p-toluene sulfonate) of 2,4-hexadiyne 1,6-diol]. The thermal expansion coefficient of the polymer chain is small and positive (0.9 ± 0.2 × 10-6 °K-) at 300°K, but negative below about 70°K. Application of 3.43 kbar hydrostatic pressure at 299°K changed the unit cell dimension in the polymer chain direction by less than 10 ppm.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140708
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  • 13
    Electronic Resource
    Electronic Resource
    Persistence vectors for polypropylene, polystyrene, and poly(methyl methacrylate) chains (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1425-1431 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Persistence vectors a ≡ 〈r〉 are calculated for polypropylene, polystyrene, and poly(methyl methacrylate) chains as functions of chain length and stereochemical constitution. Differences between the progressions of a with chain length for these vinyl polymers are related to their conformational characteristics. The preferences of the syndiotactic chains for the tt dyad conformation are manifested most strikingly in the behavior of this vector.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140806
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  • 14
    Electronic Resource
    Electronic Resource
    Small-angle x-ray and light scattering studies of the morphology of blends of poly(∊-caprolactone) with poly(vinyl chloride)Abstracted in part from a Thesis for the Ph.D. degree submitted by F.B.K. in the Polymer Science and Engineering Program, University of Massachusetts. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1391-1424 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvent-cast films of blends of poly(∊-caprolactone) (PCL) with poly(vinyl chloride) (PVC) were examined by low-angle x-ray scattering and by small-angle light scattering. X-ray scattering from crystalline compositions were analyzed using the Tsvankin-Buchanan technique and led to values of the repeat period of the lamellar structure and the thickness of the crystalline and amorphous layers. With increasing content of PVC, the amorphous layer thickness increased sufficiently to accommodate the PVC, leading to values of the linear crystallinity consistent with macroscopic measurements by density and DSC techniques up to about 50% PVC by weight. Above this concentration, the lamellar structure no longer appeared to be volume filling. At high concentration of PCL, the polymer consisted of volume-filling spherulites containing the lamellar substructure. Spherulite sizes were measured by light scattering and absolute light scattering intensities were consistent with calculations based upon the degree of crystallinity and anisotropy of the spherulites. Compositions containing more than 60% PVC were amorphous. Low-angle x-ray scattering was interpreted in terms of the Debye-Bueche theory which leads to values for a correlation distance lc and the mean-square electron density fluctuation 〈η2〉 (which was also obtained from the invariant). By the method of Porod, the correlation distances were resolved into persistence lengths within the two phases, which were determined as a function of composition. The fluctuation 〈η2〉 was analyzed in terms of a two-phase model to show that its value was somewhat larger than would be obtained if the phases were composed of the pure components. It was not possible to uniquely determine their compositions. The data were consistent with the existence of a transition zone of the order of 30 Å thick between phases.
    Additional Material: 23 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140805
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  • 15
    Electronic Resource
    Electronic Resource
    The determination of the molecular weight distribution of amylose by gel permeation chromatography (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1485-1493 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The universal calibration for gel permeation chromatography (GPC) has been applied to amylose and dextrans. The molecular weight distribution of amylose has been measured starting from known data on dextrans. The agreement found between the molecular weight averages resulting from GPC and those obtained by other methods justifies the procedure followed. The GPC measurements were performed with dimethylsulfoxide as the elution solvent and deactivated silica gel (Porasil) as the column-filling material.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140810
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  • 16
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    Changes in light scattering from poly(ethylene terephthalate) and nylon 6 films upon stretching in relation to the deformation mechanism (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1495-1512 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Unoriented T-die flat films of nylon 6 and PET films annealed at 90°C were stretched in water at 80°C. Amorphous PET films were stretched in water at 65-75°C. Changes in the light scattering patterns from these samples upon stretching were investigated. One of the observed LS patterns from the stretched samples is the Hv eight-leaf pattern consisting of four lobes and streaks. In the nylon 6 and heat-treated PET showing this pattern, spherulitic patterns can be seen in polarization microscopy. The microscopic spherulitic superstructure may possibly be the factor responsible for producing the lobe-and-streak pattern. On the other hand, many microscopic eight-leaf patterns can be observed in amorphous unannealed PET showing the lobe-and-streak pattern. These microscopic patterns are due to retardation at stress concentrations around impurities and nuclei. The superstructure giving these microscopic patterns must be the origin of the lobe-and-streak pattern from unannealed PET. Another scattering pattern, the Vv cruciform pattern, was observed in both stretched nylon 6 and unannealed PET. This pattern is due to an orientation change across the slip lines observed under a polarizing microscope. It is noted (1) that the appearance of the slip lines in PET coincides with the occurrence of oriented crystallization on stretching, (2) that the lobe-and-streak pattern from PET in which orientation crystallization has taken place is fairly stable to heat treatment and does not disappear until just before melting, and (3) that the superstructures produced at low stretching seem to be deformed on further stretching, in accordance with affine deformation theory.
    Additional Material: 17 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140811
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  • 17
    Electronic Resource
    Electronic Resource
    A kinetic effect in the environmental stress cracking of polyethylene due to liquid viscosity (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1567-1573 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An Interesting kinetic effect in the environmental stress cracking (E.S.C.) of polyethylene has been observed, in which the liquid viscosity plays an important role. E.S.C. of a low density, high melt index polyethylene due to silicone oils has been studied using constant load creep experiments. For relatively low stresses, it has been found that the time to fracture is independent of the viscosity of the silicone oil, all other factors being approximately equal. However, at high stresses, the time to fracture increases with increasing viscosity for a given stress. This effect has been shown to be due to the relative ease with which the liquid penetrates a growing crack and thus always be at the crack front. Times to fracture for viscous liquids at high stresses are longer since crack propagation continues partially with and partially without liquid contact, fracture rate being much slower when not in the presence of the liquid.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140904
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  • 18
    Electronic Resource
    Electronic Resource
    Directional anisotropy of dielectric β-relaxation in oriented poly(ethylene terephthalate) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1591-1599 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric β-relaxation in oriented poly(ethylene terephthalate) was investigated over wide ranges of frequency and temperature, with the electric field applied at inclinations of 0°, 45°, and 90° to the draw direction. Pronounced directional anisotropy is observed over the entire range of temperature and frequency. With the external field parallel to the draw direction the dielectric loss is considerably smaller than the value obtained with the field normal to the draw direction. The value obtained with the electric field at 45° to the draw direction is intermediate between the other two. On the other hand, the activation energy is largest for 0° inclination and smallest for 90° inclination. It is suggested that motions of the dipoles involve localized rocking of the molecular chain backbone, particularly when the external electric field is parallel to the chain direction.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140906
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  • 19
    Electronic Resource
    Electronic Resource
    Mechanical relaxations in γ-ray-polymerized polyethylene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1659-1669 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic mechanical properties of cold-compacted films of polyethylene prepared by γ-ray-induced polymerization in bulk at 30°C are discussed in connection with the fine structure. The cold-compacted films show a broad α-relaxation at a lower temperature than do single-crystal mats or melt-crystallized polymer. From the effects of annealing and swelling by carbon tetrachloride on the relaxation, it is concluded that the α-relaxation, like the α-relaxation in the single-crystal mats, originates from molecular motions within lamellar crystals. This is consistent with the finding that these films are composed of stacked small irregular lamellar crystals. The γ-relaxation is also similar to that in crystal mats.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140911
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  • 20
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    The drawing behavior of linear polyethylene. I. Rate of drawing as a function of polymer molecular weight and initial thermal treatment (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1641-1658 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The drawing behavior of a series of linear polyethylene homopolymers with weight-average molecular weight (M̄w) ranging from 67,800 to ∼3,500,000 and variable distribution (M̄w/M̄n = 5.1-20.9) has been studied. Sheets were prepared by two distinct routes: either by quenching the molten polymer into cold water or by slow cooling below the crystallization temperature (∼120°C) followed by quenching into cold water.When the samples (2 cm long) were drawn in air at 75°C using a crosshead speed of 10 cm/min it was found that for low M̄w polymers the initial thermal treatment has a dramatic effect on the rate at which the local deformation proceeds in the necked region. At high M̄w such effects are negligible. An important result was that comparatively high draw ratios (λ 〉 17) and correspondingly high Young's moduli could be obtained for a polymer with M̄w as high as 312,000. It is shown how some of the structural features of the initial materials (mainly studied by optical microscopy, small-angle x-ray scattering and low-frequency laser Raman spectroscopy) can be interpreted in terms of the molecular weight and molecular weight distribution of the polymers. Although crystallization and morphology can be important at low M̄w, it suggested that the concept of a molecular network which embraces both crystalline and noncrystalline material is more helpful in understanding the drawing behavior over the whole range of molecular weights.
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    Carbon-13 NMR spin-lattice relaxation times of isotactic and syndiotactic sequences in amorphous polypropylene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1693-1700 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Spin-lattice relaxation times (T1) for methyl, methylene, and methine carbons in an amorphous polypropylene have been measured as a function of temperature from 46 to 138°C. The carbons from isotactic sequences characteristically exhibited the longest T1's of those observed. The T1 differences increased with temperature with the largest difference occuring for methine carbons where a 32% difference was observed. Activation energies were determined for the motional processes affecting T1's for isotactic and syndiotactic sequences with essentially no dependence upon configuration noted.
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    Design considerations for measurement of gas sorption in polymers by pressure decay (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1903-1907 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180141014
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    Epitaxial crystallization of cellulose II on valonia cellulose (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1913-1916 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180141016
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    Extensional infrared orientation (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1921-1929 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In evaluating molecular orientation by dynamic infrared techniques, it is shown, subject to certain restrictions, that an extensional mechanism plays an important role in the measured orientation. Dichroic measurements can indicate a change in segmental orientation without any change occurring in the chain axis orientation. Extensional orientation was evaluated for a general helical molecule in terms of singular and coupled vibrational modes. Significant orientation changes can occur by the extensional mechanism, the sign and magnitude of which depend on the components of the transition moment vector.
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    A method for the evaluation of the activation energy from relaxation experiments (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1801-1812 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is proposed for calculating the activation energy over the entire temperature range from relaxation measurements at two frequencies as a function of temperature by taking into account the entire experimental curve. The method is independent of the distribution of relaxation times, but assumes the validity of the time-temperature superposition principle.
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    The effect of sorbed oxygen on the γ and δ dielectric relaxations in polystyrene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1871-1875 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The γ and δ relaxations of polystyrene (PS) are rendered more active dielectrically by sorbed oxygen. This effect, coupled with comparative work on molecularly similar systems has led to the assignment of the γ relaxation to a rotational libration of the phenyl ring in PS. Specific interactions of the pendant phenyl ring with molecular oxygen to induce off-axis dipole moments in the phenyl moiety is proposed. It is concluded that this interaction is strong enough to influence the dielectric relaxation strength of other relaxations in PS. It is further concluded that because of the interactions occuring in aromatic polymers containing sorbed oxygen, care must be taken to exclude oxygen or to vary its content, in order that intrinsic motions in the polymer system can be studied.
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    Brillouin scattering from amorphous poly(ethylene terephthalate) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1909-1912 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180141015
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    Broadline NMR study of plasma-polymerized styrene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1917-1919 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180141017
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    High-resolution gel-permeation chromatography of high molecular weight polymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2105-2108 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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    Phenoxy single crystal aggregates (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2109-2112 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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    Characterization of polystyrene networks by small-angle neutron scattering (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2119-2128 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polystyrene networks prepared by anionic polymerization have been characterized by small-angle neutron scattering. Two kinds of systems have been examined:(A) networks with labelled branch points allowing characterization of the spatial distribution of crosslinking points; (B) networks containing a low proportion of chains labelled with perdeuterated polystyrene in order to characterize the conformation of individual elastic chains of the polymeric network. The dependence of the results on swelling and uniaxial extension is discussed.
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    Birefringence and stress relaxation in polyisobutyleneThis work was part of the research program of the Rheology Research Center, University of Wisconsin, Madison, Wis. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2129-2136 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Relaxation of birefringence and stress in simple extension has been studied for polyisobutylene at -26.0°C and 25.0°C for extension ratios ranging from about 1.2 to 2.0. The dependence of both the stress and birefringence on the extension ratio, for a given time, is well described by equations of the Mooney-Rivlin form. The Mooney-Rivlin treatment of the birefringence experiments was found to reinforce but not add to information available from the stress-relaxation experiments alone. At 25.0°C, the stress-optical coefficient is found to be stress dependent. Possible explanations of this behavior are discussed. An experiment is also reported in which the birefringence is observed under zero stress immediately after cutting a strained sample. The zero stress birefringence is believed to be due to regions of stress-induced crystallization taking a finite time to melt after the stress is removed.
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    Environmental effects on the mechanical properties of reconstituted collagen hollow fiber membranes (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2195-2209 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The lateral swelling, changes in length and tensile stress-strain curve of reconstituted collagen hollow fibers, crosslinked with uv irradiation, were measured as a function of the pH and ionic strength of their aqueous environment. From pH 5 to pH 10 the lateral swelling and length are constant; at lower and higher pH the lateral swelling increases rapidly while the fiber shrinks in length. Corresponding to these changes, a pronounced toe develops in the stress-strain curve and extends to a higher strain in more acid (or basic) media. This toe is attributed to the straightening of a microcrimp in the collagen fibrils; the microcrimp is accentuated by the repulsion between the charged fibrils in acid or basic media. Direct small-angle x-ray evidence of these microcrimp structure changes at low pH is presented. Increasing the ionic strength of an acid solution by adding NaCl decreases the lateral swelling, increases the length, and decreases the extent of the toe on the stress-strain curve. These changes result from an increased screening of the charge on neighboring fibrils at higher ionic strengths thus decreasing the repulsion between fibrils and the resulting microcrimp. Although the zigzag elastica model of the crimp developed by Diamant et al. [Proc. Roy. Soc., Ser. B, 180, 293 (1972)] provides a good empirical fit to the stress-strain data, it is shown to be inappropriate where the crimp results from repulsive forces between fibrils. A new model taking these forces into account is developed and is shown to be in reasonable agreement with the experimental results.
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    Dipole moments of poly(ethylene oxide) and poly(hexamethylene oxide) chains (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2231-2240 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mean-square dipole moments of poly(ethylene oxide) and poly(hexamethylene oxide) chains have been determined from dielectric constant measurements on dilute solutions of the polymers in benzene. The values obtained are in good agreement with those predccted using the rotational isomeric state models for these chains. In addition, the unperturbed dimensions of poly(hexamethylene oxide) have been calculated as a function of molecular weight, using the isomeric state theory.
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    The theory of phase transition kinetics with growth site impingement. II. Heterogeneous nucleation (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2253-2257 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of phase transformation are treated for heterogeneous nucleation, where all nuclei are simultaneously initiated, and where initiation follows first-order kinetcs. The phase transformation curves are sigmoid. For simultaneous initiation in two dimensions, a(t)/(1 - a(t)) ∝ t2. For first-order initiation, we have, approximately, a(t)/(1 - a(t)) ∝ t2.85, and v(t)/(1 - v(t)) ∝ t3.74.
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    Effects of inorganic salts on the properties of aqueous poly(ethylene oxide) solutions (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2241-2251 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cloud-point curves have been determined for aqueous solutions of poly(ethylene oxide) (PEO) at several concentrations for a variety of inorganic salts (sulfates, carbonates, nitrates, and chlorides). From these, theta conditions have been determined. The resulting dependences of the critical temperature θ (mostly between 300 and 360°K) on the molar concentrations (or ionic strengths) of the salts in solution cannot wholly be summarized in sequences of ion effects. The major findings are that sulfates and carbonates are much more effective in reducing θ than the chlorides and nitrates at the same concentrations. The trends found depend on salt concentration, i.e., certain plots of the data cross over, but they broadly agree with those found for comparable systems by other workers. Exceptional are the chlorides of Group II and LiCl which show minima when θ is plotted against molar salt concentration. While interpretations based on solvent structure-breaking are not adequate, there are similarities in behavior with the structure-breaking attributes of the ions based on independent studies (infrared). The results are briefly discussed in terms of current postulates: a more detailed discussion will accompany further experimental studies on these systems.
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    Mechanical relaxations in some ionene polymers. II. Influence of counterions and absorbed water (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2273-2284 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Six 6,10-ionenes with different counterions were prepared by ion exchange reactions in aqueous solutions. The counterions were Br, I, CIO4, BF4, SCN, and B(C6H5)4. The dynamic mechanical properties of these polymers were investigated by use of a torsional braid analyser. Three relaxations α (25-140°C), β (-30-0°C), and γ (-140-120°C) were observed at the frequencies of 0.3-0.8 Hz. The temperature of the α and β relaxations were largely dependent on the size of counterions, but those of the γ relaxations had little variation. The effects of electrostatic forces in the polymers on each relaxation was discussed. The influence of absorbed water on the α, β, and γ relaxations was examined. The absorbed water in the polymers greatly depressed the temperature of the α relaxations and this phenomenon was interpreted to be the result of the specific hydration on ionic portions.
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    Rapid small-angle and wide-angle x-ray studies of crystallization behavior in polymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2291-2311 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle and wide-angle x-ray scattering measurements, using a position-sensitive detector, were made during melt-crystallization of linear polyethylenes and PEO-PS-PEO triblock copolymer. The scattering measurements indicated that the triblock copolymer grew by the enlargement of regions in which lamellae are regularly stacked. During primary crystallization at higher temperatures similar behavior is observed in two linear polyethylenes. At lower temperatures, changes in the shape of small-angle scattering curves during the primary stage of crystallization indicate that amorphous gaps within the lamellar stacking become filled in. During secondary crystallization at higher temperatures new crystallites appear to grow between those formed in the primary stage. Concurrent decrease of the overall scattered intensity leads to the conclusion that secondary crystallization has two components: crystallization of new lamellae behind the spherulite growth front and the thickening of existing lamellae.
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    A crystallographic study of polymers exhibiting side-chain crystallization (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1241-1255 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fibers were drawn from polymers of octadecyl acrylate, octadecyl methacrylate, N-octadecylacrylamide, and a series of N-substituted acrylamides with a second amide group in the side chain as well as from copolymers of octadecyl and methyl esters of acrylic and methacrylic acid. Wide-angle and small-angle x-ray diffraction patterns were recorded for these materials. The interpretation of the characteristic difference between the behavior of the polycrylates and polymethacrylates, as proposed by Platé and his collaborators, is found to be inconsistent with a number of features of the experimental evidence. In the case of poly(octadecyl methacrylate) the data allow the estimation of two parameters of the electron density distribution in the side-chain crystallites. With polyacrylamide derivatives, a second amide group in the side chain is found to destabilize the side chain crystallites. The bahavior of the copolymers is very complex and exhibits, in one case, evidence for a long periodicity parallel to the fiber axis.
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    Surface properties of styrene-ethylene oxide block copolymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1287-1295 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrophobic-hydrophilic block copolymers were prepared by “living” anionic polymerization. They consist of polystyrene and poly(ethylene oxide) blocks, and are soluble in water. Their interfacial properties were investigated, employing aqueous solutions. The block copolymers lowered the surface tension of water in analogy with the low molecular weight surfactants such as sodium lauryl sulfate and heptaethylene oxide n-dodecyl ether. Their aqueous solutions exhibited solubilization properties differing from those of polyethylene glycol. Therefore, it is thought that the polystyrene blocks produce solubilization phenomena. In samples of the same styrene content, the precipitation temperature of a high molecular weight copolymer in water was lower than that of a low molecular weight copolymer at the same concentration in the same solvent. The surface tension and precipitation temperature of aqueous solutions seem to be influenced by molecular weight and composition.
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    Potentiometric titration of polyelectrolyte gels equilibrated with a solution of a strong polyelectrolyte: Influence of gel swelling (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1317-1324 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A weak acid gel (carboxylmethyldextran) was titrated with sodium hydroxide while equilibrated with a solution sodium poly(vinyl sulfate), a salt of a strong acid polyelectrolyte.It was found that the quantity \documentclass{article}\pagestyle{empty}\begin{document}$$ S = {\rm pH} - {\rm pNa} + \log (V/V_0) $$\end{document} in which V/V0 is the volume of gel relative to its volume in acid form in pure water, is independent of the concentration Cp of the polyelectrolyte solution and of the relative volume of gel.The relation \documentclass{article}\pagestyle{empty}\begin{document}$$ S - \log \left({\frac{{\alpha ^2}}{{1 - \alpha}}} \right) = {\rm pK'} + \log \gamma _{{\rm Na}}^{\rm g} + \log (v/V_0) $$\end{document} where α is the degree of ionization, pK′ is the apparent pK of the gel, γnAG is the activity coefficient of the counterion in the gel phase, and v is the number of ionizable groups, is found to be constant for all values of Cp and for 0.1 〈 α 〈 0.9. These results can be extended to highly crosslinked ionexchange resins.
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    Isothermal and nonisothermal creep of lightly crosslinked cis-1,4 polybutadiene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1891-1901 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A nonisothermal creep experiment has been analyzed to ascertain its suitability for determining the temperature dependence of low activation energy viscoelastic processes in elastomers far above Tg. The nonisothermal method was employed to determine the activation energy for creep near 35°C in a lightly crosslinked cis-1,4 polybutadiene elastomer at small strains within the linear viscoelastic region, and at various large deformations up to rupture. The observed activation energy was essentially independent of the level of strain, and the value of ΔHa (∼11 kcal/mole) determined via the nonisothermal creep method was in good agreement with the result (∼12 kcal/mole) obtained via time-temperature superposition of isothermal linear viscoelastic creep data. The nonisothermal data allowed for an estimate of the volume of the “flow unit” associated with the controlling viscoelastic creep mechanism, attributed here to slippage of entanglements within the lightly crosslinked network.
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    Studies of molecular relaxation of poly(propylene oxide) solutions by dielectric relaxation and brillouin scattering (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1877-1890 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric relaxation and Brillouin scattering are jointly used in studying molecular relaxation in poly(propylene oxide) (PPO) and its solutions in methylcyclohexane. The dielectric method was applied to the more concentrated (100%, 80%, 60%, by volume) solutions over a wide temperature and frequency range (30 Hz to 8 GHz) in order that the variation in activation energy characteristic of a glass-forming substance could be delineated. The present work extends previous work on the undiluted polymer to higher frequencies so that range of 12 decades in the dielectric loss maximum fmax as a function of temperature is now available. The “Antoine” equation is found to represent the behavior of log fmax, of the bulk concentrated solutions very well. The more dilute (40%, 20%) solutions were studied only in the high-frequency (GHz) region since phase separation occurred at low temperatures. Both the temperature and dilution effects were interpreted in terms of free-volume theory. Brillouin scattering spectra were obtained at several scattering angles and a wide range of temperatures. A maximum in the curve of hypersonic attenuation versus temperature was observed in each polymer solution. The attenuation maximum shifts toward lower temperature upon dilution, in agreement with the dielectric relaxation result. The Brillouin scattering follows different activation parameters and evidences a more rapid process than does the dielectric relaxation. It is speculated that it monitors a secondary or subglass relaxation, due perhaps, to damped torsional oscillations.
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    Preparation and characterization of copolymers of chloroprene and methyl methacrylatePresent at 108th Rubber Division Meeting at New Orleans, Louisiana, October 1975. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 165-171 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The preparation of chloroprene-methyl methacrylate copolymers in the presence of Lewis acids (Et1.5AlCl1.5) in hydrocarbon solvent and the effect of Lewis acids concentration on copolymer composition are described. 13C NMR spectra were obtained on these copolymers. In samples of high MMA content, tactic placements of MMA were observed as well as several different kinds of sequences for chloroprene and MMA. In samples of low MMA content, no tactic placements of MMA were found but several different kinds of chloroprene sequences were observed. From the analysis of the 13C NMR spectra of the different copolymers examined, it is apparent that all the various kinds of chloroprene sequences in these copolymers can be determined.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140114
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  • 45
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    Polyethylene networks crosslinked in solution: Preparation, elastic behavior, and oriented crystallization. I. Crosslinking in solution (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 187-210 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study has been made of the crosslinking of linear polyethylene in solution. Networks containing a low number of trapped entanglements and elastically ineffective chain ends were prepared by crosslinking high molecular weight linear polyethylene in 1,2,4-trichlorobenzene solutions with dicumyl peroxide at 120°C. No syneresis was observed during crosslinking except at high peroxide concentrations. The networks were characterized by swelling measurements, infrared spectroscopy, and differential scanning calorimetry. The crosslinking efficiency, calculated from swelling, was found to be proportional to the square of the polymer volume fraction. The proportionality constant was 0.8, indicating close to unit efficiency for undiluted polymer.Chemical modification of the polyethylene chains by attachment of peroxide and solvent fragments was of the order of one foreign unit per elastically active network chain, depending on peroxide and polymer concentration. Sol-gel analysis indicated that no chain scission occurred. These results are shown to be consistent with a “cage” mechanism for crosslinking. The possible topological consequence of this mechanism, preferential crosslinking of entanglements, is discussed. The concentration of trapped entanglements was also found to be proportional to the square of the polymer volume fraction. The proportionality constant corresponds to a molecular weight between entanglements of 4000 for the undiluted polymer, which is close to the value of 4200 found for networks prepared from the undiluted polymer. Since the results obtained are based mainly on the use of the swelling equation, different aspects of the applicability of this equation for the evaluation of the crosslinking process are discussed. As regards the reference dimensions, which should be known for a quantitative application of the elastic theory, the results strongly support the use of the dimensions of the network chains after completion of crosslinking.
    Additional Material: 12 Ill.
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  • 46
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    Structural studies of single spherulites and partially spherulitic films of poly(methyl-D-glutamate) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 251-262 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isolated spherulites of poly(methyl D-glutamate) (PMDG) were nucleated in bromoform. The morphology of these spherulites was investigated by SEM and photographic small-angle light scattering (SALS). From the SALS patterns, the development and growth of the spherulites could be noted. Films of PMDG cast from bromoform solution were found to be partially spherulitic. The mechanical properties of these films, prepared by different procedures, were compared with the general behavior of PMDG films cast from chloroform, the latter of which does not contain spherulitic texture.
    Additional Material: 13 Ill.
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  • 47
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    Generalized correlations for molecular weight and concentration dependence of zero-shear viscosity of high polymer solutions (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 299-308 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data are presented to show that two correlations of viscosity-concentration data are useful representations for data over wide ranges of molecular weight and up to at least moderately high concentrations for both good and fair solvents. Low molecular weight polymer solutions (below the critical entanglement molecular weight Mc) generally have higher viscosities than predicted by the correlations.One correlation is ηsp/c[η] versus k′[η], where ηsp is specific viscosity, c is polymer concentration, [η] is intrinsic viscosity, and k′ is the Huggins constant. A standard curve for good solvent systems has been defined up to k′[η]c ≍ 3. It can also be used for fair solvents up to k′[η]c ≍ 1.25· low estimates are obtained at higher values.A simpler and more useful correlation is ηR versus c[η], where ηR is relative viscosity. Fair solvent viscosities can be predicted from the good solvent curve up to c[η] ≍ 3, above which estimates are low. Poor solvent data can also be correlated as ηR versus c[η] for molecular weights below 1 to 2 × 105.
    Additional Material: 4 Ill.
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    The existence of mosaic block structures in polymer single crystals (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 317-322 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray line broadening measurements were used to determine the apparent “mosaic block” sizes of randomly oriented polyethylene and polyoxymethylene single crystals. Both dried-down and uncollapsed crystals were examined. PE lamellae were grown at 80, 85, and 90°C by isothermal crystallization from a 0.1% solution in xylene. POM crystals were grown at 125°C by self seeding from an 0.05% solution of the polymer in o-dichlorobenzene. A given preparation was split into two parts. One part was dried down in the usual manner, the other was exchanged to paraffin oil and the crystals never permitted to dry down. Previously reported studies used dried-down crystals and gave crystallite sizes of approximately 300 Å. More recently, using electron microscopy, it has been postulated that PE single crystals are free of “mosaic block” over regions of several thousand angstroms. It is evident from this present study that crystallite sizes in uncollapsed lamellae are significantly larger than those observed for the same crystals dried down. In the case of uncollapsed lamellae, one can explain the observed crystallite sizes solely on the basis of chain obliquity rather than by invoking the “mosaic block” model. It has also been determined that there is an upper limit to the crystallite sizes that can be observed in PE and POM crystals using wide-angle x-ray techniques. This limit may account for discrepancies between x-ray and electron diffraction.
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    Morphology and thermodynamic properties of solution-grown single crystals of trans-1,4-polybutadiene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 323-342 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology and thermal behavior of trans-1,4-polybutadiene single crystals prepared from dilute solutions in n-heptane have been investigated by electron microscopy, wide-angle and low-angle x-ray diffraction, and differential scanning calorimetry. The thickness of the single crystals of trans-1,4-PBD is much greater, for the same undercooling, than that of other linear polymers. From the calorimetric study, convincing evidence of the presence, in the single crystals, of crystalline blocks of form 1 with two different thermodynamic stabilities is obtained and the relative amounts are calculated. From thermodynamic considerations we find a value of 75°C for the equilibrium transition temperature between forms 1 and 2, 139°C for the equilibrium melting temperature of form 2, and 31.2 erg/cm2 for the fold-surface free energy of modification 2.
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  • 50
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    Nuclear magnetic resonance studies on microstructure of ethylene copolymers. VII. Proton resonance spectra of hydrolyzed ethylene-vinyl acetate copolymers1 (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 343-352 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Complete and partial alcoholyses of ethylene-vinyl acetate (E-VA) copolymers yield ethylene-vinyl alcohol (E-VOH) copolymers and ethylene-vinyl acetate-vinyl alcohol (E-VA-VOH) terpolymers, respectively. From the 220-MHz proton NMR spectra of E-VOH copolymers the stereoregular and chemical sequence distributions of the comonomers can be readily determined. Partially hydrolyzed E-VA polymers were acetylated with perdeuterated acetic anhydride. The monomer distributions in the terpolymers were then quantitatively determined by examining the proton spectra of the derived products. It was found that alcoholysis of E-VA polymers occurs preferentially at VA units which have neighboring VA groups.
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    On the structure of glassy polymers. IV. Small-angle x-ray scattering from rigid polyvinyl chloride (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 353-365 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The small-angle x-ray scattering (SAXS) from quenched and annealed rigid polyvinyl chloride (PVC) has been measured using a Bonse-Hart system. After correcting for absorption, background, and beam divergence, the scattering has been placed on an absolute basis using a standard silica suspension as a reference. The scattering from annealed (6 days at 75°C) and unannealed PVC was identical within experimental error, varying with scattering angle in a manner similar to the SAXS from other amorphous polymers. The intensity decreases rapidly with increasing scattering angle over the ranges from 20 sec to 20 min. Beyond 20 min the intensity is fairly constant, decreasing only slightly with increasing angle. At the largest angles of measurement (in the range of 120 min), the measured intensity is close to the value calculated for thermal density fluctuations frozen-in at the glass transition.The angular variation of intensity is well described by the scattering from heterogeneities of various sizes and concentrations superimposed on the scattering from thermal density fluctuations. These heterogeneities range in radius from 50 to 4500 Å and, assuming the crystalline excess density, the total concentration of heterogeneities is less than 0.5%. The mean-square fluctuation in density, determined from the measured intensity invariant, is also consistent with such a distribution of heterogeneities.The present SAXS results on rigid PVC are inconsistent with the presence of nodular features as representative of the bulk polymer. Rather, it is suggested that they are associated with surface effects. It is further suggested that previously indicated volume fractions of crystallinity in rigid PVC (generally in the range of 5-12%) are incorrect, and that the model of a three-dimensional network of crystallites used to explain the rheological behavior of this material should be re-examined.
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    Crystal structure of poly(m-phenylene isophthalamide) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 427-435 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal structure of poly(m-phenyulene isophthalamide) was determined by x-ray analysis. The triclinic cell, with a = 5.27 Å, b = 5.25 Å, c (fiber axis) = 11.3 Å, α = 111.5°, β = 111.4° and γ = 88.0° and space group P1, contains one monomeric unit. The crystal density is 1.47 g/cc. The molecules in the crystal are contracted by 1 Å per monomeric unit from the fully extended conformation, and the planes of the benzene rings and adjacent amide groups make angles of about 30°. The crystal is composed of molecular chains connected by N—H···O hydrogen bonds along the a and b axes forming a “jungle gym” network structure. The low tensile modulus of this polymer as compared with that of poly(p-phenylene terephthalamide) is attributed to the contracted molecular conformation.
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    A Raman study of the phase transition in crystalline trans-1,4-polybutadiene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 521-529 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman spectroscopy has been used to analyze the characteristics of the crystal-crystal phase transition of trans-1,4-polybutadiene. The low- and high-temperature structures were found to coexist at the transition. The Raman spectra obtained at high temperature can be understood on the basis of the change in chain conformation associated with the phase transition.
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    Nonlinear relaxation of stress and birefringence in simple extension of 1,2-polybutadieneThis work was part of the research program of the Rheology Research Center, University of Wisconsin. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 509-520 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Relaxation of stress and birefringence in simple extension has been studied for two samples of 1,2-polybutadiene with 95% and 88% vinyl content and weight-average molecular weight 1.9 and 2.9 × 105, respectively. The extension ratio, λ, ranged from 1.14 to 2.08, temperatures from 0 to 15°C, and times, reduced to 0°C, up to 3 × 105 sec. The stress-optical coefficient C was negative and positive, respectively, for the two samples, the difference being attributable to opposite signs and very different magnitudes of the contributions of the 1,2 and 1,4 moieties to the birefringence. For each polymer, C was independent of time but increased (algebraically) with temperature. For one polymer a very minor dependence of C on λ was observed. At any instant of time, the dependence of both stress and birefringence on λ could be described by equations of the Mooney-Rivlin form with coefficients C1,C2 and B1,B2, respectively. At short times the contributions of the C1 and C2 terms to the stress and of the B1 and B2 terms to the birefringence are roughly equal. With increasing time, C1 and B1 decrease gradually while C2 and B2 remain constant over several decades in time. Finally, C2 and B2 decrease rather rapidly. A tentative interpretation of these phenomena in terms of motions of entanglements is given.
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    Dilute solution properties of styrene-acrylonitrile and styrene-methyl methacrylate copolymers. II. Short-range and long-range interactions from intrinsic viscosity data (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 759-768 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental data on styrene-acrylonitrile (St-AN), and styrene-methyl methacrylate (St-MMA) copolymers reported in Part I of this series are tested by “two-parameter” theoretical relations. The Fox-Flory (F-F) parameter K is estimated using the F-F, Stockmayer-Fixman (S-F), and Inagaki-Ptitsyn (I-P) equations. In general, the K values obtained by the F-F equation are low for the three St-AN copolymer samples in the systems studied while the values obtained from S-F and I-P equations agree within the limits of experimental error. Values of K obtained from Kurata-Stockmayer (K-S) equation for sample SA1 agree with values obtained by the S-F and I-P equations. The specific solvent effect on the K values is discussed. Values of the unperturbed dimension r̄02/M̄w, calculated from the K values estimated from the S-F equation and from the homopolymer data are compared. Except in one case, the calculated r̄02/M̄w values from homopolymer data are low in comparison with the values obtained from experimental data, which shows that the presence of the repulsive interactions between unlike monomer units brings about an expansion of copolymer molecule. The effect of composition on the steric factor σ values is discussed. The long-range interaction parameter B, the excess interaction parameters ΔBAB, and χAB are calculated. The effects of composition and solvent on these parameters are discussed.
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    Temperature-induced reversible changes in long spacing in oriented polyethylene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 821-831 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The possible explanations for the temperature-induced reversible changes in long spacing in polymers are reviewed. The observation of particularly large changes in certain irradiated samples of oriented low-density polyethylene is reported. By combining these results with those obtained by DSC and other means it is concluded that the spacing changes are caused by partial melting of small lamellae within the lamellar stacks which alters the mean periodicity. The requirement of an irregular lattice explains why the effect is observed primarily in bulk samples and especially in materials which contain intrinsic irregularities.
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    Ultrathin sectioning of rubbery block copolymers: Thickness test and observations of separate microphase units (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 861-867 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A technique is described which enabled exceptionally thin sections of rubbery material to be cut for electron microscopy, and applied to samples of polystyrene-polybutadiene-polystyrene (SBS) copolymers which contain the segregated S phase in the form of cylinders arranged in a regular hexagonal macrolattice throughout the macroscopic specimen, with center to center distance of 300 Å. The technique consisted of sectioning the material hardened by a combination of osmic acid treatment and cooling with liquid air. By this method longitudinal sections containing single layer S rods could be obtained as verified by appropriate tilting tests. Such sections enabled the viewing of single cylinders without overlap which in turn enables the study of the structure of individual cylinders and the effect of various treatments on this structure. Examples quoted include the yielding or breaking of individual cylinders on longitudinal deformation of the macroscopic sample relating to our mechanical studies to be reported elsewhere. The technique also enabled sectioning in the swollen state of samples which are not sectionable other wise and this leads to the recognition of new structures and results in an overall improvement of image quality even when the thinness itself is not the prime requirement.
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    Electron donor-acceptor properties of thin polymer films on silicon. II. Tetrafluoroethylene polymerized by RF glow discharge techniques (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 879-895 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Metal-insulator-semiconductor (MIS) techniques were used to show that 86-210 nm thick plasma-polymerized tetrafluoroethylene films on silicon stored only negative charge (electron acceptors). This property persisted at a reduced level when a 7 nm thick inner layer of hydrolyzed γ-aminopropyltriethoxysilane was combined with an outer layer of plasma-polymerized tetrafluoroethylene. The dispersion force contribution to the surface energy, γds, for the fluorocarbon films was found to be 6 mJ/m2 (erg/cm2) which is comparable with the lowest values found in the literature. X-ray photoelectron spectroscopy (XPS) revealed a substantial content of —CF3 groups in the fluorocarbon films. This finding coupled with the reported effects of noncrystallinity, crosslinking, and branching on the surface energies of fluorocarbon systems were used to explain the low surface energy and electrophilicity of the plasma-deposited poly(tetrafluoroethylene)s.
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    A raman spectroscopic determination of the interlamellar forces in crystalline n-alkanes and of the limiting elastic modulus Ec of polyethylene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 913-920 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple treatment based on continuum mechanics shows that weak interlamellar forces in crystalline n-alkanes should result in a characteristic upward shift of the frequencies of the longitudinal acoustical (LA) modes, which is independent of the chain length and decreases inversely with the mode order. A raman spectroscopic determination of the LA mode frequencies of a series of different n-alkanes confirms the theoretical conclusion and permits a derivation of a force constant characteristic of the interlamellar forces. The discussion results in a new formula valid for the LA mode frequencies of the orthorhombic n-alkanes in the acoustical limit and yields a new determination of the limiting elastic modulus Ec of crystalline polyethylene. The value obtained, Ec = 2.9 × 1012 dyne/cm2, is markedly smaller than the value derived by Schaufele and Shimanouchi neglecting the influence of the interlamellar forces on the LA mode frequencies.
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    Recycle gel permeation chromatography: Its use for determination of separation efficiency and polydispersity of narrow fractions (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 959-961 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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    Spectrum of light scattered from viscoelastic gels (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1097-1109 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Spectra of polarized light scattered from model networks of polystyrene swollen by benzene have been measured by optical mixing spectroscopy. Various series of networks of different functionalities and different lengths of the elastic chain elements have been investigated. A theoretical expression for the characteristic time constant of fluctuations has been derived from rubber elasticity theory. An analysis of the experimental results within the framework of this theory allows determination of the frictional constants of the gels.
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    Determination of surface area of copolymer latex particles by surface tension measurements (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1451-1459 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The surface tension γ of four copolymer latices, of their respective serums, and of aqueous solutions of dispersant alone were measured at various dilutions. By extrapolating the surface excess of dispersant (calculated by the Gibbs adsorption equation) both at the aqueous solution surface and at the serum surfaces to 1/c = 0 (c being the bulk concentration of dispersant) the same limiting site area Alim per adsorbed molecule was determined. Amounts of dispersant adsorbed by copolymer particles at various dilutions were determined from differences between the known total concentrations of the dispersant in latex and in serum at the same γ. These values were then extrapolated to the maximum adsorption at 1/c = 0 in latex. The surface area of copolymer particles was determined therefrom by using Alim. The average particle radius calculated this way agrees reasonably well with electron microscope measurements. Thus it appears that the method for determining latex particle surface area by surfactant titration may be calibrated by means of the Gibbs adsorption equation, provided one uses Alim and not the site area at the critical micelle concentration of dispersant.
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    Determination of composition of ethylene-propylene copolymers by intrinsic viscosity (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1629-1639 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Intrinsic viscosities have been measured at 25° on five ethylene-propylene copolymer samples ranging in composition from 33 to 75 mole-% ethylene. The solvents used were n-C8 and n-C16 linear alkanes and two branched alkanes, 2,2,4-trimethylpentane and 2,2,4,4,6,8,8-heptamethylnonane (br-C16). This choice was based on the supposition that the branched solvent would prefer the propylene segments and the linear solvent the ethylene segments, due to similarity in shape and possibly in orientational order. It was found that [η]n - [η]br ≡ Δ[η] is indeed negative for propylene-rich copolymers, zero for a 56% ethylene copolymer, and positive for ethylene-rich copolymers. The Stockmayer-Fixman relation was used to obtain from Δ[η] a molecular-weight independent function of composition. The quantities (Δ[η]/[η])(1 + aM-1/2) and Δ[η]/M are linear with the mole percent ethylene in the range investigated with 200 ≤ a ≤ 2000. The possibility of using these results for composition determination in ethylene-propylene copolymers is discussed. Intrinsic viscosities in the same solvents are reported for two samples of a terpolymer with ethylidene norbornene.
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    The viscosity of concentrated solutions of a heterocyclic polymer (BBB) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1717-1720 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140916
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    Nonlinear viscoelasticity of polystyrene solutions. III. Stress development at the start of steady shear flow and an experimental check of some constitutive models (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1701-1715 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The development of the shear stress at the start of shear flow at constant rate of shear κ was measured for polystyrene solutions in diethyl phthalate with a cone-and-plate rheometer. Ranges of molecular weight M and concentration c were 3.10 × 106-7.62 × 106 and 0.112-0.329 g/cm3, respectively. The shear stress as a function of time t exhibited a marked maximum at large κ when either M or c was relatively low. When M and c were high, the maximum was broad and low. In a few extreme cases no maximum was observed in the range of κ studied. The constitutive model of Bernstein, Kearsley, and Zapas could describe approximately the shear stresses at a sudden start and on cessation of steady shear flow with a memory function evaluated from the strain-dependent relaxation modulus. The strain dependence of the memory function for solutions of low M or c was approximately expressed as exp{-α|s|} where α is a constant (ca. 0.37) and |s| is the absolute value of shear strain. When M and c were high, the strain dependence was found to be more diffuse and to require several terms if approximated by exponential functions of |s|. The Lodge model based on a strain-rate dependent relaxation spectrum was not able to describe the strain-dependent relaxation modulus as well as the interrelation between shear stresses at a sudden start and a cessation of steady shear flow.
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    Melt viscosities of viton fluoroelastomer and EPDM blends (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1729-1730 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140919
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    Reduction of dielectric loss in radiation-polymerized polyethylene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1755-1767 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low dielectric loss polyethylenes have been produced by γ-radiation polymerization of oxygen-free ethylene monomers. Dielectric measurements were made at 500 MHz and 20°C. The lowest dielectric loss tangent of the polyethylene was 3.3 × 10-5. Polar groups contributing to the dielectric loss have been found to be carbonyl groups, terminal vinyl groups, methyl groups, and hydroxyl groups contained in the polyethylene. The contribution of each group to the loss tangent has been calculated from a comparison of the variation of the loss tangent with the content of each group as determined by infrared analysis. It has been found that the reduction of the loss tangent is mainly due to the decrease in the concentrations of the carbonyl groups and the terminal vinyl groups and that the presence of a considerable amount of the hydroxyl groups prevents a further reduction of the loss in the polyethylenes. The results obtained from the analysis of the radiation-polymerized polyethylenes were applied to commercially available polyethylenes.
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    High resolution 1H-NMR relaxation study of polyisobutylene in solution (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1789-1800 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: From the temperature dependence of integrated intensities and from line widths in high-resolution 1H-NMR spectra, the relaxation times T1 and T2 of protons in CH2 and CH3 groups of polyisobutylene in CCl4 solution have been determined. Although the relaxation time T1 of methylene protons is determined mainly by intragroup interactions, intergroup interactions of two methyl groups from each two consecutive monomer units were found to contribute considerably to T1 of methyl protons. The Structure and mobility of polyisobutylene (PIB) molecules in solution is discussed on the basis of the relaxation time data.
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    Poly(styrene sulfonic acid)-poly(vinylidene fluoride) interpolymer ion-exchange membranes. I. Preparation and characterization (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1839-1854 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Highly porous interpolymer ion-exchange membranes have been prepared from poly(styrene sulfonic acid), PSSA and poly(vinylidene fluoride) PVdF using a casting solvent of dimethylformamide and hexamethylphosphoramide. The membranes have been characterized by their water content, concentration potential, ionic conductivity, and their hydraulic permeability. An estimation of the porosity of the membranes has been made from the relative conductance of the potassium and the tetrabutylammonium ions in the film. This porosity has been compared with that derived from a consideration of the water flux through a Poiseuille-type pore.
    Additional Material: 8 Ill.
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    Activation energy for viscous flow and melt structure of linear polymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1725-1727 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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    Light scattering from spherulitic materials (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1743-1753 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The azimuthal angular dependence of the depolarized component of the light scattered from spherulitic materials is derived by an algebraic method that avoids the difficult angular integrations of the usual approach. The result appears as a sum of products of two factors, a molecular factor, that depends only on the structure and the scattering angle θ, and a geometrical factor that depends only on the azimuthal angle φ and the scattering angle θ. The molecular factors are evaluated for models of spherulitic structure that assume a constant tilt of the optical polarizability tensor. The radial distribution, in principle, is arbitrary, and an evaluation for the layered spherulite is made. If the tilt angle is ω when the azimuthal patterns depend only on a linear combination of P2(cos ω) and P4(cos ω), where Pn(x) is the Legendre polynomial of order n. In our theory the VH scattering pattern is a four-leaf clover whose axes are restricted by the theory to be at either 0 or 45° to the polarization directions.
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    Incompatibility of polymer solutions. I. Binodals and spinodals in the system polystyrene + polyisobutylene + toluene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1943-1952 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The incompatibility of polystyrene (PS) and polyisobutylene (PIB) in toluene is characterized by binodals obtained from phase separation and spinodals obtained from light scattering at zero scattering angle. From these the interaction parameter χ23, between unlike polymer segments was calculated. It appears to be dependent on molecular weight and composition. The nature of χ23, especially its low value, is discussed.
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    Incompatibility of polymer solutions. III. Critical opalescence in the system polystyrene + polyisobutylene + toluene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1967-1977 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The angular dependence of light scattering from the homogeneous ternary system polystyrene + polyisobutylene + toluene was measured at a fixed (critical) concentration as a function of temperature. On approaching the critical temperature the scattering becomes very large and strongly angle-dependent. The experiments show that the interaction range rG is of the same order of magnitude as the molecular radius of gyration of the polymer, but cannot be set equal to it as in the case of a binary system of one polymer in a single solvent. The temperature dependence of the various interaction parameters does not depend on the molecular weights of the polymers.
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    Effect of solvent on depolarized light scattering in dilute polymer solutions (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1931-1941 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An optical model of a system in which both polymer segments and solvent molecules are described as point dipoles has been used to calculate the intensity of light depolarized in scattering. The final expression consists of six terms, the physical meaning of which is briefly discussed. An approximation procedure has been worked out for the calculation of two interaction terms due to deviations of the local field in solution from the Lorentz-Lorenz field; the terms have been calculated for simple models of flexible and rigid molecules. Their dependence on molecular weight appears to be approximately the same as the intrinsic anisotropy of the polymer molecule; their contribution is nonzero even for a solvent isorefractive with the polymer.
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    Incompatibility of polymer solutions. II. Concentration and angle dependence of the light scattering in the system polystyrene + polyisobutylene + toluene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1953-1965 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Light scattering experiments are described on the system polystyrene (PS) + polyisobutylene (PIB) + toluene at constant temperature. At a fixed concentration of the nearly “invisible” PIB the light scattering at various angles was measured as a function of varying PS concentration up to the region of incompatibility. For interpretation of the results use is made of an extension of the classical fluctuation theory for multicomponent systems to finite scattering angles. The experimental data can be described qualitatively with this theory. Addition of a second polymer has little influence on the size of the other polymer. The variation of the light scattering with the wavelength can be explained in terms of the (negative) adsorption of one polymer by the other.
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    Lactone polymers. VIII. Dynamic mechanical properties of ∊-caprolactone and γ-(tert-butyl)-∊-caprolactone copolymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2011-2017 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature dependencies of dynamic mechanical properties have been determined with a torsional pendulum for copolymers of ∊-caprolactone and γ-(tert-butyl)-∊-caprolactone over the entire composition range. Copolymers containing at least 25 mol % (33 wt %) of γ-(tert-butyl)-∊-caprolactone units are amorphous in nature. The experimentally obtained glass transition temperatures of the copolymers and poly(γ-(tert-butyl)-∊-caprolactone) were used to calculate the glass transition temperature of amorphous of poly(∊-caprolactone) according to the Fox relation. This value of -70°C is in excellent agreement with values obtained from similar calculations based on compatible blends of poly(∊-caprolactone) with other homopolymers.
    Additional Material: 4 Ill.
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    Persistence vectors and higher moment tensors of polyoxyalkanes (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1337-1349 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Statistical mechanical averages of vectors and tensors characterizing the spatial configurations of polyoxymethylene (POM) and polyoxyethylene (POE) chains, i.e., the chain vector r connecting the ends of the chain and the tensors formed from this vector, are evaluated in internal reference frames attached to the first two bonds of each chain as functions of its length. Convergences of the persistence vectors a ≡ 〈r〉 with chain length to their limits a∞ are delineated. For POE, the orientation of a∞ with respect to the X1 axes (the direction of the first bond) depends markedly on the choice of the initial bond and hence also on the internal frame of reference. Cartesian tensors up to fourth rank formed from the displacement vector ρ = r - a are evaluated for n = 4-1922 bonds for POM and n = 3-300 bonds for POE. The second moment tensor 〈ρρT〉 calculated for POM is nearly cylindrically symmetric about the axis perpendicular to the plane of the first two bonds. Corresponding symmetry is absent in POE. Correlation with the freely jointed chain is investigated for the components of the tensors of fourth rank formed from the reduced vector \documentclass{article}\pagestyle{empty}\begin{document} $\tilde \rho = \left\langle {\rho \rho ^{\rm T} } \right\rangle ^{ - 1/2} \rho $\end{document}. Use of the equivalent chain model for this purpose is validated for POE but not for POM, even at n = 2000 bonds. At the limit 1/n = 0, the parameter m, representing the number of bonds of the real chain equivalent to one of the model, is estimated to be ca. 31 for POM. For POE a value of m = 10.3 ± 1.3 holds for n 〉 20 for all components. Results are compared with those calculated previously for polymethylene, poly(dimethylsiloxane) and polypeptides. The fact that values of m derived by analysis of moments are larger than those obtained in the usual manner by fitting the model chain to 〈r2〉0 and rmax for the real chain demonstrates the inadequacy of artificial models for the representation of the real chain.
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    Crystallization of bisphenol-A polycarbonate. I. Influence of trimellitic acid tridecyloctyl ester on the kinetics of crystallization (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1367-1377 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization of bisphenol-A polycarbonate plasticized by trimellitic acid tridecyloctyl ester (Morflex 525) has been studied. A half-crystallization time of 100 min is observed at 170°C with 10% of plasticizer compared with a figure of 18,000 min for the unplasticized material. The kinetic study is limited to the primary crystallization process which can be described by an Avrami equation; however, the Avrami coefficients are much higher than usual. Studies on the effect of the preparation procedure of the samples and of premelting indicate that nucleation is at least partially heterogeneous.
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    Structure-chain length correlations in poly(N-vinylcarbazole) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1433-1449 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Narrow molecular weight distribution samples of PVK have been prepared over the molecular weight (Mn) range of 3.7 × 103 to 2.7 × 106. No evidence of influence of the synthetic procedure on polymer tacticity has been observed. The glass-transition temperature Tg was linearly dependent on 1/Mn (Tg∞ = 227°C) as predicted by the Fox-Flory chain-end free-volume model but no measurable change in free volume was detected. Crystallizability decreased with Mn and was zero in fractions below Mn = 46,000. This behavior coincides with that predicted by the nucleation theory outlined by Hoffman.21 This indicates that the chain-end free energy controls the stability of PVK folded-chain nuclei. The critical molecular weight for nucleation at 305°C was found to be some where in the range Mn = 1 ± 0.5 × 105. No change in the structure of the folded-chain lamellae with Mn was observed but evidence was obtained to support adjacent reentry of chains and a resulting localized crystal distortion.
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    Molecular orientation in poly(ethylene terephthalate) by means of laser-raman spectroscopy (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1461-1484 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intensity of the Raman scattering from uniaxially oriented amorphous poly(ethylene terephthalate) tapes at wave number shifts of 1732, 1616, 1286, 857, and 632 cm-1 has been observed for various combinations of incident and scattered light polarization vectors with respect to the draw direction. An attempt has been made to analyze the data to provide values of 〈P2(ζ)〉 and 〈P4(ζ)〉, where Pn(ζ) is the nth order Legendre polynomial in ζ,ζ is the cosine of the angle between the draw direction and a typtical chain axis in the polymer, and the angle brackets denote the average value over all repeat units. This attempt was successful for the 1616 and 632 cm-1 lines but less successful for the other three, although the data for the 1732 and 1286 cm-1 lines could be analyzed to provide quantities proportional, but not equal, to 〈P2(ζ)〉. In the analysis and discussion two possible models were considered for the conformation of the terephthaloyl residues in the amorphous polymer but it was not possible to reject either model conclusively. The results suggest, in agreement with previous studies by other methods, that the drawing of PET at 80°C takes place essentially as the extension of a rubberlike network which is frozen on subsequent cooling to room temperature.
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    Thickening of crystals during rapid heating. II. Crosslinked polyethylene and methoxymethylated nylon 6 (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1527-1540 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of modification of polymer chains on crystal thickening during heating was investigated with an apparatus devised for rapid measurement of small-angle x-ray diffraction. Thickening of crystals still occurred even at a heating rate of 18°C/min in polyethylene irradiated with gamma ray doses of 30-300 Mrad, and the melting point was depressed. These results showed that the melting point depression due to irradiation is not due to a restriction on crystal thickening but rather to crystal lattice distortion. On the other hand, although methoxymethylation of nylon 6 completely inhibits crystal thickening, the melting point increases or decreases depending on the temperature of annealing preceding methoxymethylation. From these results we are led to conclude that irradiation and methoxymethylation are not effective means of obtaining the relation between melting point and crystal thickness.
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    A simple phenomenological approach to the thermal behavior of glasses during uniform heating or coolingDedicated to Prof. G. Champetier for his 70th birthday (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1575-1590 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermal behavior of glasses, as observed from the isobaric variations of volume, v, and enthalpy, H, is analyzed in terms of retardation kinetics. A phenomenological theory involving a single retardation time, τ, is developed, assuming that molecular mobility is controlled essentially by the actual free volume, or configurational entropy of the glassy specimen. The characteristic features of the v and H isobars, as derived from the theory, are examined as a function of the thermal history of a typical glassy specimen. The respective contributions of temperature and structural parameters to τ, are also discussed in terms of the characteristic parameters of the isobars. The theoretical predictions are compared with some dilatometric data obtained with an atactic polystyrene. The comparison reveals the limitations of the theoretical treatment and suggests that glass-transition phenomena involve more than one retardation mechanism.
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    Application of fourier transform infrared spectroscopy to the study of semicrystalline polymers: Poly(ethylene terephthalate) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1731-1741 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An infrared absorbance subtraction technique has been used to “isolate” bands in the composite spectrum of semicrystalline polymers according to their crystalline or amorphous character. Amorphous and crystalline spectra for annealed, melt-quenched, and solution-cast poly(ethylene terephthalate) have been separated. The spectra of the amorphous component show an increased intensity of bands associated with the trans configuration of oxygen about the C—C bond when the polymer is annealed. This increased “trans” band intensity reflects the increased proportion of trans structures as a result of annealing. The amorphous trans bands are shifted approximately 1-3 cm-1 from their positions in the crystalline “trans” spectrum. The frequency shift of these bands can be attributed to the differences in chain interactions that exist in the amorphous phase and the crystalline lattice. We have also found that under identical anealing conditions the amorphous phase of the melt-quenched polymer contains an increased intensity of conformational trans bands compared to the sample cast from solution.
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    Ionic transport in a sulfonated polystyrene-polyethylene copolymer (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1769-1787 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conductivity of a grafted copolymer composed of 21% sulfonated polystyrene and 79% polyethylene has been investigated as a function of temperature and absorbed moisture for membranes containing the monovalent counterions H+, Li+, Na+, K+, Rb+, Cs, and Ag+. The mobility of Ag+ was measured directly in an experiment analogous to that used for the mobility of F-centers in alkali halides. The mobility and density of free counterions depend on the amount of absorbed water, but only the mobility and not the density of free counterions is a thermally activated process. Current is carried by both intrinsic counterions and, in samples containing absorbed water with greater than 1.5 V applied, by protonic carriers created when the absorbed water is electrolyzed. Thermal depolarization studies indicate that persistent polarization observed is the result of homogeneous volume polarization, due to the orientation of sulfonic acid side groups.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180141004
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    Structural studies of polyesters. VIII. Molecular and crystal structure of polydiketene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 81-92 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular and crystal structures of polydiketene were studied by infrared spectroscopy and x-ray diffraction. It was confirmed from the infrared spectra that diketene molecules in the crystal polymerize by ring opening upon γ-ray irradiation. The unit cell of the product as polymerized is orthorhombic, P22121-D23, with a = 5.43 Å, b = 8.94 Å, and c (fiber axis) = 7.75 Å. Two molecules pass through the unit cell The molecule has a conformation shown by the Fischer projection for a lefthanded (2/1) helix; The internal rotation angle around the O - C bond is nearly gauche (-84°), unlike other polyesters. On the basis of x-ray analysis, several molecular conformation models were selected by utilizing calculations of intramolecular interaction energies.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140106
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  • 86
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    Gelation-crystallization in isotactic polystyrene solutions and its implications to crystal morphology, to the origin and structure of gels, and to the chemical homogeneity of polyolefins (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 39-61 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As part of a wider study on the crystallization of isotactic polystyrene solutions it was observed that at sufficient concentrations (〉 3-5%) gelation sets in below a certain (very high) supercooling in competition with the usual single crystal formation which in itself produces turbid suspensions. It was established that gelation is a form of crystallization (mode A) which must be of fringed micellar type to provide the connectedness as opposed to the chain folded lamellae (mode B) which gives rise to discrete particles. The gel crystals (A) display sharp melt endotherms and produce distinct x-ray diffraction patterns both of which, however, differ decisively from those provided by crystals B, a distinction which can be preserved even after removal of the solvent. The melting points of A are significantly lower than those of B and the x-ray diffraction patterns of A are incompatible with the recognized structure of polystyrene (31 helix) possessed by B; they point to a broadly planar zig-zag arrangement of the chain. This strongly suggests that we have blocks of chemically distinct sequences which could be syndiotactic or head-to-head tail-to-tail (presently with substantial support for the latter) which is responsible for the gel forming crystallization. However, so far the C13 nuclear magnetic resonance (NMR) results do not provide the evidence for these distinct species but explanations for our observations on any other basis seem to lead to unsuperable difficulties from other points of view. Consequently, the paper is left open ended with the possibilities discussed. Amongst these the existence of a very few but long, chemically distinct sequences seems most attractive. The wider implications of the facts as they stand for crystal morphology (fringed micelles versus lamellae), for the origin and structure of gels in general, for the crystallization of block copolymers and for issues relating to chemical homogeneity (tacticity, head-to-head tail-to-tail) are discussed and preliminary effects are quoted which indicate that these issues may also be relevant to the usual atactic polymers.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140104
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    Brillouin scattering from polymer films (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 143-149 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Many polymers cannot be prepared as clear amorphous blocks suitable for classical light scattering studies. However, most linear polymers can be prepared as films which are somewhat transparent. With the advent of high contrast multipass interferometers, these films can now be studied by Brillouin scattering. This work demonstrates the wide range of polymeric materials that can now be studied by Brillouin spectroscopy.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140112
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    Bromination of single crystals of trans-1,4-polybutadiene. Thermal behavior (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 151-164 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is demonstrated by several methods (DSC, infrared spectroscopy, and small-angle and wideangle x-ray diffraction) that bromination of suspensions of single crystals of trans-1,4-polybutadiene is selective at the fold surface. As the thickness of the single crystals is increased, a larger number of double bonds per fold are brominated, i.e. a larger number of repeat units become accessible to bromine. This is consistent with an increase in the thickness of disordered surface layers with the crystallization temperature. A reduction of 40-60% in overall apparent enthalpies of transition and of melting and reduced ability of brominated single crystals to refold following annealing are also observed. Crystallization from the melt of trans-1,4-PBD with [ CH2—CHBr—CHBr—CH2 ] units along the chain is interpreted by assuming that some of these units are incorporated in the crystal lattice as defects.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140113
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  • 89
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    Low-frequency dielectric behavior of hydrated poly(L-proline)II (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 211-222 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric behavior of poly(L-proline) II has been studied by the dc transient method and a contactless pendulum technique. The comparison of measurements performed with and without contacting electrodes shows that the static and low-frequency dielectric behavior are due to bulk phenomena. Both mechanisms are strongly dependent upon the water content of the sample. At low hydration, the static conduction may be attributed to an electronic process. The observed low-frequency relaxation can be characterized by a relaxation time which increases with the water content. This behavior can be explained by an increase in stiffness of the poly(L-proline) chain: two adjacent carbonyl groups of the chain may be hydrogen bonded by two water molecules.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140202
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    Crystal orientation in a semicrystalline polymer in relation to deformation of polymer spherulites. IV. Crystal orientation mechanism of nylon-6 under uniaxial stretchingPresented partly at the 22nd Annual Meeting of the Society of Polymer Science, Japan, Kyoto, May, 1973, and partly at the 22nd Annual Symposium on Polymer Chemistry, Japan, Tokyo, November, 1973. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 223-238 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model relating crystal orientation to the deformation of nylon-6 spherulites under uniaxial stretching is discussed in terms of the orientation distribution functions of reciprocal lattice vectors of crystal planes, such as the (002) and (200) planes. The distribution functions calculated from the model are compared with those obtained from x-ray diffraction experiments. It is found that the crystal a axis and, consequently, the direction of hydrogen bonds within the crystal (α modification) orient parallel to the lamellar axis in the undeformed state, and that the crystal orientation behavior of nylon-6 is much different from that of low-density polyethylene, being characterized by much smaller values of the reorientation parameters of crystallites within orienting lamellae.Moreover, small-angle light scattering for Hv and Vv polarization is also calculated on the basis of the spherulite deformation model by taking the nylon-6 crystal as having orthogonal-biaxial symmetry in optical anisotropy. It is concluded that the Hv scattering can be realized in terms of the proposed model for spherulite deformation by taking into account a considerable contribution of hydrogen bonds to the molecular polarizability, so as to make the polarizability along the crystal a axis larger than that along the b axis. In other words, this conclusion suggests positively birefringent spherulites in the nylon-6 samples studied.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140203
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    Investigation of poly(trans-1,4-butadiene) crystals using the spin-probe method (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 275-284 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The spin-probe technique has been employed to study the nature of the surface regions of poly(trans-1,4-butadiene) crystals grown from dilute heptane and toluene solutions. The narrowing of the ESR spectrum of the nitroxide radical probe added to the PTBD crystals and the activation energy for the rotational motion of the probes were found to very with the crystallization solvent and annealing temperature; in every case heptane-grown crystals showed a higher line narrowing temperature and activation energy than toluene grown crystals. Annealing at 80°C raised the narrowing temperature and the activation energy for crystal preparations from both solvents used, but annealing at high temperatures, near to but below the melting point, lowered both parameters again. These results support earlier assertions, based on infrared spectra, surface epoxidation, differential scanning calorimetry, broad-line nuclear magnetic resonance, and dynamic mechanical results concerning the nature and location of the amorphous regions in PTBD crystals.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140207
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    Abnormal viscosimetric behavior of homopolymers in mixed solvents and preferential solvation (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 309-315 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that the applicability of the Stockmayer-Fixman-Burchard plot is much more limited in the case of solvent-precipitant mixtures than in the case of pure solvents. The observed deviations can be explained by taking into account the variation of preferential solvation as a function of the molecular weight of the polymer. More precisely the average density of the segments in the region occupied by the coiled molecule seems to be the parameter governing both changes in viscosity and in preferential solvation.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140210
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    Effect of drawing on the unit cell dimensions of crystallites in commercial PET fibers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 373-376 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140216
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    High-pressure phases in polymers. IV. Skeletal growth in cis-polyisoprene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 391-399 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization of cis-polyisoprene even at moderately elevated pressures results in the formation of a single-crystal species which develops through skeletal growth. The nature of these crystals, which are produced at relatively low supercooling, is described. They occur concurrently with spherulites but exhibit a much higher growth rate. In common with single crystals grown from solution the size and shape of the species is a function of the supercooling.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140302
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    On the structure of glassy polymers. III. Small-angle x-ray scattering from amorphous polyethylene terephthalate (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 415-425 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The small-angle x-ray scattering (SAXS) from glassy polyethylene terephthalate has been measured using a Bonse-Hart system. The data cover the angular range (2θ) between 20 sec and 2 deg. After correcting for absorption, background, and beam divergence, the data have been placed on an absolute basis by comparison with the scattering from a standard silica suspension. The corrected absolute intensity decreases strongly with increasing angle over the range between 20 sec and 15 min, decreases more gradually in the range between 15 min and 45 min, and reaches a nearly constant asymptotic value over the range between 45 min and 2 deg. The magnitude of the scattering in the constant range, about 0.4 (electrons)2 Å-3, is very close to the value predicted by the thermodynamic fluctuation theory for fluids applied at the glass-transition temperature [0.34 (electrons)2 Å-3]. The increase in intensity at angles smaller than about 45 min cannot be described by structures on the scale and volume fraction of the nodules reported in amorphous PET (50-100 Å), but can be well represented by small concentrations of heterogeneities, ranging in size from 100 to 2000 Angstroms, superimposed on the thermal density fluctuations frozen-in at the glass transition. The bulk structure of this material seems well described as a random amorphous solid, containing simple thermal fluctuations and a small concentration (〈1 vol-%) of heterogeneities covering a range of sizes. The heterogeneities in the small end of the range may well be crystallites which formed on cooling.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140304
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    Thermal-mechanical studies on a heterocyclic polymer (BBB). I. Tensile creep and recovery (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 451-478 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Creep and recovery measurements have been used to study the thermal-mechanical properties of polybisbenzimidazobenzophenanthroline-dione (BBB) over the temperature interval 30-500°C (in vacuo). The creep measurements were augmented by x-ray diffraction, isothermal contraction, and solubility measurements. It is found that extensive intermolecular association giving a supramolecular structure with (nearly) planar polymeric repeat units stacked in a “graphite-like” array dominates the properties of BBB, and that this structure is maintained at temperatures as high as 500°C. The principal mode of creep gives rise to fully recoverable Andrade creep for which the strain depends on the cube-root of time.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140307
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    Direct observation of polyethylene molecules with electron microscopy (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 479-484 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Individual polyethylene molecules have been imaged in the electron microscope. Preparative difficulties are overcome by the following procedures. (1) The polymer is dissolved in n-hexadecane at 130°C; (2) the solution is deposited on a cooled substrate by spraying in an atmosphere of cold nitrogen; (3) the deposited polymer molecules were shadowed by platinum. Molecular weights obtained are in good agreement with those from light scattering.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140308
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    A dielectric study of the amorphous fraction in oriented nylon 610 (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 499-508 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Since some dielectric loss peaks can be assigned to amorphous phase motions, it would appear that dielectric measurements should be a good probe to study the effects of macroscopic plastic deformation on the structure of the amorphous phase. We report here results of measurements of dielectric constant and loss in nylon 610 measured both parallel (∥) to and perpendicular (⊥) to the extrusion direction in specimens prepared by extrusion through a die at 160°. It is found that the intensity of the (∥) loss was nearly zero and the (⊥) loss intensity was greatly reduced compared to unoriented material. The other relaxation parameters (loss width and location) were largely unaffected. Since the amide dipole is nearly perpendicular to the chain axis and alternates in direction in the extended conformation, a considerable degree of chain alignment parallel to the draw direction is indicated. These results therefore show considerable permanent amorphous phase orientation even though the deformation was carried out 100° above its glass temperature.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.180140310
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    Observation of interface melting in polyethylene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 555-558 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140315
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    Deformation of the crystal lattice by water absorption and piezoelectricity of cellulose triacetate (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 565-567 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140317
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