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  • 1995-1999
  • 1980-1984  (655)
  • 1983  (655)
  • Physics  (538)
  • Physical Chemistry  (117)
  • Nuclear reactions
  • 101
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1807-1814 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In a previous paper a two-network model for an elastomer in which crosslinks have been introduced in the strained state, similar to that proposed by Green and Tobolsky, was used to calculate the dependence of the incipient characteristic tearing energy on the number of chain segments in each of the two networks, the number of links in these chain segments, and the deformation at which the crosslinking takes place. The tearing energies were calculated for tearing on planes perpendicular to the principal directions of this deformation. Here the calculations are extended to cover tearing on a plane with arbitrary orientation.
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  • 102
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1815-1823 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The differential orientation of polymer chains has been measured in polystyrene (PS)/poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) compatible blends. Density measurements are reported as a function of binary blend composition at 23°C. Drawing was performed by solid-state coextrusion. PS/PPO blend compositions of 90/10 and 75/25 were drawn within sandwiches of polyethylene at 145°C and isotactic polypropylene at 155°C, i.e. at ca. 25°C above the glass transition temperatures of the two blends. The change in Fourier-transform infrared dichroisms on drawing these blends was measured at 906 and 1190 cm-1, corresponding to predominantly PS and PPO, respectively. The orientation of PS and PPO was observed as a function of draw ratio λ in the range 1-5; orientations increased with λ for both PS and PPO in both blends but to different degrees. Both polymers decreased in orientation with increasing PPO content. Annealing with fixed ends showed that the PPO chains disorient more slowly than those of PS. All binary systems were found to be amorphous and compatible.
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  • 103
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1839-1849 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The GPC-sedimentation velocity method proposed earlier for the determination of long-chain branches was examined quantitatively by using model star-shaped and comb-shaped polystyrene samples of known degree of branching. The results showed that separation by sedimentation velocity was more sensitive to branching variations than separation by GPC. The results showed also that at low and moderate levels of branching the GPC-sedimentation velocity method reflected accurately the amounts of branching in the model samples. At high levels of branching, the method underestimated the amount of branching. The discrepancy, however, appears to have been caused by the inadequacy of the theories used in the interpretation of the raw data and not by any inherent problem in the method itself. The relative sensitivities of the GPC-sedimentation, GPC-viscosity, and GPC-light scattering methods are discussed.
    Additional Material: 7 Ill.
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  • 104
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1825-1837 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solutions of poly(p-phenylene terephthalamide) in fuming sulfuric acid were characterized by 13C NMR spectroscopy and solution viscosity measurements over the 2-28% w/w concentration range. The spectra showed the presence of two distinct amide carbonyl resonances at low concentration, tentatively assigned to cis and trans conformations. As the concentration increased, additional carbonyl lines were observed along with significant broadening. Peak area measurements showed that only the polymer molecules in the isotropic environments contributed to the 13C NMR spectra and a considerable amount of the polymer remained in the isotropic phase at concentrations previously considered to consist of polymer in highly anisotropic regions. Spin-lattice relaxation times were measured at six concentrations using the inversion recovery method. The aromatic carbons relaxed at a much faster rate (ca. 0.10 s) than the carbonyls (ca. 0.45 s), but the relaxation rates for both carbons were essentially constant over the concentration range, indicating that the observed isotropic phase is not affected by changes in the macroscopic solution behavior so as to alter spin-lattice relaxation mechanisms.
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  • 105
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1883-1887 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 106
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1873-1881 
    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 pressure on the viscosity of dilute solutions of anionically polymerized polystyrene (M̄w = 209,000; Mw/Mn = 1.12) in toluene has been studied at different temperatures and concentrations using a falling-body viscometer. Measurements were performed in the concentration range from 0.0025 to 0.02 g/mL and at temperatures from 25 to 45°C under pressure up to 1057 bars. The viscosity coefficient η increases exponentially with pressure at a given temperature and concentration, while the apparent volume of activation V
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  • 107
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1851-1872 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low-molecular-weight 4′-acetoxyphenyl-4-acetoxyoinnamate, as well as several polyesters synthesized from this monomer and aliphatic dibasic acids, exhibit thermotropic nematic phases. DSC heating curves for all of the polymers exhibit multiple transitions. The amount of crystallinity of these polymers at room temperature is small and the degree of order along the chain axis in the crystalline phase is poor. For the lower homologues the nematic phase exists over a broad temperature range of approximately 100°C. The polyester from chiral (+)-3-methyl adipate forms a thermotropic cholesteric phase. Both the diacetoxy monomer and azelate polymers of low molecular weight adopt the homeotropic texture on glass slides, but with increasing molecular weight the planar texture becomes preferred. Investigation of the effects of electric fields in the conduction regime upon the nematic phase of the diacetoxy monomer revealed that Williams domains are formed only with difficulty. In most cases, a stationary pattern appeared instead. At higher voltage the dynamic scattering mode (DSM) was obtained, and above this a field-induced transition to the isotropic phase. The azelate polyesters exhibited Williams domains and the DSM in the conduction regime. The formation time for Williams domains was fairly short for polymers having ηinh 〈 0.44 dL/g, but increased to 80 min when ηinh = 0.68 dL/g. The DSM was only observed for polymers having ηinh 〈 0.61 dL/g. For these polymers the critical frequency separating the conduction and dielectric regimes exhibits a stronger temperature dependence than that of low-molecular-weight nematogens. A new instability pattern is reported for the azelate polyesters in the dielectric regime.
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  • 108
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1897-1902 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photon correlation spectroscopy has proven to be a very useful technique for studying slowly relaxing density and optical anisotropy fluctuations in bulk polymers near the glass transition. When some of the fluctuations achieve relaxation times much longer than the typical averaging time for the intensity autocorrelation function (104 s), the result must be treated in the partially heterodyned limit. Also, when the sample is near the glass transition but not at equilibrium the correlation function is not stationary in time because the system is relaxing as a whole toward the equilibrium state. The above effects are discussed theoretically and demonstrated experimentally in polystyrene as a function of temperature and pressure. Light scattering with coherent excitation also fluctuates in space as well as in time (as shown in the accompanying paper). The consequences of this effect are discussed. When most of the intensity is associated with fluctuations whose relaxation times are very long in polystyrene, there is still a broad relaxation function evident. This is characteristic of a secondary relaxation process.
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  • 109
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1913-1926 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An investigation of the reflective component of small-angle x-ray scattering patterns of polystyrene crazes is performed. It is shown that the strong streak parallel to the tensile axis consists predominantly of reflected radiation, while the remaining pattern is composed entirely of diffracted radiation. X-ray reflection off unparallel regions of crazes is discussed and the nature of the reflection is also considered in terms of collimation quality. An analysis methodology based on craze tip angular distribution is proposed.
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  • 110
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1927-1953 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melt-spun poly(ethylene terephthalate) fibers were isothermally heat-treated at constant length. Microstructural changes occurring during the heat-treatment were monitored using specific gravity, wide-angle x-ray scattering (WAXS), small-angle x-ray scattering (SAXS), optical birefringence, and static mechanical testing. Major changes in the density of the most highly oriented fiber examined occurred in times below 100 ms. For less oriented fibers, the time scale for significant density change increases to the 1-10 s range. The course of birefringence increase approximates that of the density. WAXS measurements show that crystallinity develops at essentially constant crystal perfection, but that the orientation of the crystallites first decreases and then increases with time. SAXS results show development of a four-point pattern, the azimuthal angle of the lobes decreasing with initial orientation, with temperature, and with time. A streak transverse to the fiber axis develops more rapidly than do the lobes. A two-stage transformation process is envisaged, the first stage being the formation of defective crystal fibrils and the second being internal rearrangement of the fibrils to form more perfect crystallites, separated by more amorphous zones. Changes in the crystallite orientation are related to constraints of the noncrystalline material on the crystallites.
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  • 111
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1889-1896 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Laser light scattered from a block of polystyrene is observed to have a pattern of bright and dark regions called speckle. We observe that the speckle pattern has a lifetime consistent with that of the average relaxation lifetime 〈τ〉 of the intensity fluctuations of the medium as determined by photon correlation spectroscopy. In order to study the pattern of the scattered light, a series of photographs was taken at a variety of exposure times. For each series, the value of the average relaxation lifetime is defined by the temperature and pressure of the polystyrene sample. When the value of 〈τ〉 is short relative to the exposure time, the photograph displays only a random pattern of exposed grains. This is due to the large number of fluctuations that have occurred during the exposure time with random phases relative to one another. As the average relaxation time is increased at a constant exposure time, the speckle pattern appears when the value of 〈τ〉 becomes comparable to the exposure time. The phenomenon of laser speckle allows the time scale of the slowly relaxing fluctuations near the glass transition to be visualized. A digitized series of such pictures could be analyzed to obtain the average relaxation time for the fluctuations, just as in normal photon correlation spectroscopy where the intensity of one coherence area is measured as a function of time.
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  • 112
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), 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: The dependence of the elution volume Ve on the concentration of injected polymer c in gel chromatography is presented for several systems including poly(styrene) and poly(methyl methacrylate) in a number of pure solvents with SiO2-based gels. The linear dependence of Ve on c and Kav on c (where Kav is the distribution coefficient) is confirmed in the region of very low concentration. The slopes k of the straight lines increase with increasing relative molecular masses M of the polymer injected and with increasing thermodynamic nonideality of the system (as expressed by the second virial coefficient A2). The significance of the slope of the GPC calibration curve for meaningful comparison of the concentration effects in various chromatographic systems is pointed out. A recently found correlation between k and (A2M)γ is confirmed with a γ value of about 0.8. A possible theoretical explanation for the deviation of γ from unity is discussed. Finally, the influence of both the polymer concentration and the thermodynamic quality of the eluent on the resolution index of the chromatographic system is evaluated with the conclusion that thermodynamically poor solvents should be preferred for preparative GPC separations with very high loads.
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  • 113
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1955-1969 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fibers of poly(p-phenylene terephthalamide) (PPTA) have a fibrillar morphology, the individual fibrils having a high proportion of extended chains passing through periodic defect layers. A pleat structure is superimposed. The fibers are fully crystalline (within the limits of determination) with a small fraction of randomly oriented crystalline material. The major distinction between PPTA and conventional fibers lies in the high level of extended chains passing through the defect layers of the former structure. These extended chains result in crystallographic register being maintained between adjacent ordered zones. Quantitatively, a measure of this order is obtained from a comparison of the correlation length, obtained from meridional x-ray peak widths, and the defect spacing. In conventional fibers the defect spacing, i.e., long period, is longer than the correlation length (i.e., crystal size). In PPTA, the analog of the long period, the defect spacing (about 35 nm) is smaller than the correlation length, which is over 80 nm.
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  • 114
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1971-1979 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is possible to prepare “model” elastomeric networks having known values of the molecular weight Mc between crosslinks by endlinking functionally terminated polymer chains having number-average molecular weights Mn equal to the desired values of Mc. If chains having chemically inert groups at both ends are intentionally included during the preparation of such a system, they will remain unattached, merely reptating through the subsequently formed network structure. This technique was used to prepare a series of tetrafunctional polydimethylsiloxane (PDMS) networks having essentially the same degree of crosslinking (10-3Mc = 11.3 g mol-1) and constant amount of diluent in the form of unattached PDMS chains having molecular weights of 10-3Md = 26.4, 18.6, 15.8, 9.8, 6.7, 1.2, and 0.70 g mol-1. Because of the very high mobility of PDMS, it was also possible to introduce essentially the same amount of the same diluents into already formed PDMS networks having the same Mc. Extractions carried out using tetrahydrofuran at room temperature showed that the diluent (“sol fraction”) introduced by swelling the network is more easily removed than that present during the endlinking, possibly because of less convoluted arrangements within the network structure. Chains with the largest values of Md which were present during the endlinking were found to be very difficult to remove entirely. It is therefore extremely important to carry out exhaustive extractions to obtain reliable values of network sol fractions, particularly when such data are to be used to estimate extents of reaction in the preparation of end-linked elastomers.
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  • 115
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2003-2010 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hwang and Cheng have studied the recombination reaction of allyl radicals in irradiated polyethylene by including the effects of (i) diffusion of macroradicals by jumps of finite size in the crystalline phase and (ii) a caging reaction with a finite rate in the disordered region. In this work their results are used to analyze cumulative reaction rate data on the decay of allyl radicals in extended-chain and Marlex film polyethylene. The kinetic parameters obtained show the effects of reaction temperature, irradiation dose, and morphological differences.
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  • 116
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2011-2026 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The permanganic etching technique has been studied as a function of time, temperature, and concentration for a series of polyethylenes. Kinetic studies show that a film of reaction products builds up on the surface, impeding further etching, an effect which is greatest for the lowest-crystallinity polymers. SEM studies combined with EDS show that the film contains sulfur, potassium, and some manganese. An artifact is produced by the etching process which is impossible to remove by washing procedures if certain limits of time, temperature, and concentration are exceeded. For lower-crystallinity polyethylenes multiple etching and washing steps were required for optimal resolution. Plastic deformation during specimen preparation, whether from scratches or freeze fracturing, enhances artifact formation. When appropriate procedures are used virtually artifact-free surfaces can be produced allowing a combination of permanganic etching and scanning electron microscopy to give a rapid method for detailed morphological characterization of bulk specimens.
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  • 117
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1981-1992 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fluorescence polarization has been used to measure the orientation during stretching of a polystyrene chain embedded in a matrix of narrow-dispersion polystyrene chains of a different molecular weight and labeled by an anthracene group covalently bound at the middle of a chain. Strong coupling between the relaxation of the labeled chain and the matrix chains is evidenced, the orientation of the labeled chain being partially governed by the molecular weight of the matrix. This behavior is interpreted qualitatively on the basis of a molecular model showing that the relaxation of a polymer chain is strongly affected by the entanglements acting on the chain, the number of which is also related to the motion of the surroundings. Good agreement is found between experimental data and the behavior predicted by the model.
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  • 118
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1993-2001 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Equations used for the determination of polymer-polymer interaction parameters for narrow molecular weight distribution polymers which have undergone phase separation in solutions are discussed. Binodals with tie lines and plait points are presented for ternary systems polystyrene-polybutadiene-toluene and polystyrene-polybutadiene-tetrahydrofuran. Typical interaction parameters determined from the experimental data for the polystyrene-polybutadiene systems are presented.
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  • 119
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2037-2043 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The model of Doi for the rotational dynamics of rodlike molecules in solution is compared with that of Warchol and Vaughan and Wang and Pecora. The similarities in the results for dielectric relaxation are discussed and the application of the models to the behaviour of isotropic solutions, anisotropic (lyotropic-nematic) solutions, and mixtures of small molecules with polymers is briefly discussed.
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  • 120
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2045-2048 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electron Spin Resonance (ESR) measurements of the polydiacetylene 4BCMU in the solid-state indicate the presence of a thermally activated paramagnetic center with g ≈ 2.002 and first-derivative peak-to-peak linewidth of ≈ 17G. An abrupt and irreversible decrease in ESR signal intensity is observed at ca. 400 K, and appears to be associated with the solid-state planar-nonplanar conformational transformation manifested by an irreversible color change from metallic brown to red.
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  • 121
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2027-2036 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report a melt spinning and viscosity study of two semiflexible homopolyesters containing both rigid and flexible segments in the repeating unit. Single filaments of the polyesters formed from 4,4′-diacetoxybiphenyl and azelaic acid (PB7) and sebacic acid (PB8), and from 4′-hydroxyphenyl-4-hydroxycinnamate and azelaic acid (C7), were spun at temperatures between 205 and 255°C. The temperature dependence of the Newtonian melt viscosity of PB7 and C7 was investigated, and a range of molecular weights was studied for PB7. The spinning parameters, fiber characteristics, and viscosity-temperature behavior are related to the type of mesophase formed. The mechanical properties of fibers spun from both the nematic and smectic phases of these semiflexible chain polymers were poor. Increasing the polymer molecular weight or extrusion rate only afforded a modest improvement in fiber properties. Most polymers could not be spun at temperatures corresponding to the existence of the single mesophase. Hence the low viscosity typical of the nematic mesophase is not necessarily an advantage in fiber formation from the melt. It appears from these results that this type of polyester does not possess adequate chain extension to develop ultrahigh-modulus properties. The director, which describes the local orientation of molecules within the mesophase, may undergo more frequent variations than is the case for rigid chain polyesters. Mechanisms relevant to flexible polymers may contribute to the development of orientation for this class of nematogenic melts.
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  • 122
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2049-2056 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The segment fraction Ψ1 activity coefficients, a1/Ψ1, of solvents have been determined by the piezoelectric sorption method for 0.1 ≤ Ψ1 ≤ 0.5 in binary solutions of chlorinated methanes [carbon tetrachloride (CCl4), chloroform (CHCl3), and dichloromethane (CH2Cl2)] with aromatic hydrocarbons (benzene and toluene) in poly(methyl methacrylate), poly(methyl acrylate), poly(ethyl methacrylate), and poly(n-butyl acrylate) at 23.5°C. The present results for toluene in PMMA agree with previously published values obtained by gas-liquid chromatography. For CCl4 and the aromatic hydrocarbons, the polymer-solvent interaction parameter χ is positive and constant, while for the polar solvents (CHCl3 and CH2Cl2), χ is negative and increases with increasing Ψ1. The effect of the polymer side chains on vapor sorption in nonpolar and polar solvent systems is discussed in terms of the χ parameter.
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  • 123
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2057-2065 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model is derived which incorporates and unifies many of the diverse observations occurring in diffusion in glassy polymers. This unification is made possible by explicitly formulating the common property of a glassy polymer in all its various modes, namely the finite relaxation time due to its slow response to changing conditions. The application and use of the model in various situations is discussed.
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  • 124
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2085-2096 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two methods based on polarization infrared spectroscopy are described for measurement of polypropylene orientation. One method, for the crystalline phase, allows precise measurement of polypropylene orientation in three orthogonal directions. It is based on the polarization characteristics of two crystallinity bands, those at 841 and 809 cm-1, which exhibit opposite polarization characteristics. The other method, for the amorphous phase, provides a semiquantitative estimate and is suitable for uniaxially oriented films. It is based on polarization characteristics of the 1155-cm-1 band. Both methods are applied to the measurement of orientation in polypropylene films uniaxially stretched at various speeds and temperatures.
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  • 125
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2067-2083 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reversible and irreversible spectral changes are observed on heating of solvent-cast films of poly(ethylene terephthalate) (PET) between 30 and 230°C. The irreversible changes are due to the gauche-trans isomerization of the ethylene glycol segments and the corresponding changes in the symmetry and resonance characteristics of the aromatic rings. On the other hand, there are thermally reversible spectral changes. These reversible effects are primarily observed for the modes of the aromatic ring and the trans ethylene glycol segment. These reversible spectral changes include intensity variations and frequency shifts and are found to be linearly dependent on the measurement temperature. These reversible changes arise from changes in intermolecular and intramolecular forces as the temperature changes.
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  • 126
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2097-2108 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theoretical stress relaxation of polymer melts is derived from a new solution of the response of Doi's slip-link model in the plateau zone of the rubberlike part of the spectrum. The results of this treatment, based on the application of the statistical theory of elasticity to a virtual transient network of monodisperse entangled chains, are applied to the calculation of stress-strain relations for uniaxial extension performed at constant strain rate and to that of stress relaxation after such an elongation.
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  • 127
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2123-2134 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A unique retainer/transparent quartz die assembly was designed and fabricated to fit on a melt extruder. It permitted visualization of polymer flow behavior during melt spinning. Tracer particles were mixed with polymer chips prior to extrusion. A laser beam was directed through a lens system and used to illuminate the tracer particles in the melt only in a thin, vertical cross section of the transparent quartz die. Streak photography was used to determine the cross-sectional velocity distribution of the melt as it passed through the die.
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  • 128
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2135-2157 
    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 low-molecular-weight miscible additives on the sub-Tg (β) relaxation process in bisphenol-A polycarbonate (BPAPC) was studied using high-resolution carbon-13 solid-state NMR. The trend of the spin-lattice relaxation times T1 at 50 MHz suggests that strong intermolecular interactions occur upon mixing when BPAPC is physically stiffened by the antiplasticizing diluent, diphenylphthalate. The values of 13C T1 at 15 MHz in d-chloroform solutions for similar BPAPC-diluent mixtures suggest that diluent effects on the megahertz mobility of the polymer occur exclusively in the solid state. These results are explained using equilibrium thermodynamics, in the Ehrenfest sense, at the second-order glass transition temperature Tg. Theory predicts that the temperature dependence of the Flory-Huggins interaction parameter ∂χ/∂T changes abruptly as the polymer-diluent blends are cooled below Tg from the molten state. The difference between ∂χ/∂T in the liquid and glassy states is the major factor which determines the diluent concentration dependence of Tg. A method is developed to estimate the relative magnitudes of χ for polymerdiluent blends in the glassy state.
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  • 129
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2109-2121 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stress measurements have been performed at constant-strain-rate stretching of narrow distribution polystyrenes with various molecular weights elongated up to 300% at about 30°C above the glass transition temperature. The experimental stress-strain curves are compared with those calculated on the basis of a new treatment of Doi's molecular model (Part I). Satisfactory agreement is obtained, leading to a rather precise estimate of the equilibration time. The latter has a theoretical dependence on the square of molecular weight.
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  • 130
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2201-2201 
    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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  • 131
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2169-2180 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Wide-angle x-ray line broadening methods have been used to determine the crystallite size and degree of distortion for the crystalline hard domains in MDI/diol polyurethane elastomers. Crystallite widths have been determined from the integral breadths of the 00l reflections following correction for distortions of the second kind according to the method Hosemann for polymers prepared using ethylene glycol, propandiol, butandiol, and hexandiol as the chain extender. These data relate to the width of the crystallites along the chain axis and thus can be interpreted in terms of the morphology of the hard domains. The crystallite sizes increase and the distortions decrease with increasing elongation and annealing time, and the sizes tend toward asymptotic values which correspond approximately to the average lengths of the hard-segment chains. These results rule out any appreciable folding of the hard-segment chains and point to a model for the hard domains formed by lateral aggregation of extended hard segments.
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  • 132
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2159-2167 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel method of following polymerization kinetics in dilute solutions of ionic monomers is described. The method, based on conductimetry, is very well adapted to follow polymerization of ionic species in very dilute solutions, in micellar solutions, or at interfaces, i.e., in all systems in which the polymerization process involves a shift in ionic equilibria. The method is applied to matrix polymerization of p-styrene sulfonate-(2,2,2)4-ionene complex and yields results in full agreement with the standard spectroscopic method frequently used in such systems. The conversion curves obtained by conductimetry are satisfactorily explained by Manning's ion condensation model and are in agreement with a previously proposed mechanism, based on ion condensation theory, for matrix polymerization of ionized monomers on polyelectrolytes.
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  • 133
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2181-2200 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffuse phase boundary thicknesses of two segmented polyurethane block copolymers have been determined by small-angle x-ray scattering analyses of deviations from Porod's law. A self-consistency test of these measurements is performed by comparing results of experiments carried out under a variety of collimation geometries, and using a number of different analytical procedures. Self-consistent values of the diffuse phase boundary thickness are obtained for both of the materials examined. The discrepancies between these values and previous literature values are discussed and possible origins of these differences are presented.
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  • 134
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2205-2217 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ba, Ca, Mg, and Zn short-length carboxylato-telechelic polybutadienes (M̄n = 4,600) exhibit thermorheological simplicity. A secondary relaxation characteristic of ionic aggregates obeys an Arrhenius type of activation, the energy of which is in inverse proportion to the ionic radius of the cation, whereas the mean size of the ionic aggregates is proportional to it. The glass transition of the carboxy-telechelic polybutadiene is quite independent of the degree of neutralization and of the subsequent phase separation by the metal cations. The increase in cation size favors the growth of the multiplets into layered structures. Two sets of relaxation times are reported for the smallest alkaline-earth cation (Be). They suggest the existence of small multiplets unable to grow except into clusters.
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  • 135
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2219-2242 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Streak-photographic and stress birefringence techniques were used to analyze the flow of poly(ethylene terephthalate) through potential chain-ordering die geometries. The streak photographs were used to determine velocity distributions and streamlines in various convergent dies. The different contours were seen to have a significant effect on the polymer streamlines and velocity distributions. The measured velocities were used to develop empirical equations, specific for each geometry, which relate velocity to position within the die and to throughput rate. Flow birefringence was used to determine the extent of molecular ordering. The optimum chain-ordering die geometry was determined to be one which included a rapid initial decrease in cross-sectional area. Birefringence was also used to monitor polymer flow instability. An unusual mechanism for instability was observed at intermediate throughput rates.
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  • 136
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2263-2274 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier-transform infrared spectroscopy has been used for the detection of conformational changes induced by plasticization in atactic poly(vinyl chloride) (PVC). The amount of short trans syndiotactic sequences decrease upon plasticization. This change depends on the amount and kind of plasticizer. Difference spectra emphasize changes in the distribution of gauche defects in the chains as a function of temperature in plasticized PVC films.
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  • 137
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2243-2262 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Wide-angle x-ray diffraction studies are reported on polyacrylonitrile (PAN) (homopolymer powder and fiber samples) and its random copolymers with methyl methacrylate (MMA) and methacrylonitrile (MAN). A new method of determination of degree of order which involves resolution of the individual maxima in the diffraction pattern is described and compared with the methods used in the literature. Comparison of the results on untreated fibers with those on untreated homopolymer powder samples, and the effect of heat treatment, suggest the molecular rod conformation of the PAN molecules in the amorphous phase. Heat treatment or the orientation induces a parallel alignment of the molecular rods in the amorphous phase, similar to the cyrstalline structure of PAN. Copolymerization with both the comonomers MMA and MAN produces qualitatively similar effect on the structure of PAN, which depends on the comonomer content. Below a critical comonomer content c* (c* = 12 mol % for MMA and 25 mol % for MAN comonomer), the crystalline lattice remains that characteristic of PAN, whereas above the critical comonomer content some modification in the crystalline lattice is apparent.
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  • 138
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2287-2298 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rheological properties of narrow-molecular-weight-distribution linear and star-branched polyisoprenes have been determined using both shearing and stretching deformations. At all strain rates studied the tensile stress measured under transient and steady-state conditions did not increase above the linear viscoelastic value. The absence of an enhanced tensile stress for the branched polymer is in contrast to what is observed for branched low-density polyethylene. An explanation for the difference is proposed. Additional remarks are made about the broad distribution of relaxation times observed for star-branched polyisoprenes and about the approach to steady state in constant-strain-rate and constant-stress tests.
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  • 139
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2275-2285 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(∊-caprolactone) and low-molecular-weight esters (methyl acetate and propyl propionate) were dissolved in binary solvent mixtures. The relative ability of the two solvents to associate with the ester group was then determined by examining the equilibrium between the two solvation states of the ester using infrared and nuclear magnetic resonance spectroscopies. The ability of the solvents to associate with the chosen esters was found to be in the sequence α-hydrogenated chlorocarbons 〉 β-hydrogenated chlorocarbon 〉 carbon tetrachloride ≈ aliphatic hydrocarbons. The association-state equilibrium was also shown to be concentration dependent and the polyester was shown to become involved in specific interactions to a lesser degree than the model esters. The relevance of these results to the nature of the specific interactions in polyester/halogenated polymer blends is discussed.
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  • 140
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2299-2309 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Proton spin-spin relaxation times have been measured as a function of temperature for ultradrawn polypropylene with draw ratios λ up to 24. The three relaxation times T2a (the longest), T2i (intermediate), and T2c (the shortest), observed for all the samples, have been ascribed to the relaxations of the amorphous, constrained amorphous, and crystalline components, respectively. T2i and T2a, which reflect the changes in structure and mobility in the noncrystalline regions, decrease with increasing λ; T2i becomes saturated at λ 〉 9, whereas T2a shows a substantial decrease up to λ = 24. The continued decrease in T2a indicates that the constraint on the amorphous segments keeps increasing up to the highest λ. The associated mass fractions Fa, Fi, and Fc also change with λ. At λ 〈 9, the increasc in Fi with increasing λ is accompanied by a decrease in Fa, with Fc remaining unchanged. At higher λ, however, Fa is almost constant, and stepwise rises in Fc at about λ = 12 and 24 are accompanied by corresponding drops in Fi. It seems that, in this high draw ratio range, some of the taut molecules are fully extended and are in sufficiently good lateral register to transform into crystalline bridges. This conjecture is supported by the similarity in the λ dependence of Fc and the mass-fraction crystallinity obtained from the heat of fusion.
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  • 141
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Concentration-dependence coefficients kDφ of the mutual diffusion coefficient of poly(2-vinyl pyridine) in tetrahydrofuran in the temperature range 15-55°C are compared with predictions of recent theories of macromolecular diffusion. In this temperature range a change in local conformation of the polymer occurs. The accompanying changes in chain solvation and coil hydrodynamics result in a sizable decrease in the hydrodynamic interaction parameter X defined by Akcasu. The formulation of theory appropriate for comparison with frame-indifferent experimental diffusivities is discussed. We find that current theories predict qualitatively, but not quantitatively, the change in temperature dependence of kDφ that occurs at the conformational transition. The discrepancies closely parallel those reported in recent independent comparisons of theoretical kDφ versus experimental data for flexible-coil molecules. No theory can adequately predict kDφ over a wide range of X.
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  • 142
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2319-2335 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The carbon-13 spin-lattice relaxation times T1 of the crystalline portion of a set of polyethylenes have been studied. Chain structure and crystallization conditions have been varied over the widest possible extremes so that large differences are developed in the level of crystallinity, the supermolecular structure, and the crystallite thickness. Concomitantly, the observed crystalline T1 values cover the extraordinarily wide range of about 40-4500 s. They bear a one-to-one relation with the crystallite thickness, which is found to be the key structural variable determining this property. A correlation with the temperature for the α-transition can be established, which implies a similar type of segmental motions for the two phenomena. Major changes in the interfacial structure can also have a drastic influence on the value for the crystalline T1. Analysis of the magnetization decay curve also allows for a quantitative determination of the degree of crystallinity, which is found to be in excellent agreement with the corresponding value found from Raman spectroscopy.
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  • 143
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2337-2347 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model is presented for the adsorption of water by ions in a deformable matrix. Only two opposing “effects” are included. The first is the mechanical resistance of the matrix to deformation which is treated within the framework of linear elasticity extended to the case of large deformations. The other effect is of electrical origin which is shown to be much more important than the purely entropic osmotic pressure. In the model only one immobile ion located at the center of a spherical droplet of water is considered. It is shown that the result does not significantly depend upon the dielectric constant of water, provided it is much larger than that of the matrix. The thermodynamic relations reveal that in fact most of the properties of the system depend mostly on the dielectric and elastic coefficients of the matrix. This simplified model should be considered as a guide for the understanding of the behavior of such systems rather than as a precise description of real materials. Some quantitative comparisons are made with a few experimental results.
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  • 144
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2349-2363 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal structure of oriented poly[di-(3,4-dimethylphenoxy) phosphazene] (PDMP) was determined by x-ray diffraction. Unit-cell parameters were found to be a = 15.85, b = 19.43, and c = 9.85 Å. The unit cell is metrically orthorhombic with monoclinic space group P21. There were 48 refinable diffraction spots in the observed reciprocal lattice region, of which 28 were observed and 20 were unobserved. A refined model yielded the following residuals: R(obs) = 0.162 and 0.138. It was shown that a two-chain unit cell with a [T3C]2 (trans, trans, trans, cis, trans, trans, trans, cis) backbone conformation was the correct structure. The dimethylphenoxy side groups were arranged in nearly parallel planes, slightly off-normal to the fiber c axis. The polymer chains are extremely tightly packed and contain close but reasonable steric contacts.
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  • 145
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2365-2378 
    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 kinetic measurements using FT-IR have been carried out in order to clarify the mechanism of the gauche-trans isomerization process and the time-temperature-transformation relationships in poly(ethylene terephthalate). Two-stage isomerization isotherms are distinguished on the logarithmic scale of annealing time: a primary transformation stage with an activation energy of 40 kcal/mol characterized by a sigmoidal curve, followed by a linear secondary process. The activation energies of the secondary transformation obey an equation of the Arrhenius type InaT = B(1/T - 1/Tm) where 160 〈 T 〈 260°C ≈ Tm and can be used to describe the effects of annealing time and temperature on the isomerization process of PET in the secondary transformation region. On the basis of these analyses, the morphology and microstructure of PET in these temperature regimes of the isomerization process are proposed.
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  • 146
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2379-2387 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Computer models of a series of liquid n-alkanes were generated, allowing for continuous variation of torsion angles and of atomic positions. Torsional and intramolecular and intermolecular non-bonded potentials were introduced. Calculated fractions of gauche bonds are slightly higher than those calculated from a rotational isomeric state model. Calculated radial distribution functions exhibit peaks in good agreement with experimental data. No directional correlation between chains is found, except at very short distances. Calculated end-to-end distances and radii of gyration indicate random coil conformations. These results are unaffected by extension of the range of interaction to the attractive region and by variations of temperature and density.
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  • 147
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2419-2424 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 148
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2389-2402 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Methyl acrylate polymer colloids can be hydrolyzed self-catalytically by bound strong acid surface groups derived from the polymerization initiator. The kinetics of hydrolysis were earlier shown to be apparently pseudo-zeroth-order for any given latex, and first order with respect to surface strong acid concentration. A surface reaction zone model was proposed to explain the kinetics. This model leads to the prediction that the polymer particles will possess a core-shell morphology after some hydrolysis has occurred. This study employs 13C NMR spectroscopy to investigate the particle morphology in the wet latex, a new application for this method. The temperature dependence of the 13C NMR integrated intensities at various levels of hydrolysis provides strong evidence that the particles do possess core-shell morphology, and that the shell is composed of PAA/PMA copolymer. This shell is swollen and plasticized by water, resulting in greatly enhanced segmental mobility of the polymer chains as evidenced by marked narrowing of the NMR lines. Thermal measurements alone cannot distinguish particle morphology because PMA appears to be somewhat compatible with its partially hydrolyzed analog at the temperatures of measurement.
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  • 149
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2425-2426 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 150
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The strength of interaction of infrared radiation with relatively thick polymer films was systematically studied by internal reflection spectroscopy. The so-called “effective thickness” was used as a measure of the strength of interaction. The experimental and theoretical effective thickness were compared, and it was found that the theoretically predicted effective thickness can be approached or achieved experimentally with film samples routinely encountered in the polymer industry when moderate attention is paid to surface preparation and clamping force on the film in the internal reflection sample holder. A series of curves for various types of film samples was developed and found to be useful in predicting the spectral contrast for KRS-5 and germanium internal reflection elements. These data were collected for infrared radiation polarized parallel and perpendicular to the plane of incidence and for unpolarized radiation. The data for unpolarized radiation was checked for the effects of the inherent polarization of the Fourier-Transform Infrared Spectrometer used by comparing it to the arithmetic mean of the data for parallel and perpendicular polarization. These data were in good agreement and this indicated that the inherent polarization of the instrument introduced only minor errors into the data collected with unpolarized radiation. The concept of the “sampling depth” was established where the sampling depth ds was defined as the depth normal to the surface sampled. The sampling depth was found to be on the order of three times the value of dp, the depth of penetration, at 45° for polypropylene and polystyrene on KRS-5 and was observed to exceed the effective thickness values at the same conditions. The value of the electric field amplitude was observed to fall to 5% of its value at the surface at ds.
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  • 151
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2427-2444 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theory for the relaxation of large strains in polymer melts is outlined. It is based on the Doi-Edwards slip-link model and the new concept of tube relaxation. Self-consistency makes this concept necessary when polymer melts are concerned. The discrepancy with previous non-self-consistent theories is not negligible and should be easy to observe experimentally. Special attention is given to the overall size and to the mean orientation of a labeled N-chain in a step-strained melt of P-chains. Using semiquantitative arguments, we predict different regimes depending on the respective values of N and P, and propose approximate evolution equations for each case. These equations may be used to design and interpret a variety of fluorescence, infrared, or NMR polarization measurements, as well as small-angle neutron scattering experiments.
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  • 152
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2445-2451 
    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 the α-methyl group on the mobility of the main and side chains of methacrylateacrylate copolymers has been investigated. Poly(ethyl acrylate) shows a small secondary loss maximum (attributed to the rotation of —COOR side chains) at 145 K, while in the case of poly(n-butyl acrylate) this relaxation process is smeared out or possibly absent. On the contrary, poly(n-butyl methacrylate) and poly(2-hydroxyethyl methacrylate) exhibit secondary relaxations at about 278 and 301 K, respectively. From the dynamic mechanical response spectra of methacrylate-acrylate copolymers one can see that the removal of the α-methyl group causes a qualitative change in the molecular mechanism of the secondary relaxation, presumably as a consequence of the different participation of the main chains. The existing data, however, are insufficient to quantify these differences. The low-temperature relaxation attributed to internal motion within the side groups is not distinctly affected by the presence of α-methyl groups. If both components of the copolymer display the low-temperature relaxation (above 77 K), the loss maxima preserve their identity to a large extent. The effect of copolymer composition on the main (glass) transition temperature has been described by means of a one-parameter equation.
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  • 153
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2453-2463 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Difficulty in controlling and determining the structural parameters of polymer networks has hindered experimental studies on the glass transition in crosslinked polymers. A series of wellcharacterized networks of poly(propylene glycol) having narrow network chain-length distributions and average molecular weight between crosslinks Mc in the range of 425-3000 has been prepared. The glass transition temperatures Tg of these networks were found to vary linearly with Mc-1, consistent with several theoretical treatments. Both the physical crosslinking and the incorporation of crosslinking agent into the system (a “copolymer” effect) are shown to be responsible for increase in Tg upon crosslinking in this system.Varying the network chain-length distribution without changing Mc did not affect the Tg of the system. The chemical nature of the crosslinking agent, however, does affect the Tg of the network, particularly at high crosslink densities.
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  • 154
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2465-2471 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Changes in the light-scattering components (λ = 0.53 μm) induced by a strong picosecond optical field (λ = 1.06 μm) applied to macromolecular transfer ribonucleic acid (tRNA) solutions were studied. Two beams were polarized vertically, and the intensity of the vertical and horizontal components of the light (λ = 0.53 μm) scattered at an angle of 90° were measured. The electric field of the strong 30-ps laser pulse was 5.0 × 103 esu cgs. The experimentally determined changes allowed for calculation of the mean third-order optical polarizability c, and its anisotropy δc. The measurements were performed in three different solutions: salt free, with magnesium ions, and without magnesium ions. Changes in tRNA structure reflected in changes of nonlinear light scattering, third-order optical polarizability, and its anisotropy were observed.
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  • 155
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2473-2482 
    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 polymer networks were prepared by trifunctionally endlinking poly(diethylene glycol terephthalate). The elastomeric properties of these materials were studied at constant temperature using experiments that involve both the elastic force and birefringence. Whereas the stress-strain isotherms show an anomalous increase in the modulus at very high elongation ratios, a downturn appears in the birefringence-strain isotherms at the same extensibilities. These results suggest that the upturn that appears in the force should be attributed to maximum chain extensibility rather than to strain-induced crystallization. A variety of additional thermoelastic experiments were carried out on these networks, to elucidate the dependence of the glass transition temperature on strain. It was found that for the elongation ratios at which the networks exhibit Gaussian behavior, the free-volume effects on the glass transition temperature Tg (decreasing Tg with increasing free volume) offset the conformational effects (increasing Tg with decreasing entropy). However, the contrary occurs in the region where the stress increases anomalously with increasing strain.
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  • 156
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2483-2494 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Resonance Raman spectroscopy has been used to measure the frequencies of the vibrational modes of the polymer backbone of fully and partially polymerized crystals of an ethyl urethane diacetylene. The data have assisted in the assignment of crystallographic structures to the different modifications of the crystals. Effective interatomic force constants have been derived and used to estimate the Young's modulus. For fully polymerized crystals a value of approximately 76 GPa was found. The dependence of the frequencies on elastic tensile strain parallel to the polymer chain direction was determined. By comparing the strain dependence of frequencies of partially polymerized singlecrystal fibers with those expected for model composites, it was concluded that the polymer chains in thermally polymerized crystals are considerably longer than in those polymerized using γ rays.
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  • 157
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2511-2524 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A moment analysis of dipolar-decoupled 19F NMR spectra of deformed polytetrafluoroethylene leads to an expansion which approximates the crystallite orientation distribution function. The resulting distributions are then interpreted in terms of this polymer's known mechanical properties, and an attempt is made to model these functions.
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  • 158
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2495-2509 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Epitaxial crystallization of polyethylene, n-paraffins, aliphatic polyesters, and various polyamides has been achieved on benzoic acid crystal substrates, specifically on their (001) crystals faces, which are made up of the aromatic rings. The epitaxial relationship is very similar for all polymers investigated: it is characterized by a unique chain orientation (parallel to the b axis of the substrate) and a plane of contact which is either the b-c, plane of polyethylene, or crystallographically similar ones for polyesters, or the plane of the hydrogen-bonded sheet for polyamides. Since benzoic acid is structurally similar to its alkali-metal salts, it is inferred that the nucleating efficiency of the latter toward chemically different but structurally similar polymers may well rest on an epitaxial relationship. Finally, the highly oriented morphology made it possible, for some polyesters with a monoclinic cell, to determine the angle between the chain axis and the Z axis of the optical indicatrix, a quantity not measured so far in polymers.
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  • 159
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2525-2541 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Highly oriented poly(vinylidene fluoride) rods have been produced by drawing isotropic polymer through a conical die. A range of oriented products was obtained, depending on the drawing temperature and the deformation ratio achieved. At low draw temperatures the draw ratio and final modulus are comparatively low, but a high Form I crystal content is obtained. At high draw temperatures the Form I content varies greatly with draw ratio, reaching high values at large draw ratios, where the highest-modulus samples were obtained.
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  • 160
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2551-2559 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of magic-angle sample spinning (MAS), high-power decoupling, and resonance frequency on the 13C NMR linewidths of bulk polyisobutylene and bulk trans-polybutadiene are examined. The 13C linewidths increase with resonance frequency, are unaffected by high-power decoupling, and are reduced to different extents by MAS. The dominant contribution of the natural linewidth of the polyisobutylene lines is confirmed. The two carbons of trans-polybutadiene have approximately equal linewidths under all conditions, a result that eliminates residual chemical shift anisotropy as a major contributor to the linewidths. The large reduction of the trans-polybutadiene linewidths with MAS, coupled with the above result, suggests that microscopic variation of magnetic susceptibility is the major factor for this semicrystalline polymer. Cross-polarized 13C spectra of trans-polybutadiene were obtained with and without MAS. With MAS, resonances due to the crystalline and amorphous components were resolved. The principal components of the chemical shift tensor of the vinylene carbons were obtained from the spectrum without MAS.
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  • 161
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2543-2549 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The extended Hückel method was employed to calculate electronic band structures in trans-poly(p-phenylene benzobisthiazole) (trans-PBT) in an attempt to elucidate the packing and electronic properties of these chains in the crystalline state. The unit-cell energies thus calculated indicate that the most stable arrangement for trans-PBT corresponds to the chains in planar configurations, at an interplanar spacing of 3.5 Å, and shifted axially by 3.0 Å relative to one another. These calculated results are in good agreement with experimental results obtained on the polymer and on relevant model compounds. No discernible dispersion of the energy bands perpendicular to the planes is observed, indicating that the neighboring chains are electronically noninteractive, as was found earlier for trans-polyacetylene and polyethylene. Similarly, the band gap of 1.69 eV in the axial direction for one of a pair of chains was nearly the same as that, 1.73 eV, calculated previously for an isolated trans-PBT chain. These values are in the range 1.4-1.9 eV reported for trans-polyacetylene, which has been extensively studied because of its promise as a semiconductor.
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  • 162
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    Topics: Chemistry and Pharmacology , Physics
    Notes: A simulation has been made of the dielectric relaxation behavior of poly(n-hexylisocyanate) in solution covering the isotropic, biphasic, and anisotropic ranges. The simulation incorporates the Flory-Abe statistical mechanical theory for the phase behavior of rodlike macromolecules in solution and the Warchol, Vaughan, Wang, and Pecora theory for the dynamics of a rodlike molecule in a virtual cone prescribed by the neighboring molecules. It is shown that asymmetric Gaussian, Gaussian, or Poisson distributions of molecular weight do not lead to dielectric behavior of the type observed experimentally by Moscicki, Williams, and Aharoni but addition of a high-molecular-weight “tail” to such distributions and taking account of the dependence of relaxation time on molecular length gives a simulation of the dielectric increment Δε, the loss maximum ε″m, and frequency of maximum loss fm, which vary with polymer concentration in a manner entirely consistent with the experimental data.
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  • 163
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 605-611 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photon correlation spectroscopy is employed to study the slowly relaxing density and anisotropy fluctuations in bulk atactic polystyrene as a function of temperature from 100 to 160°C and pressure from 1 to 1330 bar. The light-scattering relaxation function is well described by the empirical function φ(t) = exp[-(t/τ)β], where for polystyrene β = 0.34. The average relaxation time is determined at each temperature and pressure according to 〈τ〉 = (τ/β)Γ(1/β) where Γ(x) is the gamma function. The data can be described by the empirical relation 〈τ〉 = 〈τ〉0 exp[(A + BP)/R(T - T0)] where R is the gas constant and T0 is the ideal glass transition temperature. The empirical constant A/R is in good agreement with that determined from the viscosity or the dielectric relaxation data (1934 K). The empirical constant B can be interpreted as the activation volume for the fundamental unit involved in the relaxation and is found to be comparable to one styrene subunit (100 mL/mol). The quantity B appears to be a weak function of temperature. The use of pressure as a tool in the study of light scattering near the glass transition now has been established.
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  • 164
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 625-645 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The most striking feature of the mechanism of thermal annealing of doubly oriented samples of low-density polyethylene (LDPE) and probably of high-density polyethylene (HDPE) is a progressive tilt of lamellar crystals around their crystallographic b axis. Such a rotation does not occur on thermal annealing in doubly oriented nylons. However, this rotation mechanism occurs during the thermal annealing of doubly oriented samples of nylon 11 in contact with a solvent below its dissolution temperature. As for oriented samples of polyethylene (PE), a correlation between the changes of macroscopic dimensions and long spacing obtained from the small-angle x-ray pattern is difficult to establish. In doubly oriented samples of nylon 11, the basal faces of the lamellar crystals are parallel to the a axis of the unit cell. Nevertheless, simple Miller indices cannot be assigned to the basal planes of the lamellae. On thermal annealing in formic acid, the basal planes of the lamellar crystals are, in some cases, parallel to (00l) planes. Annealing in formic acid at room temperature induces a phase transition: the chain c axis remains oriented along the rolling direction and the (00l) planes become parallel to the limiting planes of the lamellar crystals. Bulk doubly oriented samples of nylon 11 annealed in formic acid just below the “dissolution temperature” have the same texture of orientation as filter mats of single crystals grown from dilute solution; moreover, as these bulk specimens remain doubly oriented, they can be used for further physicochemical investigations. The usual interpretation of the small-angle x-ray pattern is also discussed on the basis of the results reported in this paper.
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  • 165
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 647-655 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The optical absorption spectrum of poly(methyl methacrylate) (PMMA) has been obtained in the wavelength range 570-780 nm via laser calorimetry (employing a dye laser source). Because of the low thermal conductivity of PMMA, the complete solution to the heat conduction equation (carried out numerically) was required in the analysis of the data. At the wavelength of minimum absorption (near 647 nm), the absorption coefficient had the value 153 dB/km.
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  • 166
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 657-665 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal expansivities along (α∥) and perpendicular (α⊥) to the draw direction of poly(methyl methacrylate) (PMMA) with extrusion draw ratios 1 ≤ λ ≤ 4 have been measured between 150 and 298 K. As λ was increased from 1 to 4, α∥ decreased 2-3 times, whereas α⊥ increased only 20-35%. The orientation function f calculated from thermal expansivity using the aggregate model is found to change linearly with birefringence, indicating that each property provides a sensitive measure of molecular orientation. For PMMA, however, only thermal expansivity can give an absolute f, with results at 150 K in reasonable agreement with previous studies using other techniques. At higher temperature, i.e., above ambient, PMMA side-group motions are excited, expanding volume, and calculations based on the aggregate model may not be valid.
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  • 167
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1251-1253 
    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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  • 168
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1255-1274 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A group of rodlike polymers soluble only in strong protic acids was studied using light scattering and viscosity techniques. These include poly(1,4-phenylene benzobisoxazole), poly(1,4-phenylene benzobisthiazole) and poly(1,4-phenylene terephthalamide). The solution properties were dependent on the ionic strength of the acid used as solvent. In a low ionic strength acid such as chlorosulfonic acid, the polymer solutions exhibited decreased unpolarized scattering, an extremely small translational diffusion coefficient, and high viscosity. All of these effects could be eliminated by the addition of a salt such as lithium chlorosulfonate, which increased the ionic strength of the solvent. The effects were attributed to a pseudo ordering of the polymer solvent system caused by electrostatic repulsions between protonated polymer chains effective over large distances (ca. 100 Å) in the low ionic strength solvent. This type of ordering is distinct from actual anisotropic phase formation, which occurs at higher concentrations in these systems. Analysis of data at infinite dilution gave a persistence length of at least 45 nm for poly(1,4-phenylene terephthalamide), larger than previous experimental results, but in accord with recent rotational isomeric state calculations and similar to experimental data for poly(p-benzamide).
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  • 169
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1313-1322 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As in the two-dimensional case, the density change due to crystallization leads to a buildup of internal strain in some regions of a polymer melt occluded by growing spherulites. The occluded parts of the sample are called “weak spots.” Computer simulation of spherulite growth in bulk samples shows that the largest weak spots have the size of an average spherulite. The total volumes of weak spots are 0.47, 0.094, and 0.119% of the sample for athermal, thermal, and mixed primary nucleation, respectively. The weak spots in the bulk material exhibit distance correlation. Within weak spots, internal strain is released (Raman spectroscopy), and holes develop. Polypropylene bulk spherulite samples contain holes distinctly visible under a microscope with infrared optics and illumination. The number of visible holes is in agreement with the computer prediction. The increase of impact strength with decreasing spherulite size is explained in terms of changes in the number and size of weak spots.
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  • 170
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1341-1346 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The longitudinal acoustic elastic modulus of polyethylene has been calculated with the aid of the ab initio crystal orbital method applying corrections also for electronic correlation effects. The basis set and correlation dependence of the elastic modulus have been investigated. The best theoretical value of 305 GPa of this modulus is in reasonable agreement with the published experimental values. At an elongation of ca. 0.1 the deviation from Hooke's law is found to be substantial.
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  • 171
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1381-1388 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A three-component system containing a polymer (2), a good solvent (1) for that polymer, and a second polymer (3) that is compatible with component (2) and isorefractive with the solvent (1) has been studied by static and dynamic light-scattering methods. In concentrated toluene (1) solutions of poly(vinyl methyl ether) (3), where appreciable chain overlap occurs and excluded-volume effects are reduced, polystyrene (2) may be studied in the dilute-solution limit. Consequently, these light-scattering measurements provide an explicit measure of both thermodynamic and hydrodynamic changes that occur as the total polymer concentration is increased from dilute to concentrated solution. Precise numerical coefficients, correct scaling exponents, the radius of gyration, and the effective hydrodynamic radius can be measured directly along with the observation of long-wave single-chain reptation motions and short-range cooperative motions in semidilute and concentrated solutions.
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  • 172
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1427-1438 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The linear thermal expansivity of poly(ethylene terephthalate) extruded at 50 and 90°C to extrusion ratios λ of 1-4.8 has been measured between 120 and 300 K. With increasing λ, the expansivity along the extrusion direction (α∥) decreases sharply, while that in the transverse direction (α⊥) shows a slight increase. For λ 〈 3, the large drop in α∥ and the accompanying increase in the axial Young's modulus E∥ can be ascribed to chain alignment in the crystalline regions and to an increase in number and tautness of intercrystalline tie chains. At higher λ, however, the crystalline orientation apparently becomes saturated, so that taut tie molecules are solely responsible for further changes in both α∥ and E∥. On the other hand, α⊥ is mainly determined by crystalline orientation for all λ, thus showing very little increase at large λ. For the highly oriented samples (λ ≥ 3), the Takayanagi model provides a reasonable description of the behavior of α∥ and α⊥.
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  • 173
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 413-424 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two crystal modifications are found in α-helical poly(δ-N-carbobenzoxy L-ornithine). In films as cast, the two-dimensional unit cell is pseudohexagonal and contains two chains. This form transforms irreversibly into a pseudotetragonal form at about 140°C. A second-order transition associated with the onset of the side-chain motion is observed at about 30°C for the bulk sample (by dilatometry) and for the crystalline phase (by x-ray diffraction). The dielectric behavior of the side-chain dispersion suggests that the side chains interact with one another. The temperature dependence of the infrared absorbance due to the NH stretching vibration reveals that about half the side chains are associated via hydrogen bonds at room temperature and become dissociated at higher temperature. The enthalpy and the entropy of the hydrogen bond formation is estimated to be ΔH = -5.0 ± 0.5 kcal mol-1 and ΔS = -15 ± 1 e.u. mol-1.
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  • 174
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 441-465 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diffusion and solubility coefficients have been determined for the CO2-, CH4-, C2H4-, and C3H8-polyethylene systems at temperatures of 5, 20, and 35°C and at gas pressures up to 40 atm. Diffusion coefficients were obtained from rates of gas absorption in polyethylene rods under isothermal-isobaric conditions by means of a new diffusivity apparatus. The concentration dependence of the diffusion coefficients was represented satisfactorily by Fujita's free-volume model, modified for semicrystalline polymers, while the solubility of all the penetrants in polyethylene was within the limit of Henry's law. Semiempirical correlations were found for the free-volume parameters in terms of physicochemical properties of the penetrant gases and the penetrant-polymer systems. These correlations, if confirmed, should permit the prediction of diffusion and permeability coefficients of other gases and of gas mixtures in polyethylene as functions of pressure and temperature.
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  • 175
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 483-492 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle electron scattering (SAES) has been used to examine the structure of crazes in polystyrene. It has been shown theoretically that the analysis of SAES is similar to the equivalent x-ray patterns (SAXS) except perhaps for the higher-angle scattering. A direct comparison of the SAES patterns from crazes in films of ca. 400 nm thickness with SAXS patterns from crazes in films of ca. 1 mm thickness has shown that the craze structures are similar in form for the thin and thick films but the fibrils are about three times larger in the thin films.
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  • 176
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 467-481 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Permeability coefficients have been measured for CO2, CH4, C2H4, and C3H8 in polyethylene membranes at temperatures of 5, 20, and 35°C and at applied gas pressures of up to 30 atm. The temperature and pressure dependence of the permeability coefficients was represented satisfactorily by an extension of Fujita's free-volume model of diffusion of small molecules in polymers. The results of the present steady-state permeability measurements provide further support for the conclusion reached from previous unsteady-state diffusivity measurements that Fujita's model is applicable to the transport of small molecules, such as CO2, CH4, C2H4, and C3H8, in polyethylene. It was previously thought that this model is applicable only to the transport of larger molecules, such as of organic vapors, in polymers.
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  • 177
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 493-504 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bounds on the elastic constants are derived for semicrystalline polymers whose local morphology is lamellar. Local response matrices (stiffness and compliance) are formulated in three dimensions that simultaneously incorporate uniform in-plane strain and additive forces from layer to layer of crystalline and amorphous phases and uniform stress and additive displacements normal to the lamellar surfaces. Spatial averaging of the stiffness and compliance matrices under the assumption of axially symmetric orientation gives the upper and lower bounds on the longitudinal and transverse tensile moduli and the axial and transverse shear moduli as functions of the separate phase elastic constants, the volume percent crystallinity, and the moments of the orientation 〈cos2θ〉 and 〈cos4θ〉. The bounds are much tighter than the Voight upper and Reuss lower bounds that do not recognize phase geometry. Using the known crystal elastic constants of polyethylene, sample calculations on isotropic unoriented materials show that the divergence of bounds at high crystallinity necessitated by the extreme crystal anisotropy shows up only at very high crystallinity. At low temperature the bounds are tight enough to specify G1, the amorphous modulus, from the measured G and the known crystal elastic constants. At higher temperatures and lower G, the bounds are not tight enough for this purpose but the shear modulus versus crystallinity and temperature data are well fitted by the lamellar lower bound using a temperature-dependent, crystallinity-independent G1.
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  • 178
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 505-514 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The problem of representing the dielectric constant of semicrystalline polymers in terms of the dielectric constants and volume fractions of the constitutent crystalline and amorphous phases is considered. For locally lamellar morphology, bounds based on uniform electric and displacement fields are derived. The equations also include the degree of crystal orientation as a parameter. For unoriented polymers the bounds are considerably tighter than the Hashin-Shtrikman bounds, the latter being the best possible without knowledge of phase geometries. The bounds presented here are sufficiently tight to represent the dielectric constant with practical accuracy for a number of examples of semicrystalline polymers. A treatment is also given of the dielectric constant where the lamellar morphology is further specified as being organized into spherulite-like structures. These bounds are somewhat tighter than the lamellar bounds.
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  • 179
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 515-522 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Methylol cellulose solutions in dimethylsulfoxide exhibit a viscosity maximum at 18% w/v followed by a minimum at 20%, as is characteristic of lyotropic liquid crystals. The biphasic solutions exhibit areas of clear and cloudy appearance. The latter are birefringent. The highly anisotropic solutions are uniformly briefringent and in the 25-33% w/v concentration region they are brightly colored. The optical rotations of the mesomorphic phases are high, indicating a cholesteric structure. The sign of the optical rotation depends on the solution concentration and at high concentrations (25+% w/v) varies with the area of the solution viewed.
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  • 180
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 573-581 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 13C NMR spectra of propylene-1-butene copolymers have been studied at 90.55 MHz. At this high field, many lines previously not resolvable were found to be sensitive to comonomer sequence distribution; these microstructures have been fully assigned. Each NMR spectrum was analyzed by a reaction probability model. Information available includes polymer composition, comonomer sequence distribution, and Markovian reaction probabilities. The use of this model reduces errors in the determination of sequence distribution and furthermore enables the product r1r2 of the reactivity ratios to be determined for the copolymer/catalyst system.
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  • 181
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 553-572 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When natural rubber crystallizes at low temperatures, there is an increase in elastic modulus of up to two orders of magnitude. This phenomenon has been studied at various temperatures in the range 0 to -55°C for samples held at tensile strains of up to 500%. There is an induction period associated with the nucleation of crystallites, before any increase in modulus is observed. The induction period increases with decreasing strain and passes through a minimum with increasing temperature at -25°C. The growth rate subsequent to nucleation is successfully described in terms of Avrami-type rate relationships. The Avrami rate coefficient is independent of temperature and follows a simple exponential function of strain. The equilibrium extent of the modulus increase has also been studied by means of experiments of up to three months' duration. The equilibrium modulus increases with decreasing temperature - as predicted by Flory's thermodynamic theory.
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  • 182
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 537-551 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ion implantation of impurities into thin films of poly(p-phenylene sulfide) (PPS) is found to increase the conductivity of the material by up to 12 orders of magnitude. The increase is stable under exposure to ambient conditions, in contrast to the instability of the conductivity increases in PPS produced by chemical doping with AsF5. PPS films 0.1-0.2 μm thick are spin cast from solution onto interdigitated electrodes patterned on an oxidized silicon substrate. The room-temperature interelectrode resistance is measured as a function of implantation fluence. An estimate of film conductivity is obtained from this resistance with a simple model for the electrode and film geometry. A first experiment yielded similar conductivity increases for implantation of either arsenic or krypton. At a fluence of 1 × 1016cm-;2, which corresponds to an average impurity concentration of 2.5 × 1021cm-3, the conductivity reaches an apparently saturated value of 1.5 × 10-5 (Ω cm)-1. Infrared spectra of the films before and after implantation suggest that crosslinking may be present in the implanted films, and Auger studies show stoichiometric changes throughout the implanted layer. These results suggest that the observed conductivity changes are the result of molecular rearrangements produced by the implantation rather than the result of specific chemical doping. Specific chemical doping may, however, explain the results of a second experiment in which implantation of bromine resulted in substantially larger conductivities found to increase at an approximate linear rate from a value of 1.0 × 10-4 (Ω cm)-1 at a fluence of 1 × 1016 cm-2 to a value of 4.0 × 10-4 (Ω cm)-1 at a fluence of 3.16 × 1016 cm-2.
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  • 183
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 595-603 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic mechanical and optical transparency methods were used to investigate the compatibility of a series of blends of sulfonated cis-1,4-polyisoprene and styrene/4-vinylpyridine copolymers. It was found that compatibilization occurs at a degree of substitution less than 5%. It is suggested that proton transfer from the sulfonic acid group to vinyl pyridine, which results in the generation of specific anion-cation interactions, is responsible for the compatibilization, since the removal of ionic interactions through esterification destroys the compatibility.
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  • 184
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 613-623 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(methyl methacrylate) (PMMA) has been studied by photon correlation spectroscopy in the temperature range 120-150°C. The relaxation functions for longitudinal density fluctuations were determined and analyzed using the empirical function φ(t) = exp[-(t/τ)β]. The average relaxation times were calculated for each temperature and compared to mechanical and dielectric relaxation data. The agreement between the various techniques for the primary glass-rubber relaxation was good. The relaxation function observed by light scattering became increasingly broad as the temperature was lowered. This is similar to the results reported previously for poly(ethyl methacrylate) (PEMA). In fact, the light-scattering relaxation function is dominated by the secondary relaxations in these two polymers. Nevertheless, the average relaxation time 〈τ〉 is dominated by the longest relaxation times associated with the primary glass-rubber relaxation.
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  • 185
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 667-684 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscosity η0(M) of polymeric liquids of molecular weight M is calculated on the basis of the tube model formulated by Doi and Edwards (ref. 3). The contour length fluctuation of polymers along the tube, which was neglected in ref. 3, is now explicitly taken into account. The result is where Mc = 2Me, and Me is the molecular weight between the entanglement points. This result is numerically close to the empirical 3.4-power law, η0(M) = η0(Mc)(M/Mc)3.4, for 10Mc ≲ M ≲ 100Mc but approaches the result in ref. 3 for very high molecular weight. We thus conclude that the 3.4-power law is actually an approximate expression for the real curve which slowly approaches the asymptotic form calculated in ref. 3.
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  • 186
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 685-697 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electron-beam-induced conductivity (EBIC) studies were carried out on fluorinated ethylene propylene copolymer (FEP) and its acrylonitrile graft copolymer (FEP-g-AN). The current transport parallel to the surface under the influence of an electron beam of medium energy (6-30 keV) is reported. The gain in EBIC is calculated and its characteristic variation as a function of beam energy is studied. Minima in the gain versus energy curves have been obtained around 21 keV for FEP, 12 and 18 keV for FEP-g-AN, and 12 keV for polyacrylonitrile (PAN). This behavior is explained by assuming the existence of electron trapping bands close to the surface, at characteristic distances below the surface of the polymeric film corresponding to the range of incident electrons. Gains of the order of 5, 12, and 30 have been obtained respectively for FEP, FEP-g-AN, and PAN for the maximum energy of incident electrons used.
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  • 187
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 699-716 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The impact fracture mechanisms of rubber-toughened nylon are analyzed by measuring the energy dissipated in several different processes during notched fracture. An energy balance is thus established for the impact fracture. The stress-whitened zone is shown to be the energy dissipation zone, having an energy dissipation density of 5.30 cal/g. About 25% (i.e., 1.44 cal/g) of the impact energy is dissipated by matrix crazing. About 75% (i.e., 3.86 cal/g) is dissipated as heat by matrix yielding, causing a temperature rise of 9.1 °C in the energy dissipation zone. Surface energy storage on the fracture surfaces is negligible (i.e., 1.45 × 10-5 cal/g). During matrix yielding, about 12% of α-triclinic nylon crystals is transformed into pseudohexagonal crystals.
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  • 188
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1173-1185 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Elastomeric networks were prepared from polydimethylsilmethylene (PDMSM) [—Si(CH3)2CH2—], a polymer closely related to polydimethylsiloxane (PDMSO) [—Si(CH3)2O—] and polyisobutylene (PIB) [—C(CH3)2CH2—]. The birefringence of PDMSM in elongation was found to be qualitatively similar to that of PDMSO, in that there was no evidence for strain-induced crystallization. However, the values of the optical-configuration parameter Δa were considerably larger, and both Δa and its temperature coefficient are essentially the same as those of PIB. Swelling the PDMSM networks generally decreased Δa; the largest decreases, obtained as expected with the most nearly symmetrical diluent, were also approximately the same as those observed for PIB. Use of cyclic PDMSO pentamer as diluent in a PDMSM network was found to increase the birefringence, presumably because of orientational effects. Various network-diluent combinations involving the significantly anisotropic PDMSM and the more nearly isotropic PDMSO should be extremely useful for elucidating the nature of these intermolecular correlations. Results obtained from rotational isomeric state theory considerably underestimate both Δa and its temperature coefficient for PDMSM, as they do for PIB. Although the origin of the discrepancy is not necessarily the same for both polymers, the results on PDMSM suggest that the discrepancy for PIB is not due to the severe steric congestion known to be present in this polymer.
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  • 189
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1195-1203 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric methods have been employed to study the high-pressure behavior of a polyurethane elastomer (Solithane 113) in the vicinity of its α transition. The α-loss peak is shifted to higher temperatures and broadened somewhat with the application of hydrostatic pressure up to 6.4 kbars. The slope of Tα vs. P, or dTα/dP, obtained at low frequencies was found to be equal to dTg/dP obtained by a volumetric method. Moreover, it attained a nonzero limiting value at high pressures for each frequency tested (3 - 30,000 Hz) and the limiting value itself increased with increasing frequency from 10.5°C/kbar at 3 Hz to 18°C/kbar at 30,000 Hz. The activation enthalpy ΔH* was found to be nearly constant over the pressure range tested, but the activation volume ΔV* decreased with increasing pressure. The relation dTα/dP = T (ΔV*/ΔH*) was shown to hold for the elastomer.
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  • 190
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1187-1194 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theoretical study is made of three-phase separation in a ternary solution consisting of a pure solvent and two homologous monodisperse polymers with relative chain lengths P1 and P2. The Flory - Huggins interaction parameter X is assumed to depend linearly on the volume fraction φ of the polymer mixture: χ = χ0(T) + k(T)φ. For a given P1 the ratio of P2 to P1 for the onset of three-phase separation increases with an increase in k, first gradually and then sharply. Loci of critical points for this condition on the χ0 vs. φ diagram are determined for a series of fixed values of P1 and their significance is discussed.
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  • 191
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1205-1216 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of the viscosity coefficient η of solutions of polystyrene (Mw = 6.0 × 105 and 1.77 × 106) in trans-decalin (TD, θ solvent) and toluene (TL, good solvent) as function of shear rate (11-104 s-1), concentration (4.24-11.21 wt %), and temperature (10-50°C) are reported. As a new theoretically grounded method for the determination of the zero-shear viscosity η0 it is proposed to plot η as a function of $\left({\eta \dot \gamma} \right)^3$. The intercepts of the straight lines obtained by this procedure give η0 in good agreement with directly measured values.
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  • 192
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1243-1246 
    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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  • 193
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1247-1249 
    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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  • 194
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1227-1242 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We consider the variation of the coherent elastic scattering structure factor S(q) with momentum transfer q for a solution of block copolymers at finite concentration. We introduce the effect of concentration using a generalization of Zimm's model to copolymers which enables us to express intermolecular scattering functions in terms of intramolecular form factors only. We show that the shape of the scattering curve is very sensitive to the polymer concentration as well as to the contrast factors, the relative composition of co units, and the second virial coefficients characterizing constituents of the copolymer. In particular, we show that the scattering curve develops a maximum at low q for certain values of these parameters. We also discuss the variation of the apparent radius of gyration with polymer concentration.
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  • 195
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1217-1226 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscosity data of moderately concentrated polystyrene solutions in trans-decalin (TD) (θ solvent, θ temperature 21°C) and toluene (TL) (good solvent) reported in Part I are discussed in terms of Graessley's entanglement theory. Under good solvent conditions, Graessley's master curve provides an excellent fit up to high shear rates, whereas in the vicinity of the θ conditions the data have to be modified by a parameter ηfric introduced by Ito and Shishido. The characteristic time of mechanical response to flow of chains approximately given by the shift factor τ0 is found in good solvents to be on the order of the Rouse relaxation time. In poor solvents, close to demixing, τ0 tends to much higher values, indicating a reduced chain mobility. The influence of temperature on the viscosity decreases with increasing shear. The resulting apparent energy of activation of flow shows very small or even negative values at high shear rates. This behavior can be explained by the modified Graessley theory, however, in a quite natural way.
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  • 196
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1275-1298 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Steady-state permeability coefficients have been measured for equimolar mixtures of CO2-C2H4, CO2-C3H8, and C2H4-C3H8, as well as for a mixture of 74.9 mol % CO2 and 25.1 mol % C2H4 in polyethylene membranes. The measurements were made at 20, 35, and 50°C and at pressures of up to 28 atm. Each component of the permeating mixtures studied had the effect of increasing the permeability coefficient for the other component. Furthermore, at equal partial pressures and at the same temperature, the component exhibiting the highest solubility in the polymer had the largest effect in increasing the permeability coefficient of the other component. This behavior is in agreement with the predictions of a free-volume model for the permeation of gas mixtures proposed by Fang, Stern, and Frisch. From a quantitative viewpoint, the permeability coefficients for the components of the mixtures agreed, on the average, to better than 25% with the predicted values. The theoretical permeability coefficients can be estimated from the model by using parameters determined with the pure components only.
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  • 197
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1299-1312 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two-dimensional spherulite growth leads to the encirclement of regions of molten polymer in a polymer film. On further crystallization localized volume defects arise, resulting in thin spots in the film. Since this effect lowers the mechanical strength of films, we call these volume defects “weak spots.” A computer program is developed to evaluate the number, size, and shape of such volume defects for athermal, thermal, and mixed modes of primary nucleation of spherulites. It is shown that the total area of weak spots exceeds 10% of the sample area for all types of nucleation studied. The largest weak spots arise in samples crystallized via athermal and mixed nucleation; their size is of the same order as that of an average spherulite. Formation of weak spots is observed in thin films of poly(ethylene oxide) and poly(methylene oxide). The disadvantageous role of weak spots is confirmed by observation of electric breakdown occurring preferentially in weak spots in polypropylene films.
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  • 198
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1347-1356 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoluminescence (TL) has been observed in γ-irradiated extended-chain crystals of polyethylene above room temperature. The TL curve, which exhibits four peaks at 50, 90, 120, and 140°C, is different from that given by folded-chain crystals, in both shape and intensity. In particular, a shape, strong glow peak is observed at 140°C, corresponding to the melting temperature of the extended chain crystals. These results are discussed in relation to independent measurements by differential scanning calorimetry and electron spin resonance.
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  • 199
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1357-1380 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel theoretical scheme is developed which enables the determination of the LAM-like vibrations of polymer chains made up of crystalline and amorphous parts as they occur in partially crystalline structures. The boundary conditions effective at the junction points are formulated in terms of the compliances of the associated amorphous sequences. These compliances can be derived from their eigenfrequencies and eigenvectors in a disconnected state. The treatment uses a matrix formalism which can be extended to include bending and torsional motions in a general state of vibration of the crystalline stem. A first numerical example demonstrates that the LA mode of a crystalline stem can be strongly perturbed by the coupling to the adjacent amorphous sequences. Interpretation of frequencies and line shapes of observed LA modes should always include these coupling effects; their neglect can lead to considerable errors.
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  • 200
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1389-1401 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nafion membranes neutralized with Ni2+ have been examined by extended x-ray absorption fine-structure (EXAFS) and x-ray absorption near-edge-structure (XANES) spectroscopy. The results indicate that in both the dry and water-soaked membranes, the nickel is in an octahedral site with six oxygen atoms as nearest neighbors. The degree of disorder in the Ni—O distance is comparable to that in ionic crystals in both the dry and hydrated materials. A contribution from a second shell of neighbors is very weak in the dry samples but, surprisingly, this contribution is strongly accentuated in the hydrated membranes. The data indicate that this contribution is due to neighboring Ni2+ cations. Thus the water absorption seems to enhance the local ordering of the cation environment. The local structure does not depend strongly on the concentration of ionic groups in the materials.
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