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  • Physics  (1,075)
  • 1995-1999
  • 1985-1989
  • 1980-1984  (1,075)
  • 1982  (517)
  • 1980  (558)
  • 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.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180801
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  • 18
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    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.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180804
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  • 19
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    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 
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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: 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.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180807
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  • 20
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    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 
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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: 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.
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    URL: http://dx.doi.org/10.1002/pol.1980.180180809
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  • 21
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    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
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    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 
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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: 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.
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    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.
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    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 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray 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.
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    Electronic Resource
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    Concentrated protein solutions in the analytical ultracentrifuge (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1963-1978 
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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: 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.
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    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 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In 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.
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    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 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In 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.
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    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 
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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 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.
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    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 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180181013
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    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 
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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 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.
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    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 
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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: 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.
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    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 
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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: 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.
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    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 
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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 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.
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    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 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1980.180181115
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    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 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The lateral 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.
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    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 
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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 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.
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    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 
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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: 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.
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    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 
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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 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.
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    Effect of disorder in the twist angle on light scattering by a three-dimensional spherulite (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1-13 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Light scattering patterns are calculated for imperfect three-dimensional spherulites with fluctuations in the twist angle. The fluctuations are described in terms of a parameter characterizing the distance correlation function. Cases are considered in which (i) the principal axis of the scattering element makes a constant angle with the radius but there is disorder in the twist angle about the axis, and (ii) there is combined twist disorder and orientation disorder of the scattering elements. Calculations suggest that the disorder in the twist angle may lead to a decrease in the higher-order variation of scattered intensity with scattering angle and deviation from the four-leaf-clover-type scattering characteristic of a perfect spherulite at lower scattering angles. On the other hand, disorder in orientation has little effect on the scattering pattern.
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    Effect of glass filler size on the tensile properties and tear strength of polybutadiene (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 49-63 
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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 study of the tensile properties, tear strength, hysteresis, and swelling ratio of model composite elastomeric compounds consisting of polybutadiene filled with glass beads has been carried out as a function of the size of the beads. The diameter of the beads ranged from 25 to 1000 μm and the volume fractions examined were 0.16, 0.092, and 0.048. Mechanical properties of the filled elastomers were functions of the loading (separation distance), the particle size (surface area/volume), and the elastomer-filler systems studied.
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    Concentrated solution viscosities of polymeric associates (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 99-106 
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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: Reasons have been advanced why in some cases concentrated-polymer-solution viscosity measurements are not a suitable method for determining the degree of association of groups attached to polymer chains. These are based on the finite lifetimes of associates compared with the finite lifetimes of the entanglements, which are the major contributors to concentrated-polymer-solution viscosities. The validity of these reasons has been checked in a system where the degree of association of polymer chains can be measured spectroscopically. It was found that the viscosity of these solutions was considerably less than that calculated by the concentrated-solution viscosity equation for solutions of polymers of the average molecular weight expected from the spectroscopically found degree of association.
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    Poly(P-phenylene sulfide) hexafluoroarsenate: A novel conducting polymer (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 117-130 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(p-phenylene sulfide) (PPS) is a melt- and solution-processible polymer which on treatment with AsF5 forms a blue-black material with a conductivity of 1-10 Ω-1 cm-1. Thermopower measurements indicate that the resulting polymer is p type, consistent with partial oxidation of the PPS by the AsF5. The rate and extent of this doping process prove to be particularly sensitive to the degree of crystallinity of the starting polymer. There is also evidence of crosslinking of the polymer chains during the reaction with AsF5. The details of both the chemistry and physics of the doping of PPS and several of its derivatives are presented.
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    Use of quantum chemistry relations in cationic polymerization: A critical examination (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 131-139 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature dependence of the reactivity ratio r2 (subscript 2 for styrene) is reported for 1-and 2-vinyl naphthalenes, 4-halogeno-1-vinyl naphthalenes, 2- and 3-vinyl phenanthrenes, and o-methylstyrene. The monomers are classified with respect to In (1/r2) and ΔH # and ΔS# (the differences in activation parameters for homopropagation and crosspropagation). It is shown that the reaction is entropically controlled. It appears that there is no correlation between stabilization energy (ΔE)rs and ΔH# and that the correlation with In(1/r2) is only apparent. The origin of this lack of correlation is analyzed and a new index of reactivity is proposed; its correlation with ΔH# is quite satisfying.
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    Miscibility of polycaprolactone/chlorinated polyethylene blends (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 191-203 
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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 polycaprolactone (PCL) with chlorinated polyethylenes (PECls) having chlorine contents of 25, 30, 36, 42, and 48% by weight were prepared and studied by differential scanning calorimetry and small-angle light scattering (SALS). It was found that blends made with PECls containing 30% or more chlorine are completely miscible with PCL (a single glass transition temperature Tg is found) while the PCL/PECl(25) blends are immiscible. PCL crystallizes in the miscible blends at any composition and it has an enthalpy of fusion which decreases only slightly with PECl content. Blends in the PECl composition interval of 0-80% are spherulitic, as shown by SALS, but a rodlike morphology is found at the 85% composition and dispersed crystals are observed at higher compositions. It is suggested that the k parameter of the Gordon-Taylor equation can be taken as a measure of the strength of the specific interaction between PCL and PECl. Low values of k (0.26 and 0.35) are found for PCL/PECl blends but a higher value of k (0.51) has been reported for PCL/poly(vinyl chloride) (PVC) blends, indicating a stronger interaction in the latter mixtures. In agreement with these findings poly(α-methyl-α-n-propyl-β-propiolactone) and poly(valerolactone) are not miscible with PECl, whereas they were previously shown to be miscible with PVC.
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    Comparison between neutron and quasielastic light scattering by polyacrylamide gels (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 225-233 
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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 authors describe small-angle neutron scattering measurements of the screening length ζ in polyacrylamide-water gels. Although these are inhomogeneous systems, the screening length is clearly observable and is in good numerical agreement with the relation E = 3kT/4πζ3, where E is the longitudinal elastic modulus of the gel obtained from measurements of the intensity of qu-asielastically scattered light. Static light scattering observations reveal a larger-scale (ca. 30 nm) superstructure in the gel.
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    Melt rheology of ion-containing polymers. I. Effect of ionic content in a model polyesterionomer (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 259-268 
    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 copolymerizing small amounts of an ionic moiety (0-7 mol %) into the backbone of a polycondensation polymer have been investigated by a combination of linear viscoelastic, steady-shear, and extensional testing. At a constant viscosity in dilute solution, both the zero-shear-rate viscosity and the maximum relaxation time in the melt increase monotonically with an increase in the ionic character. These effects are present after the data are normalized to remove the increase in the glass transition temperature Tg with increased ionic content. Large-strain, steady-shear flow experiments showed that the viscoelastic memory of the melt is affected by ionic content. An increase in ion content causes a decrease in the effect of strain on the memory function. This effect is not apparent in extensional flow experiments, which indicate that the ionic content does not affect the response if the tests are conducted at a constant temperature above Tg.
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    Studies of tensile failure in oriented polymeric fibers by quantitative fractography (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 297-305 
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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: For some fibers, such as the nylon monofilaments studied here, quantitative information may be obtained from scanning electron micrographs of fracture surfaces. On these surfaces the segment of the cross section that supports the load at the instant of rupture is seen distinctly, and its area can be measured. Normalizing breaking load by this area provides a breaking stress characteristic of the final supporting segment. “Ultimate” breaking stresses calculated in this way indicate (i) For notched filaments, the ultimate breaking stress is almost constant with notch depth and also with strain rate. (ii) For un-notched filaments, there is an increase of breaking load with strain rate, due in part to the extent of the slow cleavage that precedes failure; however, the ultimate breaking stress increases as rate of strain decreases. These two findings are incompatible with mechanisms of failure based on growth of microcracks by heat- and stress-activated chain breakage. A possible explanation involves rearrangement of microfibrils within the fiber which alters their strength distribution. (iii) The apparent strength reduction on wetting nylon filaments in water is due to a faster rate of growth of the slow-cleavage area; the ultimate breaking stress is unchanged, except at high rates of strain.
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    Investigation of local order in unreacted DGEBA epoxy resin monomers by light scattering (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 327-344 
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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 existence of local order in two epoxy resins of the diglycidyl ether of bisphenol-A (DGEBA) type has been investigated using Rayleigh scattering and Brillouin spectroscopy. The resins differ in their molecular weight distributions and their relative concentrations of epoxide and hydroxyl groups. The complementary use of both techniques in elucidating the thermal behavior of local order is illustrated, and the use of the latter technique to study thermal acoustic phonons and hypersonic relaxation is discussed. Both techniques independently show that molecular aggregates exist in each resin system. The scattering-envelope dissymmetry shows that the resin with the high epoxide/hydroxyl group ratio contains aggregates up to 20 nm in size, and the low-ratio resin exhibits sizes up to 70 nm. These aggregates are thermally unstable in the temperature range studied (293-443 K). Dissolution in chloroform shows that these aggregates are reduced in size and that further structural changes occur which are dependent on solvent concentration. Aggregate volume fractions were determined for a range of aggregate size. Brillouin spectroscopy indicated that both resins exhibit hypersonic relaxation in the temperature range studied. The complex longitudinal moduli of the resins were superimposable under a WLF temperature transformation comparable to the difference in their static glass transition temperatures. Molecular aggregate size, number, and stability are related to the epoxide/hydroxyl ratio of the resins and the degree of intermolecular hydrogen bonding.
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    Reduced-variable mechanical characterization of styrene-butadiene rubber with varying crosslink density, temperature, and finite strain statesThis research was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under Contract No. NAS7-100, sponsored by the National Aeronautics and Space Administration.Corrected proofs received January 4, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 363-374 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A single master logarithmic stress relaxation curve of reduced modulus as a function of reduced time is established for a styrene-butadiene rubber (SBR) system, accounting for the effects of crosslinking density, temperature, and time. The results from recent tests involving uniaxial and various biaxial strain states at finite strain levels may be represented by a unique strain-energy function W of the Valanis-Landel separable symmetric type, \documentclass{article}\pagestyle{empty}\begin{document}$ W = \sum\limits_{i = 1}^3 {w(\lambda_i)} $\end{document} where the λi are principal extension ratios. These two representations demonstrate that the mechanical response of whole families of elastomeric materials may be predicted once a single member of the family is fully characterized.
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    Characterizing the kinetics of volume recovery in glasses by instantaneous temperature-jump experimentsThis work was supported by the U.S. Department of Energy, under Contract No. DE-AC04-76-DP00789 and by the National Science Foundation under Contract No. DMR 78-24185. (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 375-387 
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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: This article proposes a temperature-jump (T-jump) approach for characterizing the kinetics of volume recovery in glassy materials. The kinetic characterization is based on the Kovacs-Aklonis model. This incorporates a retardation-time spectrum which shifts according to both the temperature and the instantaneous volume. The proposed experiments involve measuring the change in recovery rate caused by an abrupt temperature jump. Although an analogous procedure has been used to determine the activation energy for linear viscoelastic creep, the analysis for volume recovery is complicated by its inherent nonlinearity. Nevertheless, accounting for the nonlinearity by a reduction of the time scale permits the T-jump results to be analyzed. In particular, the T-jump approach can be used to: (i) test a particular functional form for the shift factor and (ii) determine the previously unmeasurable parameter x, which defines the relative importance of the temperature dependence and the volume dependence in this function. In addition, numerical simulations indicate that the proposed method can be implemented in the laboratory.
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    Structure-property behavior of films containing disk spherulites: A model study (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 457-472 
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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: Thin films of a polyester of lactic and glycolic acid were prepared to give controlled amounts of disk spherulites. The spherulite contents ranged from zero to 100% and were accurately measured. The stress-strain properties of the films were then determined at 60°C, i.e., about 20°C above the glass transition temperature Tg. The mechanical behavior varied quite systematically with spherulite content and displayed little dependence on spherulite size. It was found that much of the mechanical data could be reasonably well described by a simple composite model. In addition, the yield strain as well as the strain to break could be principally coupled to the deformation of only the amorphous phase. SEM and optical microscopy studies supported the above conclusion, also demonstrating that the isolated spherulites adhered well to the amorphous matrix and behaved as stress concentrators in the system when the deformation temperature was above Tg.
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    Model networks of end-linked polydimethylsiloxane chains. XIV. Stress-strain, thermoelastic, and birefringence measurements on the bimodal networks at very low temperaturesPresented in part at the 27th International Symposium on Macromolecules, Strasbourg, France. 1981. (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 473-480 
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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: Bimodal networks consisting of very short and relatively long poiydimethylsiloxane (PDMS) chains were studied from 30 to -52°C in an attempt to elucidate the anomalous increases in modulus [f*] exhibited by such elastomeric materials at high elongations. Temperature was found to have very little effect on (i) the elongation at which the upturn in [f*] becomes discernible, (ii) the elongation at which rupture occurs, and (iii) the total increase in [f*] up to the rupture point. The standard force-temperature (“thermoelastic”) plots were linear, but gave values of the energetic contribution to the total force which were significantly smaller than those universally obtained on unimodal, long-chain PDMS networks. Birefringence-temperature relations were also found to be linear, and yielded values of the optical-configuration parameter and its temperature coefficient which were in satisfactory agreement with the corresponding values reported for unimodal PDMS networks. These results indicate that even at very low temperatures the observed increases in modulus (and consequent improvements in ultimate strength) are due to non-Gaussian effects arising from limited chain extensibility, rather than from intermolecular reinforcing effects such as strain-induced crystallization.
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    Increased water sorption of poly(methyl methacrylate) after removal of methanol (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 557-560 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    A neutron scattering analysis: How does the conformation in polyethylene crystals reflect that in the melt? (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 561-578 
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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: Neutron scattering data for melt-crystallized polyethylene have been analyzed in order to clarify to what extent the chain folding is randomly reentrant. No attempt has been made to specify the molecular conformation in every detail, and the emphasis is on distinguishing between different classes of conformation. The most random folding corresponded to a model where the folding is imposed solely by the criterion of the chain segments moving the least possible distance during the crystallization process (a “freezing-in” model). This has been shown not to be compatible with published data. For this model analytic calculations are possible based on the projection of a three-dimensional Gaussian distribution onto a plane. A subunit model is then proposed which requires substantial local rearrangement of the chain as it folds during crystallization, but where the distribution of the subunits within the whole molecule is imposed by the preexisting Gaussian chain of the melt. Arguments based on space filling considerations are invoked, with the postulate of a surface structure which is neither crystalline nor truly amorphous. Anything approaching a random switchboard model (e.g., the freezing-in model which we consider) is contrary to both space filling considerations and to the comparison of observed and calculated neutron scattering. The analytical calculation which was performed for the freezing-in model was employed so as to simplify calculations for the subunit model. For scattering intensities over a wide range of scattering angle it is deduced that only the structure within the subunit need be considered. Numerical computer calculations involving only a small number of stems were then carried out for a number of different subunit structures, and some general features are noted which restrict the type of model which can explain the data. As in previously published analyses, a very high proportion of adjacent folds is not compatible with the results. A row model for the stems within a molecule can achieve good agreement, either with straight rows or with a certain amount of “stagger” incorporated. Up to about 40% of the folds could be adjacent. Models based on two-dimensional random walks did not give good agreement.
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    Stress relaxation of a polymer solution in double-step shear deformations: A separate evaluation of the stress components due to entangled segments of different orientations (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 623-632 
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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: When two shear deformations γ1 and γ2 are successively applied to an entangled polymeric system, a composite temporary network is formed. In this article a simple method is proposed for evaluating separately the contributions from the component networks of different deformations, γ1 + γ2 and γ2, to the observed shear and normal stresses. The method is applied to literature data for a polystyrene solution. It is revealed that the entangled chain segments formed between the applications of two deformations relax very rapidly, while those formed prior to the first deformation do not relax for quite a long time. The result is in accord with the conjecture based on the tube model of entanglement that the chain ends lose their orientation as the chain creeps out of an oriented tube.
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    The use of chemical contrast in the SEM analysis of polymer blends (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 651-658 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel method for investigating the morphology of multiphase polymers is discussed. In this procedure, inherent differences in secondary and backscattered electron emission from the various components rather than topographical variations are used to produce image contrast. The combined use of various selective stains and energy-dispersive x-ray analysis to accentuate and positively identify individual phases is discussed. The effects of coating thickness and type and changes in accelerating voltage on image quality are also described.
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    The characteristic ratios of stereoirregular polybutadiene and polyisoprene (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 743-750 
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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 characteristic ratios of stereoirregular polybutadiene and polyisoprene have been evaluated by a combination of intrinsic viscosity and light-scattering measurements under θ conditions. The polydienes were synthesized by anionic polymerization and thus had near-monodisperse molecular weight distributions and were of uniform microstructure. The polybutadiene C∞ was found to be 5.1, which is in good agreement with the Abe-Flory predictions. However, the value of 5.1 for polyisoprene is somewhat higher than prediced by theory.
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    Styrene-acrylonitrile random copolymer in ethyl acetate (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 773-775 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Studies of magnetic resonance phenomena in polymers. I. The effects of free volume and segmental mobility on the motion of nitroxide spin probes and labels in poly(methyl methacrylate)This paper presents the results of one phase of research carried out at the Jet Propulsion Laboratory, California Institute of Technology, under Contract NAS7-100 sponsored by the National Aeronautics and Space Administration, and supported in part by the Encapsulation Task, Low Cost Solar Array Project, and also in part by the RAD Task of the Solar Thermal Power System Project, funded by the Department of Energy. (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 763-772 
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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: Thin films of spin-probed and spin-labeled poly(methyl methacrylate) (PMMA) have been examined by electron spin resonance (ESR) at X-band frequency (9.2 GHz) and at various temperatures. Direct spectral evidence is presented to indicate that the composite ESR spectra observed in a certain temperature range originate from two states of distinctly different mobility, one with slow motions corresponding to a glassy state and the other with fast motions corresponding to a liquidlike state. The coexistence of these two states at temperatures considerably below the glass transition temperature can be explained as a result of the effect of free volume in a solid polymeric glass.
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    An expression for local composition in polymer-solution thermodynamics (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 783-791 
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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 expression for local composition which describes nonrandom interactions between unlike molecules in polymer solutions is proposed. This expression makes the nonrandom model compatible with the one-fluid hypothesis and satisfies the limits of randomness when experimental conditions evolve in such a way. Data on several binary systems are studied using this model which represents simultaneously activity and heat-of-mixing data.
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    Molecular aggregation of solid aromatic polymers. II. Mechanical properties of aromatic polyimide film (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 837-844 
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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: Molecular aggregation of the aromatic polyimide poly(4,4′-oxydiphenylene-pyromellitimide) is influenced by the initial imidization temperature and by cold drawing. The effect of molecular aggregation in polyimides on their mechanical properties has been investigated. The density of a polyimide in which molecular aggregation gives an amorphous state is increased slightly by cold drawing. On the other hand, if molecular aggregation leads to a heterogeneous two-phase structure, the density is decreased by cold drawing. With increasing initial imidization temperature, the α absorption peak in dynamic tensile measurements becomes broader and smaller, and shifts to a higher temperature. From analysis of correlations between molecular aggregation and mechanical properties, it is concluded that the mode of molecular motion corresponding to the α dispersion in polyimide is a long-range cooperative motion of the main chain which is associated with the glass transition.
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    Phase relationships in a ternary solution composed of a solvent and two monodisperse homologous polymers (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 893-898 
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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: Exact expressions are derived for the spinodal, critical conditions, and separation factor of a ternary solution consisting of a pure solvent and two monodisperse homologous polymers in which the Flory-Huggins interaction parameter χ depends separately on the concentrations of the polymer components. The results allow one to see the difference from previous expressions obtained with χ depending on the total concentration of the polymer, and are expected to be useful for experimental determination of the Gibbs free energy of ternary solutions.
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    On the mechanism of fibril growth in polycarbonate and poly(methyl methacrylate) crazes (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 929-930 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Fluorescence depolarization in polymers: The microviscosity of bulk polybutadiene and of solutions in cyclohexane (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 953-959 
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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 reorientational relaxation of 9-cyananthracene fluorescent label molecules has been measured in bulk polybutadiene and solutions with cyclohexane by a fluorescent depolarization technique. The procedure adopted consists in the incorporation of an Arrhenius temperature dependence of the orientational relaxation time in the Perrin equation, thus obviating the necessity of an independent determination of the intrinsic polarization ratio P0 and enabling one to obtain the preexponential factors and the activation energies of the reorientational relaxation times. The most noteworthy result in our view is the validity of the Arrhenius equation for the effective microviscosity as opposed to the validity of the Fulcher-Vogel-Tamann equation with a glass point of T0 = 136 K for the shear viscosity of a polymer solution (90%).
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    Birefringence of highly oriented fibers (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 981-987 
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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 spectrophotometric method was developed for measuring the birefringence of highly oriented synthetic fibers. This method surmounts the low birefringence limit of the standard quartz compensator method and the difficulties in interpretation of the photographic fringe method. A highly oriented aramid fiber gave birefringence values of 0.60-0.75 by this method, compared with 0.25 for polyester and 0.06 for nylon by other conventional methods. The operating principles and excellent results of this new method provide a basis for the extension of routine birefringence characterization to highly oriented fibers.
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    Three-dimensional crystalline order in an atactic comblike polymer (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1013-1018 
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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 production of oriented “crystalline” fibers of an atactic polymer, poly{1-[6-(4-biphenylyloxy)hexyloxycarbonyl]ethylene} is reported. The x-ray diffraction is consistent with a two-chain unit cell with a = b = 23.5 Å, c = 6.48 Å, and γ = 120. Although the cell is essentially hexagonal, the absence of screw symmetry along the polymer chain reduces the crystal symmetry to P A packing model consistent with these data is proposed.
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    FTIR studies of calcium and sodium ionomers derived from an ethylene-methacrylic acid copolymer (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1069-1080 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A systematic study of the sodium and calcium salts of an ethylene-methacrylic acid copolymer is reported. Fourier-transform infrared spectroscopy (in the midinfrared region) is applied to the characterization of structural changes as a function of temperature and time of annealing. In the spectra of calcium ionomers, bands associated with carboxylate dimers are identified and assignments of specific spectral features to multiplets and clusters are discussed. The spectroscopic changes observed in the spectra of sodium ionomers differ somewhat from their calcium counterparts in that a single infrared band attributed to isolated carboxylate groups is observed. Assignments of specific bands to multiplets and clusters can, however, be made in a manner consistent with the interpretation of the spectra of calcium ionomers.
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    Structural studies of ultrahigh-modulus polyethylene using nitric acid etching and gel permeation chromatography. II. Influence of polymer molecular weight, draw temperature, and annealing (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1107-1128 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The technique of nitric acid etching followed by gel permeation chromatography has been used to determine the crystal length distribution in ultrahigh-modulus polyethylenes. The crystal length distribution has been studied as a function of draw ratio, polymer molecular weight, processing conditions, and annealing. The results confirm that although there is a considerable broadening of the crystal length distribution on drawing, the majority of crystals have lengths less that 500 Å. There are detailed changes in the length distribution due to changes in draw temperature, molecular weight, and annealing which are not always reflected in corresponding changes in the long period determined from small-angle x-ray scattering. Possible reasons for these discrepancies are discussed.
    Additional Material: 16 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200702
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    The entanglement network and craze micromechanics in glassy polymers (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1129-1141 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crazes have been grown from crack tips in thin films of the following five polymers: polytertbutylstyrene (PTBS), polystyrene (PS), poly(styrene-acrylonitrile) (PSAN), poly(phenylene oxide) (PPO), and poly(styrene-methyl methacrylate) (PSMMA). These polymers represent a wide range of le values, where le is the chain contour length between entanglements. Quantitative transmission electron microscopy has been used to analyze the extension ratio λcraze and displacement profiles for these crazes. From these measurements the craze surface stresses have been computed by using the method of distributed dislocations. This analysis also permits an accurate measure of the level of the applied stress σ∞. These measurements show that the stress necessary for crazing increases as le decreases and that the higher surface stresses present at crack tips generate crazes that have higher λs than isolated crazes in the same polymers. Surface drawing is shown to be the dominant mechanism for craze thickening in all five polymers.
    Additional Material: 6 Ill.
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    Shrinkage and retractive forces during the annealing of drawn low-density polyethylene (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1175-1192 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Shrinkage of unconstrained low-density polyethylene samples and the retractive stress of samples with ends fixed have been investigated as a function of the annealing time tA and temperature TA on material drawn at room temperature to draw ratios λ between 4 and 6. The shrinkage increases with tA and TA. The retractive stress on a sample annealed with ends fixed goes through a maximum as the sample is annealed and then drops to a limiting value which increases with TA as long as TA is at or below 80°C and rapidly decreases with higher TA. The drop from the maximum to the limiting retractive stress, slow at lower TA and rapid at higher TA, seems to be a consequence of rapid pulling of chain segments out of crystal block in which interfibrillar tie molecules are anchored. This process is facilitated by the high TA, which softens the crystal matrix. At constant end-to-end distance, the contour length of the tie molecules is irreversibly increased, and this causes a reduction in the contribution of the affected tie molecules to the overall retraction stress. Hence one finds a substantially higher retraction stress during first heating than during subsequent cooling and heating of the drawn sample.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200706
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    Theoretical birefringence of ultraoriented polyethylene from model structure calculations (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1193-1205 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The birefringence of model structures of ultraoriented polyethylene has been calculated by using the point-dipole concept and the polarizability tensor of the methylene group derived recently by Pietralla. For well-oriented chains the birefringence is determined by the combination of a negative anisotropy of the polarizability tensor of the methylene group and a positive anisotropy of the Lorentz tensor, both with respect to the chain direction. As a consequence it decreases with increasing density. The results are in agreement with experimental values of Mead, Desper, and Porter. In the model the amorphous regions are regarded as a mixture of planar and helical segments arranged in nematiclike bundles which additionally may have a certain distribution of orientation. The birefringence is not much affected by defects which, on the other hand, strongly influence the ultimate mechanical properties.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200707
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  • 72
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    Effect of substituents in the styrene ring on the dynamic mechanical relaxations of a styrene-crosslinked unsaturated polyester resin (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1223-1232 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic mechanical properties of a series of polyester resins made from a maleic/phthalic anhydride-based unsaturated polyester crosslinked with each of styrene, 4-methyl styrene, 4-ethyl styrene, 4-n-butyl styrene, 4-isopropyl styrene, tertiary butyl styrene, 4-chlorostyrene, and 3,4-dichlorostyrene were studied. The order of the α transition temperatures was as expected from that for the homopolymers, except in the case of the chlorostyrenes, for which dipolar interactions with the polyester chain may be important. The styrene bridges appeared to be involved in a steric interaction (and in the case of the chlorostyrenes, a dipolar interaction) with the β relaxing ester species. It is suggested that both the γ and γ′ relaxations involve similar interactions between the matrix and the relaxing moieties. For the 4-n-butyl styrene resin, an additional relaxation below -170°C was observed, and is ascribed to relaxation of the n-butyl group.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200709
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    Polyelectrolyte solutions: Counterion condensation and intermolecular interactions (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1233-1247 
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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: This article demonstrates that the neglect of nonlinear effects in the conventional counterion condensation theory for the double layer about a charged cylinder can be significant, especially for phenomena involving intramolecular or intermolecular interactions in dilute solutions. For concentrated solutions the Manning theory derives from a linearized superposition approximation for the potential, in contrast to the cylindrical-cell model, which explicitly treats interactions within an ordered array of parallel cylinders. A new theory which treats interactions explicitly while permitting disorder in two dimensions is presented, and predictions for the osmotic pressure are compared with those from the Manning and cylindrical-cell models.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200710
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    Additive moduli for crosslinked epoxies (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1269-1278 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ultrasonic measurements were made on a series of eight crosslinked polyepoxides over the temperature range from 0 to 60°C at a frequency of 2 MHz. From these measurements the bulk (K) and shear (G) moduli were calculated. These data were then analyzed in terms of molecular component properties. Proceeding by analogy with Rao's rule for liquids, the authors found that K is not an additive property but the function U = V(K/ρ)1/2γ is an additive property. Here V is molar volume, ρ is the density, and γ is the Gruneisen parameter (for interchain vibrations). A similar relation was found to hold for shear modulus. In particular, G is not an additive property but W = V(G/ρ)1/2g is an additive property, where g = (1/2α) (∂ InG/∂T)p - 1/2 is the shear analog of the Gruneisen parameter. Using U and W, calculations were made of K and G as functions of temperature for the eight epoxies. These results agree with the measured values within the experimental uncertainty of the measurements.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200713
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    Dynamic birefringence studies of high-density polyethylene (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1279-1287 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A rheo-optical investigation has been carried out on a sample of high-density polyethylene (HDPE) in an attempt to examine the nature of the α-relaxation mechanism. Dynamic mechanical and bi-refringence behavior was measured over the frequency range of 0.008-4.3 Hz and temperature range -40 to 100°C. The dynamic mechanical and birefringence data were reduced to a reference temperature of 50°C by a combination of horizontal and vertical superposition. The significance of the vertical shift factor has been discussed extensively in previous papers and is not dealt with here. An Arrhenius plot was made of the log of the horizontal shift factor versus reciprocal temperature for the mechanical and optical data. The mechanical data exhibited three distinct regions, the slopes of which led to activation energies of 70, 90, and 150 kJ mol-1. The temperature at which these dispersions occurred suggested the observation of the β, α1, and α2 relaxation processes. The optical data contained two distinct regions from which activation energies of 55 and 95 kJ mol-1 were obtained. The high-temperature α2 process was not observed in the Arrhenius plot; however, a maximum in K′ and a change in sign of K″ probably reflects a contribution from the α2 relaxation mechanism.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200714
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    Etude cinétique des effets de fluence énergétique, de débit de fluence, et d'effacement induits par des ions lourds et des photons γ dans le triacétate de cellulose (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1313-1326 
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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 kinetic interpretation of the damage produced by heavy ions (3684Kr and 1735Cl from 1 MeV/amu) and γ radiation in cellulose triacetate leads to an exponential dependence on the ion fluence. A comparison of the fading effect produced by heavy ions and γ rays shows that the heavy ions, unlike γ rays, cause irreversible damage. Finally, a nonlinear dependence on the flux of ions and γ rays is found in the kinetics of radiation damage. This result is contrary to the usual assumption that heavy-ion flux, like γ-ray flux, is additive, at least for the fluxes of 109-2 × 1010 ions/cm2s and dose rates of 103-104 Gy/h used in this work.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200716
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    Observations par microscopie électronique de traces d'ions lourds dans le triacétate de cellulose (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1327-1340 
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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: Tracks of heavy charged particles have been observed in cellulose acetate by conventional electron microscopy (100 kV) and by high voltage microscopy (1, 2 MV). The tracks are formed of successive islets following each other at distances of 70-150 Å. With the evolution of the diameter of these zones is shown the existence of a highly perturbed cylindrical volume (diameter 400 Å for the case of krypton) corresponding to regions in which free radicals have been created. The different techniques used do not allow observation of the latent track because of the complications of energetic phenomena: the electron beam current density being limited, the contrast is small and hence the resolution is restricted.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200717
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    Distribution spatiale des dommages produits par les ions 3684Kr (1 MeV/amu) et 1735Cl (1 MeV/amu) dans le triacétate de cellulose (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1289-1311 
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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: Our earlier results on ασ and heavy-ion-radiation damage in cellulose triacetate (CTA) are compared with those of previous authors on UV-and γ-radiation damage in the same material. Thus the common effects of these different methods of irradiation can be distinguished from those characteristic of the radiation employed. With heavy-ion radiation the production of stable radicals is accompanied by C - O cleavage. In the case of 3684Kr (1 MeV/amu) ions, the number of free radicals produced is investigated, without distinguishing the species, by using the scavenger technique in the solid phase, combined with UV spectroscopy. On the other hand, C - O cleavage is observed by IR spectroscopy, with its inherent selectivity. A statistical study shows that the experimental curves representative of the evolution of the optical transmittance ratio before and after irradiation L(N) versus the ion fluence N are of exponential type: $$ L(N) = \alpha e^{\beta N} $$ where β is a parameter related to the volume damaged by a single ion and, therefore, to the latent track size. The latter is approximated by a cylinder whose height is equal to the range of the ion. For 3684Kr8+ (1.1 MeV/amu) the track length is 21 μ. For each type, damages are localized within a radius of 250 Å for free-radical yields, 148 Å for cellulosic chain cleavages, 108 Å for deacetylation, and 100 Å for opening of pyrannosic rings. The track length is 14 μ for 1735Cl6+ (1 MeV/amu), while the radius of the cylinder in which free radicals are produced is only 80 Å.
    Additional Material: 18 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200715
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    Liquid-crystalline textures in binary and ternary block copolymer-solvent systemsCorrected proofs received May 3, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1341-1353 
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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 number of characteristic liquid-crystalline textures can be obtained in binary and ternary systems (i.e., including one or two solvents) based on polystyrene-poly(ethylene oxide) (PS-PEO) and polystyrene-polyisoprene block copolymers. These textures include oily streaks, myelinic figures, and vesicles, all characteristic of a lamellar structure; fan-shaped textures of cylindrical structure; and isotropic domains indicative of a cubic structure. Experimental conditions used to systematically produce the mesomorphic textures are described, and the rather critical solubility conditions which the solvents must meet are indicated. The rules and described procedures should be quite general and applicable to other copolymers as well. Finally, highly unusual examples of “pseudomorphosis” typical of liquid-crystalline textures occurring in bulk upon melting and crystallization of the PEO sequences in PEO-PS copolymers are also reported.
    Additional Material: 11 Ill.
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    Thermodynamic properties of a polyelectrolyte solution containing a mixture of counterions of the same chargeCorrected proof received April 27, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1355-1364 
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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: Electrostatic internal and free energies are calculated for the cell model of a polyelectrolyte solution having two kinds of counterions of the same charge but different size. The calculation is based on the solution of the Poisson-Boltzmann equation obtained previously. The electrostatic contributions to the internal and free energies are presented as functions of valences, radii, and mole fractions of counterions, and their application to interpretation of experimental results is discussed.
    Additional Material: 4 Ill.
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    Absolute integrated SAXS measurements during the crystallization of linear polyethyleneResearch sponsored by the Army Research Office (Durham) under Grant No. DAAG 29-77-G-0201 and by the Department of Energy, Division of Materials Science, under Contract W-7405-eng-26 with the Union Carbide Corporation.Corrected proofs received April 29, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1365-1369 
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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: Absolute intensity measurements of a dynamic small-angle x-ray scattering from a linear polyethylene were carried out during polymer crystallization from melt in a temperature range of 113.5° to 124.5°C. The mean-square modulation of the electron density over the irradiated volume was evaluated and the feasibility of dynamic experimentation for crystallization kinetic analysis was established. The results provide an absolute value of mass density of the amorphous phase of a semicrystalline polymer at the crystallization temperature.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200803
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    Effects of high-pressure CO2 on the glass transition temperature and mechanical properties of polystyreneCorrected proofs received May 20, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1371-1384 
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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: Hydrostatic pressure usually increases the glass transition temperature Tg of a polymer glass by decreasing its free volume; if the pressurizing environment is soluble in the polymer, however, one might expect an initial decrease in Tg with pressure as the polymer is plasticized by the environment. Just such a minimum in the Tg of polystyrene (PS) is observed as the pressure of CO2 gas is increased over the range 0.1-105 MPa from both ultrasonic (1 MHz) measurements of Young's modulus E and static measurements of the creep compliance J. A time-temperature-pressure superposition law is obeyed by PS which allows a master curve for the compliance to be constructed and shift factors to be determined. A master curve for E is then obtained by using the Boltzmann superposition principle. The compliance J reaches a maximum, and E and Tg reach minima, at a CO2 pressure of ca. 20 MPa at both 34 and 45°C, which are above the critical temperature (31°C) of CO2. At the minimum, Tg is 41 at 45°C and 36 at 34°C, the larger depression at 34°C evidently corresponding to the higher solubility of CO2 at the lower temperature. The plasticization effect due to CO2 can be isolated by subtracting the effect of hydrostatic pressure alone from the experimental data. The results leave no doubt that at high pressures CO2 gas is a severe plasticizer for polystyrene.
    Additional Material: 12 Ill.
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    Pressure-volume-temperature properties of blends of poly(2,6-dimethyl-1,4-phenylene ether) with polystyreneCorrected proofs received May 3, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1385-1397 
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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 pressure-volume-temperature (PVT) properties of blends of poly(2,6-dimethyl-1,4-phenylene ether) (PPO) with polystyrene (PS) have been studied experimentally in both the glassy and melt states at 0, 20, 40, 50, 60, 80, and 100% PPO content. In all compositions a strong glass transition was observed varying linearly with composition. For all but the 40% PPO composition this was the only transition, indicating molecular compatibility of the components in these blends. The 40% PPO composition showed a very weak second transition near the glass transition of pure PS. A small amount of phase separation may have occurred in this blend. The data for the glassy and melt states were fitted to an empirical equation of state based on the Tait equation. The volume of the melts at constant pressure and temperature showed a virtually linear dependence on composition. Any negative excess volume of mixing compatible with the data would have to be very small, smaller than expected from previous measurements in the glassy state. Various properties relating to the glassy and melt states and to the glass transition were evaluated and are discussed as a function of composition. It was found that most properties of the glasses could not be modeled by simple functions of composition.
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    Theoretical equation of state of polymer blends: The poly(2,6-dimethyl-1,4-phenylene ether)-polystyrene pairCorrected proofs received June 1, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1399-1408 
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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 recent theory of multicomponent fluids is applied for the first time to a compatible binary polymer blend. Good accord between the experimental pressure-volume-temperature measurements over the whole range of compositions by Zoller and theoretical predictions obtains. In particular, satisfactory predictions of high pressure from low-pressure information result. From the interplay between experiment and theory, the scaling quantities and thus the characteristic self- and cross interaction parameters are derived. The excess volumes are discussed and estimates of excess enthalpies presented. The theory predicts the actual enthalpy of the components or mixtures once the scaling parameters have been determined by means of volume-temperature data at atmospheric pressure. Enthalpy measurements to test these predictions are highly desirable.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200806
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    Infinite-dilution oscillatory flow birefringence properties of polystyrene and poly(α-methylstyrene) solutionsCorrected proofs received June 3, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1409-1425 
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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: Oscillatory flow birefringence (OFB) measurements have been carried out for an extensive series of solutions containing narrow-distribution, atactic, linear polystyrenes PS (10, 000 or 390, 000 Mw) or poly(α-methylstyrene) PMS (400,000 Mw) in a high-viscosity solvent, Aroclor 1248. The concentration ranges examined are such that the concentration dependence is obtained in both the “dilute” and “semidilute” regimes; the data are sufficiently precise to permit extrapolation to obtain for the first time the infinite-dilution properties. Various plotting formats are explored to determine an appropriate extrapolation procedure. The infinite-dilution OFB properties are compared with the bead-spring model (Zimm) theory which predicts quantitatively the frequency dependence of the observed properties for the PS and PMS solutions studied except for the high-frequency regime. The sensitivity and precision of the OFB experiment is such that the extrapolation curves-and the resulting infinite-dilution properties-show substantially less scatter than comparable visco-elasticity (VE) data. There is no evidence of a change in the character of the concentration dependence for the range of concentrations studied.
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    Stress response and energy dissipation in a linear viscoelastic material under periodic triangular strain loading (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1437-1442 
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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 general equation is derived for the stress response of a linear viscoelastic material to periodic strain excitation at constant strain rates. The energy dissipated in any cycle, especially in a steady-state loop, is discussed. The results can be used to analyze test results in determining mechanical properties of polymers. A simple Maxwell model and a three-parameter Maxwell model are used to illustrate the calculation of stress response and energy dissipation under constant-strain-rate loading.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200809
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    Crystalline order in polyethylene: A 13C NMR CP/MAS solid-state T1 studyCorrected proofs received June 2, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1427-1435 
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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 carbon-13 spin-lattice relaxation times T1 of the crystalline components of four solid ethylene-octene copolymers have been studied as a function of thermal history, branching number, and branching distribution. Slowly cooled samples (1 deg/min from melt to room temperature) exhibited similar or longer T1s with respect to the same sample quench cooled (from the melt into 20°C water). The greater the degree of branching and the more homogeneous the branching distribution, the shorter were the observed crystal lattice T1s. Differences of up to a factor of 3 in T1 were observed for the same sample undergoing the two thermal treatments. Different degrees of branching homogeneity (for the same total number of branches) resulted in differences approaching a factor of 7 for samples with the same thermal history. These variations were attributed to the differing effects of side-chain disruption of the crystal lattice.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200808
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  • 88
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    Effects of data analysis on accuracy and precision of GPC results (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1443-1451 
    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 data imprecision and baseline uncertainties have been investigated by computer simulation of GPC data from a polymer sample with a truncated log-normal molecular weight distribution. If the data are very accurate, as few as five data points can be sampled without serious error in computed molecular weight averages. The number of data points required is much larger, however, if these are taken at equal increments of molecular weight rather than elution volume. The effects of noise can be counteracted by increasing the sampling frequency. Baseline uncertainties present a more serious problem, especially for broad-distribution samples. If the detected signal is too noisy to permit accurate location of the baseline, errors can be minimized by using a second, more sensitive detector to determine the peak start and end. It is very difficult to estimate M̄z and higher molecular weight averages accurately if the noise level is greater than 0.5%.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.180200810
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  • 89
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    A study of the pressure-volume-temperature relationships of four related amorphous polymers: Polycarbonate, polyarylate, phenoxy, and polysulfone (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1453-1464 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pressure-volume-temperature (PVT) relationships of bisphenol-A polycarbonate, polyarylate, and phenoxy were studied at pressures to 1800 kg/cm2 and in both the glassy and melt states. Earlier data on polysulfone are included in the analysis and discussion of the results. All four polymers contain the bisphenol-A residue in their repeat unit, together with a moiety of varying complexity, and are therefore somewhat related. At the glass transition, equations of the Ehrenfest type hold, provided the pressure dependence of the glass transition temperature is defined from the line obtained by intersecting the quasiequilibrium PVT relationship of the glass with the equilibrium PVT surface of the melt. The Prigogine-Defay ratio r = ΔκΔCp/TgVg(Δα)2 at P = O is unity within experimental error for all four polymers. The melt data were fitted successfully to the Simha-Somcynsky theory. Molecular parameters deduced from the reducing parameters vary in a reasonable manner among these four related polymers, lending support to the foundations of the theory.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.180200811
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  • 90
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    The effect of anhydrous ammonia on the crystalline-state deformation of nylons 6 and 6,6 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1485-1496 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The aliphatic polyamides nylon 6 and 6,6 have been cold drawn by using the new concept of reversible plasticization with NH3. Two aspects were investigated: the effect of NH3 plasticization on the stress-strain behavior of nylon 6,6, and the extent of NH3 absorption as determined by x-ray analysis for the structurally simpler nylon 6. X-ray analysis shows that ammonia is absorbed preferentially by the amorphous phase and that the plasticization has a significant effect on the unit-cell orientation, the small-angle void scattering, and the interplanar spacings between sheets of hydrogen-bonded chains. The effect of plasticization was seen in the lower yield stress, the higher draw ratio (up to 8X) and tensile modulus (10 GPa) not attainable with unplasticized specimens.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.180200813
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  • 91
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    Supermolecular structure of poly(ethylene oxide) fractions (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1465-1484 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystalline morphology, or supermolecular structure, of poly(ethylene oxide) has been studied as a function of molecular weight and crystallization conditions. Molecular weight fractions, covering the range 6 × 103 to 1 × 107 are used over the range of accessible temperatures for isothermal crystallization as well as for a large set of controlled nonisothermal crystallization conditions. A morphological map is constructed from these studies and compared with the literature results. Prior reports were primarily confined to low molecular weights, which restricted the generalization of the findings. In the present work, as a consequence of the extended molecular weight range, conditions are established for the systematic development of several different, well-defined, organized super-molecular structures as well as for highly crystalline but disorganized systems. Strong similarities are found between the results for poly(ethylene oxide) and previous reports for linear polyethylene. A generalization for all chain molecules is suggested.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.180200812
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  • 92
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    Light-scattering studies on polystyrenes in isorefractive poly(methyl methacrylate)-toluene “solvents” (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1497-1502 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rms radii of gyration 〈S2〉1/2 and second virial coefficients Γ2 of five monodisperse polystyrenes (M × 10-5 = 1.6, 2.8, 4.2, 6.6) were measured in isorefractive toluene-poly(methyl methacrylate) (M̄v = 4.0 × 104, 1.6 × 105, and 6.3 × 105) “solvents.” For a given PMMA, the concentration at which the θ condition (defined by Γ2 = 0) was reached was independent of PS molecular weight, but varied inversely with PMMA molecular weight (0.10, 0.056, and 0.023 g/mL, respectively). When this θ condition is reached by adding PMMA to toluene, the radii of gyration are decreased by only about 15%, much less than when it is reached by going to a poor, low-molecular-weight solvent. This reflects the exclusion of PMMA from the PS coils, the internal environment of which is essentially pure toluene.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200814
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  • 93
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    Microphase separation in sulfonated polystyrene ionomers (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1503-1509 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small- and wide-angle x-ray scattering results for a series of un-neutralized and neutralized sulfonated polystyrenes are presented for the range of sulfonation from 0 to 7.26 mol %. From the small-angle scattering it is shown that above the 3 mol % level for both the zinc and sodium salts, a Bragg spacing (37 Å) and diameter (6.9-8.4 Å) of the scattering unit can be calculated. When the concentration of salt is increased, there is no appreciable change in the latter two measurements. The wide-angle data indicate that the cations do not influence to any large extent the basic intramolecular and intermolecular structure of polystyrene. All the data are consistent with the onset of clustering above a critical ion concentration.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.180200815
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  • 94
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    Optical and calorimetric analysis of stress-induced crystallization in natural rubber networksCorrected proofs received July 14, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1525-1531 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stress-induced crystallization of natural rubber networks is studied. The analysis is carried out using two different experimental techniques and the results are compared. In particular, the microcalorimetric and photoelastic results seem to be in disagreement, but the disagreement can be resolved by assuming that organization phenomena take place even at strains less than the critical value at which thermally detectable crystallization occurs. It is believed that such organization phenomena give rise to highly defective crystallites which behave as nucleation agents in the crystallization process that is induced at larger strains.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200902
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  • 95
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    Dynamical behavior of xanthan polysaccharide in solutionPaper presented at A.I.Ch.E. National Meeting, March 1981, Houston, TX.Corrected proofs received June 23, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1513-1524 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dilute-solution hydrodynamic data for xanthan biopolymer in water suggest a rodlike molecule of dimensions 15,000 × 20 Å, and molecular weight 2.2 × 106 g/mol. Upon addition of NaCl to this system, the xanthan molecules self-associate to form stable aggregates. The native xanthan conformation can be thermally denatured to a disordered coil which can be stabilized at room temperature in 4M urea. The transition to semidilute solutions is manifested by discrete changes in the concentration dependence of diffusion coefficient and zero-shear viscosity at c ≈ 2.0 × 10-4 g/mL. At higher concentrations c ≥ 1.0 × 10-3 g/mL, the light-scattering and shear-viscosity data are qualitatively but not quantitatively consistent with predictions of the dynamical theory of Doi and Edwards for an isotropic entangled solution of rigid-rod molecules. Measurements of latex sphere diffusion in xanthan-water solution show a sudden retardation at c ≈ 1.0 × 10-3 g/mL, consistent with the cooperative formation of a motionally restricted network of long, thin, rigid fibers. At high shear rates, flow birefringence experiments indicate enhanced ordering of the xanthan chains in the semidilute regime.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.180200901
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    Some evidence against the existence of the liquid-liquid transition. I. Transitions or dispersions: A quantitative explanation of one torsional braid log decrement peak (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1533-1550 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some of the history of the proposed liquid-liquid transitions Tll and T′ll that have been reported to exist above the glass transition temperature Tg and the role played by the torsional braid analyzer are outlined. Confusion has been created by the failure to clearly distinguish such kinetic phenomena as viscoelastic and dielectric loss processes from thermodynamic transitions. It is shown quantitatively how the log decrement of an oscillating system can exhibit one more peak than is found in the loss tangent-temperature curve of a viscoelastic liquid.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.180200903
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  • 97
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    Some evidence against the existence of the liquid-liquid transition. II. Properties of and measurements with a torsional braid analyzerCorrected proofs received July 2, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1551-1564 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A torsional braid analyzer (TBA) has been constructed for an investigation into the behavior of this instrument. An explanation was desired for the presence of the proposed second liquid-liquid transition T′ll peak in the log decrement-temperature curve of a low-molecular-weight polystyrene whose loss tangent increases monotonically as a function of increasing temperature at constant frequency. The response of the TBA was studied as a function of amplitude of oscillation, the nature of the braid, the braid tension, frequency, and the nature of the impregnant. All of the braids examined were shown to be extremely nonlinear in their response. Two peaks in the damping of the composite system as a function of temperature are attributed to the interaction between the impregnant properties and the nonlinear response of the glass fiber braid.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.180200904
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  • 98
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    Some evidence against the existence of the liquid-liquid transition. III. The evaluation of the Tll event by differential scanning calorimetryCorrected proofs received July 12, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1565-1574 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The liquid-liquid transition Tll has been examined by using differential scanning calorimetry as the tool of measurement. The results presented show that for the case of polystyrene, the Tll event appears to be an artifact caused by the presence of volatile components. Purified samples of polystyrene, polydienes, and poly(1-butene) do not show the Tll transition.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200905
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  • 99
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    Some evidence against the existence of the liquid-liquid transition. IV. The temperature dependence of shear viscosityCorrected proofs received July 2, 1982 (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1575-1583 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscosity data available for four anionically polymerized polystyrenes ranging in molecular weight from 1100 to 47,000 for the temperature range Tg to Tg + 100°C have been fitted by computer programs to both the Vogel, Fulcher, Tamman, and Hesse (VFTH) equation and to two optimum intersecting Arrhenius equations. The intersection point has been interpreted as a manifestation of a liquid-liquid transition. The fits to the VFTH equation were in every case found to be far superior. Systematic deviations of the residuals were observed for the best Arrhenius fits which indicate the lack of any validity for such a representation of the data.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.180200906
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  • 100
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    Properties of aqueous salt solutions of poly(ethylene oxide) (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1585-1592 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The determination of the properties of aqueous salt solutions of poly(ethylene oxide) has been extended to cloud-point and θ-temperature measurements in sodium acetate, potassium fluoride, sodium thiosulfate, and potassium phosphate. The Hofmeister series for the decreasing effect of anion species in salting out the polymer is accordingly extended. However, the order of the effect depends on whether it is made on the basis of molar anion concentration the molar concentration of unit anion charge, or the ionic strength. Viscosity measurements on θ and non-θ solutions containing zinc sulfate, potassium fluoride, and potassium phosphate gave polymer dimensions (in addition to limiting viscosity numbers etc.), and characteristic ratios in good agreement with theoretical predictions (Abe and Mark), and enthalpy and entropy parameters χH and χs; the latter values, nominally -0.14 and 0.63, are identical at 298 K for the three salt species.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1982.180200907
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