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  • 1
    Electronic Resource
    Electronic Resource
    High-temperature morphological transition in a styrene-butadiene-styrene block copolymer (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1237-1242 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electron microscopy reveals a high-temperature morphological transition in a styrene-butadiene-styrene block copolymer of 7000 polystyrene block molecular weight and 43,000 polybutadiene block molecular weight (7S-43B-7S). Samples quenched in liquid nitrogen from temperatures above 150°C show no structure, whereas those quenched from temperatures below 140°C clearly show a multiphase structure. We previously reported that the 7S-43B-7S polymer exhibits a relatively sharp melt rheological transition in the temperature region between 140 and 150°C from highly viscoelastic and nonlinear viscous behavior to linear viscous behavior with insignificant elasticity. The dynamic viscoelastic properties are measured at different strain amplitudes in this study, and the results show that the melt rheological transition behavior is not influenced by the strain amplitude. This study clearly shows that the melt rheological transition in the 7S-43B-7S results from a morphological transition from a multiphase structure below about 140°C to a single-phase structure above about 150°C.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180606
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  • 2
    Electronic Resource
    Electronic Resource
    Glass transition in semicrystalline polycarbonate (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1257-1270 
    Details
    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 glass transition in semicrystalline polycarbonate was measured by differential scanning calorimetry and by thermally stimulated discharge of electrets. Solution-cast and bulk-crystallized samples possessing widely varying crystallinities and morphologies were investigated. It is shown that the intensity of the glass transition is governed by the extent of primary crystallization and is a linear combination of intensities from the bulk amorphous regions and from noncrystalline polymer within semicrystalline aggregates such as spherulites. The intensity of the glass transition within spherulites is about 0.1-0.3 as great as that in bulk amorphous regions. A three-phase model incorporating two distinct types of noncrystalline polycarbonate is proposed to account for the properties of this polymer.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180608
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  • 3
    Electronic Resource
    Electronic Resource
    Morphology and melting behavior of semicrystalline poly(ethylene terephthalate). I. Isothermally crystallized PET (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1311-1324 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A detailed description of the morphology and the complex melting behavior of poly(ethylene terephthalate) crystallized isothermally in the range 100-245°C is presented. Double or single melting endotherms can deliberately be obtained by varying the heating rate in the differential scanning calorimeter (DSC). In the case of double melting peaks, the first endotherm (I) corresponds to the melting of the crystalline material formed at the crystallization temperature Tc. The second melting endotherm (II) originates from the melting of a fraction of the original crystalline material reorganized during the DSC scan. The appearance of one melting endotherm (I or II) relates to the melting of the original structure or the melting of a completely transformed structure. Taking the end of the melting endotherm I as the final melting temperature TM of the material, an equilibrium melting temperature of 290°C is obtained from a plot of TM vs. Tc. A detailed morphological study of the isothermally crystallized samples by electron microscopy and both small-angle and wide-angle x-ray scattering raises questions about the use of the two-phase concept in relating morphological parameters and melting behavior at low crystallization temperatures.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180612
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  • 4
    Electronic Resource
    Electronic Resource
    Model of partial crystallization and melting derived from small-angle X-ray scattering and electron microscopic studies on low-density polyethylene (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1361-1381 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A temperature-dependent small-angle x-ray scattering and electron microscopic study on a sample of low-density polyethylene affords a determination of the structure changes in a heating and cooling cycle and suggests a new model of partial crystallization and melting. The analysis of SAXS data is based upon some general properties of the electron-density correlation function. Electron micrographs are obtained from stained sections γ irradiated at elevated temperatures and are analyzed quantitatively by statistical means. According to the model proposed here the thickness distribution in the amorphous layers, rather than that of the crystalline regions, is the essential factor governing the crystallization and melting behavior. The temperature-dependent changes in this thickness distribution provide a natural explanation for the large reversible changes in long-spacing.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180615
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  • 5
    Electronic Resource
    Electronic Resource
    Structure of polyethylene solid solutions from vibrational spectroscopy and thermal analysis (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1421-1431 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solid solutions of two low-molecular-weight polyethylene fractions, formed by rapid quenching from the melt, were studied by differential scanning calorimetry, low-frequency Raman spectroscopy, and Fourier-transform infrared spectroscopy. Two kinds of defects exist in these solid solutions; namely, a disruption of chain extension and the presence of monoclinic packing. The distribution of fully extended chain-segment lengths and the intensity of the 717 cm-1 infrared band, characteristic of the monoclinic phase, are found to be composition dependent. Our spectroscopic studies of the solid solutions support the model first proposed by Ott and Slagle.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180620
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  • 6
    Electronic Resource
    Electronic Resource
    Thermal behavior of α nylon-12 (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1413-1419 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal behavior of α nylon-12 film cast from a phenol-ethanol mixture has been studied by differential scanning calorimetry. Polymorphism has been analyzed by x-ray diffraction. The γ form exhibits a single endothermic melting peak in the thermogram, whereas the α form exhibits double peaks. Samples with mixed α and γ forms show double peaks at the same positions and the area ratio changes in accordance with the amounts of the two forms. The appearance of the γ peak, even for the α sample, is explained by recrystallization to the γ form after melting of the α form. The melting point of α nylon-12 is ca. 173°C, which is lower by 6-7° than that of the γ form. Once the α or γ sample has been melted and then cooled, its heating thermogram shows a small peak before the appearance of the main peak. The small peak seems to be due to incomplete and/or smaller crystallites formed during cooling. Heat treatment below the melting point of α nylon-12 is effective in transforming the α form to the γ form, probably via a melt-recrystallization process.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180619
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  • 7
    Electronic Resource
    Electronic Resource
    Phase transitions in mesophase macromolecules. I. Novel behavior in the vitrification of poly(ethylene terephthalate-co-p-oxybenzoate) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1433-1438 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A 40:60 mole ratio poly(ethylene terephthalate-co-p-oxybenzoate) was studied by dynamic scanning calorimetry. Vitrification occurred in two steps, which could be linked by optical microscopy to a two-phase structure. For the lower glass transition, hysteresis was absent on heating and cooling through the transition temperature. Since all prior studied glasses show such hysteresis, this may be linked to the mesophase structure and raises the question whether mesophases always display such glass-transition behavior.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180621
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  • 8
    Electronic Resource
    Electronic Resource
    SAXS analysis of a linear polyester and a linear polyether urethane - interfacial thickness determination (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1469-1480 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A small-angle x-ray scattering (SAXS) investigation of two linear segmented polyurethanes was carried out to learn about the respective domain structure (morphology). Both urethanes had a hard segment of methylene-bis(4)phenyl isocyanate (MDI) and butanediol. These two components comprised 28% by weight of each system. The soft segments differed in that one was a polyether (tetramethylene oxide, molecular weight 1000), while the other was a polyester (polytetramethylene adipate, molecular weight 1000). Both of these segmented urethanes were stored at room temperature for over 6 months prior to investigation. Using an automated Kratky camera, SAXS scans were made. By detailed analysis (using the computer program of Vonk) the average interfacial thickness E of the domains was determined by two approaches. The value of E for the polyester was 10-12 Å, while it was 5-7 Å for the polyether. Within the limits of the assumptions used for analysis, these data directly support the conjecture that polyether urethanes generally lead to better phase separation. Other aspects of the analysis provided further information on the morphological structure. Some cautionary comments are provided on the use of quantitative SAXS data obtained from these or similar systems.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180624
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  • 9
    Electronic Resource
    Electronic Resource
    Thermal conductivity of ultrahigh modulus polyethylene (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1481-1482 
    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.1980.180180625
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  • 10
    Electronic Resource
    Electronic Resource
    Use of electron microscopy to obtain quantitative information about the melting behavior of branched polyethylene (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1513-1522 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting behavior of low-density polyethylene was studied by electron microscopy. The experimental techniques and method of evaluation chosen were such as to deliver quantitative numerical data. The values which could be derived from suitably prepared histograms were the minimum, maximum, average, and most probable values of the crystal thickness d and long-spacing L. All these values were in good agreement with small-angle x-ray scattering results. The histograms also show the distribution functions for d and L, so that effects leading to changes in the average values can be observed in detail. The results provide further support for a model of melting and crystallization proposed in a previous paper.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180703
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  • 11
    Electronic Resource
    Electronic Resource
    Kinetic studies of structure formation during anionic adiabatic polymerization of ε-caprolactam (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1523-1532 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of crystallization and structure formation of polycaproamide (PCA) during anionic adiabatic polymerization of ε-caprolactam was studied. The adiabatic crystallization was shown to comprise three successive stages. In the first stage PCA forms dendritelike structures, the space between which is filled with the monomer. In the second stage rather rapid crystallization proceeds to give large loose spherulites. The dendritic structures serve as nuclei for development of spherulites. In the third stage slow secondary crystallization occurs. It is accomplished by crystallization of the residual amorphous substance located both in the dendritic nucleus and throughout the volume of the spherulites. This process is followed by the partial disappearance of the dendritic nuclei and by thickening of lamellae, which results in a substantial densification of initial structures and appearance of fine spherulites. As a result, a fine spherulitic structure with 50% crystallinity is formed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180704
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  • 12
    Electronic Resource
    Electronic Resource
    Study of crystal texture in pvc gels by x-ray diffraction and infrared dichroism (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1533-1559 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An enquiry is presented into the nature and origin of thermoreversible gelation of poly(vinyl chloride) (PVC). In line with a previous paper it is demonstrated by direct x-ray diffraction evidence that the origin of the gelation is crystallization, and that this crystallinity can be conspicuously apparent even for the usual technological polymer. In addition some unusual diffraction effects become apparent such as do not obviously follow from existing notions of the PVC structure. Combined infrared dichroism and x-ray studies revealed that these new effects are attributable to a two-component nature of the crystallinity where the components are distinguished by their orientation behavior, lateral extension, and possibly morphology of the crystallites. Some of the crystals orient with their a axes (type A crystals) and some with their c axes (type B crystals) along the stretch direction. Other more complex orientability differences are also manifest during film formation. Crystals B are smaller, and are believed to correspond to the network forming junctions, hence to fringed micellar crystals. Crystals A have a less evident connection with the network and are hypothesized to be of lamellar character, the behavior of which is closely simulated by lamellar crystal additives (stabilizer crystals). High-temperature x-ray work revealed no melting of crystals even in the temperature range where endotherms appear in the thermograms.
    Additional Material: 21 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180705
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  • 13
    Electronic Resource
    Electronic Resource
    Sequence distribution in ethylene-propylene copolymers. II. The 13C NMR spectra, multad populations, and kinetic parameters (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1587-1597 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Monad, dyad, and triad populations have been derived from the 13C NMR spectra of eight ethylene-propylene copolymers. Using these values, Kinetic parameters of the polymerization have been calculated, including conditional probabilities, and reactivity ratios. The fraction of propylene entering in an inverted order has been found to be about 20%. The copolymerization is dominated by the relatively large reactivity of ethylene. There is an alternating tendency for the two monomers which is evident both in the normal addition of propylene and the inverted addition. Penultimate effects do not play a significant role.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180708
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  • 14
    Electronic Resource
    Electronic Resource
    Effect of molecular weight on the diffusion coefficient of carbon dioxide in polystyrene (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1621-1632 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The permeability and time lag at pressures below 1 atm were measured for carbon dioxide in five polystyrene samples with different molecular weights at 25 to 40°C. The apparent permeability coefficient decreases with increasing carbon dioxide pressure and also decreases with increasing molecular weight of polystyrene, whereas the apparent diffusion coefficient calculated from time lag increases with pressure and is independent of molecular weight. Parameters for the partial-immobilization model were determined from the apparent diffusion and permeation coefficients by using a nonlinear least-squares optimization program without using sorption data. The results suggest that the void-saturation constant C′H decreases as the molecular weight of the polymer increases or as the chain-end free volume decreases. The significance of these observation and their interpretation is discussed in terms of free-volume theory for glassy polymers.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180711
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  • 15
    Electronic Resource
    Electronic Resource
    Cold crystallization of polytetrafluoroethylene by γ irradiation (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1643-1650 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Changes in density and in the corresponding degree of crystallinity with radiation dose are studied experimentally for γ-irradiated polytetrafluoroethylene (PTFE) in the dose range from 1 X 103 to 1 X 109 R. The relation between the amorphous fraction and the radiation dose is derived from a quantitative analysis of cold crystallization by scission of polymer backbone chains. The characteristic radiation dose, at which one break occurs on the average per initial molecule, is estimated as about 3 X 104 R on the basis of a derived kinetic equation. The theoretical relation is modified by considering microvoids produced in the irradiated samples. The radii of microvoids in the form of spheres are evaluated as about 0.2 nm, and are also related to cage spheres relevant to the chain scission process. Good agreement between the modified theoretical relation and experimental data is attained over the entire range of radiation dose.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180713
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  • 16
    Electronic Resource
    Electronic Resource
    Wide-angle x-ray diffraction of stress-crystallized poly(cis-1,4-butadiene) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1663-1664 
    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.1980.180180717
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  • 17
    Electronic Resource
    Electronic Resource
    Dilute solution properties of a polybenzimidazole (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1673-1683 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Light scattering and viscometric studies have been carried out on dilute solutions of a polybenzimidazole in N,N-dimethylacetamide. The data, which span the molecular weight range 2.9 ≦ 10-4Mw ≦ 23.3, and the temperature range 290 ≦ T/K ≦343, yield the dependence of the mean-square radius of gyration 〈s2〉LS, the second virial coefficient A2, and the intrinsic viscosity [η] on molecular weight Mw and temperature. The unperturbed mean-square radius 〈s20〉LS was calculated using experimental values of 〈s2〉LS and A2. It was found that excluded volume effects on 〈s2〉LS are very small. The unperturbed hydrodynamic chain dimension 〈s20〉η was estimated by considering draining effects. A small value of the draining parameter was obtained. Analysis of the temperature dependence of A2 and [eta;] leads to the conclusion that this system approaches a lower theta temperature with increasing temperature. The steric factor σ = 〈s20〉/〈s20〉f, based on the value of 〈s20〉f calculated for the polymer chain with free rotation, is nearly unity. Most of these properties can be interpreted in terms of long rotational units within the main chain.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180801
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  • 18
    Electronic Resource
    Electronic Resource
    Dynamics of noncrystalline polyethylene (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1707-1716 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An anisotropic dispersive continuum model for the collective modes of polyethylene of any degree of crystallinity is suggested. The model successfully explains the experimental results for specific heat of polyethylene of 100%, 84.1%, 74.5%, 45.9%, and 0% crystallinity in the temperature range 2.5-60 K, where the specific heat of amorphous polyethylene is markedly different from that of crystalline polyethylene. The variation of specific heat with degree of crystallinity can be obtained by varying only one parameter θ1 (characterizing the low energy cubic modes), keeping the other two parameters (characterizing the transverse and longitudinal chain modes) constant. Thus, in going from the crystalline to the amorphous state, it is essentially the interchain binding which is affected, the chain modes being left undisturbed. Using the calculated values of specific heat for varying degrees of crystallinity, the variation of θ1 with the crystallinity is reported. Observed high-temperature specific heats for crystalline and amorphous polyethylene up to 300 K are also explained using additional optical modes. The anisotropic Mössbauer elastic scattering fraction (MESF) for polyethylene of different degrees of crystallinity in the temperature range 0-425 K is obtained. For a given degree of crystallinity there is marked anisotropy in MESF which increases with increase in temperature. For a given direction, longitudinal or transverse, there is a large difference between the MESF of 0% and 100% crystalline polyethylene, which also increases with the increase in temperature. It is quite possible that the MESF experiment may prove to be more sensitive than the usual method for the determination of degree of crystallinity.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180804
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  • 19
    Electronic Resource
    Electronic Resource
    Environmental stress cracking of polyethylene: Analysis of the three zones of behavior and determination of crack-front dimensions (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1747-1752 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Previous work has shown that in the environmental stress cracking (ESC) of polyethylene, there are three major zones of behavior depending on the applied stress and the nature of the liquid environment. These three zones correspond to “pure” ESC (zone 1), ESC controlled by the speed of penetration of the liquid within a growing crack (zone 2), and behavior as in the absence of liquid (zone 3). Analysis of the transitions between zones has shown that, in the present case, a given liquid will either be capable of giving rise to all three types of behavior depending on the stress applied, or will be totally inactive. A related analysis has enabled the order of magnitude of the dimensions of the crack tip to be estimated and this has been found to be in the range of a micron.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180807
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  • 20
    Electronic Resource
    Electronic Resource
    High-conversion emulsion polymerization in a continuous reactor: Predictions using smith-ewart kinetics (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1771-1780 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Smith-Ewart Case-2 kinetics are applied to a continuous stirred tank reactor operating at steady state in the high and middle range of conversion. Above the conversion CD at which the monomer droplets disappear in a batch reaction, the predictions are surprising. The particle size is predicted to be inversely proportional to the effective soap concentration S and independent of mean residence time θ below CD it is predicted to be proportional to the one-third power of θ and independent of S. Above CD the particle concentration should be proportional to the cube of S and independent of θ; below this it should be as predicted by previous workers. The expressions for conversion are also different above CD. A new, more instructive, derivation is used. Simple analytic expressions are given for commonly used breadth parameters of the particle size distribution. It is shown that when conversion is low, an approximation made by previous workers is invalid, in that the growth rate can no longer be considered continuous.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180809
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  • 21
    Electronic Resource
    Electronic Resource
    Effects of energy dissipation on t-peel strength of plastic ethylene copolymer adhesives (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1847-1851 
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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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180816
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  • 22
    Electronic Resource
    Electronic Resource
    Fluorescence polarization measurements of orientation in labeled polyisoprene networks (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1879-1890 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fluorescence polarization was used to measure segmental orientation in stretched polyisoprene networks. Stress and orientation of chemically bonded fluorescent labels were simultaneously recorded during stretching. Two deviations from the classical theory of rubber elasticity were observed: (i) an extra orientation of dry networks, which was interpreted by assuming the existence of weak nematiclike interactions between segments, and (ii) a saturation of orientation at high elongation which could be due to local conformational changes.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180902
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  • 23
    Electronic Resource
    Electronic Resource
    Hydrodynamic studies on model branched polystyrenes (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1907-1917 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The measurement of the sedimentation velocity coefficient of narrow distribution linear, four-arm and six-arm star and comb polystyrenes in a theta solvent permits the experimental determination of h, i.e., the ratio of the translational friction coefficients of the branched polymer to that of its linear homolog. A comparison of experimental h/g1/2 values with theoretical predictions can then be made. It was observed that the equivalent hydrodynamic radii derived from sedimentation and intrinsic viscosity measurements are identical within experimental error.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180904
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  • 24
    Electronic Resource
    Electronic Resource
    Piezoelectricity and pyroelectricity of polyvinylidene fluoride corona-poled at elevated temperature (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1945-1954 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray diffraction, thermally stimulated depolarization, and piezoelectric and pyroelectric current measurements have been carried out on biaxially oriented polyvinylidene fluoride film, corona-poled both negatively and positively, at elevated temperature. Larger piezoelectric and pyroelectric coefficients are obtained at lower values of the poling field, when corona charging takes place at elevated temperature rather than room temperature. Negative charging is more effective than positive. The polarization mechanism is dipole alignment, and a conversion of Form-II crystallites to Form I. The large space-charge injected by the corona, and trapped in the material, acts through creation of high internal fields, and shows little, if any, piezoelectric and pyroelectric effects of its own.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180907
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  • 25
    Electronic Resource
    Electronic Resource
    Concentrated protein solutions in the analytical ultracentrifuge (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1963-1978 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Concentrated solutions of transferrin, albumin, immunoglobulin, chymotrypsinogen, transfer-RNA, dextran, and polystyrene were pelleted in the analytical ultracentrifuge. The proteins developed a solvent/pellet boundary which was chracterized at equilibrium by an asymmetric schlieren peak with a “shoulder”. The schlieren curve was at the same level inside the protein pellet as in the solvent above the pellet, indicating that the protein molecules had been packed homogeneously. The protein concentration in the pellet ranged from 0.6 to 0.7 g/ml. Immediately after deceleration was begun, the “shoulder” of the pellet boundary changed into a very sharp peak, leading to a boundary composed of two schlieren peaks. Sedimentation rates were measured for transferrin solutions at concentrations up to 0.3 g/ml.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180909
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  • 26
    Electronic Resource
    Electronic Resource
    Crosslinking chemistry and network structure in organic coatings. II. Effect of catalysts on cure of melamine formaldehyde/acrylic copolymer films (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2015-2025 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In a previous paper, the extents of reaction of various functional groups in different acrylic copolymer melamine-formaldehyde crosslinked formulations were measured by infrared spectroscopy. From these data and a statistical model, various network structure parameters could be calculated. One of these, effective crosslink density, was found to correlate well with film solvent resistance. In this paper the effects of the addition of strong acid catalysts on cure chemistry and network structure are determined. Both solvent-based and water-based formulations have been studied. In the solvent-based formulations studied, the addition of acid catalysts greatly enhanced the crosslinking reactions at low temperatures and dramatically lowered the cure temperature. Acid catalysts also lowered the cure temperature of a water-based formulation based on a high (180°C) cure temperature melamine. In contrast, the addition of acid catalysts had a negligible effect on the cure chemistry of a water-based formulation crosslinked with a low (130°C) cure temperature melamine. For this case the rate limiting process was found to be the rate of removal of neutralizing amine from the film. Cure temperatures in this system could only be lowered by replacing the amine used with a more volatile amine.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180181002
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  • 27
    Electronic Resource
    Electronic Resource
    A constitutive equation derived from the model of doi and edwards for concentrated polymer solutions and polymer melts (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2055-2067 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In deriving a constitutive equation from a molecular model of polymers in concentrated solutions and melts, Doi and Edwards used a mathematical approximation, the “independent alignment approximation,” which has recently been shown to produce significant error in the particular case of stress relaxation following a double-step strain in opposite direction. In the present paper, in order to examine the approximation in general cases, we derive a new constitutive equation without using the independent alignment approximation. The new equation is a nonlinear integro-differential equation and is solved numerically for several cases, i.e., steady shear and elongational flows, and the transient flows after the start of shear and elongation. It is found that, in the cases examined here, the new constitutive equation gives nearly the same results as the old one: the rheological functions calculated from the two theories differ no more than 30%. This substantiates the expectation that the independent alignment approximation does not produce drastic error as long as the flow direction is not reversed.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180181005
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  • 28
    Electronic Resource
    Electronic Resource
    Transport properties of annealed, drawn low-density polyethylene (LDPE) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2083-2096 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The specific concentration ca of methylene chloride, the zero-concentration diffusion coefficient D0, and the concentration coefficient γD of the diffusivity in drawn and annealed LDPE were measured. The influence of the drawing rate, of annealing with the ends of the sample free and fixed and the effects of time of standing at room temperature after annealing were investigated. The observed transport properties are in good agreement with the microfibrillar model of fibrous structure, its relaxation during annealing, and the slow crystallization of relaxed tie-molecules upon standing at room temperature.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180181008
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  • 29
    Electronic Resource
    Electronic Resource
    Temperature dependence of the viscosity of aqueous poly(vinyl alcohol)-borax solutions (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2149-2153 
    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.1980.180181013
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  • 30
    Electronic Resource
    Electronic Resource
    Melting and crystallization of poly(ethylene terephthalate) under pressure (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2181-2196 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A piston-cylinder-type high-pressure dilatometer has been built and the effect of pressure on melting behavior of poly(ethylene terephthalate) (PET) has been studied. The melting temperature increases but the rate of change of the melting temperature decreases with increasing pressure. Poly(ethylene terephthalate) crystallized from the melt at elevated pressure and temperature was studied by thermal analysis, and wide-angle and small-angle x-ray diffraction and electron microscopy. Chain-extended PET crystals were observed for the first time and some of their properties are described. A similarity to extended-chain polyethylene is suggested.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180181103
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  • 31
    Electronic Resource
    Electronic Resource
    Heat capacity of a polydiacetylene single crystal from 3 to 300 K (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2227-2241 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Heat capacities Cp of a polydiacetylene-bis(toluene sulfonate) single crystal and its monomer have been measured in the temperature range from 3 to 300 K. The temperature dependence of Cp for both monomer and polymer crystals differs from that for monoatomic solids. By applying a chain lattice model for a polymer crystal, the temperature dependence of the heat capacity can be described assuming a phonon density of states given by bending and stretching modes of the polymer backbone. With a combination of one-dimensional and three-dimensional elastic continuum approximations, the heat capacity has been calculated and a good fit to the data has been obtained. A small peak in Cp was detected at 161 K for the monomer and at 198 K for the polymer. This may be ascribed to a lower-temperature phase transition in the polydiacetylene crystals evidenced by previous x-ray and spectroscopic measurements.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180181107
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  • 32
    Electronic Resource
    Electronic Resource
    Incompatible blends: Thermal effects in a model system (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2257-2261 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: There has been a growing interest in compatible blends in which one of the polymers is crystallizable. At appropriate compositions some of this polymer will crystallize, the remainder forms a compatible blend with the other polymer component; attempts have been made to relate melting point depression of the crystalline component to diluent effects, i.e., polymer/polymer interactions. Melting point is also a function of lamella thickness, the determination of which is very difficult in such systems. It is assumed in this type of study that the melting point of a crystal in an incompatible matrix will be unchanged. In an attempt to test this assumption we have determined the melting behavior of isothermally grown, single crystals of polyethylen (from the same preparation) embedded in a variety of incompatible matrices. The matrices used were polybutadiene, polystyrene, and polyphenylene oxide. This work shows that polymer single crystals embedded in an incompatible polymer matrix can show apparent melting point depressions of up to 5°. This size of depression represents a significant part of that reported for compatible systems.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180181109
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  • 33
    Electronic Resource
    Electronic Resource
    High-resolution NMR spectra and phase equilibria in poly(phenylacetylene)-diluent mixtures (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2277-2286 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The C-13 NMR spectra of partly crystalline poly(phenylacetylene) (PPA) in CDCl3 CCl4 are rather well resolved and the peaks can be matched with those of 1, 3,5-triphenylbenzene. A different, less-well-resolved C-13 spectrum is characteristic of a disordered PPA obtained by heating. We conclude that crystalline PPA has the chain conformation of a cis-cis-oid helix. This interpretation is consistent with the proton NMR spectra and is supported by the fluorescence spectra, which can display two bands, one concluded to be characteristic of the cis-cis-oid conformation, the other of chain conjugation in the disordered polymer. Phase equilibria of PPA in the presence of chloroform were determined and are represented as those of the quasiternary mixture cis-cis-oid helix, disordered polymer, and chloroform.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180181112
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  • 34
    Electronic Resource
    Electronic Resource
    Compatibility of blends of polyesters with the polyhydroxyether of bisphenol-A (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2299-2301 
    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.1980.180181115
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  • 35
    Electronic Resource
    Electronic Resource
    Negative thermal expansion of polymer crystals: Lattice model (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2313-2322 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The lateral thermal motion of atoms in an inextensible polymer chain would cause a shortening along the chain direction. This effect could explain the observed negative thermal expansivity α along the chain direction of a polymer crystal. Using this idea, the expansivity α is calculated for a lattice of parallel linear chains. A value of -1.3 × 10-5 K is obtained for chains with a carbon backbone, in good agreement with data for polyethylene.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180181201
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  • 36
    Electronic Resource
    Electronic Resource
    Diffusion in a multicomponent inhomogeneous multiphase system with moving boundaries. II. Increasing or decreasing volume (swelling or drying) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2323-2336 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mathematical solution of the following problem is given. Simultaneously with diffusion-controlled mixing of two phases (e.g., gel formation), a third substance diffuses from one of the two pure phases into the other and through the inhomogeneous mixing phase which expands at a rate proportional to the square root of the time. The phases may change their volumes.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180181202
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  • 37
    Electronic Resource
    Electronic Resource
    Morphology of melt-crystallized linear polyethylene fractions and its dependence on molecular weight and crystallization temperature (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2347-2367 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Replicas and thin-section electron microscopic studies were made of fractions of linear polyethylene covering the molecular weight range 2.78 × 104 to 6.0 × 106 for a variety of crystallizing conditions. Lamellar crystallites were found under all circumstances; and the supermolecular structure, or crystalline morphology, is in agreement with that previously reported from an analysis of the small-angle light-scattering patterns of the same samples under similar crystallization conditions. Details of the crystalline microstructure are also described, which range from truncated hollow pyramids which degenerate as the molecular weight or the undercooling are increased. From these results, it is possible to describe the mechanism of formation of polyethylene spherulites.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180181204
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  • 38
    Electronic Resource
    Electronic Resource
    Transient decay studies of photophysical process in aromatic polymers. I. Multiexponential fluorescence decays in copolymers of 1-vinylnaphthalene and methyl methacrylate (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2401-2413 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The considerable potential of high resolution time-resolved spectroscopic data for copolymer systems in elucidation of the intramolecular photophysical processes which occur in polymer systems is illustrated. Such information can not be gleaned solely from studies of homopolymers. Kinetic data and time resolved fluorescence spectra of copolymers of 1-vinylnaphthalene and methyl methacrylate indicate that conventional kinetic schemes are inappropriate for the discription of excimer formation in 1-vinylnaphthalene polymers. Evidence is presented for the presence of an emitting species in addition to the expected monomeric and excimeric forms. The nature of this third species is discussed and photophysical kinetic schemes are proposed to describe intramolecular excimer formation in such systems. Kinetic data have been derived for the principle deactivation pathways through investigation of the observed fluorescence decays upon the intrachain concentration of aromatic species.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180181208
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  • 39
    Electronic Resource
    Electronic Resource
    Polymer diffusion at intermediate concentrations (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1219-1236 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Schlieren optics in conjunction with a modified Claesson cell allows free-diffusion experiments to be performed over a wide range of polymer concentrations. A data analysis procedure is presented for computation of the mutual diffusion coefficient using this technique. The dependence of the diffusion coefficient on concentration in polymer solutions is satisfactorily explained in terms of free volume, and a relation is proposed for correlating the mutual diffusion coefficient and zero-shear viscosity.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180605
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  • 40
    Electronic Resource
    Electronic Resource
    Hydrostatic extrusion of linear polyethylene: Effects of extrusion temperature and polymer grade (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1243-1256 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The hydrostatic extrusion behavior of linear polyethylene has been examined for two homopolymers of very different molecular weight characteristics and for a copolymer. Good unflawed extrudates could be obtained in all cases, and the extrusion behavior at a fixed temperature correlated well with the melt flow index. Although the maximum values of axial Young's modulus obtainable from the higher molecular weight homopolymer and the copolymer were lower than those possible for the lower molecular weight homopolymer, such materials do show improvements in creep behavior which could be advantageous. The effect of temperature on the extrusion behavior is discussed; the results suggest that for each grade of polymer there is an optimum temperature for effective extrusion, i.e., extrusion which gives optimum modulus enhancement. Finally, the melting behavior and the temperature dependence of the axial Young's moduli of the extrudates are considered in terms of our present knowledge of the structure of these high modulus materials.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180607
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  • 41
    Electronic Resource
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    Free-volume interpretations of self-diffusion in ternary solutions: n-Paraffin-hexafluorobenzene-cis-4-polybutadiene (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1285-1301 
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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: Self-diffusion of both diluents in the systems n-paraffin + hexafluorobenzene + cis-4-polybutadiene (paraffin = dodecane or hexatriacontane) has been measured at 80°C as function of both concentrations, using field-gradient spin-echo techniques (1H and 19F NMR). The data follow the free-volume model in the form of the Fujita-Doolittle equation, or the Vrentas-Duda theory, extended to apply to ternary systems. It is found that the polymer molecular jumping segments are roughly equal in size to the diluent molecules or their jumping segments.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180610
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  • 42
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    Morphology and melting behavior of semicrystalline poly(ethylene terephthalate). II. Annealed PET (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1325-1341 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Annealing of poly(ethylene terephthalate) samples crystallized under isothermal conditions above the crystallization temperature has a marked influence on their morphology and results in increased thermal stability of the crystalline structure as indicated by the melting point increase of the samples. The morphological transformation processes induced by annealing are very complex and depend on the thermal history of the samples, i.e., crystallization temperature and heating procedure. Depending on the nature of the processes occurring during annealing, various parameters characterizing the semicrystalline state of the samples can be affected such as the degree of crystallinity, the long spacing, the thickness of amorphous and crystalline layers, the crystal perfection, the fold-surface structure, and the mosaic structure of the crystalline lamellae. Annealing involves a solid-state transformation of the original crystalline structure including crystal perfection without thickening or a melting followed by recrystallization with crystal perfection and crystal thickening. The combination of differential scanning calorimetric (DSC) measurements and small-angle x-ray scattering is a powerful analytical tool to detect morphological changes and helps in deciding on the processes which are involved in the transformation of the microstructure upon annealing.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180613
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  • 43
    Electronic Resource
    Electronic Resource
    Thermochromism in polydiacetylene solutions (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1383-1391 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel planar ↔ nonplanar visual thermochromic conformational transition of polydiacetylene molecules in poor solvents is reported. The conformational transition is associated with both a color change (blue or red ↔ yellow) and a change in the state; the yellow solution (liquid) transforms to a blue or red gel (solid). The color transition occurs within a narrow range of temperature and has a large associated hysteresis. The enthalpy of the conformational transition is 29 kJ/mole of repeat unit. Fourier-transform infrared studies show that molecules acquire a planar conformation in red or blue gels by formation of intramolecular H bonds between the adjacent substituent groups. Virtually all H bonds break (a nonplanar conformation) when the gels turn into yellow solutions.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180616
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  • 44
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    Electronic Resource
    Electron spin resonance study of copolymerization of hexafluoroisobutylene with vinylidene fluoride (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1393-1401 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Copolymerization reaction of hexafluoroisobutylene (HFIB) and vinylidene fluoride (VF2) was studied using X-band electron spin resonance (ESR) by applying a photo-in situ method. Owing to the toxicity of HFIB monomer, the flow ESR method could not be directly applied without extensive modification. The observed ESR signal with 21-line hyperfine structure was assigned to the copolymer radical with head-to-head configuration. Although the HFIB monomer radical possesses the same hyperfine pattern, the ambiguity has been removed by using CF3 as an initiator radical. Owing to the high steady-state concentration of the observed copolymer radical with head-to-head configuration as well as the nature of the static photo-in situ ESR method, we believe the actual molecular configuration for HFIB/VF2 copolymer must be head-to-tail. The observed hyperfine constant for AβF = 1.74 mT suggests that the geometry for HFIB/VF2 copolymer radicals with both head-to-head or head-to-tail configurations is possibly similar to that of (CF3)3C· radical. The small value for AβH indicates steric hindrance to rotation about the Cα—Cβ bond, and this is also supported by the experimental results of nonalteration in linewidth during the temperature dependence study from -40 to about 90°C. Attempts to measure directly the monomer reactivities have been unsuccessful owing to the fact that not all the possible radicals were detected, but nevertheless the relative reactivities of VF2 and HFIB could be estimated. The relative reactivities of VF2 and HFIB monomers and the steric hindrance effect indicate that the conformation of the copolymer is head-to-tail; this has been further confirmed by infrared analysis.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180617
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  • 45
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    Sequence distribution in ethylene-propylene copolymers. I. Relations between multads and between multads and the 13C NMR spectrum (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1573-1585 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theoretical relations between 13C NMR line intensities and monad, dyad, and triad populations are given. In some cases only approximations are possible. The relations between monads and dyads also between dyads and triads are given. Some necessary relations between line intensities are given which provide a basis for making corrections for differing Overhauser enhancements. Included in the discussion are three lines which have not previously been discussed.
    Additional Material: 2 Tab.
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  • 46
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    Comparison of theory and experiment for diffusion in dilute polymer solutions (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1633-1641 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Results from a number of theories for the concentration dependence of the mutual diffusion coefficient in dilute polymer solutions are examined, and clarifications are made as to what forms of the equations for these theories should be used in comparisons with experimental diffusivity data. An evaluation of the available theories for the concentration dependence of the diffusivity under theta conditions is carried out using experimental diffusivity data taken using sharp fractions of polystyrene. It is concluded that the Pyun - Fixman theory appears to provide the most promising method for estimating the concentration dependence of the mutual diffusion coefficient in dilute polymer solutions at the present time.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180712
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  • 47
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    Avrami analysis: Three experimental limiting factors (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1655-1657 
    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 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180715
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  • 48
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    Melting point of oriented poly(vinylidene fluoride) form-i crystal under tensile stress (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1665-1669 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180718
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  • 49
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    High-pressure phases in polymers. V. Crystallization studies of synthetic cis-polyisoprene (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1737-1745 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of elevated pressure on the morphology and crystallization kinetics of cis-polyisoprenes containing 2-2.5% trans units have been determined. Lamellar growth rates of both α and β crystals are enhanced by elevated pressure. The degree of enhancement of α-crystal rates is much greater resulting in an effective suppression of β growth. Differences in lamellar growth rates between these polymers and cis-polyisoprene result from different preexponent values. Hedritic or axialitic growth, presumably due to low-molecular-weight fractions, is observed in shish-kebabs present in strained films. The high-pressure hexagonal phase cannot be grown in these polymers.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180806
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  • 50
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    Internal field of polymer crystals: Polarizability tensor of the methylene group from the birefringence of paraffin crystal (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1717-1735 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using the concept of a point dipole lattice, it is shown that the internal field of induced dipoles can be calculated for crystals comprised of simple chain molecules. The only structure which must be taken into account accurately is that of the chain molecule itself. From the calculations, reliable values of the polarizability tensor of the CH2 unit are deduced from the birefringence of the paraffin crystal. In addition, it is shown that birefringence measurements provide a method for demonstrating the consistency of polarizability data so that no detailed structural information is needed. For the CH2 unit, it is found by both methods that α∥ - α⊥ = - 0.63 with respect to the chain direction [the units of polarizability α are 10-24 cm3 (cgs)]. The most probable anisotropies for the bond polarizabilities are α∥CH - α⊥CH = 0.30, α∥CC - α⊥CC = - 0.62.
    Additional Material: 5 Ill.
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  • 51
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    Structure of native and regenerated cellulose as revealed by proton NMR analysis (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1801-1809 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Differences in fiber structure between cotton and cuprammonium rayon are studied by a refined broad-line proton NMR analysis of samples swollen with deuterated dimethyl sulfoxide, which has no effect on the spectra but enhances differences in molecular mobility between crystalline and noncrystalline regions. The spectra obtained are decomposed into four components: broad, medium, narrow, and extremely narrow. These components are identified as contributions, respectively, from crystalline and rigid noncrystalline (frozen glassy) material, a noncrystalline glassy component exhibiting local segmental motion, a noncrystalline rubbery component exhibiting liquidlike molecular motion, and protons included in DMSO-d6 as an impurity. The mass fraction of the narrow component in cotton was about 0.01, whereas it was as high as 0.18 in cuprammonium rayon. It is concluded that even in the swollen state, native cellulose is devoid of a liquidlike mobile component, but regenerated cellulose contains a considerable amount of a noncrystalline component involving liquidlike segmental motion of molecules.
    Additional Material: 5 Ill.
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  • 52
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    Proton NMR studies of a polybenzimidazole in solution (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1791-1800 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular aggregation of poly(4,4′-diphenyl ether-5,5′-bibenzimidazole)(PBI) in solution has been studied by high resolution proton NMR. PBI and model compounds have been synthesized, purified, and characterized. Proton resonances in the NMR spectrum of PBI are assigned by comparison with the proton resonances of the model compounds. Spectra are studied by total line-shape analysis, assuming each absorption curve to be Lorentzian. For PBI in N,N-dimethylacetamide (DMAc), the resonance due to the proton of a hydroxyl group formed by proton exchange between the imino group of PBI and the carbonyl group of DMAc is observed. The activation energy for the proton exchange, obtained from Arrhenius plots of the temperature dependence of the chemical shifts of the hydroxyl proton and the imino proton, was found to increase in the order corresponding to dissociation energy of the N—H···O=C hydrogen bond. The chemical shifts in the NMR spectra of PBI-DMAc solutions on the addition of LiCl are strongly dependent on the polymer-salt ratio; and thereby the coordination position of LiCl to PBI is tentatively identified, assuming a pseudocontact LiCl-induced shift. The dependence of the chemical shifts of protons in PBI on the dielectric constant of the solvent is demonstrated by using polar solvents of varying dielectric constant, such as N-methylpyrrolidone, dimethylsulfoxide, and formic acid. The viscosity of the PBI-DMAc solutions is reported at various temperatures and concentrations of LiCl. The results from viscometry are explicable in terms of the NMR observations.
    Additional Material: 7 Ill.
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  • 53
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    New evidence for molecular entanglements (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1837-1846 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Torsional creep and creep recovery measurements have been made on a 56% polymer weight solution of an extremely high molecular weight polystyrene (M = 4.4 × 107) in tri-m-tolyl phosphate and on the polymer itself after recovery both from relatively dilute and more concentrated solution in benzene by freeze drying. Although viscoelastic steady state was not achievable, an anomalously shorter rubbery plateau in the response of the bulk polymer relative to its solution was indicated. On the basis of the assumed presence of physical entanglements of the threadlike molecules, which determine the length and height of the rubbery plateau, it was predicted and confirmed that the undiluted polystyrene recovered from dilute solution would have the highest and shortest creep compliance plateau.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180815
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    Extracting single-chain characteristics from neutron and x-ray scattering experimentsWork supported in part by NSF Grant No. DMR-76-80152. (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1859-1861 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180818
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  • 55
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    A fourier-transform infrared spectroscopic study of the hydrolytic stability of silane coupling agents on E-glass fibers (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1931-1943 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier-transform (FT) infrared spectroscopy has been applied to the study the hydrothermal degradation of various coupling agents on E-glass fibers. The coupling agents studied include γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and cyclohexyltrimethoxysilane. The amount of coupling agents on E-fibers was measured as a function of immersion time in water at 80°C. Structural changes were also followed by obtaining FT-IR difference spectra of the coupling agent on the glass fiber surface. Silanes desorb quite differently depending on the organofunctional groups. The resistance to desorption is strongly influenced by the organization of the silane interphase as well as the solubility of the silane in water.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180906
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  • 56
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    Thermal conductivity and heat capacity of liquid and glassy poly(vinyl acetate) under pressure (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2123-2133 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dependence of thermal conductivity λ and heat capacity per unit volume pcp on temperature and pressure for poly(vinyl acetate) has been measured by a transient hot-wire probe technique. The measurements were made under pressures up to 0.5 GPa over a temperature range of 270-470 K. The temperature coefficient of thermal conductivity (∂ lnλ/∂T)p was found to increase with pressure for both the liquid and the glassy state. The change in heat capacity per unit volume in the region of the glass-transition temperature was found to decrease with increasing pressure. The Ehrenfest relation does not explain the variation of the pressure coefficient of the glass-transition temperature.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180181010
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  • 57
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    Nonequilibrium morphologies of a diblock copolymer of polyisoprene and poly(n-butyl methacrylate) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2143-2148 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180181012
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    Study of the thermal effects in the necking of polymers with the use of an infrared camera (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2169-2179 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When a polymer specimen yields under tension by the process of cold-drawing, heat is generated in the necking region. This beating effect has been studied in polycarbonate, polyethylene, polypropylene, and PVC with the use of a thermovision system which produces a real time thermal image of the necking specimen. In this way it was possible to observe the temperature distribution over the surface of the neck and to show that at least 85% of the mechanical work done on the specimen during necking was converted into heat. A semiempirical equation relating the maximum temperature to the drawing rate has been derived.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180181102
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  • 59
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    Abrupt dissolution of polydiacetylenes (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2209-2215 
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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: Polydiacetylenes, where R=—(CH2)3,4OCONHCH2COO(CH2)1,3CH3 dissolve almost instantaneously within a narrow range of temperature (ca. 3°C). The enthalpy of dissolution of these polymers is determined by differential scanning calorimetry to be 25-46kJ/mole of the repeat unit. The abruptness of dissolution is due to breaking of intramolecular H bonds, which appears to be a cooperative phenomenon. Supporting infrared evidence is cited.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180181105
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  • 60
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    Structural evolution of an ABA poly(styrene-b-isoprene) block copolymer with temperature (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2217-2225 
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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 structural evolution with temperature of an anionically synthesized ABA poly(styrene-b-isoprene) (SIS) lamellar block copolymer (total molecular weight 45,000; isoprene content 38% by weight) was studied by melt-rheological measurements, electron microscopy, and x-ray and light diffraction. Above 225°C, the dynamic viscosity was found to be independent of frequency up to a critical frequency. The variation of the elastic modulus confirmed the occurence of a transition between 215 and 225°C. For the temperature range considered, all results superimposed well on a two-branch master curve. It was concluded that above 225°C, our SIS behaves like a Newtonian material, whereas for lower temperatures and/or higher frequencies classical non-Newtonian behavior is found. The melt-rheological properties were explained by microscopy and diffraction investigations, which allowed us to follow morphological changes as the temperature was raised. It was found that the two-phase lamellar structure is progressively destroyed, and the transition temperature of 225°C corresponds to the temperature above which complete mixing occurs.
    Additional Material: 6 Ill.
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  • 61
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    Upper bound of stress for stress relaxation in entangled polymeric systems (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2421-2423 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180181211
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  • 62
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    The occurrence of head-to-head butene units in ethylene-butene copolymers and corresponding ethyl branches in low-density (branched) polyethylenes (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1955-1961 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A high resolution carbon-13 NMR study of an ethylene-butene copolymer has yielded a spectrum whose resonances could be assigned to isolated ethyl branches, 1,3-diethyl branching as well as 1,2-diethyl branches resulting from head-to-head butene polymerization. All these structures are present in the same sample. An examination of all the published spectra of low-density (branched) polyethylenes has revealed many examples of heretofore unassigned resonances which can be associated with this latter type of diethyl branching in these polymers. Spin-lattice relaxation times have been determined, when feasible, for the carbon atoms in each of the three branched structures.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180908
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    The dependence of craze velocity on the pressure and temperature of the environmental gas (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1979-1992 
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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 craze velocity was determined for poly(chlorotrifluoroethylene) (PCTFE) in CH4 and for PCTFE, polystyrene, and poly(methyl methacrylate) in N2. It was found that for temperatures near the boiling point the velocity and number of crazes depended on the relative pressure given by P exp[-(Qv/R) (TB-1 - T-1)], where P is the pressure, Qv is the heat of vaporization, and TB is the boiling point. The craze velocity was related to the coverage of the adsorbed gas. For coverages corresponding to a few monolayers the logarithm of the velocity was proportional to the relative pressure. As the temperature increases from TB, the creep rate decreases because gas desorbs with increasing temperature; the creep rate attains a minimum value at a temperature where the general process of thermally activated deformation becomes dominant.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180910
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  • 64
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    Manifestation of microgel-like particles of styrene-ethylene dimethacrylate copolymers in solution in 1H and 13C NMR spectra (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2027-2035 
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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 integrated intensities of 1H NMR bands it has been found that in solutions of styrene (St)-ethylene dimethacrylate (EDMA) copolymers, a considerable part of the monomer units do not show directly in high-resolution 1H NMR spectra and it is suggested that these monomer units form compact structures, probably acting as cores of microgel-like particles. In 13C NMR spectra all monomer units are shown, including those which are part of the compact microgel structures. From a comparison of 1H NMR spectra with other analytical methods (elemental analysis, infrared spectra) it follows that the composition of the copolymer in the core of the microgel is the same as the overall composition of the copolymer. The content of the compact structures in the microgel increases with the content of the EDMA component. The results are discussed from the point of view of structural features and of the motional restrictions of the St/EDMA copolymers in CCl4 solution. The consequences for 1H NMR analysis of copolymer composition are also discussed.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180181003
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  • 65
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    Tear strength and tensile strength of model filled elastomers (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2135-2142 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements have been made of the tear strength, tensile strength, and energy dissipated during stretching for model filled elastomers consisting of polybutadiene with glass beads incorporated. The glass beads were pretreated with various silanes, some of which could, in principle, form covalent bonds with the polybutadiene matrix during free-radical crosslinking of the latter and some of which could not. The tear strength of the elastomer was increased by the addition of glass beads, by about 25% for the largest beads, having a mean diameter of 150μm. This effect is attributed to increased roughness of the tear path. The breaking elongation in tension was reduced by the addition of glass beads but the breaking stress was only seriously reduced for the least-well-adhering beads. The stored strain energy density at break was reduced in all cases. This is attributed to large glass beads acting as fracture nuclei in tension. Calculated sizes of a Griffith crack, 150-300 μm, are consistent with this hypothesis. Strain energy dissipated due to dewetting was found to be in the range 4-13% of the input energy, depending upon the degree of interfacial adhesion, in addition to about 10% dissipated in the unfilled material. The maximum value observed is in reasonable agreement with theoretical predictions.
    Additional Material: 1 Ill.
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  • 66
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    The use of synchrotron radiation for study of structural changes in polymers during phase transition and deformation (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2155-2168 
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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 experimental method using monochromatized synchrotron radiation for a wide-angle x-ray scattering study of polymers during phase transition and deformation is described. Results obtained on low-density and high-density polyethylenes and on polypropylene are given. Melting processes could be studied conveniently by making exposures during a temperature scan; a few seconds were found sufficient to obtain a diffraction spectrum. This way relatively fast crystallization processes and the structural change accompanying stress relaxation could be followed easily. The crystalline-amorphous ratio was found to decrease continuously much below the melting temperature measured dilatometrically and by DSC, implying that in the αc-relaxation transition region of polyethylene and polypropylene a structural change takes place. At the initial state of crystallization the 040 reflection in polypropylene was found to be stronger than the 110 one, while after crystallization has been completed this ratio was inverted. Equatorial spectra made after rapid uniaxial stretching of polypropylene sheet were found to exhibit a slight time dependence demonstrating that orientation went on after stretching had been stopped.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180181101
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  • 67
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    Side-chain crystallinity, heat of melting, and thermal transitions in poly[N-(10-n-alkyloxycarbonyl-n-decyl)maleimides] (PEMI) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2197-2207 
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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 heat of melting, the melting temperature Tm, and the sub-Tg transition temperature have been studied from -120°C to above Tm in a series of 11 poly[N-(10-n-alkyloxycarbonyl-n-decyl)]-maleimides (PEMI). Side-chains from ethyl to n-docosyl with n even have been included. The contribution to the heat of melting per methylene group shows that the hexagonal paraffin crystal modification is present in these poly(N-maleimides), in agreement with x-ray data for the same compounds. The enthalpy data show that only a part of the outer methylene groups are present in the crystalline aggregates. Furthermore, DSC traces exhibit a typical distribution of crystallite sizes, which become narrower as the side-chains become longer. The critical chain length needed to form a stable nucleus includes nine methylene groups in the outer part of the n-alkyl side-chain. The influence of the side-chain length and crystallinity on the γ-transition temperature of these polymers was also investigated. In the range where these polymers are essentially amorphous the sub-Tg transition temperature decreases continuously as the number of methylene groups in the side-chain increases. This transition is attributed to internal motion within the external side-group without any interaction with the main chain. This is presumably made possibly by the partial rotation of the oxycarbonyl group. We suggest that this transition is similar to the well known γ transition which has been attributed to various segmental motions in all ethylene copolymers and in all homopolymers containing a determined number of—CH2—units in the main-chain or in the side-chain. Estimates based on the chemical structure, yield a value for the γ transition of —CH2—similar to that measured by other methods in polyethylene and related materials.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180181104
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    Longitudinal acoustic mode in linear aliphatic polyesters (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2287-2294 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The longitudinal acoustic mode has been observed in a series of linear aliphatic polyesters. In some cases, the vibrational frequencies observed do not strictly obey the expected inverse chain-length relationship. Both the periodicity measured in small-angle x-ray diffraction and the chain length deduced from Raman spectroscopy are highly dependent on thermal history.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180181113
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  • 69
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    Selective chemical modification of polyethylene single crystals (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2295-2298 
    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.1980.180181114
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  • 70
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    Origin of intercrystalline links (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 2307-2309 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180181117
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  • 71
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    Unperturbed dimensions of cyclochain polymers (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1-18 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational parameters of three polyoxadiazoles were calculated by a direct computer simulation assuming free rotation about virtual bonds. The results obtained proved to be close to those derived from viscosity and sedimentation experiments.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180101
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  • 72
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    Correlation between environmental stress cracking and liquid sorption for low-swelling liquids (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 19-26 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The environmental stress cracking (ESC) of polyethylene has been studied under conditions of dynamic equilibrium with the liquid for low-swelling liquids. Even among active ESC agents, there is a clear relative order of efficiency. It has been shown that the liquid becomes less efficient with increasing equilibrium swelling. This fact has been attributed to local plasticization of the crack front leading, in turn, to a reduction in the high-stress concentrations associated with a wedge-shaped crack. Some semiquantitative ideas are proposed in an attempt to explain the relation between ESC efficiency and volume/volume sorption.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180102
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  • 73
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    Crystallization of alkyl-aromatic polyimides (polyalkanimides) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 247-263 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyalkane imides based on 3,3′,4,4′-diphenyloxidetetracarboxylic, pyromellitic and 1,4,5,8-naphthalenetetracaboxylic acids, and aliphatic diamines containing 4, 6, 8, 10, or 12 methylene groups have been studied. Relations governing the effect of structure on solubility, heat resistance, density, and crystallizability have been established. Conformation analysis has been carried out and models of the macromolecules have been constructed. The morphology of the crystalline polymers has been studied. For the polymers of the given class, crystallization capability is shown to be associated with the conformational flexibility of the macromolecular unit determining a given acid moiety by the number of methylene groups in the diamine unit.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180208
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  • 74
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    Thermally stimulated current (TSC) study of the Tg and Tll transitions in anionic polystyrenes (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 277-284 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermally stimulated current (TSC) technique has been used to investigate three anionic polystyrenes of M̄n 17,000, 71,700, and 1.55 × 106, i.e., M 〈 Mc, M 〉 Mc, and M ≫ Mc, where Mc is the entanglement molecular weight. A current maximum near Tg designated TMg, has relaxation times which follow an Arrhenius equation. A second current maximum at T 〉 Tg appears to be the Tll process and is designated TMll. Relaxation times for it follow a Vogel equation. TMg and TMll vary with molecular weight, increasing below Mc and leveling off above Mc at a temperature of about 170°C. Values of TMg and TMll are compared with values of Tg and Tll obtained from torsional braid analysis, which involves melt flow; and with differential-scanning-calorimetric values on fused films, where there is no transport of polymer. It is concluded from such cross-comparisons that TSC, at least for polystyrene, is a quasistatic test which may involve microscopic viscosity. Macroscopic viscosity does not play a role. The ratio TMll/TMg is in the range 1.10-1.16, similar to Tll/Tg values by other methods. A few comments about Tll in atactic poly(methyl methacrylate) by the TSC method are given.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180210
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  • 75
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    Birefringence of stretched polyethylene and its relation to changes in structure (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 285-290 
    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 shown that the birefringence of a polyethylene crystal can be severely shape dependent via the internal field. Using the cluster model it is concluded that this dependence plays an important role in the structural transition in the uniaxial stretching process.
    Additional Material: 2 Ill.
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  • 76
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    Effect of casting conditions on polymorphism of nylon-12 (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 291-299 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymorphism in nylon-12 film, which appears on casting from a phenol-ethanol solution, has been investigated by x-ray diffraction and infrared absorption. The casting temperature was varied from 30 to 130°C and the ambient atmospheric pressure from 50 to 760 Torr. Casting at 30°C gives only the α form, while casting above 90°C yields only the γ form. At intermediate temperatures, both α and γ forms are obtained, with the γ content increasing as the casting temperature and/or the rate of evaporation of solvent are increased. The ethanol component of the casting solvent appears to act only as a melting-point depressant for phenol. In contrast, nylon-6 film cast from the same solvent system between 30 and 160°C gives only the α form. It is proposed that the difference in polymorphism of nylons-12 and -6 is caused by differences in molecular flexibility due to the length of the methylene chain.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180212
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  • 77
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    Morphological studies on polybutylene terephthalateSupported in part by grants from the National Science Foundation, the Petroleum Research Fund of the American Chemical Society, the General Electric Company, and the Materials Research Laboratory of the University of the University of Massachusetts. (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 327-342 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology of poly(butylene terephthalate) (PBT) crystallized from the melt at various temperatures was studied by small-angle light scattering, polarizing microscopy, and wide-angle x-ray diffraction. Spherulites with a maltese cross at 45° to the polars formed at lower temperatures while spherulites having an apparently higher melting point with a maltese cross along the polars (0°-90°) formed at higher temperatures. The spherulite size and crystallinity increased with increasing crystallization temperature. The Hv scattering patterns arising from the spherulites formed at lower temperature showed intensity maxima at azimuthal angles of 0° and 90°, while those obtained at higher temperatures showed the more common 45° intensity maxima. Microtomed samples from molded PBT bars showed spherulites with a 45° maltese cross which changed to a 0°-90° maltese cross upon heating just prior to melting. The skin-core effect due to varying thermal histories in these molded bars was clearly observed. Solvent crystallized films contained positive 0°-90° spherulites. Some changes occurring upon uniaxial stretching of PBT films are also discussed.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180215
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  • 78
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    Effects of pressure on the compressibility and crystallization of poly(ethylene terephthalate) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 343-359 
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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 effects of pressure on the compressibility and crystallization of poly(ethylene terephthalate) (PET) have been investigated. The Instron capillary rheometer was adapted as a high-pressure dilatometer to perform experiments up to 40,000 psi. Compressibilities of solid and molten PET were measured. The increases in compressibility with increase in temperature for the solid state are discussed in terms of free-volume theory. Results obtained for the melt are explained by invoking the second law of thermodynamics and the effect of pressure on the Gibbs free energy. The effects of temperature and compression rate on the pressure of crystallization (Pc) were also studied. As the crystallization temperature was increased from 240 to 286°C, Pc increased by about 16,000 psi. As the compression rate was raised from 1%/min to 8%/min, Pc increased 10,000 psi. At some undetermined compression rate above 8%/min it seemed impossible to induce crystallization in the melt, even with pressures up to 40,000 psi. Analysis of data on the kinetics of crystallization of PET melt under high pressures revealed low Avrami exponents, for which no unequivocal explanation is offered. It is possible, however, that crystallization at high pressure promotes the formation of a morphology made up of a certain percentage of “extended chains.” The alteration in the attendant spatial geometry involved in the crystallization might explain the lower Avrami exponents found. In another set of experiments, crystallization temperatures (Tc) were measured by slowly cooling PET melt under high pressures. As the pressure was raised from 3000 to 15,000 psi, Tc increased from about 246 to 282.5°C. These results are consistent with thermodynamic theory.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180216
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  • 79
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    Rheology of concentrated solutions of helical polypeptides (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 361-388 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rheological studies were carried out on concentrated m-cresol solutions of two helical synthetic polypeptides; poly-γ-benzyl-L-glutamate (PBLG; molecular weight, 150,000) and poly-∊-carbobenzyloxy-L-lysine (PCBZL; molecular weight, 200,000). Steady shear measurements were made over a range of 0.01-16,000 sec-1 to obtain steady shear viscosity and first normal stress difference. Dynamic viscosity and dynamic storage modulus were measured both by oscillatory shear between cone and plate and also by an eccentric rotating disk device over frequency ranges of 0.1-400 and 0.1-63 rad/sec, respectively. The concentration ranges were such that both liquid crystalline and isotropic solutions were investigated. The previously reported observations of an apparent negative first normal stress difference within a defined range of shear rate for liquid crystalline solutions were confirmed for the PBLG and PCBZL solutions. At high shear rates the peaks in plots of steady shear viscosity against concentration were profoundly suppressed but peaks in first normal stress difference versus concentration were not. The observation of liquid crystalline order in PCBZL/m-cresol solutions at room temperature constitutes evidence that the inverse coil-helix transition temperature is lower in concentrated solutions than in dilute solutions. The critical concentration for formation of the liquid crystalline phase was higher for PCBZL than for PBLG, despite a higher axial ratio, due to helix flexibility.
    Additional Material: 30 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180217
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  • 80
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    TEM studies of polymer blends stained with mercuric trifluoroacetate (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 393-395 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180219
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    Development of a residual shear stress in an SBS block copolymer during stress relaxation following steady-state flow (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 397-399 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180220
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  • 82
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    Dielectric relaxation of an alcohol in polyethylene (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 401-403 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180221
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  • 83
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    Cross-section factor correction in the small-angle x-ray scattering data from branched dextrans (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 405-407 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180222
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  • 84
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    Nonlinear elasticity of rodlike macromolecules in condensed state (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 409-419 
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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 finite deformation elasticity of gels of stiff rodlike polymer chains is discussed theoretically. Unlike a rubber composed of flexible polymer chains, the elasticity of this system is energetic, and arises from the elastic deformation of the stiff chains which are forced to bend under macroscopic strain. The stress-strain curve of this system is shown to be nonlinear even if the bending of the rods is small, and has a characteristic S-shaped form which is unlike that of a rubber. The effect of orientational order is also discussed.
    Additional Material: 7 Ill.
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  • 85
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    Interpretation of longitudinal-acoustical-mode spectra of polymers (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 421-428 
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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 influence of temperature, frequency, and straight-chain-length distribution on the low-frequency Raman-active longitudinal-acoustical-mode (LAM) bands of polymers is discussed. Specifically, the effect of these factors on the intensity of LAM-1, on the ratio of intensities of LAM-1 to LAM-k, and on peak position is computed or estimated. Band halfwidth and chain-length-distribution halfwidth are found not to be simply related. It is shown that the integrated intensity of LAM-1 is very nearly proportional to the total length of straight chains.
    Additional Material: 5 Ill.
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  • 86
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    Crystallization characteristics of polymer blends. I. Polyethylene and polystyrene (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 637-643 
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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: Blends of polyethylene and polystyrene have been prepared to study the effect of the morphology on their crystallization characteristics since the polymers are known to phase separate. The polymer component present in least amount formed a dispersed phase of discrete spherical particles whose number and size altered with blend composition. However, close to 50% composition cylindrical rods of polyethylene dispersed in polystyrene were observed. With polyethylene in excess the kinetics of crystallization were insensitive to the morphology, but with polyethylene present as the dispersed phase they became dependent on the size and number of the spheres, and in particular on the nucleation density. When the number of spherical particles exceeded that of heterogeneous nuclei, larger supercoolings, and so presumably homogeneous nucleation, were required for crystallization to develop further. The degree of crystallization of the blends then became dependent on the temperature of crystallization rather than on time, and the isothermal crystallization appearing to be instantaneous.
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    Properties of solution-grown crystals of fractions of isotactic polypropylene with different degrees of stereoregularity (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 619-636 
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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: Solution-grown crystals of fractions of isotactic polypropylene (IPP) with different degrees of stereoregularity have been obtained by isothermal crystallization from α-chloronaphthalene, using a self-seeding technique. Electron micrographs of samples, crystallized under the same undercooling, show that, with decreasing fraction of isotactic pentads, the perfect rectangular shape of the single crystal is lost and the presence of more complex morphologies is increasingly observed. The equilibrium dissolution temperature Td of IPP fractions, from polymers prepared with a titanium based catalyst, decreases linearly with decreasing percentage of isotactic pentads. An extrapolated value of 171°C is obtained for the equilibrium dissolution temperature of a crystal of IPP with 100% isotactic pentads, i.e., an IPP crystal free of configurational defects. The melting temperature T′m and the apparent enthalpy of fusion ΔH*f of crystallized and annealed crystal aggregates have been determined by differential calorimetry. The equilibrium melting temperature Tm also depends greatly upon the isotactic pentad concentration. For 100% concentration the extrapolated value of Tm is 181°C. Tm decreases about 1°C per 1% decrease in the isotactic pentad population. The observed equilibrium melting and dissolution temperature depression does not follow the predictions of the Flory equation for copolymer crystallization. In fact, the effect of decreasing probability of isotactic sequence propagation is to depress Td and Tm much more rapidly. The apparent enthalpy of fusion of both solution-grown crystals and melt-recrystallized samples decreases with an increase in the number of configurational impurities along the chain. For the most stereoregular fraction the average length of isotactic stereoblocks has been compared with the lamellar thickness of solution-grown lath-shaped single crystals.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180320
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  • 88
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    Rubber networks containing unattached macromolecules. IV. Stress relaxation in end-linked polybutadiene with unattached styrene-butadiene copolymerThis work was part of the research program of the Rheology Research Center, University of Wisconsin. (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 645-661 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stress relaxation has been studied in networks of dihydroxy-terminated polybutadiene (mostly cis:trans:vinyl = 34:40:26) crosslinked by triphenyl methane-4,4′,4″-triisocyanate and containing about 9.5% by weight of unattached linear random styrene-butadiene copolymer with various molecular weights (from 1.4 to 3.3 × 105) and with styrene content and butadiene microstructure chosen to match the average solubility parameter of the end-linked network. Stress relaxation measurements were made also on networks containing no unattached species and containing 9.3% hydrocarbon oil, and on the various uncrosslinked linear polymers. The stretch ratio was 1.25 and the Young's relaxation modulus was calculated from the neo-Hookean stress-strain relation. For the uncrosslinked linear polymers, the relaxation modulus E11(t) corresponds to a rather narrow distribution of relaxation times whose magnitudes were approximately proportional to the 3.4 power of viscosity-average or weight-average molecular weight; for one polymer, the time dependence agreed closely with the prediction of the Doi-Edwards theory modified for a small degree of molecular weight distribution. The disengagement times calculated from the Doi-Edwards theory as modified by Graessley appeared to be of the correct order of magnitude. The contribution of the unattached species in the networks E1(t) was calculated by difference; after multiplication by (1-v22)-1, where v2 is the volume fraction of network, and correction for the difference in monomeric friction coefficient associated with the difference in fractional free volume in the two environments, E1(t) was compared with E11(t) for each linear polymer. The relaxation was slower in the network than in the uncrosslinked polymer by about an order of magnitude, but the form of the relaxation modulus was similar in both environments except for two linear polymers for which the relaxation in the network became very much slower at long times. This behavior appeared to be correlated with a broader molecular weight distribution.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180322
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  • 89
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    Structural investigations of polymer liquid-crystalline solutions: Aromatic polyamides, hydroxy propyl cellulose, and poly(γ-benzyl-L-glutamate) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 663-682 
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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 comparative structural investigation of the characteristics of polymer liquid-crystalline solutions including Kevlar® (PPD-T)/sulfuric acid, poly(Cl-p-phenylene terephthalamide) (Cl-PPD-T)/sulfuric acid, poly(γ-benzyl-L-glutamate) (PγBLG)/dioxane, and hydroxypropyl cellulose (HPC)/water was undertaken. Experimental procedures included polarized light microscopy, light scattering, absorption spectra, and x-ray diffraction on solutions at various concentrations and temperatures. Both the two-phase region at the onset of liquid-crystal formation and the wholly anisotropic phase were investigated. Each solution exhibited distinctive characteristics. The PPD-T and Cl-PPD-T solutions were nematic, and the PγBLG and HPC solutions were cholesteric. In the two-phase region the PPD-T, Cl-PPD-T, and PγBLG (but apparently not the HPC) exhibited negatively birefringent spherulites and aggregates of spherulites. The HPC solutions only exhibited spherulitic structures in the single-phase anisotropic system. The structures and orientations in the anisotropic phase for the various polymer solutions is considered. The helicoidal structural characteristics of the PγBLG and HPC solutions are contrasted.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180401
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  • 90
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    Crystal structure of polyamides containing 1,3-cyclohexane rings (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 697-706 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of 1,3-cyclohexane rings in the chain backbone on the crystal structure of polyamides has been studied using polyamides (denoted 1,3-CBMA-n) obtained from 1,3-cyclohexane-bis(methylamine) (1,3-CBMA) and n-carbon dicarboxylic acids. The crystallinity of the 1,3-CBMA-n polymers changes greatly with variation in the value of n. This is attributed to hydrogen-bond changes associated with the relative length of the diacid moiety to the diamine moiety in the monomeric unit of each polymer. In 1,3-CBMA-6, the cis-1,3-cyclohexane rings are readily accommodated in the molecular chains to form crystals in a manner similar to the m-benzene rings in poly(m-xylylene adipamide) (MXD-6). The crystal lattice, however, is more expanded than in MXD-6 since the 1,3-cyclohexane rings is bulkier than the m-benzene ring. The crystal structure of the 1,3-CBMA-n polymers is essentially the same as that of MXD-6.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180403
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  • 91
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    Hydrodynamically induced formation of cellulose fibers. I. Observations on the formation of cellulose fibers from stirred solutions (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 707-721 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Like synthetic polymers, a natural polymer such as cellulose may crystallize in fibrous form from stirred solutions. In the present work, it is demonstrated that cellulose fibers can be formed by precipitation from dimethyl sulfoxide/paraformaldehyde solutions by two methods that involve different mechanisms of fiber formation, viz., (A) precipitation of cellulose by addition of nonsolvent to the stirred cellulose solution, and (B) precipitation of cellulose by coagulation of droplets of cellulose solution in a stirred precipitant. Both processes yield fibers with properties depending on the stirring speed and the coagulant strength. The molecular orientation and tensile strength of the fibers produced by method A was low, but increased with the stirring speed, while some fibers formed by method B reached extremely high orientation, depending on the thickness of the fibers. The two mechanisms of fiber formation are discussed on the basis of the experimental observations.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180404
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  • 92
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    Polarized Raman study of molecular orientation in uniaxially stretched atactic polystyrene (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 731-738 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polarized Raman intensities have been obtained from thin films of uniaxially oriented atactic polystyrene. The study was made using the 623 cm-1 radial skeletal η6b vibration of the benzenering. Values of the fourth-order as well as second-order terms in the expansion of the orientation distribution were obtained for draw ratios between 1.5 and 7.7. Values for P2(cosθ) agree well with the values obtained from infrared dichroism.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180406
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  • 93
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    Effect of moisture on the bulk properties of salted poly(caproamide) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 739-744 
    Details
    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 temperature (Tg) and the elastic modulus of nylon-6 and its mixtures with 4% w/w LiCl and with 2% LiCl+3% LiBr were investigated. In one set of experiments care was taken to avoid absorption of moisture during the measurements. In another set of experiments, samples were exposed to atmospheric humidity for different lengths of time. Both unoriented and oriented specimens were investigated. The presence of 4% LiCl almost doubles the amount of moisture absorbed at equilibrium by nylon-6. The Tg was found to be greatly affected by the moisture content and by salt type. When strict precautions to exclude moisture are taken, the addition of 4% LiCl raises the Tg of nylon-6 by about 25°C. The elastic modulus of oriented samples is increased by the addition of salts provided moisture is completely absent. This beneficial effect is, however, completely eliminated when samples are allowed to equilibrate with atmospheric moisture.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180407
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  • 94
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    Crystallization and morphology of melt-solidified poly(vinylidene fluoride) (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 793-809 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization of poly(vinylidene fluoride) (PVF2) from the melt yields two types of spherulites. The first consists of large, highly birefringent, and tightly banded spherulites of the α-form, which are seen at all temperatures. The second type, termed mixed, crystallizes with a newly reported unit cell which appears to be the correct one for γ-PVF2, but may contain inclusions of a different form (probably α-PVF2); it is seen only at relatively high temperatures and frequently exhibits irregular or disorganized birefringent and morphological features. In thin films, some mixed spherulites contain regions of single-crystal-like aggregates which are grown parallel to the substrate and appear essentially nonbirefringent between crossed polars. Mixed spherulites frequently undergo transformations at their growth fronts leading to initiation of α-growth. These transformations are associated with the generally higher growth rate of α-spherulites which may exceed that of their mixed counterparts by almost seven times. However, with increasing temperature this difference in growth rates is progressively reduced and ultimately reversed.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180412
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  • 95
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    Electronic Resource
    Reactivity and gelation. II. Substitution effect (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 915-915 
    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.1980.180180425
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  • 96
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    Quantitative determination of mesomorphic regions in oriented polymers from wide-angle X-ray diffraction (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 917-926 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method for quantitative characterization of the noncrystalline region in poly(ethylene terephthalate) (PET) fibers based on x-ray wide-angle diffraction data is elaborated. The procedure consists in a computational resolution of the diffracted intensity into individual peaks for 010, 110, and 100 planes and into isotropic and anisotropic components of diffuse scattering. The results show that the content of mesomorphic regions in the noncrystalline part of PET fibers with draw ratio of λ = 3.0 varies from 12% to 32% depending on the temperature of heat treatment.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180501
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  • 97
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    Piled-lamellae structure in polyethylene film and its deformation (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 971-979 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The fine structure of polyethylene film has been investigated by using a high-resolution scanning electron microscope equipped with a field emission source. The original film surface of a-axis-oriented blown polyethylene film and the surface of a necked region formed by drawing the film in the machine direction were observed. High magnification electron micrographs indicate that the basic unit of internal texture of this film consists of piled-lamellae units, each pile containing three to ten lamellar crystal sheets. The piled-lamellae unit acts as one body and does not separate into single lamellae during deformation. Many tie fibrils are formed between adjacent piled-lamellae units, when the film is drawn in the machine direction. Although little attention has been given to this mechanism, it is important in deformation. This fact seems to be reflected in different shapes of the stress-strain curves of films drawn the machine direction and perpendicular to it.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180505
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  • 98
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    Rheo-optical studies on the deformation mechanism of semicrystalline polymers. X. Orientation retardation spectrum of polyethylenePresented at the 27th Annual Symposium on Polymer Chemistry, Japan, Kyoto, 22-24 Nov. 1978. (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 951-970 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to explore the correlation between rheo-optical and mechanical dispersions, orientation and lattice-deformation retardation spectra are introduced in the phenomenological treatment of the stress-orientation coefficient and crystal lattice compliance functions in dynamic x-ray diffraction. A similar complementary treatment of the stress-optical retardation spectrum is also carried out for the dynamic birefringence. To determine the mechanical and rheo-optical retardation spectra, a deconvolution method based on the Fourier transform is developed. By this method, the mechanical and rheo-optical retardation spectra of a low-density polyethylene are computed from the imaginary components of the corresponding experimental functions; and subsequently, the real and imaginary components of the original functions are recalculated numerically from their respective retardation spectra and compared with the observed ones. The similarity of the normalized mechanical and rheo-optical retardation spectra demonstrates that the α mechanical dispersion is related to orientation retardation of the crystal grains at their boundaries. Furthermore, separation of crystalline and amorphous contributions to the stress-optical retardation spectrum is made on the basis of the two-phase hypothesis for polyethylene. The amorphous contribution to the stress-optical retardation spectrum is further resolved into two components corresponding to the α and β mechanical dispersions under the assumption that the resolved component for the α dispersion is symmetric in shape.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180504
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  • 99
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    Model for sorption of mixed gases in glassy polymers (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 981-992 
    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 is presented for analysis of the sorption of mixed gases in glassy polymers at concentrations below which significant plasticization occurs. The well-known dual-mode sorption model comprised of a Henry's law term and a Langmuir isotherm term, which has been used extensively for interpretation of single-component gas sorption data, forms the basis for the analysis of binary mixtures discussed here. Measurements using pure gases provide dual mode parameters which can then be used to predict the resultant sorption isotherms for binary mixtures of any of the pure gases. The proposed analysis is based upon recognition that the Langmuir component of the overall sorption concentration should be governed by competition between the two penetrants for the fixed unrelaxed volume in the polymer, which is believed to be the locus of the Langmuir capacity. This effect may result in a significant depression of the measured sorption of similar penetrants competing for the limited Langmuir capacity. A numerical example is considered which illustrates the range of behavior expected for CO2 and CH4 in polycarbonate. Deviations from the theoretical predictions of the simple dual-mode model for binary systems are discussed in terms of plasticizing effects on the Henry's law constant and the Langmuir affinity constant. The analyses proposed here are of direct and critical interest to the applied problems of migration of trace contaminants in glassy polymers and analysis of barrier packaging for foods since all of these applied problems involve mixed-penetrant sorption. Specifically, it is predicted that the presence of residual monomers or solvents in glassy polymers can produce both anomolously low Langmuir sorption affinity constants and sorption enthalpies compared with the residual-free case.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180506
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  • 100
    Electronic Resource
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    Molecular theory of piezoelectricity of α-helical polypeptide (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 993-1004 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A molecular theory of the piezoelectric constant of the α-helical backbone of polypeptide is developed on the basis of fluctuation formalism. The piezoelectric constant, electric susceptibility, and elastic compliance of the α-helix are calculated through the method of molecular lattice dynamics by use of normal-coordinate analysis. Displacements of each atom due to the external stress exerted upon the backbone are also calculated. The piezoelectricity of the α-helix is concluded to arise mainly from rotation of the CO—NH bond. The value of the piezoelectric constant of poly(γ-benzyl-L-glutamate) film calculated from the above theoretical constants along with a composite theory is found to agree reasonably with experiment.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.180180507
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