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  • Physics  (538)
  • 1980-1984  (538)
  • 1945-1949
  • 1930-1934
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  • 1983  (538)
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 11-27 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The objective of this research was to study the structure-property relationships of two poly(vinyl chloride) (PVC)-poly(butadiene-co-acrylonitrile) (BAN) blends which exhibit differences in blend compatibility. Studies were carried out utilizing differential scanning calorimetry, dynamic mechanical testing, stress-strain, transmission electron microscopy (TEM), and infrared dichroism experiments at different temperatures. The BAN 31/PVC (BAN containing 31% acrylonitrile) system is considered to be nearly compatible as evidenced by Tg shifts, stress-strain results, orientation characteristics, and TEM micrographs. Similar experiments indicate that the BAN 44/PVC system is incompatible, and contains a mixed phase of BAN 44-PVC and a pure BAN 44 phase. The extent of heterogeneity in the compatible BAN 31/PVC system, however, plays an important role in the orientation characteristics of the blends.
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  • 2
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1-9 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Integrated optical techniques and resonance Raman spectroscopy have been combined to investigate the intermolecular interactions at dye/polymer and dye/glass interfaces. Frequency shifts and intensity changes of bands assigned to the stretching vibrations of the bridged quinoline rings of the cyanine dye chromophore have been utilized to gain insight into the relative strength of adhesive forces at the surface. Polarized Raman measurements were made to determine the orientation of the chromophores on a poly(vinyl alcohol) surface. This was done to assess the possibility of hydrogen bond formation between the ring nitrogen atoms and the polar hydroxyl groups at the surface.
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  • 3
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 45-53 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theory of stress-induced crystallization is broadened to include a reshuffling of crosslink positions as a result of changing sizes of crystalline domains and multiple crystallites of varying lateral dimensions (i.e., lateral growth). A continuous state of equilibrium throughout the amorphous component of the stretched network is postulated and, consequently, effected by requiring crosslinks to anchor about their most probable locations, which vary continuously as crystallization changes. Such features incorporated into Flory's model of stress-induced crystallization broaden its theoretical base, placing it on a stronger, more realistic foundation.
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  • 4
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 55-63 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theory of crystallization in stretched polymer networks is developed. In it, four principal features are incorporated: (i) crosslinks are displaced by growing crystallites, (ii) network chains are constrained to positions compatible with fixed sample shape and volume, (iii) some network chains remain amorphous, and (iv) the relative direction of a chain through a crystallite may not be the same for all chains. The derived network force exhibits a V or U shape with changing temperature in the crystallization zone that is a close replica of the behavior of gutta percha networks. Postulates of fibrillar-lamellar transitions are not introduced into the calculations.
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  • 5
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 65-95 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure-property relationships of polycaprolactone-based segmented polyurethanes were studied using differential scanning calorimetry (DSC), small-angle x-ray scattering (SAXS), wide-angle x-ray diffraction (WAXD), dynamic mechanical, and stress-strain testing. The materials studied varied in hard-segment type [4,4′-diphenylmethane diisocyanate/butanediol (MDI/BD) or 4,4′-dicyclohexyl methane diisocyanate/butanediol (H12MDI/BD)], soft-segment molecular weight (830 or 2000 MW polycaprolactone), hard-segment content (23-77% by weight), and thermal history. The materials with aromatic (MDI/BD) hard segments had semicrystalline hard-segment domains, while the materials with aliphatic (H12MDI/BD) hard segment had mostly amorphous domains. Materials with the shorter polycaprolactone soft segment (830 MW) exhibited thermal and mechanical behavior which indicated a considerable degree of hard- and soft-segment compatibility. The materials which contained a 2000-MW polycaprolactone soft segment exhibited better-defined microphase separation. SAXS was used to characterize the microphase structure of each system. The effects of hard-segment content and soft-segment molecular weight were similar for the aromatic (MDI) and aliphatic (H12MDI) hard-segment-based block copolymers. Changing the hard segment from aromatic to aliphatic gave materials with larger interfacial area and slightly higher tensile strength. A range of morphologies between isolated hard domains in a rubbery matrix and isolated rubbery domains in a hard matrix was observed.
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  • 6
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 111-121 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The decay of free radicals produced in polybutadiene, polystyrene, and block copolymers of butadiene and styrene by γ irradiation at 77 K has been studied at -110°C in the case of polybutadiene and at -95°C for the other samples. The free-radical decay rate is best interpreted in terms of an equation based on a second-order decay mechanism of a fraction of the free radicals decaying in the presence of other nondecaying free radicals. Hydrogen gas accelerates the free-radical decay. Increase of radiation dose increases the fraction of the radicals that decay, while increase of the fraction of styrene segments decreases the decaying fraction. In pure polybutadiene the higher the cis content, the greater fraction of decaying free radicals, but the second-order decay constant is less in the high-cis-content polybutadiene and is also less at the higher dose, probably owing to the hindrance of the radiation-produced crosslinks on the free-radical decay. The decrease of the second-order constant with increase of dose is also true for all the block copolymers studied.
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  • 7
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 141-150 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The transitions of poly(oxy-2,2′-dimethylazoxybenzene-4,4′-diyloxydodecanedioyl) (PDAD) have been analyzed by differential scanning calorimetry, optical microscopy, and light scattering. The mesophase glass devitrifies at 288 K [ΔCp = 220 J/K mol]. Crystallization from the liquid mesophase can be described between 322 and 362 K by an Avrami expression with an exponent between 3 and 4. Results of light scattering and optical microscopy are in accord with a spherulitic morphology grown after athermal nucleation. Melting of the semicrystalline samples (crystallinity up to 58%) occurs at about 391 K. The heat of fusion of the completely crystalline sample is calculated to be only 13.55 kJ/mol. The mesophase to isotropic phase transition occurs at 418 K with a heat of transition of 4.1 kJ/mol. A general discussion of these transitions is given.
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  • 8
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 159-162 
    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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  • 9
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 189-195 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dilute-solution properties of six poly(tetrahydro-4H-pyranyl-2-methacrylate) (PTHPM) fractions covering the molecular weight (Mw) range 4.8 × 104 to 8.4 × 105 (Mw/Mn = 1.2-1.4) were studied in tetrahydrofuran, a good solvent, and in isobutanol, a θ solvent a t 30.5°C as determined by light scattering from the A2 vs. T plot. The unperturbed dimensions were calculated from a low-angle laser light-scattering and intrinsic-viscosity data. The results indicate that PTHPM is less extended chain than poly(cyclohexyl methacrylate) (PCyM). The higher flexibility of PTHPM parallels the lower T, (57°C) of this polymer relative to PCyM (66°C).
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  • 10
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 233-240 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Differential scanning calorimetry was used to determine the miscibility behavior of several polyester/Saran blends, the two polymers forming these blends being semicrystalline. It was found that Saran is miscible with polycaprolactone (PCL), polyvalerolactone, poly(butylene adipate), and poly(hexamethylene sebacate) since a single glass transition temperature Tg was observed at each composition. However, immiscibility was found between Saran and poly(ethylene adipate), poly-(ethylene succinate), poly(β-propiolactone), and poly(α-methyl-α-n-propyl-β-propiolactone) since two Tg's were recorded at several compositions. Blends were then obtained containing, over a wide range of composition, a miscible amorphous phase and two different types of crystals. From melting-point depression data on PCL and Saran crystals, thermodynamic interaction parameters χ were calculated and found to be different for PCL-rich blends and for Saran-rich blends. This result suggests a variation of χ with composition. Saran is a polymer which does not contain α-hydrogens and its miscibility with polyesters may result from a β-hydrogen bonding interaction or a C=O/C—Cl dipole-dipole interaction.
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  • 11
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 241-249 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In a search for a liquid-liquid transition in the melt of polystyrene, we have measured and analyzed a number of compression isotherms to 1800 kg/cm2 in a relevant temperature range (1.2Tg 〈 T 〈 1.4Tg). Volume data were recorded at pressure intervals of 10 kg/cm2, i.e., at pressure intervals 5-20 times smaller than used in previous work. For the analysis the data were fitted to the Tait equation. Deviations between fits and data are small, typically 0.0004 cm3/g, but nonrandom. From the absence of any systematic shifts of the nonrandom deviation patterns with temperature, we conclude that the deviations are not manifestations of a pressure-dependent liquid-liquid transition, and that there is, in fact, no evidence for the existence of such a transition in our data.
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  • 12
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 197-212 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The earlier calculations of Moscicki and Williams of the phase behavior of rodlike macromolecules in solution incorporating a Gaussian distribution of rod lengths have been extended to include, in addition to a “basic” Gaussian distribution, a small amount of high-molecular-weight species which are characterized by a δ-function or “box-function” distribution. It is shown that C*p, the concentration of polymer at which the biphasic material (isotropic plus anisotropic phase) first appears may be substantially lowered in comparison with that for the system comprising only the basic distribution. The volume fraction ΦA of anisotropic phase, the compositions of the two phases, and the distribution of species between the phases are calculated for a range of polymer concentration which spans the isotropic, biphasic, and anisotropic phase and, among several features obtained, it is shown that the high-molecular-weight species are essentially responsible for the initial formation of anisotropic phase in the biphasic system. The results of the calculations have important implications for the interpretation of published dielectric relaxation data for polyalkylisocyanates in solution at high concentration and for published shear-flow viscosity data for polyalkylisocyanates and poly(p-benzamide) in solution at high concentration and these are discussed in some detail.
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  • 13
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 263-274 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The roles of both anisotropic motion and the interdependence of multiple motions in leading to nonexponential correlation functions for NMR relaxation data are explored. A motional model is developed in which rotational motions of segments of various lengths are controlled by the formation and disappearance of a suitable conformation. Such a model gives correlation functions which can be made, through adjustment of parameters, to be almost identical to correlation functions from other, quite different, models. The ability of NMR relaxation data to identify unique motional models is thus questioned.
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  • 14
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 251-262 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Investigations were carried out on the polymer particle morphology obtained in the early stages of radiation-induced bulk polymerization of vinyl chloride with solvent added in small amounts over the temperature range of -10 to 70°C under quiescent conditions. At low temperatures, when the polymerization is carried out in the absence of solvent, there is flocculation of irregular aggregates of two types depending on polymerization conditions: (i) small primary particles that remain finely dispersed and (ii) large flocs that undergo rapid sedimentation. By addition of increasing amounts of solvent a gradual change towards single small spherical particles that remain finely dispersed is obtained. With more than 3% w/w THF, spherical particles in latexlike dispersions are obtained in polymerizations at -10 and 22.8°C, and show a small change in size with increasing amounts of THF. In the high-temperature range, 50-70°C, where spherical particles can be obtained in the absence of solvent, no significant changes are produced by addition of THF. The results are discussed in the terms of a marked increase in particle plasticization by the solvent, enabling the coalescence of flocculated particles of small size to occur also in polymerization at low temperature.
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  • 15
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 275-284 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray diffraction studies of fibers of the polyester/ether poly(ethylene-1,2-diphenoxyethane-p,p′ -dicarboxylate) (PEET) produced by high-speed melt spinning show the existence of two polymorphic forms, designated α and β, in the solid state. The α form is obtained by annealing filaments melt spun at takeup speeds below 3000 m/min and is also found in samples crystallized from the melt and from dilute solutions. The α form has a monoclinic unit cell with dimensions a = 7.83, b = 10.33, c = 18.68 Å, and β = 83.1°. The equilibrium melting temperature and heat of fusion of the α form are 288.3°C and 19.1 cal/g, respectively. The β form predominates in highly oriented filaments obtained at takeup velocities above 6000 m/min. The unit cell is orthorhombic with dimensions a = 7.28, b = 5.65, and c = 18.64 Å. The β form does not transform to the α form on annealing.
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  • 16
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 285-294 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An analysis of the Raman internal modes of dilute-solution-crystallized homopolymers and co-polymers of ethylene has been made, similar to the work previously reported for the bulk-crystallized polymers. The crystallite structure can be described in terms of the relative amounts of the crystalline orthorhombic phase, the liquidlike amorphous phase, and the interfacial region. These quantities change with the molecular constitution of the chains and the crystallization conditions. The level of crystallinity decreases significantly with increasing counit content as would be expected. In addition, an appreciable interfacial structure develops in copolymers as compared with the homopolymers. A possible relationship between the interfacial content and the relaxation transitions in polyethylene is discussed.
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  • 17
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 295-299 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By use of the Clapeyron equation for the dependence of the melting point on pressure, the heat of fusion was found to be 32.5 cal/g, in good agreement with values determined by other methods. An equation for the dependence of the melting point on the degree of polymerization gave a heat of fusion of 27.6 cal/g when applied to hydroxyl-terminated oligomers. This simple relation applied all the way down to the smallest member of the series, di(hydroxy ethyl) terephthalate.
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  • 18
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 301-308 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Annealing studies of the calcium salt of an ethylene-methacrylic acid copolymer are reported. Fourier-transform infrared spectroscopy and differential scanning calorimetry were applied to the investigation of the effect of polyethylene crystallization on ionic structure as a function of annealing temperature and time. The spectroscopic changes observed in the spectra of the calcium salt annealed at 80°C differ from those seen in the spectra of the calcium salt annealed at room temperature. These changes are interpreted in terms of the multiplet-cluster model and the effect of the polyethylene-type crystallinity on the ionic microstructure.
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  • 19
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 309-317 
    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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  • 20
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 321-328 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Potential-energy calculations are performed in order to obtain satisfactory models for folding in single crystals of polytetrafluoroethylene crystallized in the phase stable below 19°C. The folds are assumed to be tight with adjacent reentry. Folds with a variable number of bonds are analyzed. Their conformation is deduced by a method which obtains closure between two semifolds into which each fold is decomposed. The allowed models are subsequently investigated by using an energy minimization program. Some possible models are proposed. The calculations show that the folds must be described by a number of rotational isomeric states higher than is usually assumed.
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  • 21
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 353-365 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Vapor pressures and densities of solutions of poly(tetramethylene oxide) fractions (molecular weights 650, 1000, and 2000) in 1, 4-dioxane have been determined at 30 and 40°C. The data have been utilized to determine the activities and thermodynamic functions of dilution. Excess volumes have been determined from the density data. Flory's equation of state theory quantitatively predicts the reduced residual functions X, Xh, and Xs. Predicted as well as experimental values of Xs are found to be negative. The theory predicts correctly the sign of the excess volume but quantitative agreement between theory and experiment is not obtained.
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  • 22
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 367-378 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Blends of poly(butylene terephthalate) (PBT) and a copolyester of bisphenol-A with 50% terephthalate-50% isophthalate (PAr), before and after transesterification, have been studied by thermal and dynamic mechanical tests to determine crystallinity and phase behavior. Blends without transesterification, as prepared by solution precipitation, show a single Tg, indicating amorphous miscibility of PBT and PAr. A melting-point depression for PBT crystals is not observed; this means that PBT crystallizes excluding PAr and the entropy of melting is small. The highest fractional crystallinity for PBT is obtained at 20-35% of PAr. Transesterified blends were obtained by holding the physical blends at 250°C for up to 16 h. The transesterified systems show higher Tg's than the corresponding physical blends and also show a marked melting-point depression and lesser PBT crystallinity at the corresponding increased PAr content.
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  • 23
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 329-352 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic x-ray diffraction is conducted to explore the structural origin of the α and β mechanical dispersions of a melt-crystallized high-density polyethylene. It is shown that the real component of the strain orientation coefficient for the crystal c axis C′c decreases with increasing frequency at a rate which decreases with decreasing temperature. Values of C′c for the c axis are positive, C′a for the a axis negative, and C′b for the b axis close to zero, suggesting that the predominant relaxation process is crystal rotation about the b axis. The activation energy found from Arrhenius plots of C*k corresponds to that of the α1 mechanical dispersion. The dynamic birefringence in this region is dominated by the contribution from crystal orientation changes. At low temperatures, the imaginary component KC″cr of the strain-optical coefficient of the crystal phase approaches zero, while KC″am of the amorphous phase exhibits a somewhat broad dispersion peak corresponding to the β birefringence dispersion. This suggests that the principal contribution to the β birefringence dispersion arises from the amorphous phase, probably owing to the amorphous orientation process. Contrary to the case of low-density polyethylene, the dynamic crystal lattice deformation and compliance functions reveal distinct frequency dispersions corresponding to the α1 and α2 mechanical processes. The α1 lattice dispersion is thought to be associated with the α1 crystal orientation dispersion, while the α2 lattice dispersion is believed to be the inherent one arising from the onset of intracrystalline chain motions.
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  • 24
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 379-387 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phase transition behavior and the structural properties of a thermotropic polyester, poly-(chloro-1,4-phenylene-trans-1,4-cyclohexanedicarboxylate), were studied by differential scanning calorimetry, x-ray diffraction, polarized-light microscopy, and electron microscopy. The polyester shows two first-order transitions in heating, i.e., a crystal-crystal transition and a crystal-liquid-crystal transition at 190-220 and 300-330°C, respectively. The texture in the liquid-crystalline phase is very similar to that of nematic low-molecular-weight materials. Oriented films of the polyester can be obtained from the liquid-crystalline state. Many fibrils occur in a fractured lateral surface of the film. Bandlike structures 50-100 nm wide were observed in surfaces of both oriented and unoriented films. The direction of the polymer chain axis is almost perpendicular to that of band elongation. In the oriented film, the band structures are perpendicular to the direction of orientation.
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  • 25
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 389-400 
    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 initial morphology and extrusion temperature on the orientational anisotropy and conformational changes on coextrusion drawing of poly(ethylene terephthalate) (PET) have been determined by Fourier-transform polarized infrared spectroscopy. The samples were drawn from both amorphous and semicrystalline (50%) PET at 50 and 90°C. A strong influence of coextrusion drawing temperature was observed for overall chain orientation evaluated from the dichroic ratio of the 795-cm-1 band for the samples prepared from the amorphous state: this dependence was less prominent in samples drawn from the semicrystalline state. Under the same drawing conditions, the dichroic ratio for the 973-cm-1 trans band for samples prepared from the amorphous state was higher than from the semicrystalline state. Furthermore, in all samples, the relative intensity of this band was almost proportional to the degree of crystallinity. In all samples, the gauche content, evaluated from the 896-cm-1 band, decreased with increasing draw ratio. However, the dichroic ratio of this band was near unity regardless of draw ratio, initial morphology, or extrusion temperature. From these results it is considered that all gauche units in the amorphous phase are almost isotropic in the extrusion-drawn samples with overall orientation arising largely from the crystalline chains possessing totally the trans conformation (973 cm-1) in its content. In order to evaluate the deformation mechanism of the coextrusion drawing method, the relationship between the bulk and film surface orientation is also reported.
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  • 26
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 765-771 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The longitudinal piezoelectric strain of poly(vinylidene fluoride) (PVF2) films has been measured at room temperature using a high-sensitivity ac capacitance-type dilatometer. The dc bias field dependence of the piezoelectric strain coefficient d33 has been determined. The polarization-related electrostrictive coefficient Q33 obtained is several hundred times larger than the value in normal piezoelectric oxide crystals and is of opposite sign.
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  • 27
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 753-763 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Permeability data are reported for carbon dioxide in Lexan polycarbonate at 35°C. Measurements were made for both pure carbon dioxide and for a mixed feed consisting of carbon dioxide with a 117.8-torr (0.155-atm) Partial pressure of isopentane. The effects of varying upstream CO2 driving pressure from 1 up to 20 atm were studied. The permeability to CO2 is reduced significantly in the presence of isopentane; however, the fractional depression of the CO2 permeability due to the isopentane at low driving pressures is much more significant than at high CO2 driving pressures. The well-known pressure dependence of carbon dioxide permeabilities in glassy polymers, therefore, is largely diminished by introducing isopentane to the pure carbon dioxide feed. These observations are consistent with a model for transport in glassy polymers which explains the observed trends in terms of competition between the two penetrants for microvoid sorption sites existing in the non-equilibrium glassy polymer. Exclusion of carbon dioxide from microvoid sorption sites by the more condensable isopentane preempts transport through the microvoid regions, resulting in the observed depression of the CO2 permeability.
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  • 28
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 725-752 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The five independent elastic constants C11, C12, C13, C33, and C44 for uniaxially drawn polypropylene with draw ratios 1 〈 λ ≤ 20 have been measured from -40 to 130°C by an ultrasonic method (2.5 MHz). The crystalline and amorphous orientation functions fc and fa were also determined from wide-angle x-ray diffraction and birefringence; fc increases sharply at low λ and becomes saturated above λ = 8, but fa increases monotonically up to λ = 20. Below the glass transition temperature (ca. 60°C at 2.5 MHz) only the axial longitudinal and tensile moduli, C33 and E0, show large increase. At 110°C, however, all the moduli increase with λ; E0, E90 (tranverse tensile modulus), C44 (axial shear modulus), and C66 (tranverse shear modulus) increase 30, 3, 5, and 2.5 times, respectively, as λ increases from 1 to 20. The improvement in the mechanical properties can be attributed to the increase in the fraction of taut tie molecules which was monitored by fa. The results were analyzed in terms of the two-phase models of Takayanagi and Seferis et al. The effects of annealing were also studied.
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  • 29
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 773-786 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The proposion of Clark and Zimm that a dashpot and a spring can be used in place of a set of rotational barriers in polymer dynamics is studied. The simplest possible case is examined here, that of a single rotor. Reasons for altering the Clark-Zimm diffusion equation are presented and an alternative diffusion equation is proposed. The results of both diffusion equations for the correlation function 〈exp[-iθ(0)] exp[iθ(t)]〉 (θ is the angular position of the rotor) are compared with the correlation function for a rotor in an n-fold cosine potential. Although the two diffusion equations differ, both agree well with the n-fold cosine model for barriers above a few kBT. This agreement is obtained in the absence of adjustable parameters, and motivates the application of these two diffusion equations to polymeric systems.
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  • 30
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 831-833 
    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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  • 31
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 807-820 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A polynomial subdistribution method for analyzing the correlation profile in photon correlation spectroscopy of polymer solutions is described. This method generates a continuous distribution function from the measured photoelectron time-correlation function, which can be related to particle size or molecular weight distribution of solute. The method is tested using simulated data for unimodal and bimodal distributions and compared with cumulant and histogram methods, respectively. The polynomial subdistribution method has an advantage in that it not only generates a continuous distribution curve but also works well for bimodal distributions whose peaks are close together.
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  • 32
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 787-806 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The assumption of Clark and Zimm that coupled dashpots and springs can be used to model the dynamics of polymer molecules is here applied to a model different from that of Clark and Zimm. The precise differences are given in the preceding paper. The dielectric relaxation spectrum of the model is computed in time and frequency domains. The relaxation spectrum can be fitted reasonably well by the empirical Williams-Watts and Havriliak-Negami functions. The best-fit Williams-Watts and Havriliak-Negami parameters are given as functions of the parameters of the model. The model is compared with several related models found in the literature and possible interpretations are given.
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  • 33
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 821-830 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the course of melt-flow crystallization studies with ultrahigh-molecular-weight polyethylene (UHMWPE), we observed that the melt of UHMWPE is highly anisotropic above its equilibrium melting point and has a tendency to fibrillate. An examination of the melt anisotropy of UHMWPE by optical, Thermal, and x-ray analysis indicates that the melt anisotropy persists at 345°C, i.e., the temperature at which the polymer degrades under nitrogen, and appears similar to a smectic liquid-crystalline phase.
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  • 34
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 835-838 
    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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  • 35
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 841-849 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two polymer solution models have been used to analyze poly(dimethyl siloxane) (PDMS) + alkane and PDMS + ketone systems. The free-volume and nonrandom interaction contributions are studied separately in order to compare the expressions for the local site fractions used in the two models. Predictions of the reduced residual chemical potential and excess volumes are discussed and compared with those found in the literature for these systems.
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  • 36
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 851-858 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Atactic polystyrene has been densified under hydrostatic pressure, up to 2 kbar, at about 180°C. Dielectric measurements were made on densified and nondensified polystyrene samples by using the thermally stimulated depolarization current (TSDC) and the absorption and resorption current methods. The dielectric loss is modified by the densification. This effect can be explained in terms of the free-volume reduction and the internal stress induced in the material during densification.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 869-879 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Magnetic metal-polymer composites have been prepared by thermolysis of a metal carbonyl Fe(CO5) in poly(vinylidene fluoride). These composites comprise ca. 100-Å-diam iron-oxide, γFe2O3, ferrimagnetic particles dispersed in the polymeric matrix. Small-angle x-ray studies show that these particles have a radius of gyration in the range 63-315 Å. The composites were prepared with up to ca. 20 wt % iron and were crosslinked, as evidenced by insolubility. Electron diffraction indicating the formation of some FeF2 suggests metal-fluorine interaction during formation of the composite.
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  • 38
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 859-868 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The primary objective of this work is to check the utility of vapor-pressure osmometry as an experimental technique in obtaining thermodynamic data on polymer/solvent systems. The second objective is to obtain experimental values for the exchange energy parameters ΔP, X, and ζ of the theory of Sanchez and Lacombe. With respect to the first objective, solvent activities of polyiso-butylene/benzene mixtures have been measured at several concentrations up to 600 g/kg of the solvent and at two temperatures. From the activities, it is possible to determine free energies, entropies, and enthalpies and their concentration dependence. Satisfactory agreement has been found between the results obtained and data provided by other techniques such as membrane osmometry and the Cahn electrobalance. These and other data obtained by inverse gas chromatography for the same mixture in the range 35-200°C have been used in calculating the exchange energy parameter of the lattice fluid theory at different concentrations and temperatures.
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  • 39
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 893-905 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The total free energy of an amorphous, crosslinked polymer is given as ΔA = ΔAmix + ΔAel, where ΔAmix indicates the free energy of mixing of the crosslinked polymer and the solvent to which the network is exposed throughout the deformation process; ΔAel indicates the elastic free energy of the network as a function of strain, including the effect of dilation with the solvent. The explicit forms of the mixing and the elastic free energies are obtained from the molecular theory of rubber elasticity. Recent developments in this field allow accurate representation of the behavior of swollen networks under strain. Expressions for the stress in terms of strain and swelling ratio are obtained from the free energy. Formulation of boundary-value problems are discussed. Bending of a cuboid subject to the action of a swelling agent is analyzed as an example. Material parameters are chosen for a crosslinked amorphous network. The distribution of stresses, strains, and solvent in the bent cuboid are calculated numerically. The magnitude of moments applied at the two ends are calculated for different degrees of flexure. Results are compared with those obtained for the same network in the dry state.
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  • 40
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 881-892 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The variation in small-angle x-ray scattering (SAXS) for samples of crystalline polymers subjected to oscillatory strains has been observed employing the 10-m SAXS apparatus with a two-dimensional position-sensitive detector at the National Center for Small-Angle Scattering Research at Oak Ridge National Laboratory. Signal averaging has been carried out in accordance with the π/2-sector technique by gating the detection of scattered intensity in synchronism with the sample strain. In-phase and out-of-phase intensity changes have been observed for a high-density polyethylene at various frequencies (0.05-3.2 Hz) and temperatures (0-70°C). Changes are greatest at small scattering angles. Frequency dependence is greatest at lower temperatures, indicating a time-dependent response of the structural changes leading to scattering at these temperatures. The behavior is not pronounced at elevated temperatures. The similarity of the scattering at both azimuthal angles of 0° and 90° suggests the existence of an additional mechanism, perhaps microvoid formation. To evaluate void contribution, the dynamic invariant function is determined as a function of frequency and temperature. It appears that the microvoid formation lags behind the applied strain. The static and swelling SAXS studies present further evidence of void generation during elongation.
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  • 41
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 919-927 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low-frequency Raman spectra are reported for monodisperse oligo-oxyethylenes with hydroxy and alkoxy end groups. Assignments are made to the longitudinal acoustic modes. The results are modeled by a rod with a longitudinal modulus E ≥ 2.2 × 1010 N m-2 and perturbing forces as large as (alkoxy-ended oligomers) or larger than (hydroxy-ended oligomers) those suggested for the n-alkanes.
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  • 42
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 907-918 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Atactic polystyrene (aPS)/poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and isotactic polystyrene (iPS)/PPO compatible blends of varied composition were subjected to solid-state coextrusion. The efficiency of drawing, orientation, and crystallinity development were studied as a function of composition and draw ratio. The efficiency of drawing, as measured by elastic recovery, is high for coextrusion at temperatures ≲40°C above the glass transition temperature of the particular blend. The maximum attainable draw ratio for the blends decreased with increasing PPO concentration; the highest blend draw ratio attained was 6.5 for 25 wt % PPO. The orientation on drawing, as measured by birefringence, increased with draw but decreased with increasing PPO component at the same draw ratio. When PPO was 〈50% in iPS/PPO blends, iPS crystallized on draw. The morphology of drawn blends was studied by electron microscopy and wide-angle x-ray scattering.
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  • 43
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 929-937 
    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 high pressure or the combined action of high pressure and shear deformation on the conductivity G and capacitance C of metal-free polyphthalocyanines (PPhCs), differing in macromolecular size, order, and degree of crosslinking, has been studied. It has been found that both G and C increase with compression. A similar phenomenon is observed under the combined action of high pressure and shear deformation on PPhC, but in this case the critical pressure needed for change in G is lower than that observed in uniaxial compression experiments. Spectroscopic investigations show that the effects of pressure and deformation on the electrophysical properties of samples under load is not connected with changes in the chemical structure of PPhC, but appear to be due to the change in the average distance between the regions of continuous conjugation. The sizes of such regions may be increased by preliminary thermal treatment.
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  • 44
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 939-948 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The electrical conductivity of hybrid films consisting of polyacrylonitrile (PAN), ethylene carbonate (EC), and LiClO4 was investigated. In these films, EC and LiClO4 are found to be molecularly dispersed in PAN, forming solid solutions over a wide composition range. The ionic character of the electrical conductivity is demonstrated. The conductivity is not correlated with the content of LiClO4 or of PAN, but primarily with the mole ratio [EC]/[LiClO4] in the films. An increase in the [EC]/[LiClO4] ratio enhances the conductivity. When the ratio is about 2, the conductivity attains 10-4-10-5 S cm-1 at 25°C. This change in conductivity results from a change in carrier mobility. PAN makes the films solid without decreasing the carrier mobility. In the hybrid films, the carrier mobility and the macroscopic viscosity are not related by Walden's rule. The high conductivity is due to regions in the film characterized by a low microscopic viscosity. This is determined by the mole ratio [EC]/[LiClO4] and largely controls the carrier mobility.
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  • 45
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 949-956 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Quenched and annealed samples of linear low-density polyethylene (LLDPE) were irradiated with 60Co γ rays in vacuo at room temperature. The data follow rather accurately Charlesby's equation s = k/r, where s is the soluble fraction, r the dose, and k a constant from which G(X), the G-value for crosslinks, was calculated. Crosslinking in the LLDPE is about twice as extensive at equal doses as in LHDPE. Production of vinylene unsaturation was approximately the same in the two types of polyethylene.
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  • 46
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 957-967 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Quenched and annealed samples of linear low-density polyethylene (LLDPE) were γ irradiated in vacuo at 77 K; the kinetics of the alkyl free-radical decay reactions were studied at room temperature, and of the allyl free-radical reactions at 60, 70, and 80°C. The ESR signals saturate at a slightly higher microwave power in the LLDPE than in high-density polyethylene (HDPE), and the alkyl radicals start decaying at a lower temperature in the LLDPE than in the HDPE. As in the HDPE the decay of the alkyl free radicals at room temperature in the LLDPE follows the kinetic equation for two simultaneous first-order reactions with the fraction of the faster-decaying component being slightly greater in the quenched than in the annealed samples. In the case of the allyl free radicals the decay at 60°C follows the equation based on one fraction of the radicals decaying according to second-order kinetics in the presence of other nondecaying radicals. At higher temperatures the data are best understood in terms of a second-order rate equation with a continuously variable time-dependent rate constant as suggested by Hamill and Funabashi.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 969-982 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A small-angle x-ray scattering (SAXS) study of the relaxed craze structure in polystyrene was performed using the Oak Ridge National Laboratory 10-m SAXS facility. Coupled with known results from transmission electron microscopy studies, the SAXS patterns can be interpreted as scattering from an open-cell foam with void spaces interspersed among the fibrils. Results have shown the scattering centers in crazed polystyrene can be modeled as cylinders the axes of symmetry of which are parallel to the tensile axes. Scattering centers are bimodal in their size distribution, with aspect ratios of 1.0 and 2.6. Crazes in lower-molecular-weight polystyrene have more and larger scattering centers than crazes in higher-molecular-weight polystyrene, while variations in strain rate and test temperature during craze formation have no effect on the relaxed craze morphology. A comparison of SAXS patterns from polystyrene and polycarbonate indicates that the morphologies of their respective crazes are significantly different.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 999-1010 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Blends of poly(ε-caprolactone) (PCL) and poly(vinyl chloride) (PVC) were investigated at concentrations of PCL greater than 50 wt % using purified materials. For these concentrations, PCL partially crystallizes with degrees of crystallinity ranging from 50% for pure PCL to 〈 10% for the 50% mixture. Small-angle x-ray scattering was used to characterize the resultant morphologies. Model calculations for the interference functions and for the integrated scattering indicate that PVC is incorporated between the PCL lamellae and that the two polymers form a homogeneous mixture in the amorphous phase. These results were compared to previous results on the same system using the identical technique. Purification of the two homopolymers proved to play a critical role in the overall mixing characteristics of PVC and PCL
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 983-997 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When a glassy polymer containing a uniformly dispersed solute is brought in contact with a penetrant, solute diffusion will be associated with the transport mechanism and penetration velocity of the penetrant in the polymer. Analysis and prediction of mechanisms of diffusional solute release may be obtained through a new dimensionless number, the swelling interface number, Sw, which compares the relative mobilities of the penetrant and the solute in the presence of macromolecular relaxations in the polymer. It is shown that a sufficient and necessary criterion for time-independent diffusional solute release rates from these swellable systems is that the Sw be smaller than 10-2. The swelling interface number Sw may be related to easily determined structural and thermodynamic parameters of the solute/polymer/penetrant system. Preliminary experimental results of dynamic water swelling of poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) and diffusional release of theophylline from initially glassy copolymers show that decreasing values of Sw are related to increased pseudo-case-II transport kinetics of the solute.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1029-1039 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The concentration dependences of the friction coefficient(s) for poly(ethylene oxide) have been determined on well-defined fractions in dilute aqueous solution. Three independent techniques have been used: FT-pulsed field gradient NMR (self-diffusion), photon correlation spectrosccpy (mutual diffusion), and velocity sedimentation, in the concentration range 1-25 kg m-3. The results establish that, at a given concentration, the friction coefficient in self-diffusion is appreciably smaller than that operating in mutual diffusion and sedimentation; the friction coefficient in the latter processes are identical within experimental error.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1011-1016 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using a time-dependent rate constant of the form k(t) = Btα-1 it is possible to describe adequately the time-dependent reactivity of species trapped in polymer matrices. The constant 0 〈 α ≤ 1 characterizes the initial distribution of species: the smaller the numerical value of α the wider is the distribution related to the kinetic curve by inverse Laplace transformation. Data of Auerbach and Sanders and of Patel et al. on allyl radical decay in irradiated polyethylene are discussed.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1493-1500 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental values of the dipole moment ratio 〈μ2〉/nm2 and its temperature coefficient d ln 〈μ2〉2/dT, where 〈μ2〉 is the mean-square dipole moment of a chain with n skeletal bonds and m2 is the mean square of the skeletal bond dipole moments, are reported for well-characterized random copolymers of 3,3-dimethyloxetane and tetrahydrofuran. The results are interpreted in terms of the rotational isomeric state theory in a manner consistent with that developed for the parent homopolymers. The theory gives a good account of the experimental results corresponding to copolymers in which the mole fraction of tetrahydrofuran lies in the range 0.11-0.89. It is found that whenever the copolymerization obeys Bernouillan statistics, the dipole moments are quite insensitive to the comonomer distribution. The theoretical analysis suggests, however, that the value of the dipole moment ratio of alternating copolymers of 3,3-dimethyloxetane and tetrehydrofuran should be near that of the parent homopolymer of lower polarity.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1501-1511 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low-frequency Raman spectra are reported for monodisperse methylene-oxyethylene-methylene triblock oligomers. Assignments are made to the longitudinal acoustical modes (LAMs) of the oxyethylene block and the methylene block. The results for LAM-1 can be modeled by the vibrations of rods with perturbing forces and masses. The results for LAM-3 are not so readily modeled.
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  • 54
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1439-1472 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The small-angle x-ray scattering (SAXS) technique has been used to characterize the detailed microphase structure of two crosslinked segmented polyurethane elastomers. Both copolymers contain trifunctional polypropylene ether triols in the rubbery elastomeric block, but are synthesized with different hard segments: a symmetric 4,4′-diphenylmethane diisocyanate (MDI) chain extended with butanediol (BD); and an 80/20 mixture of asymmetric 2,4-toluene diisocyanate (TDI) and symmetric 2,6-toluene diisocyanate (TDI) chain extended with ethylene glycol (EG). Calculations of SAXS invariants and determinations of deviations from Porod's law are used to examine the degree of phase segregation of the hard- and soft-segment domains. Results show that the overall degree of phase separation is poorer in the asymmetric TDI/EG-based copolymer than in the symmetric MDI/BD-based copolymer. Determination of diffuse phase boundary thicknesses, however, reveals that the domain boundaries are sharper in the asymmetric TDI/EG system. The contrasting morphologies found in the two systems are interpreted in terms of differences in hard-soft segment compatibility, diisocyanate symmetry, and diisocyanate length. Coupled with conformational considerations, this information is used to construct a new model for polyurethane hard-segment microdomain structure. Important features of the model are that it takes into account the effects of hard-segment sequence length distribution and allows for folding of the longer hard-segment sequences back into the hard-segment domain.
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  • 55
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1539-1558 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using recently developed quantitative FTIR methods, the gauche and trans conformer compositions have been measured for polyethylene terephthalate (PET) samples exposed to benzene and acetone. The kinetics of the primary and secondary isomerization stages of the solvent-induced crystallization process have been studied and compared with the thermally crystallized system. The Arrhenius activation energies of isomerization in the primary stage in which Fickian diffusion behavior is followed for the benzene- and acetone-induced PET systems are 8.2 ± 0.4 and 7.7 ± 0.4 kcal/mol, respectively.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1527-1537 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption of iodine by bulk polyacetylene was studied under various I2 gas pressures at 25°C. The sorption dynamics show that the penetration of iodine into PA is not Fickian and the diffusion coefficient increases with time of sorption. A discontinuous increase in the sorption isotherm is observed at P/P0 = 0.25 (P is the pressure of the I2 gas and P0 is the saturation value at 25°C). It is due to iodine penetration into PA crystals, as evidenced by x-ray analysis. The distribution of iodine within crystals is apparently inhomogeneous: some unit cells are changed into “iodine-PA” cells, while others remain unchanged. The electrical conductivity depends not only on the amount of iodine but also on the I2 gas pressure under which sorption is carried out. At given iodine content, the conductivity of a sample doped under higher I2 pressure is greater than that of a sample doped under lower pressure.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1563-1566 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1559-1562 
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    Keywords: Physics ; Polymer and Materials Science
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  • 59
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1513-1526 
    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 experiments has been carried out investigating several features of the surface growth method for observing longitudinal growth of polyethylene fibers in Couette geometry. Attempts to obtain limiting steady-state takeup rates using a Teflon rotor were hampered by fiber breakage; however, maximum growth rates before breakage were found to be considerably higher than those observed in previous studies. Growth rates were also obtained using a static method, and for the Teflon rotor indicated above a critical concentration a linear growth rate equal to the stirrer velocity with rates essentially independent of temperature. With a silanized glass rotor, the same method gave much lower growth rates at comparable stirrer speeds and temperatures and showed a temperature dependence suggestive of a nucleation-controlled mechanism. The implications of these results for other studies of the mechanisms of growth by the surface method are also discussed.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1569-1572 
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    Keywords: Physics ; Polymer and Materials Science
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1567-1568 
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    Keywords: Physics ; Polymer and Materials Science
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1599-1609 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(4-hydroxybenzoate) was prepared from 4-acetoxybenzoic acid, 4-pivaloyloxybenzoic acid, and 4-trimethylsiloxy benzoyl chloride by condensation without the addition of a catalyst. Although various reaction conditions were used the products were always crystalline. The morphology of the as-polymerized crystals has been studied by transmission electron microscopy as a function of molecular weight and end-group type. It was possible to detect morphological features during the course of reaction from oligomers to polymer which enabled us to determine the mechanisms that are likely to control chain growth for different regimes of polymerization kinetics.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1573-1597 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Total integrated and photon correlation light scattering have been used to study two samples of poly(1,4-phenylene-2,6-benzobisthiazole) (PBT) representing two methods of precipitation to recover the polymer from the polymerization solvent. Some details of the light-scattering instrument are given. It is found that the PBT sample is rodlike, with persistence length of at least 50 nm, but that the postpolymerization processing method influences the state of interchain aggregation. The data are augmented by measurements of freezing-point depression to estimate the degree of protonation of PBT in sulfuric acid, and by measurements of partial specific volume to provide an estimate for the geometric diameter of the chain in solution. The results show a degree of protonation of 2-4 protons per repeating unit, and partial specific volumes that are appreciably smaller than the specific volume determined for the polymers. Similar data and results are reported for poly(1,4-phenyl-ene-2,6-benzobisoxazole) and poly(1,4-phenylene terephthalamide).
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1635-1646 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We show that the Rutherford backscattering technique is very useful for studying the kinetics of diffusion processes in polymers. We have measured the diffusion of iodine into low-density polyethylene (LDPE) by optical absorbance and by Rutherford backscattering. The optical results appear to be normal, and show no electric field dependence, but the backscattering results reveal that this is misleading, because there is fast diffusion in the bulk accompanied by large surface concentrations of iodine. We have studied PET by the backscattering technique, and in this case the behavior corresponds to a weakly concentration-dependent diffusion coefficient with no observable surface effects. Neither set of results gives support to the domain theories of low-frequency electrical oscillation in these materials.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1611-1633 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electron diffraction has been used to investigate the structure of a wide range of as-polymerized crystals of poly(4-hydroxybenzoate) [systematic name: poly(1,4-oxybenzoyl)]. The chemical composition and the degree of polymerization (DP) have been varied and some samples have been thermally treated. At room temperature two crystalline modifications with orthorhombic unit cells coexist. The chains adopt a 21 helical conformation in both forms, but there are differences for oligomer and polymer crystals. Oligomers of low DP have an extended chain-conformation, whereas in polymers a shortening of the repeat distance along the chain is observed as a function of both the DP and the crystallization conditions. From the most extensive data sets we have derived the lattice parameters a = 7.52, b = 5.70, and c = 12.49 Å for polymer crystals of phase I, and the subcell parameters for oligomer crystals of phase II a = 3.77, b = 11.06, and c = 12.89 Å. Both phases contain two chains per unit cell. In addition to modifications I and II several defect structures exist the unit cells of which contain more than two chains. At temperatures which depend on the degree of polymerization, a phase transition to a third modification takes place. The large difference between the densities of phase III as compared to both phase I and II suggests that torsional degrees of freedom exist in phase III which allow a certain mobility of the phenyl and ester groups. This mobility enables the end groups of adjacent layers in interlamellar regions of oligomer crystals to undergo transesterification reactions and therefore to increase the molecular weight of the samples.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1667-1674 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Methylene and phenyl C1 carbon signals of polystyrene are assigned on the basis of the signal assignments of styrene oligomers. Polystyrenes prepared with benzoyl peroxide, n-butyllithium, and trifluoroboron etherate catalysts have random distributions with probabilities of racemic dyads of 0.54, 0.56, and 0.45, respectively.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1661-1665 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Piezoelectric constant, Young's elastic modulus, and dielectric constant of undyed and dyed films of poly(L-glutamate) were measured at 10 Hz over the temperature range -120 to 120°C. The temperature of the maximum in -d″14 shifts toward higher temperature up to 0.6 mg/g polymer of dye uptake and then shifts toward lower temperature by further dye sorption. The variation of the piezoelectric modulus was interpreted by the change of mobility of impurity ions in the sample.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1675-1689 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The sorption isotherms for water on cellulose triacetate, cellulose acetate (degree of substitution 2.45), cellulose monoacetate (degree of substitution 0.89), and ethyl cellulose were measured by finite-concentration inverse gas chromatography. The isotherms for cellulose monoacetate were also measured with a vacuum microbalance. Polymer-solvent interaction parameters and partial molar heats of sorption at zero concentration of water were estimated from the extrapolated data, but kinetic effects and isotherm curvature lowered the precision of these results. The water sorption isotherms were examined according to the Zimm cluster theory, and the results were compared to those for cellulose and (hydroxypropyl)cellulose.
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    Notes: In order to gain better understanding of the molecular deformation processes occurring in poly-(methyl methacrylate), a series of studies was carried out in uniaxial tension on the simultaneous stress and birefringence response in both constant-strain-rate and stress relaxation experiments. The former covered the temperature range -120 to 75°C and the latter 0 to 90°C. Three deformation mechanisms, i.e., (i) change in intermolecular distance, (ii) distortion of the conformation of the COOCH3 group from its thermal equilibrium state, and (iii) orientation of main-chain segments, are invoked to interpret the experimental results. It is concluded that, in the temperature range from -120 to 75°C and possibly at higher temperatures as well, the polymer chains deform in the small-strain region by an orientation of those chain segments having lower potential-energy barriers to conformational changes and straining those chain segments having higher potential-energy barriers. Subsequent chain orientation of the already strained segments occur in the higher strain regions. Changes in intermolecular distances occur over the entire temperature range from -120 to 90°C, but their magnitude decreases gradually as the temperature increases from -40 to 40°C and then decreases sharply for temperatures above 40°C. Strain-induced distortion of the conformation of the COOCH3 group may involve only rotation of the OCH3 group around the C—O bond rather than rotation of the entire ester group itself.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1691-1701 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When FEP-Teflon samples are electron irradiated at room temperature in open circuit and stored in that state for varying times following the end of irradiation, the temperature of the first current peak of the short-circuit TSC plot increases with increasing storage time. A new model is presented to explain this phenomenon, its main features being (i) a quasicontinuous distribution of hole-trap activation energies, the “center of mass” of the trapped hole population moving toward the deeper end of the distribution during the storage time, and (ii) an electron/hole recombination coefficient much smaller than that implied in an earlier model. It is shown that the assumption of a single dominant type of hole trap implies an unrealistically large frequency factor.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1703-1711 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This investigation concerns the important class of fluids whose rheological properties are described by a quasilinear viscoelastic constitutive equation of the Boltzmann superposition type. The first Cox-Merz relation is closely approximated by such a fluid if its nonlinearity in shear can be described by the strain measure $ S_{12} (\gamma) = \int_0^\gamma {J_0} (\upsilon)dv $, irrespective of the distribution of its relaxation times and, hence, its linear viscoelastic properties. Here γ equals the shear strain and J0 the zeroth-order Bessel function. The second Cox-Merz relation is met by materials with a different nonlinearity, namely S12(γ) = Si(γ), where Si is the sine integral. Experimental data on melts of a polystyrene and a low-density polyethylene sample were utilized to demonstrate that both Cox-Merz relations cannot hold simultaneously.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1745-1756 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As a nondestructive method of evaluation, we have used integrated optics to investigate thin films (〈8 μm) of polyamic acid and polyimide as a function of molecular weight, initial imidization temperature, method of imidization, and annealing treatment. Polyamic acid films were found to exhibit a large optical anisotropy, indicating preferential alignment of the long axis of the molecule in the plane of the film. Imidization increased the birefringence of the film by a factor of 2.5 and reduced the film thickness. The only parameter that was found to effect the anisotropy of the films was the method of imidization. Chemical imidization was found to increase the birefringence by a factor of 3, indicative of a higher degree of molecular orientation parallel to the film surface. This effect was not observed in thicker (〉25-μm) films using x-ray diffraction where the orientation function was found to be independent of the method of imidization.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1757-1783 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Relations between the physical structure and the deformation and failure processes of poly(p-phenylene terephthalamide) (PPTA) fibers are reported. The effects of the physical processes involved in fiber fabrication, including the crystallization of PPTA-H2SO4 dopes under stress, are considered in relation to their effect on the structure of the fiber. The deformation and failure processes together with the structure of the fiber are discussed in the light of fracture-topography studies of fiber-epoxy composite strands, single filaments, HCl-etched and unetched yarns, and transmission optical microscopy studies of stressed and unstressed yarns. In view of these observations, the physical structure of PPTA fibers is discussed in terms of pleated H-bond sheets, the macromolecular chain-end concentration and distribution, and the presence of impurities. The structural parameters that affect the failure processes of these fibers and how such parameters can be modified by service environment conditions are also addressed.
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  • 74
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    Notes: The dynamic tensile deformation mechanism of spherulitic high-density polyethylene was investigated by dynamic x-ray diffraction at various temperatures and frequencies in order to assign the α and β mechanical dispersions explicity. The uniaxial orientation distribution function q(ζj,0) of the jth crystal plane and its dynamic response Δq′j(ζj,0) in phase with dynamic strain were observed for the (110), (200), (210) and (020) crystal planes. Then the orientation distribution function w(ζ,0,η) of crystallites (crystal grains) and its dynamic response Δw′(ζ,0,η), also in phase with the dynamic strain, were determined by a mathematical transformation procedure proposed by Roe and Krigbaum on the basis of the Legendre addition theorem. The temperature and frequency dependences of w′(ζ,0,η) were analyzed in terms of the model parameters for dynamic spherulite deformation combining affine orientation of crystal lamellae with several types of preferential reorientation of the crystal grains within the orienting lamellae. The following assignments are made: (i) The α mechanical dispersion must be assigned to the dynamic orientation dispersion of crystal grains within the crystal lamellae, involving two types of preferential rotations of the grains about their own crystal b and a axes. The rotation about the b axis is associated with lamellar detwisting, mostly in the equatorial zone of uniaxially deformed spherulites; the rotation about the a axis is associated with intralamellar shearing, mostly in the polar zone of the spherulites. Thus both rotations are intralamellar grain-boundary phenomena. (ii) The β mechanical dispersion must be assigned to the dynamic orientation dispersion of the crystal lamellae behaving as rigid bodies. It is not accompanied by reorientation of the crystal grains, but is associated with orientation dispersion of noncrystalline material between the lamellae. Thus it is an interlamellar grain-boundary phenomena.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1785-1796 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Densified polystyrene glasses, prepared by cooling from the liquid state under elevated pressure, were studied by small-angle x-ray scattering at ambient pressure. The density fluctuation, determined from the x-ray data, showed a decrease with increasing pressure up to about 1.5 kbar, and then leveled off to a fairly constant value. The reduction in the density fluctuation produced by the pressure is much greater than the associated decrease in the specific volume. The observed change in density fluctuation is consistent with the view that the density fluctuation in glassy polymers consists of dynamic and quasistatic components and that the first of these can be correlated with the compressibility of the glass. The present data on the density fluctuation, in conjunction with the available data on volume and enthalpy, can be interpreted to mean that in pressure-densified glasses unfavorable chain configurations are trapped in local energy minima, and the strain energy thus stored can promote segmental motion leading to volume expansion at temperatures far below Tg. Some preliminary evidence indicating the formation of microcavities in these pressure-densified glasses is also presented.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1797-1805 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In an effort to elucidate the structure of the low-temperature phase of PTFE, a spectroscopic study of the effect of progressive irradiation on the low-frequency infrared spectrum was undertaken. Previous infrared and Raman measurements indicated that irradiation of PTFE decreases its crystalline content, resulting in a lowering of the 19°C phase transition temperature due to the introduction of disorder and defect structures into the lattice by chain scission. Far-infrared studies of virgin and irradiated PTFE at liquid nitrogen temperatures show that the medium to strong bands at 45, 54, 58, and 71 cm-1, attributed to lattice vibrations, decrease in intensity as the crystalline content decreases. These findings support the assignment of these bands to intermolecular vibrations of the crystalline lattice and are an indication of the presence of more than one molecule in the crystallographic unit cell.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1807-1814 
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    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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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1815-1823 
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    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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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1839-1849 
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    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.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1825-1837 
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    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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  • 81
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    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
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  • 82
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    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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  • 83
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    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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  • 84
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    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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  • 85
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    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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  • 86
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    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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  • 87
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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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  • 88
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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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  • 89
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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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  • 90
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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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  • 91
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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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  • 92
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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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  • 93
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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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  • 94
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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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  • 95
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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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  • 96
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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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  • 97
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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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  • 98
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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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  • 99
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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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  • 100
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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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