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  • 1975-1979  (2,541)
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  • Physics  (2,541)
  • 101
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1797-1806 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By analogy with observed alteration of electron diffraction intensities from other crystalline long-chain materials (e.g., paraffins) the mosaic model for polymer single crystals is evaluated. When many strong diffracted beams are excited simultaneously, the two-beam dynamical diffraction theory (which then must be a consequence of the mosaic model) is shown not to be an adequate explanation of the electron diffraction intensities from such crystals; the n-beam dynamical theory is much more adequate. Further, observed bend contours in these crystals indicate significant bend distortion. This is confirmed by observed modulation of diffraction intensities which are well explained by Cowley's model for diffraction from elastically bent crystals. Other experiments on these crystals reveal the bends to be irregular. Rocking curves reveal that bends also explain diffraction line broadening, as also proposed by White. The most accurate description of molecular organic microcrystals is therefore that of a deformed foil and not a mosaic.
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  • 102
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1897-1901 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The filler particles in most filled polymers are not perfectly dispersed but are more or less agglomerated. The degree of agglomeration and the strength of the agglomerates, which can be modified by surface treatments, have a very great effect on the dynamic mechanical properties. Filler agglomerates which are wetted by the polymer matrix produce higher elastic moduli than similar agglomerates which are not wetted. The relative damping in most filled polymers is very temperature-dependent. A qualitative explanation is given for this temperature dependence. The degree of agglomeration and the strength of the agglomerates are important factors in determining the damping.
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  • 103
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1947-1956 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melting and crystallization measurements were made on three low-density polyethylenes claimed to be chemically similar and to have comparable flow behavior, but exhibiting differences in processing and end-use properties. These IUPAC-characterized materials were found to possess almost indistinguishable DSC melting curves obtained from the original polymers or for samples isothermally crystallized in this work. However, in isothermal melt crystallization experiments that were made at high sensitivity, readily distinguishable features were found, thus highlighting the DSC procedure as a useful, simple, and valid means of detecting subtle differences in the crystallizability. These differences are more easily revealed in solidification than in melt flow curves and are undoubtedly correlatable with physical processing where crystallization plays a significant role in determining the material end-product behavior of semicrystalline polymers.
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  • 104
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1929-1946 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The equation of state of a semicrystalline system can be expressed in terms of the corresponding functions for the crystal and the melt, extrapolated into the solid region. This relation may be employed to obtain crystal data by means of information on the semicrystalline material or vice versa. We consider four polymers, namely, polyethylene (LPE), isotactic polypropylene (PP), polyethylene glycol (PEG), and poly(tetrahydrofuran) (PTHF). For LPE, the combination of melt and crystal theories predicts satisfactorily the volume of the semicrystalline polymer at atmospheric and elevated pressures. Good agreement between theory and experiment obtains for PEG and PTHF equilibrium melts. In addition to a PP sample measured and discussed by Zoller, a second PP polymer by Leute et al. is considered. From the corresponding semicrystalline data, the equation of state of the crystal is then derived. The PVT results for the three crystalline polymers obtained in this indirect manner are in satisfactory agreement with the predictions of crystal theory. For purposes of comparison, a polymer melt with a low melting point, viz., cis-1,4-polybutadiene, is also discussed in terms of theory. A consideration of the scaling parameters and derived quantities for both crystal and melt had resulted in certain correlations encompassing LPE, PVF2, and PClF3. These cannot be generalized to the systems considered here, particularly in the crystalline state. PEG stands out in respect to several characteristic quantities in both states, whereas PP can be more nearly grouped with the previous three polymers. The theoretical equation of state for the polymer crystal does not satisfy a principle of corresponding states. However, practically useful and accurate interpolation formulas for the theoretical expressions, polynomials at atmospheric pressure, and Tait equations for the compression ratios are derived. Over certain ranges of reduced temperature and pressure, the theoretical isotherms can be approximated by master curves for the four polymers. At atmospheric pressure, such representations are limited.
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  • 105
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The different types of morphology that can be developed in a large number of low-density (branched) polyethylene whole polymers, as well as in a series of fractions, have been studied for two different extreme crystallization modes. Concomitantly, thermodynamic properties of the same samples have also been determined. After isothermal crystallization at elevated temperatures, spherulitic structures are found in all the whole polymer samples. On the other hand, after rapid crystallization a variety of different types of supermolecular structures are observed which are shown to depend systematically on the concentration of side-chain branches and the relative proportion of high molecular weight species in the sample. This temperature dependence of the morphological forms is opposite to that previously reported for linear polyethylene. The studies with the fractions show that the individual species are not the cause of this behavior; rather, the total composition is the important factor. The thermodynamic properties are also quite different from those of linear polyethylene in showing virtually no molecular weight dependence and being governed primarily by the concentration of short-chain branches. The degrees of crystallinity as determined from density and enthalpy of fusion measurements do not vary much with the two extreme crystallization conditions employed, are not sensitive to the morphology, and differ from one another, even when well-developed spherulites are formed. A major influence of the branching concentration on these properties is clearly indicated.
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  • 106
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1957-1964 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A version of the surface growth method by Zwijnenburg and Pennings is being used to produce blended fibers of polyethylene and polypropylene under conditions where polypropylene does not yield to this fiber growth technique but would grow films. The blended fiber contains intimately mixed crystalline regions of each pure component and combines thermal and mechanical properties of both. The growth method itself underlines the part played by adsorbed surface layers and entanglements within such layers which can involve the entanglement of chemically different species. This feature suggests a potentially new method for blend production.
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  • 107
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1965-1970 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Because their conformational entropy is a nonlinear function of size, polymer molecules can only solidify under conditions far from equilibrium with the formation of dissipative structures. A dissipative structure is nonhomogeneous, it evolves with time from an initially space-dependent fluctuation, and has a characteristic size that depends upon the initial perturbation and the conditions that apply during its entire history. The glass transition is envisioned as the formation of the ultimate dissipative structure where all of the latent heat of crystallization is dissipated within the structure. The mechanism of glass formation can be described as the spinodal decomposition of a homogeneous liquid into two interpenetrating networks of high- and low-energy solids with a characteristic distance and a gradient of density and/or composition extending through both high- and low-energy regions.
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  • 108
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1971-1981 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Considering one long chain (N monomeric units) in a homodisperse melt of chemically identical, but shorter, “solvent” chains (P monomers per chain), we propose some tentative scaling laws for the self-diffusion constant D(N) and the relaxation time T(N) of the solute chain. We also discuss the viscosity increment δη due to a small volume fraction Φ of the long chains. We find three regimes of behavior, depending on N and P, and on the distance between entanglement points (assumed smaller than N and P): (A) reptation of the N chain; (B) Stokes-Einstein regime; the solute moves like a usual polymer coil in a viscous fluid of P chains; (C) mixed regime, where D(N) is controlled by reptation, while δη is of type B. Contrary to our earlier belief, we find no significant regime where the process of “tube renewal” could be dominant.
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  • 109
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new method is introduced to determine the degree of partitioning of noncrystallizable comonomer units (B units) between the two phases of a semicrystalline random copolymer. The method is based on the comparison of the intensities of small-angle neutron and x-ray scattering (SANS and SAXS, respectively). By this technique two quantities can be evaluated: the difference Δρ of the mass densities between the crystalline and the disordered regions, and the concentration fluctuations of the B units in the two phases. It is found that SANS is very sensitive to the presence of small amounts of B units if their scattering length is sufficiently different from that of the A units. This will be the case for copolymers with B units, in which a hydrogen is substituted by another atom. But in addition it can also be achieved generally by deuteration of the comonomer units. So a wide range of copolymer systems can be studied by this method. The capability of the method was proved by measurements on chlorinated polyethylene and on 1,3,5-trioxane-1,3-dioxolane copolymers. Both copolymers are distinguished by a random distribution of the co-units. The results show that even at relatively low concentrations xB of the comonomer units a remarkable fraction of the B units is incorporated into the crystalline A phase and that this fraction rises if xB is increased.
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  • 110
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2145-2150 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman spectra of a series of styrene-sodium methacrylate copolymers of varying sodium methacrylate contents have been investigated in the 425-100 cm-1 region. The bands appearing at 254 and 166 cm-1 have been attributed to ion multiplets and clusters, respectively. From an analysis of the intensities of these bands and a comparison of these intensities with those obtained from an analysis of dielectric data, it seems that Raman spectroscopy is a useful method for determining the concentrations of ions in the two different kinds of sites.
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  • 111
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2151-2162 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Lithium polyphosphate crystals produced by crystallization during polymerization and crystallization from the polymer melt were analyzed by thermal analysis. The glass-transition and melting temperature, heat of fusion, and entropy of fusion were found to be 336°C, 651.5°C, 21 kJ/mole, and 23 J/deg mole, respectively. Crystallization from the macromolecular melt was followed by thermal analysis, x-ray diffraction, and electron and optical microscopy. It could be shown that chain folding may be the first step to crystallization from the macromolecular melt. Oligomers could not effectively nucleate crystallization. Lithium polyphosphate is shown to present a prime example of the processes involved in crystallization during polymerization and macromolecular melt crystallization.
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  • 112
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2163-2170 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Binary mixtures of n-paraffins have been examined by Raman spectroscopy in order to elucidate the nature of the perturbations on the chains. For a short-chain species diluted in a longer-chain species, the longitudinal acoustic mode frequency of the former decreases from its value in the pure state to that corresponding to a chain with free ends. This observation, as well as others, confirms our previous suggestions that longitudinal perturbing forces are responsible for increasing this frequency over its unperturbed value. These results also provide new insights into the structures present in solid solutions of n-paraffins. They reemphasize the necessity of incorporating the effects of such perturbations in applications of the longitudinal acoustic mode to morphological studies of polymers.
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  • 113
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2171-2180 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solid (crystalline) state coextrusion of two high-density polyethylenes (HDPE) having weight-average molecular weights (Mw) of 59,000 and 200,000 have been studied as a function of the geometrical arrangement and the volume fraction of the components. The extrusion rate increased nonlinearly with the volume fraction of the low-Mw, component. The rate was faster when the low-Mw, component was the core rather than the sheath in the initial cylindrical concentric billet. Thus the slow extrusion rate of high-Mw HDPE alone was increased up to ten times by coextrusion with a small fraction of the low-Mw, HDPE component in its center. Generally, the deformation flow profile changed gradually from a parabolic to a W-shaped pattern as the volume fraction of the high-Mw, component increased. However, the geometric arrangement of the two different Mw components also had a pronounced effect on the deformation. The deformation patterns showed that upon coextrusion the low- and high-Mw HDPE's were extruded at the same rate and extrusion draw ratio. The geometrical arrangement had no substantial effects on the tensile modulus and strength of the extrudates; i.e., they increased linearly with volume fraction of the high-Mw HDPE.
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  • 114
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2181-2188 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The stress response σ(t) to a constant rate of strain $ \dot \varepsilon $ ε during the period 0 〈 t ≤ t* and to the constant strain ε* $ ( = \dot \varepsilon t*) $ thereafter is considered in terms of the Boltzmann superposition principle. When t ≤ t*, the data directly give the constant-rate modulus F (t) ≡ σ(t)/ε(t), which can be converted straightforwardly into the relaxation modulus E(t). Results from illustrative calculations show that a reduction in the relaxation rate effects a decrease in [σ(t*)/ε*]/E(t*) and also in the time at which [σ(t)/ε*]/E(t) becomes essentially unity. To evaluate E(t) at t 〉 t*, F(t) is first obtained from σ(t) and F(t - t*) by using a derived equation similar to that presented by Meissner. Thereafter, F(t) is transformed into E(t). For illustration, E(t) for a rubbery solid is evaluated over some 2.5 decades of time from its response to a strain rate of 0.25 min-1 for 0.40 min and thereafter to the attained strain of 0.10 for 5.4 min.
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  • 115
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2241-2252 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Friction was measured and analyzed for rubber belts sliding against paper and polymer film surfaces of different roughness. As expected, increased paper smoothness created an increase in the friction coefficient. However, it was found that continuous rubber usage during testing also created an increase in friction coefficient for constant surface roughness of both paper and film. This was analyzed as due to an increase in N and C values for the load-dependent friction coefficient, μ = CW-N where W is normal load and Nmax ≈ 0.33 (papers) or Nmax ≈ 0.6 (polymer films). Using adhesion friction theory, it was shown that friction data can be fitted with a unified equation: C = μ0c-N, where μ0 = μ N = 0 and c is a constant for the rubber and belt configuration tested.
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  • 116
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2229-2240 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gels made by radical copolymerization of monofunctional and difunctional monomer units in the presence of swelling medium will tend to be heterogeneous. A case in point is acrylamide co-polymerized with N,N′-methylene bis-acrylamide in water. Such gels can be assumed to be two-phasic with both phases gels, but of different average concentration and average degree of cross-linking. As Weiss and Silberberg have shown, permeability can be used to characterize the distribution in space. In this paper, their earlier model is expanded and improved by considering specifically the permeability of each of the two phases and taking into account that each of these phases separately must have come into swelling equilibrium with the swelling medium, water. It can be shown that only the length of the Kuhn statistical element remains as a free parameter in this model. Essentially the same value of this parameter, however, accurately accounts for the measured permeability. It is found that at an overall volume fraction of about 0.16, the two-phase structure tends to disappear. For higher degrees of crosslinking, this occurs because the more dilute phase takes over the entire space; for more lightly crosslinked systems, the more concentrated phase takes over. The heterogeneity of the distribution lies in the nanometer range and reasonable agreement between the results obtainable from permeability and from viscoelasticity can be demonstrated. These results are consistent with the model for the polymerization process.
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  • 117
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 169-171 
    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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  • 118
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1709-1718 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A medium B contains a substance C which can diffuse. This mixture of B and C is brought into contact with a medium A which itself can diffuse into B. Now C diffuses through a swollen layer of A and B into A. The present study examines mathematically this process which, among other things, could serve as a model for migration in a system consisting of plastic packaging (polymer plus an additive) and the contents of the package. It is assumed that medium A (contents) with a constant diffusion coefficient diffuses into medium B (plastics) and that the diffusion of substance C (additive) in the pure B and into A can also be described by constant diffusion coefficients. The diffusion coefficient of substance C in the zone of mixed A and B is taken to be dependent on the concentration of A in B. Partition coefficients are assumed to exist at all interfaces between the media. The general equations of this coupled diffusion process are solved explicitly. The solutions are discussed and illustrated by several special cases. Furthermore, the total amount of C in A is calculated as a function of the diffusion coefficients of the partition coefficients of time, and of the concentration of A in B.
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  • 119
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1731-1739 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transitions in a polystyrene-chloranil molecular complex have been analyzed by thermally stimulated discharge (TSD) current measurements. Peaks have been observed in the current spectra at 79 (α), 128 (ρ), and at 36°C (β). These peaks are attributed to the following mechanisms: the α peak to the randomization of dipoles at the glass-rubber transition, the ρ peak to the release of space charges via long-range molecular motions at the liquid-liquid transition, and the β peak to the torsional vibrations of the phenyl side group. A high-temperature treatment is found to narrow the distribution of the α relaxation and removes the ρ peak from the TSD spectrum. Repeated TSD runs on the same sample have been found to generate charges which give a small peak at 141°C. Absorbed water is found to shift the β and α relaxations to 39 and 91°C. Activation energy, relaxation time, and relaxation constant have been calculated for the α relaxation by the method of Bucci et al. The calculated values of activation energies have been compared with those reported in the literature for pure polystyrene.
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  • 120
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1741-1756 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Type II diffusion into uniform spheres (radius R) and sheets (thickness 2l) is calculated under the assumption that the glass-gel boundary proceeds at a constant velocity v from the surface towards the interior of the sample, that the diffusion coefficient Dg in the glass is constant and that the diffusion coefficient Dr of the rubbery gel is so much higher than vR or vl that practically no sorbate gradient is needed for the transport through the gel of the sorbate. The diffusion process is completed when this boundary reaches the center of the sample. The concentration profile of the sorbate in the glassy matrix in front of the boundary varies with time and velocity v. It does not, however, influence the boundary propagation velocity. Hence the often observed increase of the rate of the weight gain just at the end of the diffusion process is not considered at all. The relative weight gain of the sample W(t)/W∞ as a function of time is the only quantity usually measured. From the ordinate intercept A and the initial slope B of the plot of W(t)/t1/2W∞ vs. t1/2, one can calculate the characteristic transport properties, i.e., the diffusion coefficient Dg of the glass and the velocity v of the glass-gel boundary.
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  • 121
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1789-1796 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric properties of low-molecular-weight propylene glycols HO—[CH(CH3)CH2O]n—H (n = 3, 4, 5) were investigated to clarify the effect of chain length on the dielectric properties. The measurement of dielectric constant and dielectric loss was carried out over the frequency range 30 Hz to 30 MHz at temperatures of -20 to -65°C. The static dielectric constants of these glycols are between 10 and 30, slightly smaller than values for the corresponding ethylene glycols of the same degree of polymerization. All of the Cole-Cole arcs, even that for pentapropylene glycol, can be represented by the empirical Davidson-Cole equation. The dielectric properties of homologous propylene glycols are compared with those for the ethylene glycols and are discussed in terms of the effects of chain length and intermolecular hydrogen bonds.
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  • 122
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1771-1787 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two series of vinyl alcohol-vinyl acetate copolymers were prepared by homogeneous and heterogeneous acetylation of the same precursor poly(vinyl alcohol). Their intramolecular monomer distributions were analyzed by IR spectrometry, calorimetry, and differential thermal analysis. The results show a more blocky distribution for the heterogeneously prepared copolymers. The properties of these (co)polymers in dilute aqueous solution were determined by means of viscometry. Whereas the copolymer-solvent interaction parameter of the homogeneously acetylated, random copolymers hardly varied with acetate content, a definite minimum was found for the blocky copolymers at about 7 mole% vinyl acetate. These findings were attributed to the incompatibility of dissimilar sequences, which sharply decreases with decreasing vinyl acetate sequence length. Up to about 17 mole% vinyl acetate content, the solvent quality for the copolymers is at least as good as for poly(vinyl alcohol). In addition, the dilute solution properties of the samples were established in water saturated with 1-butanol. For copolymers with up to about 17 mole% vinyl acetate, at 25°C this mixture is a better solvent than water. The highest increase in solvent quality was found for the homopolymer, whereas the increase diminished with acetate content, irrespective of the intramolecular vinyl acetate distribution. These findings are explained in terms of preferential adsorption of 1-butanol onto the (co)polymer backbone due to hydrophobic interactions and prevention of this process by the bulky acetate groups.
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  • 123
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recent gravimetric studies of the sorption of organic vapors by poly(vinyl chloride) and polystyrene powders have demonstrated several features which promise to be generally useful in studying the structure and properties of the glassy state. The uptake of vapor can be significantly altered by prior thermal or vapor treatment of the polymer, apparently reflecting changes in the microvoid content or free volume of the polymer. Fickian sorption in sufficiently fine powders proceeds to equilibrium in a few minutes. Upon exposure of a polymer powder to an appreciable pressure of vapor, both a rapid Fickian sorption and a slower, relaxation-controlled sorption are observed. Superposition of these processes leads to widely varied sorption kinetics; a model comprising Fickian diffusion and first-order relaxation terms accurately describes the data and allows estimation of equilibrium and rate constants for both processes. After prolonged exposure, removal of a swelling vapor induces a slow reconsolidation of the polymer structure; this deswelling relaxation can be monitored by the decreasing amounts of vapor sorbed in repeated brief exposures to low vapor pressures, and can also be described by a first-order relaxation model. In this regard, the penetrant vapor serves as a molecular probe, monitoring glassy-state relaxation occurring in the absence of penetrant. The same, presumably true equilibrium is ultimately reached both by swelling from a low free-volume state and by consolidation from a preswollen state of high free volume. The rates of both swelling and consolidation relaxations appear to be retarded by the presence of low concentrations of vapor in the polymer, suggesting that vapor molecules may preempt some of the free volume required for relaxation.
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  • 124
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1845-1854 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experiments on inflated sheets of crosslinked poly(dimethylsiloxane) covering a sixfold range of compression are combined with measurements in elongation conducted on specimens from the same sample to obtain the relationship of stress to strain over a 24-fold range in the extension ratio λ1. With increase in λ1-1 the reduced force [f] ≡ f(λ1 - λ1-2)-1 rises to a maximum near λ1-1 = 1.2-1.4, then decreases very slowly with further increase in λ1-1. The form of the relationship of [f] to λ1-1 confirms recent theory.
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  • 125
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1855-1869 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crosslinks are introduced by γ irradiation into 1,2-polybutadiene while strained in uniaxial extension near Tg with stretch ratio λ0, thereby trapping a proportion of the entanglements originally present. The stress at any subsequent strain λ is accurately given by the sum σN + σx, where σN is the stress contributed by a trapped entanglement network with λ = 1 as reference and a Mooney-Rivlin stress-strain relation, and σx is that contributed by a crosslink network with λ = λ0 as reference and neo-Hookean stress-strain relation. The birefringence is accurately given as δn = eNσN + exσx, where the e's are the respective stress-optical coefficients. From measurements at λ = λ0 where σx = 0, eN can be determined separately. For polymer with 88% 1,2 microstructure, eN and ex are nearly equal and independent of irradiation dose, though strongly dependent on temperature. For polymer with (95-96)% 1,2, eN and ex are different (even opposite in sign) and dependent on dose. This behavior is associated with a side reaction of cyclization by the γ irradiation, which is inhibited by the 1,4 moiety in the polymer with lesser 1,2 content. It is responsible for residual birefringence in the state of ease (λ = λs) where σN = -σx and the stress is zero.
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  • 126
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1891-1895 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In place of directly assaying the relative rebound height of a ball from a polymeric sample, the passage time of the ball between fixed points is used in a much more precise version of the poor man's relaxation spectrograph. Poly(oxymethylene) has a sharp transition at  -  74.8°C which progressively becomes broader and moves to  -  39.0°C as the polymer is pretreated at 70°C and exposed to 330 nm light for times up to 1038 ksec. A second transition, broad and shallow, is seen in the range 104 to 124°C and is unaffected by the pretreatment. This is attended by a slight decrease in density, proportional to the time held at 70°C, at the rate of -3.54 × 10-9 g/cm3 sec.
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  • 127
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1871-1890 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of bimodal molecular weight polystyrene blends was prepared. One component had a molecular weight greater than Mc and one less. The recoverable compliances were measured, and the retardation spectra determined via direct inversion. The retardation spectra of the blends are interpreted on the basis of the behavior of the spectra of the components, as a function of composition. It was observed that the low molecular weight component acted as a solvent. The effect of blending on the high molecular weight spectrum was to shift the position of the first peak to longer times and that of the second peak to shorter times. The peak separation was found to be proportional to the 3.4 power of the product of the molecular weight and the volume fraction of the high molecular weight component.
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  • 128
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2189-2213 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Based on creep and creep-recovery measurements, the viscoelastic functions [J(t), Jr(t), J′(ω), J″(ω), G′(ω), G″(ω), and L(lnτ)] are presented for solutions of a narrow molecular-weight-distribution polystyrene in tri-m-tolyl phosphate in the concentration range of 1% to 100% polymer. For concentrations of 25% polymer and above, two maxima are exhibited by the retardation spectrum, L(lnτ). In the neighborhood of each of the maxima the retardation spectra of the more concentrated solutions can be superimposed by translations along both the logL and logτ axes. Reflecting the increasing width of the rubbery plateau with increasing polymer concentration, the dependence of the concentration time-scale shift factors is greater for the terminal region of response. The response of the solvent is seen at the lower concentrations and it is a less sensitive function of the concentration than that of the polystyrene. This behavior is associated with the previously reported observation of two glass-transition temperatures in the middle concentration range. For the higher concentrations, both the steady-state and rubbery-plateau compliances are inversely proportional to the square of the concentration.
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  • 129
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2215-2224 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In a tensile test of a bar or fiber formed from a transversely isotropic viscoelastic material, the initial motion in regions away from the clamps is a homogeneous uniaxial extension. If the applied tensile load is “tame” in the sense that it is given by a piecewise smooth function of time, then during the early stages of loading, the homogeneous extension of the specimen is also tame. It is, however, often the case that at a time tc, previous to the instant of fracture, the motion departs from a tame homogeneous extension. The critical time tc is the “failure time” of the specimen, i.e., the time at which the motion first changes character; tc precedes, often by a constant factor, the time at which neck-down is easily visible. The problem of calculating tc for a given loading program is here treated within the framework of the general theory of nonlinear simple materials with fading memory. For such materials the instantaneous tensile modulus, i.e., the derivative of the immediate change in tensile stress with respect to a sudden change in tensile strain, depends upon the previous history of the strain. Reasons are presented here for identifying tc with the earliest time t0 at which the instantaneous tensile modulus becomes zero. It is shown that at a time at which the instantaneous modulus vanishes one cannot arbitrarily assign the rate of change of tensile stress and have the motion remain in the class of tame homogeneous extensions.
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  • 130
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2225-2228 
    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 quasielastic light scattering is utilized to determine the viscosity of fluids subjected to large hydrostatic pressures. In this method, a small concentration of insoluble polystyrene spheres of known diameter, 0.109 μm, is added to the fluid. The high-pressure cell in which the fluid is contained has three optical windows. The laser light scattered from the suspended spheres is analyzed to determine the diffusion coefficient of the spheres. Since, by the Stokes law, the viscosity of the fluid is determined from the measured diffusion coefficient and known particle radius r. A small correction is required for the contraction of the spheres and for refractive-index change of the water under pressure. Results on the viscosity of water at 25°C up to pressures of 2.5 kbar are reported and compared with published results. This method is applicable to lubricants and polymer solutions where the viscosity is many orders of magnitude greater than that of water.
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  • 131
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Linear polyethylene was crystallized isothermally from the melt. Specimens were removed at different crystallization times and quenched to room temperature. The density, static mechanical properties, and small-angle x-ray scattering (SAXS) behavior of these specimens were measured at room temperature. The density and Young's modulus increased with crystallization time, whereas the upper yield point decreased with crystallization time. SAXS data showed that a zero-angle peak gradually disappeared as crystallization time increased. Concurrently, the breadth of the SAXS peaks, the Bragg angle, and the integrated intensity decreased. Changes in the ratio of second- and first-order peak intensities were also noted. On the basis of the SAXS and density data, it was concluded that a competition exists between the thickening of existing crystals and the creation of new crystallites between the older ones. At relatively low crystallization times, numerous new crystals can form during quenching to room temperature, whereas quenching after prolonged crystallization primarily results in the additional thickening of existing crystals. No change in the density of the amorphous material is found. A model is given whereby the upper yield stress is coupled to these morphological changes through a stress concentration effect caused by a decreased population of chains connecting adjacent crystallites. The tie-chain population change occurs by their elimination as crystallites disappear.
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  • 132
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 741-751 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Odd-numbered polyamides have dipoles with components that point in the same direction in the planar zigzag conformation (rather than alternating as in the even-numbered polyamides). An investigation of the dielectric properties of two odd nylons was undertaken here to see if dipole correlation resulting from this effect could be detected. It was found that the dielectric constant and relaxation strength associated with the α loss process (amorphous phase glass-rubber relaxation) when normalized for dipole concentration was indeed markedly higher in the odd nylons. The effect of uniaxial orientation induced by solid-state extrusion on the isotropy of the dielectric properties was also studied. A previous study on nylon 6-10 found a reduction in relaxation strength of the α process in both the parallel and perpendicular directions but with the perpendicular direction being much stronger than the parallel. A similar result was found here for the odd polyamides. Thus the reduction in intensity appears to be due to effective reduction in the amount of amorphous material and not due to any change in dipole correlation induced by orientation. The anisotropy in relaxation strength can be explained by a composite material effect resulting from parallel stacking of crystal lamellas and interlamellar amorphous material and without invoking any anisotropy in the amorphous-phase dielectric strength. Thus there is no reason to conclude that the amorphous phase undergoes orientation as a result of the crystal-phase orientation.
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  • 133
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic mechanical and birefringence behavior of three kinds of test specimens, prepared from a low-density polyethylene by different heat treatments, was investigated over the frequency range 0.008 to 4.3 Hz at various temperatures from 20 to 80°C. Reduction of both kinds of data to the common reference temperature of 50°C revealed rather broad frequency dispersions, corresponding to the α dispersion, with activation energies for the mechanical and optical relaxation processes of around 25 kcal/mole for all specimens. An annealed specimen was further investigated by dynamic x-ray diffraction to determine the dispersions of crystal orientation and of lattice deformation. The mechanical and birefringence dispersions are associated with the dispersion of crystal orientation and with the relatively elastic nature of the lattice deformation. Thus, the mechanical dispersion could be assigned to an α1 mechanism arising from rotation of crystallites within the spherulites, i.e., a type of grain-boundary phenomena, but not to an α2 mechanism resulting from a crystal disordering transition or premelting. Combining dynamic birefringence with dynamic crystal orientation, the mechanical α dispersion is further discussed in terms of dynamic orientation behavior of noncrystalline chain segments in order to elucidate the nature of the grain-boundary phenomena in detail in relation to the dynamic deformation mechanism of the spherulitic crystalline texture, i.e., reorientation of “crystal grains” within orienting lamellae due to intralamellar shearing resulting from the paracrystalline nature of the lamellae. A mechanical model characterizing the grain-boundary relaxation in association with the reorientation of the crystal grain is also proposed.
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  • 134
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 799-810 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared measurements of the dichroic ratio of atactic polystyrene absorption bands provide a valuable method of determination of the overall orientation of chains as well as the particular orientation of the trans conformational segments. The orientation process produces the alignment of the chains as well as an increase in the amount of trans conformational segments. A linear relationship is observed between birefringence and dichroic ratio for the absorption bands characteristic of overall orientation. A value of 35° ± 3° is obtained for the angle between the normal to the plane of the benzene ring and the chain axis from both infrared and birefringence determinations.
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  • 135
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 825-835 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A thermally reversible crystal transition was found for γ-helical poly(γ-n-alkyl L-glutamate)s (alkyl = ethyl, propyl, butyl, and amyl). The transition temperature is higher than that of the side-chain mechanical dispersion, and decreases from 115 to -5°C, as the alkyl groups become longer. The transition in poly(γ-n-propyl L-glutamate) is clearly first order. The structures were analyzed by x-ray diffraction at various temperatures. It is noteworthy that the pseudohexagonal form observed below the transition temperature is less ordered than the hexagonal form at higher temperatures. The mechanism of this transition is discussed.
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  • 136
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 851-857 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric studies were performed on crystallized and amorphous polydimethylsiloxane which had been characterized by differential thermal analysis and polarized light microscopy. The crystallized specimen displayed one relaxation near 160 K at 1 kHz while the amorphous specimen showed absorption peaks at 155 and 165 K. For the latter material the high-temperature peak was not due to a true relaxation but resulted from crystal nucleation at 160 K and the subsequent growth of spherulites. The low-temperature peak at 155 K resulted from the relaxation associated with the glass transition. A sharp decrease of dielectric constant was observed for both specimens at the melting point (235 K). For the dielectric relaxation associated with the glass transition in crystallized specimens, the values of the dispersion amplitude, the apparent activation energy at 160 K, and the half-width of the absorption curve are 0.43 and 29 kcal/mole, and 5.6 decades, respectively, which are in marked contrast to the corresponding values of 0.82, 18, and 2.2 for amorphous specimens.
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  • 137
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 893-897 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 5 Ill.
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  • 138
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 899-903 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 139
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ultra-oriented high-density polyethylene fibers (HDPE) have been prepared by solid-state extrusion over 60-140°C range using capillary draw ratios up to 52 and extrusion pressures of 0.12 to 0.49 GPa. The properties of the fibers have been assessed by birefringence, thermal expansivity, differential scanning calorimetry, x-ray analysis, and mechanical testing. A maximum birefringence of 0.0637 ± 0.0015 was obtained, greater than the calculated value of 0.059 for the intrinsic birefringence of the orthorhombic crystal phase. The maximum modulus obtained was 70 GPa. The melting point, density, crystallinity, and negative thermal expansion coefficient parallel to the fiber axis all increase rapidly with draw ratio and at draw ratios of 20-30 attain limiting values comparable with those of a polyethylene single crystal. The properties of the fibers have been analyzed using the simple rule of mixtures, assuming a two-phase model of crystalline and noncrystalline microstructure. The orientation of the noncrystalline phase with draw ratio was determined by birefringence and x-ray measurements. Solid-state extrusion of HDPE near the ambient melting point produced a c-axis orientation of 0.996 and a noncrystalline orientation function of 0.36. Extrusion 50°C below the ambient melting point produced a decrease in crystallinity, c-axis orientation, melting point, and birefringence, but the noncrystalline orientation increased at low draw ratios and was responsible for the increased thermal shrinkage of the fibers.
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  • 140
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 907-915 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman spectroscopy, x-ray diffraction, and thermal analysis are used to investigate the structure of linear high-density polyethylene rapidly quenched from the melt to cryogenic temperatures. All the results point to the production of a glassy phase which crystallizes when heated above 170 K.
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  • 141
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 917-937 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Light scattering from concentrated solutions of cellulose acetate in acetone is discussed in terms of exponential correlation functions for refractive-index fluctuations. These are related to intermolecular aggregation. Light scattering, tensile creep and recovery, and hyperfiltration studies with films of cellulose acetate cast from acetone are discussed in terms of the state of aggregation in the films. It is concluded that intermolecular aggregates are probably small and imperfectly formed regions of microcrystallinity stable up to about 210°C, with the overall state one of near amorphous disorder.
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  • 142
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 939-944 
    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 polymer-polymer interactions and ultrasonic parameters on the ultrasonic degradation of polycaproamide in aqueous 40% H2SO4 was investigated. It was found that the rate data for the concentrations studied could be represented well by Ovenall's rate equation. However values of the rate constant chosen to fit Ovenall's equation tend to decrease with increasing concentration of polycaproamide from 0.5 to 2.0 g/100 cm3. With increasing ultrasonic power, the degradation rate increases, but it decreases as frequency is increased. This suggests that cavitation has a dominant role.
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  • 143
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 945-950 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Interaction of nonidentical polymer molecules in a dilute solution of a mixture of two polymers is quantitatively characterized by A24, the second virial coefficient for interaction of unlike species. This parameter is related to the compatibility of the two polymers in solution and is obtainable experimentally, e.g., by light scattering. With chemically markedly different polymers, A24 depends neither on the molecular weight of the polymers nor on the solvent and becomes characteristic of the polymer pair. For a mixture of two copolymers or of a homopolymer and a copolymer with similar compositions, A24 depends both on the solvent and on the molecular weight of polymers. Under such circumstances A24 ceases to be a quantity given only by the chemical structure of the two polymers; however, under suitable conditions it remains a sensitive function of the difference between the chemical nature of polymer components.
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  • 144
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 951-959 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Computer modelling studies of the progress of crystallization in polymer melts have been carried out initially on those systems analyzed by Avrami and then extended to include a number of complications which may be characteristic of real systems, in particular (a) mixed mechanism, (b) volume shrinkage, (c) variable crystalline density, and (d) nonrandom nucleation. It is concluded that the Avrami equation is a reasonable approximation to most of these systems except (c).
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  • 145
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 969-985 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The shear-dependent complex viscosity η*12, which governs the linear time-dependent stresses in a viscoelastic fluid undergoing infinitesimal shearing oscillations in-line with a viscometric motion, has been investigated. Formulas relating η*12 to measured quantities have been derived for the cone-and-plate and parallel-plate geometries. In the former case, the formula has the same form as that found when there is no steady shearing present. For the parallel-plate geometry, the formula is different because of the radial variation in the viscometric shear rate. In order to determine the empirical significance of this formula, η*12 data were obtained for two fluids, NBS nonlinear sample No. 1 and a 4.3 g/dl aqueous polyethylene oxide (molecular weight, 5 X 106) solution using a Weissenberg rheogoniometer Model R-18. Data were acquired and analyzed using a minicomputer on-line with the rheogoniometer. The obtained data indicate that good agreement between the η*12 measured using the two geometries is obtained only if the derived formulas are used. Also, it is shown that theoretical results of simple-fluid theory are valid for these data.
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  • 146
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1053-1062 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(tetramethylene terephthalate) (PTMT) undergoes a reversible stress-induced crystal-crystal phase transition. X-ray fiber-diffraction photographs were obtained from the oriented, unstressed (α) phase. Relative intensities were measured from these photographs. These were used to help check the reported structures of the α phase. Structures and observed intensity data from other authors were also utilized. Results show the α phase contains a non-trans, non-gauche bond rotation in the tetramethylene chain and a nonplanar terephthalic acid residue. A tilt of 3.5° between the fiber axis and the c axis was determined in a direction 210° counterclockwise from the b* axis.
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  • 147
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1011-1032 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting behavior of continuous fibrillar crystals of high-molecular-weight polyethylene has been investigated. The macrofibers were grown from dilute solutions in xylene subjected to Couette flow in the temperature range between 103 and 118.5°C. The thermograms, as determined by differential scanning calorimetry, exhibit three melting endotherms with peak temperatures at 141, 150.5, and 159.5°C after extrapolation to zero scan speed. All peaks were found to be strongly superheatable. Reduction of fiber length, in particular by etching with fuming nitric acid, led to the disappearance of the melting peaks at 150.5 and 159.5°C. The remaining peak at 136°C appeared not to be superheatable. The heat of fusion of the fragmented fibers was 69.8 cal/g. Wide-angle x-ray diffractograms taken on a macrofiber while gradually heated at a rate of 0.35°C/min at constant length showed that the triclinic phase present in the fiber disappeared at 130°C and that the orthorhombic cell transformed into the hexagonal modification at 150°C. This hexagonal phase was still observable at 180°C. The retractive force developed on heating at constant length displays first a slight decrease followed by a maximum at 150°C. Beyond the latter temperature the stress decays abruptly corresponding to the temperature at which fracture of the fiber could be observed visually. From all these observations it is inferred that the first melting endotherm in the differential scanning calorimeter (DSC) thermograms arises from the melting of unconstrained fibrillar crystal regions which are able to shrink during fusion. Moreover, the melting of lamellar overgrowths on the elementary fibrils on shish-kebab type may contribute to this endotherm. The second melting endotherm at about 150°C is associated with the transformation of the orthorhombic into the hexagonal lattice in constrained parts of the sample. This latter “rotator” phase allows slippage of the polymer chains past each other, giving rise to stress relaxation. The third endotherm arises from melting of this hexagonal phase and the heat take-up connected with the formation of higher energy gauche states upon randomization of the chains in the melt. Almost smooth, fully constrained fibrillar crystals grown at high temperature absorb more than 15.5 cal/g during this process, indicating that the polymer chains in such fibers must be highly extended.
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  • 148
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1063-1071 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reversible stress-induced crystal-crystal phase transition of poly(tetramethylene terephthalate) (PTMT) has been studied using infrared spectroscopy. Two spectral regions were used to study this transition: the 900-1000 cm-1 methylene rocking region and the 1300-1550 cm-1 methylene bending region. The bands at 917 and 1456 cm-1 are assigned to the ∝ phase. The bands at 935 and 1388 cm-1 have components from the α phase and the β phase. Dynamic stretching experiments performed above and below the glass-transition temperature indicated different mechanisms of the phase transition.
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  • 149
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1073-1084 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some theoretical properties of a semidilute polymer solution (in a good solvent) near a repulsive wall (no adsorption) are discussed. (i) Near a single wall, the existence of a depletion layer (where the concentration is strongly reduced) with thickness equal to the correlation length ξ(c) is predicted. Scaling laws are obtained for the concentration cs at the first layer as a function of the bulk concentration c, and for the concentration profile c(z) at distance z from the wall. (ii) When two parallel walls are separated by a slab of polymer solution (thickness d), there is an attractive interaction between the plates. The range of the attraction is ca. 3ξ(c) and can be varied by suitable choice of concentration. It may lead to destabilization of certain colloidal systems.
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  • 150
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic moduli G′(ω) and G″(ω) for two groups of linear polyethylene fractions (reported Mw/Mn 〈 1.2) were measured in the melt state using the eccentric rotating disk method. Values of zero shear viscosity η0 were obtained and compared with published results on similar fractions. Molecular weight data were converted to a common basis through intrinsic viscosities in trichlorobenzene (TCB) at 135°C. With recent data on Mw (light scattering) vs. [η]TCB, for linear polyethylene, the relationship at 190°C, η0 = 3.40 × 10-14(Mw)3.60, was obtained. The flow activation energy Ea was 6.4 kcal (T = 140-195°C). The plateau modulus G0N at 190°C was determined from the area under the loss modulus peak in one high-molecular-weight sample. The value obtained, G0N = 1.58 × 107 dyn/cm2, corresponds to an apparent molecular weight between entanglements of 1850. The storage compliance J′(ω) becomes anomalously large at low frequencies. The recoverable compliance J0e could not be determined for any of the fractions.
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  • 151
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some results are reported on the linear viscoelastic properties of polybutadienes with narrow-molecular-weight distributions. The zero shear viscosity η0 varies as M3.4 in the linear samples, and viscosity enhancement is found in star-branched samples with long arms, in good agreement with results reported earlier by Kraus and Gruver. The temperature coefficient of viscosity appears to be slightly larger in stars when the arms become long. The steady state recoverable compliance J0e is 2.1 × 10 -7 cm2/dyn in linear samples of high molecular weight, but it increases to values as much as 10 times larger in the stars. The plateau modulus G0N, obtained from a composite curve for the linear samples, is 1.32 × 107 dyn/cm2. The terminal relaxation spectrum of the stars is too broad to allow an evaluation of plateau modulus.
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  • 152
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some results on the melt rheology of hydrogenated polybutadiene (HPB) with narrow-molecular-weight distribution are reported and compared with the corresponding properties of the precursor polybutadienes (PBD) and fractions of linear polyethylene (PE). In linear samples the dynamic moduli obeyed frequency-temperature superposition. The relationship between melt viscosity and intrinsic viscosity at 190°C for HPB was indistinguishable from that for PE, but their flow activation energies were slightly different (Ea = 7.2 kcal for HPB and 6.4 kcal for PE). Like PE, but unlike the PBD precursors, the dynamic storage modulus at low frequencies was anomalous. Otherwise, the dynamic moduli of HPB and its PBD precursor were essentially superposable. Plateau moduli from different samples were somewhat variable around an average of G0N = 2.31 × 107 dyn/cm2. The dynamic moduli for the HPB stars, unlike their PBD precursors, did not obey temperature-frequency superposition. At high frequencies the temperature coefficient approached that for linear HPB, but it increased with decreasing frequency, reaching limiting values which depended on the arm length. The flow activation energy ranged from 9 kcal to more than 15 kcal as arm length increased.
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  • 153
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1251-1267 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gelation of solutions of poly(ethylene terephthalate-co-isophthalate) depends on chain structure, solvent, temperature, and concentration. Wide-angle x-ray scattering and differential scanning calorimeter experiments reveal the crystalline nature of the gel. The crystalline crosslinks, with a fringed micellar structure, are composed of terephthalate units. Orientation of the dried gels reveals the presence of crystallites with their largest dimension parallel or perpendicular to the chain axis. At high enough concentration of crystallizing units in the chain, folded-chain lamellar structures are also formed. Compared with the fringed micellar crystallization, the induction time for this crystallization is short. Melting of the folded-chain structures is very similar to the melting of pure poly(ethylene terephthalate). Because of the crystalline nature of this gelation, copolymers with only a small difference in composition can be fractionated according to the difference in micro-structure.
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  • 154
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1281-1293 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using thermoelastic measurements, specific polymer-diluent interactions have been demonstrated for atactic poly(vinyl alcohol) networks swollen in water. This was done by following a thermodynamic parameter as a function of network swelling, which was controlled by varying the extent of network crosslinking. At low crosslinking (high swelling) the ratio of the energy component fe of the force to the total force f was found to be perhaps a little less than -0.38 for poly(vinyl alcohol) swollen in water to less than 0.36 volume fraction of polymer. The method of evaluation is new and should be applicable to other polymer single component diluent systems.
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  • 155
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1317-1324 
    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 macroparticle and solvent inertia on diffusion of interacting spherical Brownian particles is studied. Results are applied to the determination of the spectrum of light and neutrons scattered quasielastically from solutions of macroparticles.
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  • 156
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1295-1305 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization characteristics of the binary system polyoxyethylene (PEO)-glutaric acid were determined. From the extrapolated melting point depression data the heat of fusion for PEO is 2506 ± 200 cal/mole of repeat unit while the heat of solution for the glutaric acid amounts to 6.7 ± 1.2 cal/cm3. A melting point of 348 K is found for the high-molecular-weight PEO. A calorimetric glass-transition temperature for mixtures of the two components is relatively independent of the melt composition and appears at 217 K. A eutectic is observed whose composition and melting temperature depend on the nature of the PEO crystal phase.
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  • 157
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1307-1315 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the existing literature various values are given for the intrinsic birefringence of the crystalline and the amorphous phases in poly(ethylene terephthalate) (PET). These values have either been calculated theoretically or obtained from experimental data on the basis of certain models. In this investigation, using the Samuels two-phase model which correlates sonic modulus with structural parameters, intrinsic birefringence values for the crystalline (Δnc) and amorphous (Δna) phases have been determined by studying 30 PET samples prepared by heat setting to have a wide range of structures; the results are Δnc = 0.29 and Δna = 0.20. These values are discussed along with others in the literature and it is concluded that in the light of the present work, the values used by many authors need reexamination.
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  • 158
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1325-1339 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Twinning in macroscopic single crystals of poly(TSHD) has been investigated using scanning electron microscopy. Two particular chain-axis rotation twins have been identified unambiguously. They have K1 twinning planes of (012) and (212). It is also thought that twins with K1 planes of (212) and (202) may possibly occur. The possible mechanisms of twinning in polymer crystals have been discussed and chain-axis rotation twinning in poly(TSHD) has been compared with a similar type of deformation that has been suggested to take place in polyethylene crystals.
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  • 159
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1367-1374 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A nematic fluid is characterized by five friction coefficients. When dilute polymer coils are added to the fluid, all these coefficients are modified. Three Miesowicz viscosities (measured under an aligning magnetic field) and two coupling coefficients between orientation and flow are discussed. In our calculation, elastic dumbbells are used to model the flexible polymer chains. The results are written in terms of two size parameters R∥ and R⊥ and two chain friction coefficients λ∥ and λ⊥ (the label ∥ refers to a direction parallel to the nematic axis). This could be compared to other experiments (such as translational diffusion) which measure λ∥ and ⊥ directly. They may give useful estimates of coil conformation in nematic solvents.
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  • 160
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1341-1354 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Consideration of crystallization kinetics in high-molecular-weight polymers shows that adjacent reentry is unlikely in melt crystallization and that sections of individual chains will crystallize concurrently at several sites. Hence the characteristic crystallization process will be that of a loop of chain with both ends attached to different sites on the crystal surface. Analysis of this process leads to predictions of crystallinity values for various conditions of chain mobility in the crystal and of entanglements in the amorphous regions. Observations on polymers crystallized at high undercoolings where a crystallinity of about 30% is usually observed suggest that the common case is that of a highly entangled amorphous layer and rapid, local annealing of the chains but with no long-range motion in the crystal. This model of loop crystallization is shown to agree with available small-angle neutron scattering data. The overall crystallization kinetics are in accord with surface nucleation controlled growth which also arises out of the Lauritzen-Hoffman adjacent reentry model and has been shown to fit experimental results on growth rates.
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  • 161
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1355-1366 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The resonance Raman spectra of polymer chains in partially polymerized crystals of 1,6-di-p-toluenesulfonyloxy-2,4-hexadiyne are reported. The polymer chain distortion is deduced using the results obtained previously for fully polymerized samples under tensile strain. Changes in crystal lattice dimensions both parallel and lateral to the polymer chains are found to be important in interpreting the variations in frequency of the Raman-active vibrational modes. Further evidence is found for the resonant interaction of backbone and side-group vibrations reported previously. This interaction is affected by the lateral dimensional changes and is also sensitive to residual strain fields in the monomer crystals. It is not necessary in the interpretation of the Raman spectra to take any account of changes in polymer chain length during polymerization.
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  • 162
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1395-1401 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric constant and loss were measured for poly(2-hydroxyethyl methacrylate) from -90 to 34°C over the frequency range 30 to 3 × 105 Hz in the γ relaxation region. The relaxation was also characterized using activation energies.
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  • 163
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1441-1456 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polystyrene networks containing controlled amounts of pendent chains and swollen to equilibrium in benzene have been investigated by inelastic light scattering and stress-strain experiments. Both the cooperative diffusion constant and compression modulus have been shown to decrease drastically when the proportion of pendent chains increased, while the equilibrium segment concentration exhibits only a small variation. The experimental results are discussed in terms of a change of structure and dimensions of the macromolecular strands of the network.
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  • 164
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1431-1440 
    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 selected area electron diffraction in the transmission electron microscope is used to examine the degree of orientation of crazed matter. The theories of electron and x-ray diffraction are compared and it is shown experimentally, by comparison with published x-ray results, that it is possible to obtain electron diffraction patterns from uncrazed polystyrene that are reasonably free of both radiation damage and multiple scattering problems. Electron diffraction patterns from crazes show a considerable degree of orientation but otherwise are very similar to those from uncrazed material, showing that crazes have no structure different from that of bulk material. Diffraction patterns are also obtained from thin films drawn to draw ratios of 4.5 and 6 at 90°C. These agree well with published x-ray results from oriented polystyrene but show less anisotropy than the craze diffraction patterns.
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  • 165
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1457-1464 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman spectra of stearyl alcohol (n-C18H37OH) indicate that vibrational bands in both the skeletal optical (1000-1200 cm-1) and longitudinal acoustical (0-500 cm-1) regions are considerably perturbed by intermolecular hydrogen bonding. The zone interior skeletal stretching mode reflecting phonon dispersion in the v4 branch of the infinite polyethylene chain is found at 1105 cm-1, approximately 20 cm-1 higher than in the corresponding n-alkane. Similarly the single nodal longitudinal acoustical mode (LAM-1) is found shifted by 12 cm-1 to higher frequency when the expected “mass effect” produced by the —OH group is considered. This shift is further increased to 16 cm-1 at -100°C indicating a further perturbation on this accordion mode due to the increased strength of the hydrogen bond at the low temperatures. The positions of the higher multinodal vibrations, LAM-3 and LAM-5, are also perturbed by the hydrogen bond but by differing amounts. The observation of a low-frequency Raman-active LAM in polytetrahydrofuran [(—CH2CH2CH2CH2O—)n] is discussed in conjunction with the expected effects of hydrogen bonding at the lamellar surface.
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  • 166
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1465-1468 
    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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  • 167
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1807-1813 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of the silane coupling agent interphase of fiber-glass reinforced plastics has been studied by Fourier transform infrared and laser Raman spectroscopy. It is found that there is a degree of order in the molecular organization of the coupling agent interphase for the vinyl and cyclohexyl functional silane coupling agents. When a cyclohexyl functional silane is used, crystalline layers of silanetriol on the glass fibers are observed. The extent of order is determined by the structure of the adsorbed species, which is influenced by the structure of the silane in the treating solution. Two factors introducing disorder in the interphase are the magnitude of aggregation of the silanes in solution and irregularities in the topology of the glass surface.
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  • 168
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1825-1844 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data on the viscosity of poly(vinyl acetate) (PVOAc) and its concentrated solutions in diethyl phthalate (DEP) and cetyl alcohol (CeOH) are examined over the molecular weight range 8 × 103 〈 M 〈 1.3 × 106, the range 0.15 〈 ϕ 〈 1.0 of the volume fraction ϕ of polymer, the temperature range 308 to 430°K for PVOAc and its solutions in DEP, and at 396°K in CeOH. The latter is the θ temperature for dilute solutions of PVOAc in CeOH. The data are analyzed with the relation η = KXc(αϕ2ϕM/Mc)a exp[1/β(T - T0)], where a is 1 or 3.4 for αϕ2ϕM less than or greater than a constant Mc, respectively, and XC, is a constant. The expansion factor αϕ of the chain dimension is found to be essentially unity for ϕ 〉 ca. 0.25, increasing with decreasing ϕ for smaller ϕ. Both β and T0 depend on ϕ, and T0 also depends on M at low M.
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  • 169
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1903-1912 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Single filaments of nylon-6 and of its mixtures with KCl, LiCl, and LiBr (salt content up to 5% w/w) were prepared by extrusion at 265°C. As-spun filaments with a varying degree of orientation were obtained by altering the take-up velocity a t constant outflow velocity. These as-spun filaments were further subjected to controlled thermal and mechanical treatments. Determinations of the elastic modulus, of birefringence, of wide-angle x-ray scattering, and of shrinkage were carried out for the as-spun and for the treated filaments. While KCl caused no detectable alteration of the properties of nylon-6, lithium halides caused a considerable increase of the elastic modulus of the polymer. Under the conditions adopted, moduli up to 14 GPa were obtained. The birefringence of as-spun fibers was, however, lower when lithium salt was present. Greater shrinkage a t 170°C was exhibited by the salted than by the pure polymer. The body of results has been interpreted in terms of a more efficient orientation of the extruded polymer when lithium salt is present. The latter effect is associated with the role of these salts in reducing the crystallization rate and in increasing the melt viscosity of the polyamide as characterized in preceding papers of this series. Lithium salts also favor the α → γ transformation between the two crystalline forms of nylon-6. The transformation was, however, reversed under sufficiently high applied stress.
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  • 170
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1983-1994 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transport properties of polymer solutions at finite concentration are derived in the partial draining case by formulating a static version of the theory given by Freed and Edwards (FE) for unentangled concentrated polymer solution. The method follows the Kirkwood - Riseman theory for infinitely dilute solutions: the dynamics of the polymer are ignored apart from the overall rotation or translation of the chain and the solvent velocity is given by the Navier - Stokes equations perturbed by point friction forces. The concentration dependence of viscosity and translational friction coefficient of finite chains obtained by numerical calculations are compared with the results of the FE closed-form solution. It is shown that the screening of the hydrodynamic interaction approximately follows Debye-like behavior in the entire range of concentration. The progressive balancing of the increasing intramolecular hydrodynamic interaction with its reduction due to the screening effects, as the molecular weight increases, is well evidenced by comparing results obtained at constant number concentration for different chain lengths.
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  • 171
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1995-2006 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(spiro[2,4]hepta-4,6-diene) (PSHD) is a random copolymer composed of 1,2 and 1,4 units. Although PSHD has been reported to have a very large Sakurada-Mark-Houwink exponent (a = 1.71) characteristic of rigid rods, a new determination of the intrinsic viscosity-molecular-weight relation for fractionated samples with known copolymer composition gives a smaller value (0.81). The rigidity of the PSHD molecule was also investigated by calculations of the conformational energy associated with the main chain and the dynamic viscoelasticity associated with the molecular motion in a solid state. A sharp potential energy minimum occurs at a dihedral angle χ1 = 260° in polymer composed of all trans 1,4 units. The dynamic loss tangent for the primary absorption decreases with increasing fraction of the 1,4 unit. These properties result from the characteristics of the stiff 1,4 unit sequences in the molecular chain. The density of PSHD decreases with increasing content of 1,4 units and was found to be considerably smaller than values for typical polymers, in relation to the occupied volume of the repeat unit. This fact can be explained by the peculiar aggregation state of molecular chains composed of rigid and flexible units.
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  • 172
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2007-2012 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Second virial coefficients have been measured in tetrahydrofuran for a series of anionically polymerized narrow distribution homopolymers and copolymers of butadiene and styrene. The results fit the general empirical equation A2 = M-1/4(0.0216wB + 0.00995wS + CwBwS), where M is the polymer molecular weight, wB and ws are the weight fractions of butadiene and styrene, and C is a constant which is zero for block polymers and equal to 7.9 × 10 - 3 for random copolymers. The equation is independent of the degree of 1,2 addition of butadiene and fits data on both linear and tetrachain star-branched polymers within experimental error.
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  • 173
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric constant measurements were carried out on a sample of poly(1,3-dioxepane) [CH2—O—(CH2)4—O—], in benzene over the range 25 - 60°C. This chain molecule was found to be very similar to poly(1,3-dioxolane) [CH2—O—(CH2)2—O—] in having a relatively small dipole moment, which increases markedly with increasing temperature. Rotational isomeric-state calculations show that these two characteristics are due to very strong preferences for gauche states in the two central bonds in the sequence CH2—O—CH2—O—CH2. Such pairs of gauche states, necessarily of the same sign, place neighboring-group dipoles in essentially antiparallel orientations. The resulting attenuation of dipole vectors is the origin of the small dipole moment, and the disruption of these preferred conformations with increasing temperature gives rise to the large positive temperature coefficient of the dipole moment.
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  • 174
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2021-2029 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cellulose acetate butyrate has been studied in regard to its hydrodynamic properties in several solvents. The polymer was fractionated by precipitation, and the molecular weight distribution of the polymer fractions was determined by gel permeation chromatography. The number-average molecular weight was estimated by osmometry. The Mark-Houwink-Kuhn-Sakurada relations between viscosity and molecular weights were established, and the unperturbed dimensions of the polymer chains were evaluated. In light of these data, current theories of polymer solutions are discussed. A new method of estimating unperturbed dimensions is proposed for semiflexible linear polymers.
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  • 175
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isobaric variations of the characteristic temperatures Tg and Tmax, obtained on uniform cooling and heating of glasses, are investigated in terms of their dependence on the relevant experimental variables, using a single retardation time model. The corresponding partial derivatives of Tg and Tmax are derived as functions of the partition parameter x (ranging between zero and unity), which determines the relative contributions of temperature and structure to the retardation time. It is shown that the variation of Tg with the cooling rate is independent of x. In contrast, Tmax critically depends on x, and its value as well as those of its three partial derivatives are linear functions of x-1. The variations of Tmax are analyzed in terms of a set of reduced variables, leading to simple reduction rules between any two of the experimental variables when the third is kept invariant. The reduction rules are further substantiated by investigating the behavior of glasses in two-step thermal cycles, which result in a unique set of inter-relationships between any pair of the partial derivatives of Tmax, whatever the value of x. The results are discussed in terms of their relevance to the behavior of real glasses.
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  • 176
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2059-2075 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the photoinitiated polymerization of lauryl acrylate (LA), 1,6-hexanedioldiacrylate (HDDA) and pentaerythritol tetraacrylate (PET4A) have been investigated using differential scanning calorimetry (DSC). An autoacceleration phenomenon is observed with the multifunctional acrylates, but not with lauryl acrylate. The empirical dependences of reaction rate on such parameters as incident light intensity, initiator concentration, and temperature have been established and are in general found to vary with monomer conversion. Apparent activation energies for the photopolymerizations have been determined from rate versus temperature data. The multifunctional acrylates show an increasing activation energy with monomer conversion, whereas the apparent activation energy for lauryl acrylate not only decreases with conversion, but becomes negative at conversions greater than about 30%. The ratio kp/kt1/2 is calculated from rate versus conversion data under constant illumination and the (independently determined) initiation rate. Analysis of rate versus time data under nonsteady-state conditions (light turned off) yields the ratio kt/kp. With these two ratios the rate constants for propagation (kp) and termination (kt) may be separated and their respective values calculated. Both kp and kt are found to decrease substantially with monomer conversion, indicating a significant change in the rates of both the propagation and termination steps as the polymerization advances. These observations are explained in terms of a radical isolation phenomenon and diffusion control of the propagation step.
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  • 177
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2091-2101 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The aromatic Polyamide-hydrazide, Monsanto X-500, has been studied by light scattering in dimethyl sulfoxide, a thermodynamically good solvent. The unperturbed dimensions, (〈r02〉av/M)1/2 = 1.93 × 10-8 at 25°C., indicate a rather highly extended chain. The persistence length falls in the range 35-63 Å, which corresponds to a length of between two and four formula units. This is considerably smaller than the values which have been reported for the aromatic polyamides, poly(p-benzamide) and poly(p-phenylene terephthalamide). X-500 appears to approximate coil-like behavior at a molecular weight of 45,000. Theoretical predictions, based upon the 〈r02〉av/bL ratio, are compared with the observation that no evidence for an anisotropic phase has been found in X-500 solutions in dimethyl sulfoxide at polymer volume ranging from 0.12 to 0.19 (depending upon the concentration of added LiCl).
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  • 178
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2077-2090 
    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 intermolecular correlations on the angular dependence of the intensity of Rayleigh scattering from a dilute solution of a flexible-chain polymer in a good solvent is studied for an approximate model that retains the random-flight intramolecular segment-pair correlation while probabilities of multiple intermolecular contacts are simplified as products of probabilities of single contacts, all conditional on a common “initial” contact. This model, unlike one in which a polymer chain is represented as a spherically symmetrical cloud of segments, gives very little deviation from Zimm's “single-contact” approximation in light scattering: i.e., the initial concentration dependence of the concentration/intensity ratio is almost the same at all scattering angles. This behavior, which appears to underestimate the intermolecular correlations, can be accounted for by the symmetry of the bimolecular cluster as represented by the model.
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  • 179
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2103-2109 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Zero-shear-rate intrinsic viscosities [η]0 in benzene at 25°C and in cyclohexane at 34.5°C were measured for two series of polystyrene samples: six fractions ranging in Mw(weight-average molecular weight) from 8.8 × 106 to 5.7 × 107 and 11 “monodisperse” samples ranging in Mw from 4 × 103 to 4.8 × 106. The results, combined with typical literature data, yielded \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {[\eta ]_0 = 7.8 \times 10^{ - 5} \bar M_w^{0.75 \pm 0.01} } & {(4 \times 10^5 〈 \bar M_w 〈 6 \times 10^7 ,{\rm benzene at }25^\circ {\rm C})} \\ {[\eta ]_0 = 8.8 \times 10^{ - 4} \bar M_w^{0.50} } & {(10^3 〈 \bar M_w 〈 6 \times 10^7 ,{\rm cyclohexane at }34.5^\circ {\rm C})} \\ \end{array} $$\end{document} These relations cover the broadest range of molecular weights reported so far in the literature on synthetic polymers. In contrast to Slagowski et al., we observe no “anomaly” in the molecular weight dependence of [η]0 for benzene solutions of very high molecular weight samples (〉107).
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  • 180
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2133-2143 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An analytical theory of block copolymer conformations is developed for systematically studying the effects of the chain length, chain architecture, and segment interactions. The main results obtained for AB diblock and ABA triblock chains are as follows: (i) In the absence of AA and BB interactions, both diblock and triblock chains collapse to a dense form if the AB interaction is attractive. In the collapsed coil form, the mean-square end-to-end distance 〈R2〉 is proportional to the square root of the number of segments n1/2. (ii) The diblock chain has a dumbbell form if AA and BB interactions are attractive and AB interaction repulsive, but the triblock chain collapses. In the dumbbell form, 〈R2〉 is proportional to n.
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  • 181
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 2111-2115 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: If Mmin and Mmax are lower and upper bounds, respectively, to the molecular weights of different molecular weight species contained in a polymer, the weight-average to number-average molecular weight ratio Mw/Mn cannot exceed (1 + Mmax/Mmin)2/(4Mmax/Mmin). The ratio attains this maximum possible value if the masses of the two species with molecular weights Mmin and Mmax are equal and the masses of all the other species are negligibly small, corresponding to maximum spread in the molecular weight distribution within the specified bounds. Also for a given value of Mw/Mn = α, the Mmax cannot be smaller than [2α - 1 + 2α1/2(α - 1)1/2]Mmin. The minimum possible value of Mmax/Mmin consistent with α given is obtained in the case of maximum spread described above. If only one species is predominant, then both Mw/Mn and Mmax/Mmin approach unity, as is well known. Similar relations hold for the ratios of higher-order average molecular weights for which the role of the mass fractions is replaced by higher-order distribution functions.
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  • 182
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 1-23 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new calculation of the vibrational frequencies of poly(ethy1 ethylene) based on the actual molecular geometry was performed. The calculation takes into account new experimental data such far-infrared spectra and Raman spectra of the stretched polymer, infrared spectra of poly(ethyl ethylene)-(2,2;d2) (P-4-1-d2) and poly(ethyl ethylene)-(3,3,4,4;d4) (P-4-1-d4), and Raman spectra of poly(ethyl ethylene)-(1,3,3;d3) and poly(ethyl ethylene)-(3,3,4,4;d4). Refinement produced a set of force constants; it is also applicable to poly(propyl ethylene).
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  • 183
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The vibrational analysis of modification I of poly(propyl ethylene), poly(propyl ethylene)-(2,2;d2), and poly(propyl ethylene)-(1,2,2;d3) has been performed using the valence force field derived for poly(ethyl ethylene) and the actual molecular geometry. The band assignments are based on infrared polarization and Raman data.
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  • 184
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 55-62 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The nucleation and growth of the crystalline core in the row structures of isotactic polystyrene were investigated by transmission electron microscopy. The number of core crystals, nucleated at a specific temperature, depends on the external strain. Their length was found to increase with time if the sample is kept at the straining temperature. If a strained sample is cooled to room temperature and subsequently reheated, no further growth of the core crystals is observed. Obstacles in the path of growth were circumvented by local changes of the growing direction. Melt-soluble noncrystallizable molecules are rejected by the growing core into the surrounding melt. The observations suggest a growth mechanism of the cores based on the successive self-induced alignment of molecules at the tip of the growing cores.
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  • 185
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 45-53 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Carbon-13 spin-lattice relaxation times (T1), nuclear Overhauser enhancements (NOE), and resonance linewidths (Δp) have been measured for a series of terephthalic acid polyesters containing ethyl, butyl, hexyl, and isopropyl groups between neighboring terephthalate units. The relaxation parameters of all carbons in the terephthalate groups are independent of the length of the separating alkyl chain. Reduced NOE's are seen for all carbons. The data are interpreted in terms of a log X2distribution of correlation times of constant width, but variable average mobility. The average mobility in the alkyl chain increases with increasing distance from the terephthalate group in a given polymer. For a given position in the chain. mobility increases with increasing chain length. This behavior is consistent with the presence of independently reorienting, highly solvated terephthalate groups.
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  • 186
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 73-79 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polytetrafluoroethylene (PTFE) was extruded from a capillary rheometer at temperatures between the first-order transition at 30°C and the melting point. Both PTFE at 50-300°C and various smectic states of certain low-molecular benzylidene anilines obey the following relationship between the shear stress τ and the apparent shear rate $ \dot \gamma :{\rm }\tau = K\dot \gamma ^{{1 \mathord{\left/ {\vphantom {1 4}} \right. \kern-\nulldelimiterspace} 4}} $. The apparent viscosities for the two classes of substances are similar even though their molecular weights differ by a factor of about 104. Both have characteristic shear planes which are parallel to the polymer chains in PTFE and normal to the long axes of the benzylidene aniline molecules. The melting process in virgin PTFE begins near 300°C. Above this temperature, the shear stress at constant shear rate increases and the rheological exponent rises from 0.25 toward 0.5 at the final melting point.
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  • 187
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 63-71 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recent experiments have supported the view that polyethylene (PE) single crystals kept in suspension, in a variety of liquids, have different physical properties compared with the same crystals after drying. The present work was undertaken in an attempt to directly measure one of the basic properties of crystals in suspension, namely their percent crystallinity (X). Differential scanning calorimetry was chosen as the primary tool for this investigation. A method has been developed to determine the weight of PE in a suspension of crystals in a nonsolvent. Thus, a determination of X can be made. For suspension crystals, X was found to be at least 88.5%, some 6% larger than that for the corresponding dried or freeze-dried material. Implications with regard to the fold-surface structure are discussed. Differences in degree of crystallinity as a function of drying procedure have also been observed.
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  • 188
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 81-85 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The far-infrared spectra of polystyrene methacrylic acid/(PSMA) ionomers have been investigated as a function of cation and ion-site concentration to obtain spectroscopic evidence of domain formation. A far-infrared band, due to the vibration of a higher-order cluster, is found at 170 cm-1in Na+-form PSMA. This band, which is observed in addition to the known cation-motion bands, is assigned to the vibrations of aggregates involving many cations and anionic sites close together, and the results are discussed in light of ion aggregation models.
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  • 189
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    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 95-101 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The charge decay of polymer electrets in the presence of solvent vapor is analyzed. In order to account for this phenomenon, several hypotheses are considered and tested experimentally. It is shown that the penetration of the solvent is responsible for the observed charge decay, and that it is the rate limiting factor. Moreover, the phenomenon is not due to the screening of the injected charges, but to the motion of these charges, which are liberated by the penetration of the solvent. Finally, the possible applications of this phenomenon in investigations on both the microscopic and macroscopic scale are outlined.
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  • 190
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 281-286 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 191
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 301-312 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Behavior of the free radical copolymerization of N-β-methacryloyloxyethyl derivatives of adenine with that of thymine was studied in chloroform solution, taking account of the specific base-base interaction of these monomers. Hydrogen bonding interaction between such monomers was observed by NMR spectroscopy. The acceleration of copolymerization was found to be greater either at lower monomer concentration or at lower polymerization temperature. When N-β-methacryloyloxyethylcarbazole was used as a comonomer, the rate of copolymerization showed a similar trend as in the case of usual free radical copolymerizations. From r1 and r2 values obtained, the copolymerization was found to be alternating, particularly in the case of copolymerization between monomers having complementary nucleic acid bases. The results suggest that the hydrogen bonding interaction between adenine and thymine plays a role in the propagation step.
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  • 192
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 385-392 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Benzaldehyde (PhCHO) is found to be able to initiate the radical polymerization of methyl methacrylate (MMA). The rate of polymerization is expressed by the following equation: Rp = const[PhCHO]0.5[MMA]1.5. The overall activation energy is estimated to be 56.3 kJ mole-1. The mechanism of polymerization is discussed.
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  • 193
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 455-464 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the intermediates in unterminated polymerization reactions were studied. It was found that in a first-order initiation (A) all intermediates accumulate monotonically. In a second-order initiation (B) the first intermediates pass through a maximum, whereas the later ones strictly accumulate. An initiator-started polymerization can follow course A or course B, depending on the initial ratio of the concentrations of the initiator and monomer.
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  • 194
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 473-484 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerizations of l-menthyl vinyl ether (l-MVE) with the monomers, that is, maleic anhydride (MAn), dimethyl maleate (DMM), and dimethyl fumarate (DMFu), were undertaken to obtain optically active copolymers. The optically active l-menthyl group in the side chain of copolymers was removed by the ether cleavage reaction with dry-hydrogen bromide gas. The ethercloven copolymers were still optically active. Hence it was concluded that asymmetric carbon atoms were introduced into the copolymer main chain, the reason given being that l-MVE and comonomers (MAn, DMM, and DMFu) made the stereoselective charge-transfer complex one another and copolymerized stereospecifically. From the results of the measurements of optical rotatory dispersion (ORD) and circular dichroism (CD) for copolymers before and after the ether cleavage reaction, the mode of bond opening for α,β-substituted monomers (MAn, DMM, and DMFu) was discussed and the microstructures of copolymers were prepared.
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  • 195
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 503-516 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stability of PTFE latex prepared in the absence of emulsifier by radiation-induced polymerization was investigated by electrophoresis and conductometric titration. The storage stability depends on total dose rather than dose rate, and the stable latex can be obtained in the region log D 〉 0.026 V1 - 0.6, where D is the total dose (104 rad) and V1 is a polymer concentration in latex (g/liter). The stability increases only during polymerization in the presence of enough TFE monomer. The ζ potential of the latex particles lies in the region from -25 to -50 mV in an as-polymerized state (near pH 3) and from -50 to -65 mV at pH 10. The number of carboxyl end groups and surface charge density were examined by conductometric titration with NaOH and calculation from the G values of radiolysis of water. All the surface charge densities measured by conductometric titration are larger than those calculated from the G values. These results suggest that some acids have been formed on the surface of the particles. The acids may be the carboxyl end groups of polymer chains or hydrofluoric acid (HF) adsorbed on the surface. PTFE particles prepared in this polymerization system are stabilized mainly due to the carboxyl end groups and adsorptions of OH- and HF on the particles.
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  • 196
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 539-550 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermodynamically effective fixed-charge density of mercuric phosphate and carbonate parchment-supported membranes have been evaluated by the most recent method of Nagasawa et al., based on the thermodynamics of irreversible processes and compared with the values obtained by the Kobatake et al. and Teorell - Meyer - Sievers (TMS) methods. Bi-ionic potential (BIP) has also been measured for these membranes with three pairs of electrolyte solutions: KCl—NaCl, KCl—LiCl, and NaCl—LiCl. Theoretical values of BIP have been calculated by using the membrane potential and BIP theories recently developed by Toyoshima et al., based on nonequilibrium thermodynamics. Various parameters have also been evaluated and it was found that the theoretical equation of BIP is applicable to these parchment-supported membranes.
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  • 197
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 927-930 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 935-935 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 199
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 943-947 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The heterogeneous polymerization of acrylonitrile photoinitiated by naphthalene is influenced by the polarity of the reaction medium. The rate of initiation increases with the increasing dielectric strength of the reaction medium. A similar trend is observable for Stern-Volmer constants of naphthalene fluorescence quenching by acrylonitrile. The ratio kp/kt1/2 of the rate constant for propagation and termination reactions is not influenced by a change in the polarity of the reaction medium. The effect of viscosity on the value of kp/kt1/2 known for polymerization in a homogeneous medium was not observed in the reaction systems studied.
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  • 200
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 937-942 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of acrylonitrile photoinitiated by naphthalene, anthracene, phenanthrene, and pyrene is accelerated by an admixture of zinc (II) chloride, acetate, or nitrate. The effect of zinc (II) salts on the rate of pyrene-photoinitiated polymerization of acrylonitrile leads to an increase in this rate in the order Zn/OCOCH3/2 〈 ZnCl2 〈 Zn/NO3/2. The maximum polymerization rate is achieved at the molar ratio [ZnCl2]/([ZnCl2] + [pyrene]) approximately 0.7. In contrast to the photoinitiated polymerization of acrylonitrile, the methyl methacrylate admixture of zinc (II) chloride exerts a smaller effect on the polymerization rate. In the pyrene-photoinitiated polymerization of styrene an admixture of zinc (II) chloride retards the polymerization rate. Fluorescence of aromatic hydrocarbon in the system acrylonitrile-aromatic hydrocarbon is efficiently quenched by zinc (II) chloride. Stern-Volmer constants determined for pyrene (80 dm3 mole-1), phenanthrene (66 dm3 mole-1), and naphthalene (49 dm3 mole-1) are higher by about 2-3 orders of the Stern-Volmer constants for fluorescence quenching of aromatic hydrocarbons by acrylonitrile in the absence of ZnCl2. The fluorescence of anthracene in acrylonitrile is not quenched by ZnCl2. The acceleration effect of Zn (II) salts on the polymerization of acrylonitrile photoinitiated by aromatic hydrocarbons depends on two factors: an increase in the ratio of the rate constant of the growth and termination reactions, kp/kt, and an increase in the quenching constant of fluorescence of aromatic hydrocarbon, kq, by the complex {acrylonitrile…ZnCl2}. ZnCl2 thus influences both the growth and initiation reactions of the polymerization process.
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