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  • 1980-1984  (517)
  • 1965-1969
  • 1920-1924
  • 1982  (517)
  • Physics  (517)
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1-13 
    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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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 49-63 
    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.
    Additional Material: 8 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 99-106 
    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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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 117-130 
    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.
    Additional Material: 7 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 131-139 
    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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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 191-203 
    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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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 225-233 
    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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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 259-268 
    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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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 297-305 
    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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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 327-344 
    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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  • 11
    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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  • 12
    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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  • 13
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 457-472 
    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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  • 14
    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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  • 15
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 557-560 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 561-578 
    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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  • 17
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 623-632 
    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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  • 18
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 651-658 
    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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  • 19
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 743-750 
    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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  • 20
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 773-775 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 21
    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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  • 22
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 783-791 
    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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  • 23
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 837-844 
    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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  • 24
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 893-898 
    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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  • 25
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 929-930 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 26
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 953-959 
    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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  • 27
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 981-987 
    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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  • 28
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1013-1018 
    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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  • 29
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1069-1080 
    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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  • 30
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1107-1128 
    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.
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  • 31
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1129-1141 
    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.
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  • 32
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1175-1192 
    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.
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  • 33
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1193-1205 
    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.
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  • 34
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1223-1232 
    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.
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  • 35
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1233-1247 
    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.
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  • 36
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1269-1278 
    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.
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  • 37
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1279-1287 
    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.
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  • 38
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    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.
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  • 39
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1327-1340 
    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.
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  • 40
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1289-1311 
    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.
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  • 41
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1341-1353 
    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.
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  • 42
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1355-1364 
    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.
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  • 43
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    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.
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  • 44
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1371-1384 
    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.
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  • 45
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1385-1397 
    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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  • 46
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1399-1408 
    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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  • 47
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1409-1425 
    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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  • 48
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1437-1442 
    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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  • 49
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1427-1435 
    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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  • 50
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1443-1451 
    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%.
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  • 51
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1453-1464 
    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.
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  • 52
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1485-1496 
    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.
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  • 53
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1465-1484 
    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.
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  • 54
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1497-1502 
    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.
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  • 55
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1503-1509 
    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.
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  • 56
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1525-1531 
    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.
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  • 57
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1513-1524 
    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.
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  • 58
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1533-1550 
    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.
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  • 59
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1551-1564 
    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.
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  • 60
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    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.
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  • 61
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1575-1583 
    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.
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  • 62
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1585-1592 
    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.
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  • 63
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1593-1607 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dilute mixtures of poly(ε-caprolactone) (PCL) in poly(vinyl chloride) (PVC), poly(p-iodostyrene) (PpIS) in polystyrene, and deuterated polystyrene (d-PS) in protonated poly(o-chlorostyrene) (PoCIS) were investigated by means of small-angle x-ray scattering and small-angle neutron scattering. The radii of gyration of PCL in PVC and of d-PS in PoCIS were found to be expanded over the θ values by 50 and 30%, respectively. Values of the second virial coefficient were positive although errors prevented definitive evaluation of the interaction parameter. PpIS was found to aggregate, with both the radius of gyration and molecular weight increasing with concentration. Concentrated mixtures of PCL and PVC were also investigated by using the Debye-Bueche correlation function analysis. Correlation distances indicated good mixing throughout the entire composition range.
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  • 64
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1609-1615 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ethylene glycol dimethacrylate (EGDM) was polymerized to provide specimens suitable for three-point bending tests. Fracture surfaces were generally similar to those reported previously for relatively brittle materials such as silicate glasses. Attention was concentrated on linear features which lay in roughly parallel arrays in the direction of crack propagation. Generally the features had a circular cross section which, in a few cases, tapered to a fine point. In other cases partially detached features were observed to have an irregular radius of curvature. The two preceding observations were interpreted as evidence of localized plastic deformation. The linear arrays of surface features were explained by adoption of Preston's mechanism for formation of “stries” in brittle materials. However, this mechanism calls for a characteristic cross section which in the case of poly(EGDM) was replaced by a circular cross section. To account for this difference, localized plastic deformation was invoked.
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  • 65
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1617-1622 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low-temperature dielectric loss measurements reveal a tendency of 4-methyl-2, 6-di-tert-butyl phenol (the antioxidant BHT) to associate with various reagents in hydrocarbon media. The affinity with carbonyl groups appears to be particularly appreciable. It is suggested that this may have a bearing on the antioxidant activity of this type of compound.
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  • 66
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1623-1632 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Association of syndiotactic (s) poly(methyl methacrylates) (PMMAs) in toluene, benzene, and acetonitrile has been studied by NMR spectroscopy, osmometry, and viscometry. It was found that in solutions of highly syndiotactic PMMA in toluene, most of the polymer exists in the associated state. Association takes place by means of stereospecific intermolecular and intramolecular interactions of long parallel syndiotactic sequences. The minimum length of syndiotactic sequences necessary for association of s-PMMA in toluene is 7-8 monomer units. Viscosity data indicate that in dilute solutions the associated structures appear as large formations which do not have the character of compact particles. The formation of the aggregates of PMMA is a relatively slow process. A model of the structure of the aggregates of s-PMMA in toluene is proposed. As compared with that in toluene, the tendency to aggregation in benzene and acetonitrile is negligible. Integral parameters currently used for the characterization of polymer-solvent interaction, like “good” or θ solvent, are not suitable for predicting the tendency of s-PMMA to aggregation. The formation of aggregates evidently has some connection with the effect of the solvent upon the conformational structure of syndiotactic sequences.
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  • 67
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1641-1645 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The origin of a previously unassigned peak in the Brillouin spectrum of an oriented polymer film has been clarified. This peak is shown to be due to backscattering from a quasitransverse acoustic phonon from the reflected laser beam. Studies of this peak are expected to provide the information concerning the birefringence effect of the oriented film.
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  • 68
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1633-1639 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The growth rates of lamellar crystals grown onto preseeded fibrillar crystals (“shishes”) in isotactic polystyrene and blends of isotactic polystyrene (iPS) with polyphenylene oxide are followed by using transmission electron microscopy. The preseeded fibrillar crystals avoid the problem of timedependent primary nucleation. The time dependence of lamellar growth is investigated. At a concentration of 50% PPO in iPS, the lateral lamellar growth rate of the precipitating isotactic polystyrene crystals conforms to a time law characteristic of diffusion-controlled growth (R ∝ t1/2). Diffusion coefficients are estimated from the growth kinetics. The method could prove a simple means of measuring diffusion coefficients in polymer blends in which one component is crystallizable.
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  • 69
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1647-1658 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A reorientational model of polymer solids is given. The solid is described as a collection of small, orientable units. The elastic constants of the oriented polymer are given as a combination of the elastic constants of the orientable units and of the orientation parameters 〈P2(cosθ)〉 and 〈P4(cosθ)〉. The elastic constants of stretched and hydrostatically extruded samples of polychlorotriflouroethylene are obtained with Brillouin light scattering. These are fitted to the model and the orientation parameters are calculated. The elastic constants from the extruded samples are fit well by the model but the fit to the stretched film is less satisfactory. Hydrostatic extrusion in polymers is thus assumed to be a reorientation process in the amorphous phase, but the stretching process is not completely reorientational.
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  • 70
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1659-1668 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polybutadiene networks were prepared by peroxide crosslinking of monodisperse 1,4-polybutadienes both in solution and in bulk. The effect of the entangled sol fraction on the elastic modulus of high-molecular-weight polybutadiene was observed in stress relaxation measurements. Sol fraction was shown to make a large contribution to the Mooney-Rivlin 2C2 term. This effect was also observed on the molecular level in NMR spin-spin relaxation measurements. For networks crosslinked in bulk the stress relaxation measurements suggest the presence of trapped entanglements. The 2C2 term is insensitive to sol extraction in these networks. NMR spin-lattice relaxation measurements in the rotating frame at 4.68 kHz verify the presence of additional effective crosslinks in these networks.
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  • 71
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1677-1685 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystal length determinations have been undertaken on ultrahigh-modulus linear polyethylene fibers by dark-field electron microscopy. There is good agreement between the results and those obtained from wide-angle x-ray diffraction line broadening. The crystal length distributions from the dark-field microscopy are also consistent with those determined by nitric acid etching. The significance of the present results is considered in the light of recent proposals for the structure of these materials and the achievement of high modulus.
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  • 72
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1669-1676 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystals of fractionated trans-1,4-polyisoprene (TPI) were grown from amyl acetate solution at two weight fractions, 5.7 × 10-4 and 0.011; for the lower concentration a precooling followed by heating and then crystallization at temperatures in the 10-32°C range was used, while for the higher concentration this method and direct crystallization at a temperature TC in the 0-32°C range were employed. The precooling method yielded samples crystallized in the α form, while direct crystallization led to formation of β-TPI at low TC and α at higher TC. The value for the DSC endotherm, characteristic of α-form melting, increased with increasing TC, with a shift to lower values with increasing concentration for precooled samples. A β to α transformation was found to occur for synthetic unfractionated TPI when swollen with amyl acetate at 35°C for 17h. Swelling in n-butyl acetate for one day at 25°C or 17 h at 35°C also led to this transformation. From experimental results 74°C is chosen as the temperature at which the α and β forms coexist in the bulk, and this is used to calculate the enthalpy of fusion of β-TPI, yielding a value of 8.6 kJ mol-1.
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  • 73
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1687-1693 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The fold periods and longitudinal acoustic modes [LAMs] for isothermally crystallized polyethylene (PE) single crystals were determined in the dried state and in the presence of decalin and silicone oil. Upon swelling with decalin, the fold period increased by 7% while the LAM peak frequency decreased by approximately 1 cm-1. Several possible explanations for the change in LAM frequency are discussed but the exact interpretation is open to question. No change in fold period was observed upon soaking a dried crystal mat in silicone oil. This fold period invariance along with the fact that silicone oil has no effect on the melting point of PE crystals indicates that there is no significant interaction between the oil and the methylene groups on the crystal surface. The effect of suspending crystals (which have never been dried down) in silicone oil should only be to increase the average interlamellar distance and, therefore, to reduce any interlamellar forces. It is shown that the LAM peak frequency for crystals suspended in silicone oil is the same as that for the dried crystals, indicating that interlamellar forces do not exert a significant perturbing influence on the LAM of polyethylene crystals.
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  • 74
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1695-1708 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Free-radical polymerization without crosslinking is considered. By taking the chain length as a continuous variable the reaction kinetics is treated in a simple way for the stationary state. Equations for instantaneous average degrees of polymerization and related quantities are generalized to allow for chain-length dependence of the termination rate constant. For the Ito model, which treats reptation-controlled termination, approximate versions of these equations are derived in the limits of low and high conversion. The observed structure in the peak of the gel permeation chromatograms is shown not to be related to the bimodality in the instantaneous molecular weight distribution. None of the results is very sensitive to the precise reptation behavior.
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  • 75
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1709-1716 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gel permeation chromatograms of a hindered-phenolic, branched condensation polymer display pronounced bimodality at high conversion. The true molecular weight distributions, obtained by means of a GPC calibration curve based on narrow-distribution fractions, exhibit corresponding anomalous high-molecular-weight “shoulders.” These results are discussed in terms of preferential aggregation and reaction of the higher-molecular-weight species during the polymerization, promoted by intermolecular hydrogen bonding in the apolar reaction medium.
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  • 76
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1749-1753 
    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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  • 77
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1717-1732 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This article is part of the general project laid out in Part I (ref. 9) and is concerned with obtaining information on primary (unthickened) crystals of polyethylene formed at low supercoolings. For this, a technique had to be devised by which crystallization could be speeded up so as to eliminate or at least reduce lamellar thickening. Indeed we were able to increase the rate of crystallization by an order of magnitude using a technique which we have called enhanced self-nucleation. Using this technique we find that when viewed under an optical microscope, spherulites crystallize uniformly over the field of view, and not, as is usual, by a radial growth process. Isothermal crystallization in bulk linear polyethylene has been studied by means of the enhanced self-nucleation technique as a function of crystallization time by using Raman LAM and melting points to assess variations of fold length Data have been obtained at very much shorter times than before. At short times, we find a constant fold length; at longer times the crystals thicken linearly with the logarithm of time. Values of the initial fold length for crystallization temperatures between 118 and 130°C are presented. Associated with the thickening at short times we find an induction time which increases with temperature.
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  • 78
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1755-1755 
    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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  • 79
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1733-1748 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyethylene melts normally cannot be crystallized in an isothermally controlled manner below ca. 110°C as crystallization is too fast owing to the presence of preexisting nuclei. We here present a new simple method for producing droplets enabling crystallization to be conducted isothermally down to 75°C and allowing measurements to be performed on them, together with the results of these measurements. We conclude that in contrast to the earlier claims the homogeneous nucleation regime has not been attained even at these low temperatures, the crystal nucleation being dominated by the polymer-substrate interface. The droplets crystallized at these low temperatures have a lamellar morphology as revealed by electron microscopy and grow at rates exceeding 1 m s-1 [i.e., six orders of magnitude faster than growth at more usual crystallization temperatures previously considered as “low” (110-120°C)]. We have measured the lamellar thickness l as a function of growth temperature, thus extending the fundamentally important l vs. ΔT (supercooling) relation beyond the previously realizable limits towards high ΔT values. The implications of all these results for the existing ideas of polymer crystallization are likely to be far reaching. Further, the new method for achieving high supercoolings opens up new possibilities for the study of annealing phenomena and the effect of nucleating agents.
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  • 80
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1771-1780 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Frictional coefficients for dextran in water have been evaluated from (i) self-diffusion coefficients determined by pulsed-field-gradient NMR, and (ii) sedimentation coefficients in concentrated solutions. The results show that these frictional coefficients are only equal at infinite dilution and that fs increases more rapidly than fD* as the concentration increases.
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  • 81
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The time-resolved fluorescence behavior of polystyrene and a series of styrene-methyl methacrylate copolymers has been examined by using pulsed laser excitation. Although the photophysical characteristics of styrene- and naphthalene-containing polymers may be described by the same general kinetic scheme, some differences in the nature of the photophysical interactions are apparent. Umambiguous evidence for the occurrence of excimer dissociation into excited-state monomer in polymers incorporating styrene chromophores is presented.
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  • 82
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1781-1787 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Changes in the backbone structure of several meta derivatives of polyphenylene sulfide upon doping with AsF5 have been investigated by IR spectroscopy. Poly(m-phenylene sulfide) does not form a conducting complex with AsF5 unless reacted under conditions where carbon-carbon bonds form intramolecularly between phenyl rings. This assertion has been verified by comparison of the IR spectra of poly(m-phenylene sulfide) and a newly synthesized derivative, poly(thio-3,7-dibenzothiophendiyl), after doping with AsF5. This new derivative forms a complex with AsF5 which exhibits a conductivity of 18.5 S/cm. A sulfone-containing derivative has also been synthesized, poly[thio-3,7-(dibenzothiophene-5,5-dioxide)-diyl]. With this polymer, a much lower conductivity, 10-3 S/cm, was obtained after exposure to AsF5.
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  • 83
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 641-650 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Carbon-13 nuclear magnetic resonance relaxation parameters have been obtained as a function of temperature for a set of branched polyethylenes whose β transition temperatures were determined independently. Resolvable spectra could be obtained at temperatures either corresponding to or very close to the temperature of the β transition. Together with results for other systems, these observations preclude the indentification of the β transition with the glass temperature. From the measured spin relaxation times and nuclear Overhauser enhancements average correlation times were calculated as a function of temperature. The average correlation times were calculated as a function of temperature. The average correlation time is on the order of 10-8-10-9 s at the β transition. These results argue strongly against it being assigned to the glass temperature.
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  • 84
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 689-699 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism of low-temperature relaxations in bisphenol-A-type epoxide resins cured with aliphatic diamines, with aliphatic diamines in the presence of salicylic acid as an accelerator, and with tertiary amines was investigated to compare the dynamic mechanical properties and the chemical structure of these networks. Mechanical relaxations are observed at about -140 and -60°C. The former relaxation is denoted the γ relaxation and the latter the β relaxation. The β relaxation of the cured epoxide resins containing hydroxyether groups is a sum of contributions from the relaxation of these groups and of other parts of the network structure. A new relaxation due only to the motion of the hydroxyether group can be estimated from the difference of tanδ curves between the aminecrosslinked and ether-crosslinked systems. The γ relaxation is attributed to the motion of a polymethylene sequence consisting of at least four carbon atoms.
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  • 85
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 729-742 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermorheological simplicity is shown to hold for poly(vinyl acetate) in the temperature range extending from Tg + 25°C to Tg + 80°C. Between Tg and Tg + 25°C the softening (glass to rubberlike) viscoelastic dispersion exhibits time-scale shift factors aT different from those of the terminal (rubberlike to steady-state) dispersion. The aT values calculated from zero-shear viscosities coincide with those from the terminal dispersion in the temperature range 60-154°C (Tg ≅ 35°C). The aT shifts obtained from the response in the terminal dispersion can be fitted to the Williams, Landel, and Ferry equation over the entire temperature range 42-154°C. The aT obtained from the softening dispersion is shown to exhibit a different functionality. An empirical modification of the Doolittle equation yields a very flexible relation which can be fitted to some aTs which cannot be represented by the usual Doolittle free-volume expression.
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  • 86
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 751-761 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The heat of fusion of virgin and melt-processed polytetrafluoroethylene (PTFE) was determined using the Clapeyron equation. Experimental data were obtained from PVT experiments and high-temperature x-ray diffraction measurements. For virgin, as-polymerized PTFE, the melting temperature is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ T_{\rm m} = A + BP $$\end{document} where, for Tm in degrees Celsius, A = 346.3±1.2, B = 0.095±0.003, and P is the pressure in kilograms per square centimeter. At the end of the atmospheric-pressure melting interval, the amorphous and crystalline specific volumes V1 and Vc are 0.6517 and 0.492 cm3/g, respectively. Thus the heat of fusion is 24.4 cal/g, or nearly twice the value reported previously. The increases in enthalpy and volume at the melting point both indicate a degree of crystallinity of about 75-80% although infrared, x-ray, and NMR data give much higher levels. Data from calorimetry, NMR, and dynamic mechanical measurements indicate that in virgin PTFE some of the crystals continue to experience torsional oscillations at temperatures below the room-temperature transitions. This indicates that there are at least two kinds of crystalline regions. For previously melted PTFE, Tm is determined by A = 328.5±0.7 and B = 0.095±0.002, the volumes are Vam = 0.6349 and Vcr = 0.4855 cm3/g, and the heat of fusion is 22.2 cal/g. The entropy of fusion for PTFE is much closer to that of polyethylene than was previously believed.
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  • 87
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 815-823 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The osmotic compressibility of chemically crosslinked poly(vinyl acetate) (PVAc) gels in equilibrium with pure diluent has been determined by the method of decreasing equilibrium swelling in different swelling agents. The concentration dependence of the osmotic compressibility has been found to follow a scaling law with an exponent which was greater than that predicted by the mean-field theory. A comparison has been made between the elastic moduli determined by unidirectional deformation measurements and the compressional moduli obtained from the osmotic compressibility data.
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  • 88
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 805-814 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Vapor sorption isotherms in binary solutions of polyisobutylene (PIB), (Mη = 4.7 × 106 g/mol) in hydrocarbons (cyclopentane; cyclohexane; n-heptane; 2,2-dimethyl butane; and 2,2,4-trimethyl pentane) and chlorinated methanes [carbon tetrachloride (CCI4) and chloroform (CHCI3)] have been determined at 23.5°C using the piezoelectric sorption method. The polymer-solvent interaction parameter χ obtained agrees with previously published values determined by using gas-liquid chromatography and a quartz-helix vapor sorption apparatus. The Flory theory of corresponding-states has been applied to the experimental results through the χ parameter and affords a good prediction of the concentration dependence of χ for solutions of chloroform, carbon tetrachloride, n-heptane, and 2,2-dimethyl butane in PIB. The experimental values of \documentclass{article}\pagestyle{empty}\begin{document}$ [\partial (a_1 /\psi _1 )/\partial a_1 ]_{T,P} $\end{document} for the PIB solutions are constant over the measured concentration range, for example \documentclass{article}\pagestyle{empty}\begin{document}$ [\partial (a_1 /\psi _1 )/\partial a_1 ]_{T,P} $\end{document} = -4.1 for CCI4, -3.65 for CHCI3, -3.0 for 2,2-dimethyl butane and n-heptane, -2.7 for 2,2,4-trimethyl pentane, -2.7 for cyclohexane, and -1.7 for cyclopentane, where a1 is the solvent activity and ψ1 is the solvent segment fraction. The correlations between the values of \documentclass{article}\pagestyle{empty}\begin{document}$ [\partial (a_1 /\psi _1 )/\partial a_1 ]_{T,P} $\end{document} and the theories of Guggenheim, Miller, Huggins, and Flory are discussed.
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  • 89
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 857-865 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Partitioning of three dextrans and bovine serum albumin (BSA) in controlled-pore glass beads was measured by a batch mass balance technique. For all solutes the measured partition coefficient increased with bulk phase concentration, and the relationship appeared to be linear up to 0.05 g/mL for the dextrans. The measured slopes of partition coefficient versus concentration were compared with predictions using a hard-sphere theory, and while the agreement was tolerable for BSA, the dextran results were much lower than the theory dictated except for very small pores, in which case it was speculated that molecular weight polydispersity resulted in anomalous partitioning of the smaller components.
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  • 90
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have used the pulsed-gradient spin-echo technique to measure self-diffusion in low-molecular-weight polymers in the melt and dissolved in identical polymers of high molecular weight. Specimens used were cis-polyisoprenes and polydimethylsiloxane. We find that, except for substantial free-volume corrections, self-diffusion in unentangled polyisoprene melts scales inversely with molecular weight. The results include sensitive determinations of chain-end free volume.
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  • 91
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1081-1088 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of the degree of polymerization (DP) of cellulose was evaluated in the preparation of micron-sized cellulose IVII lamellar crystals in order to ascertain whether a regular chain-folded morphology could develop during their growth. For this purpose, sharp fractions of cellulose acetate were collected by preparative gel permeation chromatography. Aliquots of these fractions were deacetylated and crystallized in dilute solutions containing water, methylamine, and DMSO, and held at 150°C under pressure. Well-developed cellulose IVII lamellar crystals were obtained with fractions of DP 22-24 whereas higher-DP material gave polycrystalline aggregates. This behavior indicates that large lamellar crystals of cellulose IVII can be obtained only with unfolded short cellulose chains. The occurrence of chain-folded crystals with high-DP cellulose samples cannot be demonstrated.
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  • 92
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1089-1106 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of elasticlike uniaxial tension on molecular mobility in polymers have been studied over a wide temperature range using the broad-line NMR technique. The studies were carried out on oriented semicrystalline samples of nylon 6, poly(ethylene terephthlate), polypropylene, polyethylene, polyoxymethylene, poly(vinyl alcohol), and polytetrafluorethylene. Above the low-temperature transition the NMR spectra are reversibly transformed under tension. Increases in the second moments of the spectra are attributed to weaker molecular motion in stressed polymers. The only exception is polypropylene, in which the reverse, i.e., enhancement of molecular mobility, can be observed in a certain temperature range. In the spectra of polymers stretched above the glass transition temperature the narrow component decreases, thus indicating inhibition of micro-Brownian motion, a phenomenon we call “mechanical vitrification.” Such mechanical vitrification is proved to result from reduction in the number of possible tie-chain conformations in the non-crystalline regions and not from closer packing of chains. In discussing the results we use the experimental data on the reduction of the number of gauche isomers under tension (on average, one transition of a gauche link to the trans state causes at least five methylene groups in the main chain to become immobile). The results of studies of molecular mobility in stretched polymers are used for more accurate definition of the mechanisms of molecular motion at different temperatures. A method for evaluation of the energy of intermolecular interactions which hinder small-scale motion at low temperature is suggested.
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  • 93
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1249-1258 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Complex moduli are calculated for the lowest-order deviations from linearity of the stress in an oscillatory shear field. The calculations involve solution of an equation, recently proposed by Doi, which goes beyond the “independent alignment approximation” of the Doi-Edwards theory of polymer dynamics. The new equation incorporates various reptative motions of a polymer in the effective constraining tube induced by entanglements, viz. Brownian motion along the tube and the systematic motion in response to changes in the length of the tube accompanying affine deformation.
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  • 94
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1259-1267 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The compatibility of poly(ethylene oxide)-poly(vinyl acetate) (PEO-PVA) blends was examined at five compositions covering the complete range. Samples were prepared by coprecipitation and solution casting. Dynamic mechanical properties were studied at 110 Hz between -120 and 65°C for dry, quenched, and annealed samples. The study also included tensile testing at 25°C, examination of blend morphology, and DSC measurements at elevated temperatures. Optical microscopy revealed that crystallization of PEO proceeds essentially unhindered at up to 25% poly(vinyl acetate) content by weight. Higher levels of this component drastically reduce spherulite size, and at the highest PVA compositions there was no evidence of crystallization. Thermomechanical spectra of quenched and annealed samples indicate limited mixing of the two components except for the higher (〉75%) PVA compositions. Tensile properties show a mutual reinforcement at 10-25% PVA content due to possible polymer segment association. The melting-point depression of PEO is significant above 25% PVA and has been attributed to morphological changes of the PEO crystalline phase.
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  • 95
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 2197-2208 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Effects of carbon filler on the sorption and diffusion of carbon dioxide in natural rubber and in styrene-butadiene rubber have been studied. Sorption isotherms conform to Henry's law in unfilled rubber and to Langmuir's law in carbon black. The isotherms in filled rubber exhibit a combination of the two sorption modes. The Henry's law solubility parameter kD increases with carbon filler content; the Langmuir saturation constant C′A initially is constant with filler level, but then decreases abruptly when carbon particles begin to aggregate. The diffusion coefficient decreases with increasing filler content, presumably owing to geometric effects and to polymer chain immobilization in the interfacial regions.
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  • 96
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 2209-2217 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(hydrogenated butadiene-b-styrene) copolymers are very effective emulsifiers for blends of polystyrene and low-density or high-density polyethylene. It is shown that the extent of improvement in mechanical properties is dependent not only on the molecular weight but also on the structure of the diblock copolymer. A comparative study of the morphology and the mechanical behavior of modified low-density polyethylene/polystyrene blends demonstrates that a tapered diblock is more efficient than a pure diblock with the same composition and molecular weight. It is assumed that the unique behavior of the tapered sample results from its particular miscibility characteristics at the blend interface. The tapered copolymer could behave essentially as a solu-bilizing agent for the homopolymers at the interface and provide a “graded” modulus responsible for the improved mechanical response of the material.
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  • 97
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 2243-2259 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Blends of poly(vinylidene fluoride) (PVF2) and poly(methyl methacrylate) exhibit complex melting behavior when crystallized at low undercoolings. Three crystals comprised of two different PVF2 forms grow. Hoffman-Weeks plots of the observed melting points Tm of these crystals versus crystallization temperatures are constructed. The lowest-melting-point species, the α form, shows a change in slope which is attributed to fewer head-to-head PVF2 units trapped in the crystal at higher temperatures. Defect energies in the crystal due to these units are calculated to be from 6.3 to 10.3 kJ/mol. Estimating lamellar thicknesses from the slopes of the two regions gives much more reasonable values when the high-temperature data are used. Removal of kinetic effects that lower the observed Tm by extrapolating the data to obtain Tm0 permits the thermodynamic interaction energy density B between the two polymers to be obtained. The low-temperature α-form data give B = -8.83 × 106 J/m3. The high-temperature α-form data and the Tm0 of the γ-form crystals both show B to vary from -5.40 × 106 to -2.96 × 107 J/m3 as the blend composition goes from 40.1 vol % to pure PVF2.
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  • 98
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 2229-2241 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The tensile strength of oriented polyethylene filaments is discussed in relation to molecular weight. Short-term tensile properties at room temperature were obtained in our laboratory and from the literature for polymer samples covering the molecular weight (Mw) range from 54 × 103 to 4 × 106, and polydispersities ranging from 1.1 to 15.6, oriented by solid-state extrusion, melt spinning/drawing, solution spinning/drawing, and “surface growth.” It was found that both the molecular weight and its distribution markedly affected tensile strength. The breaking stress σ of highly oriented fibers varied with molecular weight roughly as σ ∝, M0.4, at constant Mw/Mn over the entire range studied. Reduction of polydispersity from 8 to 1.1 by an increase of Mn with Mw approximately constant at 105 increased tensile strength of oriented polyethylene filaments by a factor of nearly 2.
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  • 99
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 2261-2275 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Both pure poly(vinylidene fluoride) (PVF2) and its blends with poly(methyl methacrylate) (PMMA) develop a variety of morphologies when they are crystallized above the 420-424 K range. Two populations of spherulites as well as axialitelike growths are observed. Addition of the PMMA lowers the temperature where these new morphologies develop, makes the spherulites more open, causes the banding periodicity to decrease, and increases the number of small, coarse spherulites. These structures melt in three regimes. The highest-melting-point crystals arise only from a solid-solid transformation of the lowest-melting-point ones. This solid-state transition sometimes causes mixed spherulites to be formed in the blends. Electron and wide-angle x-ray diffraction show the lowest-melting-point species to be α crystals, while the other two are γ crystals. The highest-melting-point species, labeled γ′, and the α crystals seem to be more ordered than the other γ crystals.
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  • 100
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    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 2277-2295 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recently developed data processing techniques have been applied to determine the complete spectra of the trans and gauche isomers of PET and to use these spectra to determine the conformational composition of PET samples isothermally crystallized from the glassy state between 75 and 240°C. A linear correlation was found between normalized absorbance of conformational bands and density measurements, with the trans bands showing a positive slope and the gauche bands a negative slope. Extrapolation of the results from trans bands to zero percent of trans yields the density of the pure gauche isomer, 1.326 ± 0.002 g/cm3. Similarly, from the gauche bands the density of 100% crystalline trans is found to be 1.510 ± 0.014 g/cm3. Meanwhile, the density of the amorphous trans is calculated to be 1.430 ± 0.003 g/cm3. From these values and the combined density and infrared measurements, the content of trans isomers in the amorphous phase is calculated. It is found that the content of amorphous trans is a function of both annealing temperature and time. It is observed that the amorphous trans content decreases as the crystalline trans content increases. At high crystallinity, the amorphous trans content approaches zero. These amorphous trans isomers are associated with the extended units making up the interlamellar links. The loss of these extended trans interlamellar links is reflected in the mechanical properties of PET.
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