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  • Physics  (505)
  • 101
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1789-1800 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High-speed gel-permeation chromatography (GPC) of water-soluble polymers has been investigated by using TSK-GEL, type-PW columns packed with small porous particles. Being semirigid, the column packing could be operated under high pressure and, therefore, it was possible to achieve high-speed GPC. A resolution higher than that of ordinary GPC in organic solvent system was attained when the measurement of one sample was completed within 40 min with a 6-ft column set. Samples with a wide range of molecular weights, from oligomers to polymers having a molecular weight greater than 106, could be fractionated. Dextran, polyethylene glycol, polyacrylamide, poly(vinyl alcohol), and poly(vinyl pyrrolidone) were separated according to molecular size with no evidence of adsorption. Investigation of other water soluble polymers is now in progress.
    Additional Material: 14 Ill.
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  • 102
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1817-1828 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gelation and melting of aqueous gelatin were investigated by differential scanning calorimetry. This phenomenon can be analyzed as a conventional crystallization process assuming predetermined primary nucleation and unidirectional growth. The results were interpreted in terms of the fringed micelle model. Calculated values of the diameter of the renatured collagen fibril were found in excellent agreement with those determined previously by electron microscopy.
    Additional Material: 9 Ill.
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  • 103
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1801-1815 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Optical and ESR spectra of polymer-Cu(II) complexes in polymer films have been studied. The dependence on F1 = [Cu2+]/[MU] and F2 = [OH-]/[Cu2+], where [MU] is the molar concentration of monomeric units of the polymer, has been obtained. Optical spectra and potentiometric titration curves in solution have also been studied. There exists a buffer region 0 ≲ F2 ≲ 2. Optical spectra in films are slightly different from those in solutions. At least five different ESR signals, designated as A, B, C or D, and E, have been found in poly(vinyl alcohol)-Cu(II). These signals appear successively with increasing F2. Assignments are proposed as follows. Signal A (F2 ≈ 0), also found in poly(acrylamide)-Cu(II) and poly(vinyl pyrrolidone)-Cu(II), is due to a single Cu(II) coordinated with two water molecules and chelated with two oxygens or nitrogens attached to the polymer. A chain of Cu(II) ions singly and double bridged with OH- ions is responsible for the B signal (F2 ≈ 1). The C and D signals (F2 ≈ 2) appear to be caused, respectively, by a dimeric Cu(II) complex singly or doubly bridged with OH- ions. The E signal (F2 ≈ 7) appears to be due to a monomeric Cu(II) complex, different from that responsible for the A signal.
    Additional Material: 11 Ill.
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  • 104
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1861-1868 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoluminescence from polyethylene terephthalate (PET) has been investigated. A correlation was found between thermoluminescence (TL) and thermally stimulated current (TSC). The apparent activation energy was estimated at 0.23-0.50 eV for both TSC and TL from -170 to 0°C. This activation energy presumably indicates the trap depth, which is decreased by molecular motions, since both TSC and TL are quenched efficiently with visible light, but not with infrared light of energy of the magnitude of thermal activation energy. The spectrum of TL glow curves agrees with the photoluminescence spectrum at -185°C, which is composed of an excimer and a monomer fluorescence and also a structured phosphorescence at wavelengths longer than 400 nm.
    Additional Material: 7 Ill.
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  • 105
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1849-1859 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the epoxidation reaction between metachloroperbenzoic acid (MCPBA) and poly-(trans-1,4-butadiene), (PTBD), crystals in toluene suspension was investigated in the 6-21°C range using infrared spectroscopy. Crystals of PTBD with M̄n = 36,000 grown from heptane and from toluene solutions and crystals of PTBD with M̄n = 5500 grown from heptane were studied. For toluene-grown crystals the total number of double bonds available for reaction increases with reaction temperature. For all preparations studied the epoxidation reaction is initially second-order - first-order with respect to [MCPBA] and first-order with respect to the concentration of the available double bonds. The second-order rate constant is found to be dependent on temperature, on molecular weight, and also on the crystal preparation conditions. The bromination of PTBD crystals was studied in CCl4 suspension at 0°C; this reaction was found to be complete within 1 hr with the fraction of double bonds brominated consistent with the epoxidation results. The IR spectra for dried mats of brominated and of epoxidized PTBD crystals were obtained: Changes in the amorphous band at 1335 cm-1 due to reaction of double bonds at crystal surfaces were observed. The results of this investigation are discussed in terms of the amorphous content of the PTBD lamellas.
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  • 106
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1869-1875 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier transform infrared spectroscopy provides a sensitive method allowing one to detect easily changes in the syndiotactic sequence content in polystyrene. The method is based on analysis of the 540-cm-1 absorption band, which is conformationally sensitive. Results in the solid state and solution are presented. A shift of 2.5 cm-1 of the 540-cm-1 band towards the high-frequency side is observed between the solid state and solution.
    Additional Material: 5 Ill.
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  • 107
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of low-molecular-weight polystyrene (PS) in poly(methyl methacrylate) (PMMA) were prepared by first dissolving PS in methyl methacrylate monomer and then polymerizing the monomer. Forty-three specimens of varying number-average molecular weight (2100-49,000) and composition (5-40 wt %) of PS were prepared, and the surface morphology and phase relationships studied by scanning electron microscopy. Four distinct types of phase relationships were observed: (i) a single phase consisting of PS dissolved in PMMA; (ii) PS dispersed in PMMA; (iii) PMMA dispersed in PS; and (iv) regions of PS dispersed in PMMA coexisting with regions of PMMA dispersed in PS. Values of the size and population density of the dispersed particles are reported. Finally, the size and distribution of the dispersed particles and the various types of phase relationships are discussed in terms of the ternary polystyrene/poly(methyl methacrylate)/methyl methacrylate phase diagram.
    Additional Material: 20 Ill.
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  • 108
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1877-1877 
    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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  • 109
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1883-1885 
    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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  • 110
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1887-1889 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 111
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 112
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1891-1895 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 6 Ill.
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  • 113
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1917-1925 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: With a glass apparatus which is capable of measuring the thickness of adsorbed polymer layers with as accuracy of 0.5 nm, determinations on adsorbed polystyrene layers in contact with extremely dilute solutions (ca. 10-7 g/ml) in toluene were performed. Thermodynamic equilibrium was proved to exist between the adsorbed polymer layer and bulk solution. The thicknesses found suggest that a fluid mechanical effect is operative, as has recently been calculated. It was shown that in the very dilute region the thickness of the adsorbed layer is initially a linearly increasing function of concentration, and that regions of (very low) concentrations exist over which a first plateau arises, where the layer is as thin as might be expected from isolated, adsorbed coil analysis. A second much higher plateau arises at concentrations in excess of 10-5 g/ml, which is the plateau usually described.
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  • 114
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1927-1933 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that the first-order perturbation coefficient C1 of the cubed viscosity-radius expansion factor αη3 of nondraining flexible chains with excluded volume may be evaluated without great labor and with sufficient accuracy by solving numerically the Kirkwood-Riseman-type integral equations with a digital computer. The value 1.18 for C1,r obtained for ring chains is in good agreement with the corresponding value of Norisuye and Fujita, while the value 1.14 for C1,l obtained for linear chains is appreciably smaller than the corresponding value 1.29 of Fujita et al. despite the fact that the starting equations are the same. However, it is shown that the calculated value of C1,l of Fujita et al. is incorrect. Thus, the present result that C1,l 〈 C1,r is consistent with the earlier conclusion of Yamakawa and Tanaka derived in the Zimm-Hearst scheme.
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  • 115
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1897-1915 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The isothermal adsorption of high-and low-molecular-weight poly(γ-benzyl-L-glutamate) (PBLG) onto (100) alkali-halide surfaces has been studied with the intent of developing a model for the adsorption process. Data from both the solution and adsorbed phases were correlated in this study. The α-helical conformation was maintained in solution and on the substrate for all molecular weights investigated. Fourier-transform infrared spectroscopy proved to be a sensitive technique for conformational analysis of adsorbed PBLG films as thin as 200 Å. High-molecular-weight PBLG was adsorbed as an interwoven fibrous mat, homogeneously covering the entire substrate surface. This morphology was independent of the substrate. Adsorption of low-molecular-weight PBLG took on a lamellar morphology, often exhibiting epitaxial orientation in the substrate 〈100〉 directions. Quasielastic laser light scattering studies showed that low-molecular-weight PBLG had a much higher degree of aggregation in nonpolar solvents than did high-molecular-weight PBLG. The proposed adsorption model is essentially a modification of one suggested by Silberberg. It involves segmental adsorption of aggregates, as opposed to single macromolecules of PBLG. The unadsorbed segments of the aggregates form a concentrated interfacial region directly above the substrate. Further interaction and association of PBLG may occur in this region, thus reducing the epitaxial ordering influence of the substrate. Consequently, polymers which do not interact strongly in the concentrated interfacial region, such as polyethylene, are expected to be adsorbed epitaxially, as has been reported.
    Additional Material: 10 Ill.
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  • 116
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1935-1946 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several primary amines have been examined as selective degradative etchants for the investigation of poly(ethylene terephthalate) (PET) morphology. The objective is to remove less ordered regions, leaving crystals intact. The amines include 40% and 20% aqueous methylamine, 70%-40% aqueous ethylamine and pure and 40% aqueous n-propylamine. Weight-loss and x-ray diffraction data show that certain concentration of aqueous amine solution simultaneously degrade and crystallize PET. This observation indicates the hazard of using some of these amine reagents to characterize PET morphology since the crystalline structure found after etching is likely to be a result of solvent-induced crystallization during degradation. Data for 40% aqueous methylamine used at room temperature shows that crystallization does not occur during etching, and in light of earlier research indicates the favorable nature of this reagent as a selective degradative medium for PET. Application of this reagent disclosed that in oriented PET fibers chemical stress cracking occurs, causing the degradative reagent to lose its selectivity.
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  • 117
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1947-1963 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High-pressure CO2 sorption data in semicrystalline poly(ethylene terephthalate) (PET) are presented for temperatures ranging from 25 to 115°C. The results are described by Henry's law above the glass-transition temperature of PET, while a dual-mode sorption model comprised of a Henry's law and a Langmuir isotherm applies in the glassy state. The disappearance of the Langmuir capacity of the polymer above Tg presumably results from the elimination of regions of localized lower density which are frozen into the glass upon quenching from the rubbery state. Exposure of PET to a high CO2 pressure produced a systematic variation in the apparent sorption equilibria. Correlation of the Langmuir capacity of PET with the dilatometric parameters of the polymer provides a useful framework for understanding the origin of the Langmuir sorption mode and for interpreting annealing and conditioning effects in glassy polymers.
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  • 118
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1965-1971 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermally stimulated current (TSC) has been observed in extended-chain crystals of polyethylene above room temperature. The TSC spectra exhibit two current peaks of opposite polarity. The peaks were separated into separate components by curve fitting. The position of the negative peak, which appears at 123°C, is independent of charging conditions. The positive current increases after γ irradiation or aging of the samples.
    Additional Material: 7 Ill.
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  • 119
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1973-1982 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Analysis of ESR spectra of mechanoradicals from poly(methyl methacrylate) reveals that after mechanical degradation in vacuo at 77°K, the sample contains two types of primary radicals—CH2—C(CH3)(COOCH3) (I) and CH2—C(CH3)(COOCH3)—CH2 (II) produced by the breaking of the polymer chain, and secondary radicals —CH2—C(CH3)(COOCH3)—CH—C(CH3)—(COOCH3)—CH2— (III). With increasing temperature, radical I remains stable while II reacts with methylene hydrogen of the polymer chain giving rise to the secondary radical III, which decays and finally disappears as the temperature rises. After admission of oxygen at 113°K, the polymer radicals react with oxygen with formation of polymer peroxy radicals ROO. and diamagnetic dimers. With increasing temperature the latter dissociate again to the original polymer peroxy radicals which gradually decay, if the temperature is increased further. The present results are compared with earlier ones obtained on poly(ethylene glycol methacrylate) (PGMA).
    Additional Material: 4 Ill.
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  • 120
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1983-1987 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystalline elastic modulus of poly(cis 1,4-isoprene) has been measured by x rays and calculated by molecular mechanics. The experimental modulus is E = (2.3 ± 0.3) × 109N m-2. The calculated modulus is E = (8.8 ± 0.1) × 109N m-2 for chains in S+ cis S-T conformation and E = (6.1 ± 0.1) × 109N m-2 for chains in S+ cis S+T conformation. The modulus calculated for a statistical structure including both conformation is E = (6.7 ± 0.1) × 109N m-2. The experimental modulus is thought to be a lower limit because of partial crystallinity of the sample. The chief mechanism of deformation is rotation around single bonds adjacent to the double bond.
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  • 121
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1989-2003 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal structure of the β form of poly(ethylene oxybenzoate) was analyzed by x-ray diffraction. Four nearly extended molecular chains pass through a unit cell with parameters a = 8.19 Å, b = 11.07 Å, c (fiber axis) = 19.05 Å, β = 114.8°, and the space group P21/n-C2h5. The structural difference between the α and β forms is mainly due to the internal rotation angles for the virtual bond and the —CH2—CH2— bond. They are essentially in trans confirmation in the β form, while the α form contains cis and gauche (—CH2—CH2—) conformations.
    Additional Material: 6 Ill.
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  • 122
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2015-2030 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Oriented rods of linear polyethylene have been prepared by hydrostatic extrusion at 100°C. Materials having a range of different molecular weights were investigated and their behavior was found to correlate well with the melt flow index. The differences in extrusion process characteristics for large- and small-diameter products are discussed. In this context the effect of deformational heating is important and criteria are suggested for determining its significance and also for determining the stability of the process in terms of a critical extrusion pressure.
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  • 123
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2031-2047 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The hydrostatic extrusion behavior of polyoxymethylene (POM) is described. Extrusions were performed at 164°C for a range of different molecular weight grades. Excellent unflawed lengths of extrudate were obtained with axial Young's moduli, measured at room temperature, reaching values as high as 24 GPa. The extrusion characteristics are discussed in terms of the very strong dependence of the flow stress of POM on strain and strain rate and pressure. In addition to measurements of Young's modulus over a wide temperature range, data for shear modulus and transvers modulus are also presented. A limited amount of other structural measurements is presented.
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  • 124
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2005-2014 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High-resolution electron microscopy studies have been carried out on four glassy polymers examined in previous small-angle x-ray scattering (SAXS) investigations. The polymers include polycarbonate, poly(ethylene terephthalate), poly(vinyl chloride), and polystyrene. For all four polymers, both bright field and dark-field observations indicate the general absence of microstructural features of a size down to the resolution limit of the electron microscope. Only “pepper and salt” features on a scale ca. 5 Å are seen as characteristic of the structures. These features reflect simple interferences as the resolution limit is approached, and are seen for single crystal and oxide glasses as well as for the polymers. The present results, taken together with structural information from light scattering, SAXS, and small-angle neutron scattering, indicate that glassy polymers should be regarded as having rendom structures. The combined results are inconsistent with heterogeneous microstructures having regions of locally high order present in large volume fractions.
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  • 125
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), 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: Epitaxial crystallization of polyoxymethylene (POM) during cationic polymerization of trioxane in ethane dichloride was studied. Nascent POM crystals grew epitaxially on the surface of drawn, high-molecular-weight POM and on the (001) surface of KCl single crystals. Half-hexagonal crystals several thousand angstroms in thickness were formed on these substrates. No discrete diffraction maximum could be observed in small-angle x-ray scattering patterns, but diffuse streaks were present on both the equator and the meridian of the pattern. These diffuse streaks are due to inhomogeneities in the nascent crystals. It is proposed that the crystals contain voids due to occlusion of reactive chain ends in the crystal. The optical diffraction pattern from a model made up of rectangles agreed qualitatively with the actual x-ray pattern.
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  • 126
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2079-2081 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 127
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2057-2077 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(ethylene terephthalate) (PET), after certain thermal and mechanical histories, exhibits stress cracking when exposed to 40% aqueous methylamine. This reagent has also been used for selective degradation of PET films. Stress cracking is shown to occur during degradation only when a specimen supports an internal or externally applied stress, above a critical level. The cracking density in a filament is shown by the present work to increase as the draw ratio is increased or when the fiber is highly annealed. This increased cracking is associated with an increase in the magnitude of the internal residual stress resulting from molecular orientation developed during these processes. Because of this, crack density and fiber birefringence were found to correlate well. In addition, the geometry of the stress-cracking pattern along a filament is affected by internal residual stress since the propagation of spiral and helical cracks results from the effect of a biaxial stress field remaining at the filament surface after processing.
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  • 128
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2087-2103 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Quenched, quenched and annealed, and slowly cooled branched low-density polyethylene films were drawn at 25, 40, and 60°. The true draw ratio λL of the volume element was obtained and used to characterize the dependence on plastic deformation of the density, drawing stress, and work of plastic deformation, and the sorption and diffusion of methylene chloride. The effects observed are similar but less drastic than on linear high-density polyethylene. In particular, the transformation from the original lamellar to the final fibrous structure seems to be fastest for λL between 3 and 4. But the changes of vapor transport clearly indicate that the transformation is not yet complete even at the highest draw ratio λL = 6, just before the sample breaks. Annealing at 90°C of the drawn samples with free ends restores or even increases the transport properties beyond those of the undrawn sample without causing the fibrous structure to revert to the original lamellar structure.
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  • 129
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2105-2114 
    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 LAM-3 frequency on the various parameters of a perturbed composite elastic rod has been calculated. Together with the previously calculated nonlinear variation of LAM-1 with these parameters, it can be expected that experimental measurements of both of these bands will permit a more detailed analysis of properties of long-chain molecules. The predictions of the theory are in complete agreement with experimental results on n-paraffins. For data on polyethylene and poly(ethylene oxide) reasonable solutions can be found, although the experimental information on polymers is not yet accurate enough or sufficiently devoid of assumptions to permit definitive conclusions to be reached.
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  • 130
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2083-2086 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 131
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2139-2145 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Removal of the ultrahigh molecular weight fraction in high-density polyethylene by hydrodynamic crystallization and analysis of the subsequent drawing behavior leads to the conclusion that the small portion of extremely long chains present in polymers with a log-normal molecular weight distribution is not necessary for the achievement of high draw ratios, that is, in excess of 30×. Furthermore, a certain minimum weight, and therefore chain length, is required for the attainment of high draw ratios. For example, paraffins with a molecular weight of 23,000 draw only up to about 5×. A logical extension of these concepts to other polymer systems is presented.
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  • 132
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2115-2138 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ratios of the intensities of Raman scattering in the C—CI stretching region for eight combinations of sample orientation and directions of polarization of incident and scattered light have been measured for 15 samples of poly(vinyl chloride) (PVC) containing 0, 5, 10, 15 or 20 pph dioctyl sebacate (DOS) plasticizer which had been drawn uniaxially at 22, 70, 75, 80, or 90°C to draw ratios in the range 1-4.5. The birefringences of the samples were also measured. The Raman data were analyzed to give 〈P2(cosθ)〉cryst and 〈P4(cosθ)〉cryst, the values of the second- and fourth-order Legendre polynomials in cosθ averaged over the distribution of orientations of the crystallites, where θ is the angle between the c axis of a typical crystallite and the draw direction. Comparison of 〈P2(cosθ)〉cryst with the birefrigence showed that the crystallites are more highly oriented than the noncrystalline material in samples containing the higher amounts of plasticizer drawn at the higher temperatures. A value of 13.0 × 10-3 was deduced for the birefringence of fully oriented PVC. The values of 〈P4(cosθ)〉cryst for a given 〈P2(cosθ)〉cryst were found to be higher than predicted by calculations based on two simple models, the pseudoaffine rigid-rod rotation model and the affine rubber elasticity model.
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  • 133
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2147-2155 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The role of the intrinsic viscosity [η] as separation parameter in gel permeation chromatography (GPC) was studied for dextrans (from Leuconostoc mesenteroids B512) dissolved in water with deactivated silicagel (Porasil) as the column-filling material. For that purpose specific viscosities of dextran fractions eluted by GPC were measured as a function of the elution volume v. Provided that the elution volumes are corrected for zonal spreading, they are related to the intrinsic viscosities in an unambiguous way, probably reflecting a unique relationship between degree of branching and molecular weights. This was further investigated by developing an iteration method to prepare two calibration curves γ(v) and g(v), respectively, relating ln[\documentclass{article}\pagestyle{empty}\begin{document}$\left[ {\bar \eta } \right]$\end {document}] and InM (M is the molecular weight) to v. It required that the weight-average molecular weight Mw, the number-average molecular weight Mn, and the average intrinsic viscosity [\documentclass{article}\pagestyle{empty}\begin{document}$\left[ {\bar \eta } \right]$\end {document}] for a number of dextran samples (broad distributions) be previously known. The calibration curves found lead to consistent values of the above-mentioned averages. Moreover, they allow-establishment of the [\documentclass{article}\pagestyle{empty}\begin{document}$\left[ {\bar \eta } \right]$\end {document}]-M relationship over the range 5000 〈 M 〈 500,000.
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  • 134
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2171-2187 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transient and steady-state permeation data are reported for CO2 in semicrystalline poly(ethylene terephthalate) for temperatures ranging from 25 to 115°C over the pressure range from 1 to 20 atm. The pressure dependency of the time lag and permeability disappears completely above the glass transition of the polymer, and Fick's law with a concentration-independent diffusion coefficient applies. In the glassy state, a concentration-dependent diffusion coefficient is necessary to describe the data. The form of this concentration dependence is described well by the partial immobilization transport model that attributes a different mobility to each of the two populations of sorbed gas which exist in local equilibrium with each other in glassy polymers. The importance of reporting the pressure used in transport experiments involving glassy polymers is emphasized by comparing the difference in the activation energy of the apparent diffusivity calculated from the measured time lag at 1 and 20 atm. Also, the magnitude of the observed slope discontinuity at Tg in Arrhenius plots of these apparent diffusities is shown to be a function of the upstream pressure used in the experiment. The independently measured time lags are compared with the predicated values calculated from various transport models and found to be described best by the partial immobilization model.
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  • 135
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2189-2214 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Oriented fibers of poly(pentamethylene terephthalate) will crystallize in one of two phases. In one phase (designated α), which is preferred in the unstressed fiber at room temperature, the chain is contracted from its chemical repeat length. In the other (designated β), induced by tension, it is nearly fully extended. The structural analysis of both forms is described. The unit cells of both phases are triclinic. The parameters of the α phase are a = 4.7 Å, b = 5.8 Å, c = 24.7 Å, α = 112°, β = 94°, γ = 105°. For the β phase they are a = 5.0 Å, b = 5.8 Å, c = 28.2 Å, α = 126°, β = 74°, γ = 120°. The methylene sequence is all trans in the β phase but, surprisingly, in the α phase, three of its bonds are near the eclipsed conformation. The other surprising feature is the departure from planarity of one of the terephthaloyl residues in the β phase. These, and other features of the structures are compared with those of other chemically similar materials, both monomeric and polymeric.
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  • 136
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2215-2236 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A quasi-one-dimensional model for the dynamics of a polymer in dilute solution is described. The diffusion equation in the presence of energy barriers to conformational change is solved approximately for the case of high barriers, by a method closely analogous to the method of configuration interaction in molecular quantum mechanics. The dynamic shear viscosity is calculated in terms of the model and the ultrasonic absorption is discussed.
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  • 137
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2157-2169 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman polarization measurements of atactic polystyrene (APS) films were recorded after uniaxial stretching. Twelve different polarization directions were observed by varying the direction and polarization of the laser and scattered radiation. The polarization behavior of several vibration modes were shown clearly in the Raman spectra. On the basis of these polarization properties and previous vibrational studies of model compounds of polystyrene as well as of monosubstituted benzene derivatives, a reassignment of some of the vibrational modes of APS is made and discussed.
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  • 138
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2237-2244 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle x-ray scattering (SAXS) from glassy atactic polystyrene has been measured using a Bonse-Hart system. After correcting for absorption, background, and beam divergence, the scattering has been placed on an absolute basis using a standard silica suspension as a reference.The desmeared absolute intensity decreases strongly with increasing scattering angle over the range between 20 sec and 20 min. At larger angles, the intensity decreases much more slowly with increasing angle and approaches the value expected for density fluctuations frozen-in at the glass transition. The angular variation of intensity is well described by the scattering from heterogeneities of various sizes and concentrations superimposed on the scattering from thermal density fluctuations. These heterogeneities range in radius from 10 to 4000 Å. The present SAXS results on glassy polystyrene seem inconsistent with the presence of nodular features as representative of the bulk polymer.
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  • 139
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 37-48 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polarized Raman intensities have been obtained from thin films of oriented low-density polyethylene (PE) immersed in silicone oil to minimize surface scattering. Studies were made using the 1170 cm-1 crystalline band and the 1081 cm-1 amorphous band, and from these the orientation averages 〈cos2 θ〉 and 〈cos4 θ〉 were calculated. These were found to compare favorably with the values of 〈cos2 θ〉 for the polymer chain in the crystalline and amorphous phases obtained from measurements of infrared dichroism. Both orientation averages could be theoretically fitted by using reasonable parameters.
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  • 140
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 201-214 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A technique for the selective degradation of amorphous regions in nylon 6,6 is reported. Samples of unoriented film and single-crystal mats have been subjected to selective degradation by refluxing in hydrazine. Weight loss, viscosity-average molecular weight, density, and small-angle x-ray scattering of these samples were monitored as a function of time of degradation. In addition, selected samples have been investigated by gel permeation chromatography (GPC) and transmission electron microscopy. Based on the results of these investigations it is concluded that the reported degradation technique is unique in that the debris is not monodisperse in molecular weight distribution. The Weight loss, density, small-angle x-ray scattering, and microscopy data demonstrate that the unordered or noncrystalline regions of the material are removed upon treatement. However, the relatively high molecular weight and broad molecular weight distribution of the debris indicate that regular folds at lamellar surfaces are intact after degradation treatment.
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  • 141
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 265-270 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nuclear magnetic resonance (NMR) spectroscopy reveals that solution-grown polyethylene samples have a unique phase structure independent of molecular weight. The lamellar crystallites are composed of about 85% crystalline material with the noncrystalline overlayer as large as 15%. The molecular motion in the overlayer is comparatively hindered and the liquid-like component, which is generally recognized in melt-grown crystals, cannot be produced appreciably, even at 60°C. Such hindered molecular mobility can be understood in terms of a rather restricted conformation of the molecular chains in the noncrystalline overlayer, arising from the special mode of crystallization from dilute solution.
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  • 142
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 319-333 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Statistical mechanical correlations of ethylene and nitrogen solubility in molten, low-density polyethylene at several temperatures and at pressures to 69 atm are presented. The solubilities are taken from data previously published by us and by other workers. The data are modeled with a corresponding-states solution analysis applicable to mixtures of high-and low-density fluids. The model is based on a simple variation of the Flory and Prigogine corresponding-states theories. Gas sorption data are modeled well within experimental precision.
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  • 143
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 367-369 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 144
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 379-386 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The chain axis tilt which occurs when tensile stress is applied to one face of a thin crystal has been estimated by imitating the strain produced at the interface by means of a regular array of dislocations. The calculation also includes image dislocations introduced to make the crystal boundaries stress free. The tilt is found to be small (〈1° and probably ≪1° over most of the crystal) for all strains up to the point where plastic deformation mechanisms prevail. The implications of the results are discussed in the context of the electron image contrast.
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  • 145
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 695-701 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The refractive index increment of macromolecules in solution has been observed to be a function of concentration, temperature, molecular weight, wavelength of light, and solvent. Most of the studies have been performed in dilute or semidilute solutions, and therefore the concentration dependence of the refractive index increment was too small to be accurately observed. This study was performed on solutions of polystyrene in trans-decalin at mass fractions, w2, from 0.01 to 0.11 and at 436 and 546 nm wavelengths. The concentration and temperature dependence of the refractive index increment were measured, and comparisons were made with previous theories.
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  • 146
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 735-751 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solubility of carbon dioxide in symmetric (dense) cellulose 2.4-acetate has been measured at temperatures from 0 to 70°C and pressures up to 45 atm. The polymer samples were prepared by slowly drying asymmetric reverse osmosis membranes. The solubility isotherms can be described satisfactorily up to 60°C by the “dual-sorption” model for glassy polymers. The model cannot represent the experimental data above 60°C, possibly because of a second-order transition in the polymer between 60 and 70°C. An analysis of the dual-sorption parameters and of the heats of solution and “hole filling” suggests that the polymer samples contained a relatively large volume of microcavities. Gas solution appears to occur predominantly in microcavities, a large fraction of the penetrant moleculers being immobilized or partially immobilized. The solubilities obtained in this work are compared with similar data computed from time-lag measurements of other investigators, and the validity of the dual-sorption model is examined for the present case.
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  • 147
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 793-802 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diffusion of α and β cyclodextrin (α-CD and β-CD, respectively) has been studied in aqueous solutions of poly(methacrylic acid), sodium poly(styrene sulfonate), having three different degrees of sulfonation (DS), and copoly(styrene-methacrylic acid) containing three different amounts of styrene. N-Acetylglucosamine and raffinose were included as reference diffusants. It was found that a decrease of the diffusion coefficients of the CD's in these polymer solutions is characteristically dependent on the polymer concentration, DS, Styrene content, and the degree of neutralization. The results were interpreted by assuming a 1:1 complex formation between CD and an appropriate residue in the polymer. The complex diffusion behavior of CD in the copolymer solutions suggested that the ability of the polymer residue to form complexes with the CD is lost when the polymer chain dimensions are reduced with decreasing neutralization.
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  • 148
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 821-832 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier transform infrared studies of the thermal degradation of polyacrylonitrile (PAN) conducted at 200°C in air and under reduced pressure are presented. The spectra are markedly superior to those published previously. A mechanism consistent with the infrared results obtained under reduced pressure is advanced, and assignments for the infrared bands occuring in the spectrum of both the reduced pressure and air degraded PAN are given.
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  • 149
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 883-894 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In co[poly(ethylene terephthalate)-p-oxybenzoate] containing 30 mole % oxybenzoate units, the ethylene terephthate units crystallize. The copolymer melts in the temperature range 180-210°C to form a nematic phase which, at a higher temperature, transforms to an isotropic liquid. The latent heat of the first transition is 5 cal/g, and the thermodynamic melting temperature, 247°C, is essentially that expected for a random copolymer of this composition. The nematic → isotropic transition occurs at 244°C, with an enthalpy change of 3.2 cal/g (10% of the heat of fusion of poly(ethylene terephthalate)). We conclude that semiflexible polymers form a nematic phase which is rather highly disordered. The model of the nematic phase treated by Flory is modified to increase its entropy through incorporation of chain bends (which must be correlated in position and direction with those in neighboring molecules). This increases the chain extension, as measured by the fraction (1-f) of collinear chain bonds, required to form the nematic phase. For binary polymer-solvent systems, an appropriate scaling of f values leaves the phase diagram as predicted by Flory's treatment essentially unchanged.
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  • 150
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 935-937 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 151
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 945-948 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 152
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 971-976 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polymorphism of isotactic poly(pentene-1) form I was studied by x-ray diffraction. Upon quenching from the melt at a temperature below 25°C, the films crystallized in a stable monoclinic form, which we have designated as form I (a = 22.4 ± 0.2 Å, b = 6.49 ± 0.05 Å, c = 21.2 ± 0.2 Å, β = 91 ± 1°). For higher quenching temperatures, a metastable form, form I′, appeared, which transforms to the normal modification upon aging (monoclinic, with: a = 24.3 ± 0.2 Å, b = 6.50 ± 0.05 Å, c = 19.3 ± 0.2 Å, β = 96 ± 2°). Both modifications have a 31 helical conformation. Limited changes in the packing mode could explain this polymorphism.
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  • 153
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 999-1007 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: First-order excluded-volume effects on the intrinsic viscosity and translational friction coefficient of nondraining flexible ring polymers were calculated on the basis of the Kirkwood-Riseman formalism of polymer hydrodynamics. The cube of the viscosity expansion factor αη,r was found to be represented by α3η,r = 1 + 1.18z + …, where z is the usual excluded-volume parameter. Combination of this result with the corresponding calculation by Fujita et al., for nondraining linear polymers, yielded α3η,r/α3η,l = 1 - 0.11z + … (αη,l denotes the viscosity expansion factor for linear chains). The negative coefficient of the z term contradicts the conclusion by Tanaka and Yamakawa who used the Zimm-Hearst theory of polymer dynamics. The friction expansion factor αf,r, for ring polymers, was obtained in powers of z as αf,r/αf,l = 1 + 0.773z + …. The earlier evaluation of αf,r by Fukatsu and Kurata was in error. The ratio αf,r/αf,l (αf,l is the friction expansion factor for linear chains) was given by 1 ± 0.182z ± … when the corresponding result on αf,l was used. This expansion compares well with Casassa's result αs,r/αs,l = 1 ± 0.147z + … for the ratio of the radius expansion factors of ring and linear chains.
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  • 154
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization behavior of random block copolymers of (tetramethyl-p-silphenylenesiloxane) and dimethylsiloxane has been studied over a wide range of temperature and composition. The copolymer melting temperature, glass transition temperature, rate of crystallization, crystallinity, and density decrease in magnitude as the dimethylsiloxane block content are raised in this two-component system. The crystal end-surface (interfacial) energy increases as the dimethylsiloxane mole fraction decreases in accord with other morphological observations. The morphological changes observed in these copolymers are consistent with the conclusions deduced from the crystallization kinetics. Negatively, birefringent spherulites are observed over the entire crystallization range investigated.
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  • 155
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1277-1290 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermoelastic effect has been measured in compression on four glassy polymers; namely, polystyrene, poly(methyl methacrylate), polycarbonate, and epoxy resin. Quantitative results have been obtained for the first time on three of these polymers. It has been shown that by paying attention to specimen geometry and instrumentation results can be obtained to a high degree of accuracy (better than ±1.5% on a given set of measurements). The polymers are shown to obey the classical Thompson equation for thermoelasticity in solids over the temperature range studied (ca. 220-350°K). By inference such materials can be expected to behave classically in general. The results have been used, as first suggested by Trainor and Haward, to obtain values for the linear thermal expansion coefficient and the values so obtained are shown to be in excellent agreement, in general, with literature values obtained by more conventional methods. Results are given for a range of stress from 5 MN m-2 to between 25 and 50 MN m-2 according to ambient temperature. The method affords a measurement of parameters, in particular, linear thermal expansion coefficient. Values of specific heat for the four plastics have been measured by differential scanning calorimetry and the results compared with published data.
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  • 156
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1329-1354 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle x-ray scattering (SAXS) of isotropic or uniaxially oriented nylon 6 was investigated as a function of thermal and mechanical history. In addition to the peak position and linewidth of the SAXS maximum, the integrated SAXS intensity was measured. It was found that the radial intensity distributions of isotropic or arced patterns are controlled to some extent by the small width of the semicrystalline macrolattice, rendering the conventional long period and line shape analysis inapplicable to these patterns. A two-dimensional analysis is possible with well-oriented fibers; the major structural changes which are seen in fibers after annealing above 190°C are associated with melting and recrystallization. Extensive cold drawing and subsequent annealing cause rather modest (ca. ∼30%) changes in the integrated SAXS intensity. These effects are consistent with the generation of homogeneous interfibrillar regions during the latter stages of plastic deformation. On annealing a quenched film on nylon 6, the transformation of the crystals from a pseudohexagonal to a monoclinic habit occurs above 170°C.
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  • 157
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1389-1397 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Synthesis of poly(isopropenyl cyclohexane) via the hydrogenation of poly(α-methyl styrene) is described. Depending on the reaction time and catalyst system a homopolymer or a copolymer is obtained. Under the conditions of synthesis both materials are highly syndiotactic. For the pure hydrogenated homopolymer (〉99.9%) the glass transition temperature was found to be 185.4°C, about 20°C above Tg of poly(α-ethyl styrene). Contrary to expectations, the glass transitions of the 92/8, 33/67 poly(isopropenyl cyclohexane-co-methyl styrene) and poly(α-methyl styrene) are almost identical, as are the decomposition temperature ranges. Thermal data indicate that the decomposition mechanism of the copolymers and hydrogenated homopolymer is random scission. The thermogravimetric curves also indicate that the copolymers are random. Thus, chain stiffness appears not to increase rapidly with hydrogenation of this highly syndiotactic polymer.
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  • 158
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 81-89 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An equation has been derived for the development of crystallinity from heterogeneously nucleated spherulites which impinge with a small number of neighboring but randomly centered spherulites. The crystallization-time dependence calculated from the equation conforms to an Avrami equation with initial fractional values for the n exponent, and the equation appears to be a better fit of the initial time dependence of the crystallization of polyethylene than the Avrami equation itself. It appears to account satisfactorily for the observation of fractional n values in the analysis of the crystallization curves of this polymer. The derivation of the equation only accounts for the impingement of spherulites in pairs and does not allow for multiple impingements. This limits its fit to less than the total primary crystallization. The effect on nonrandom centering of spherulites is discussed.
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  • 159
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 117-120 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Vapor sorption measurements of Flory-Huggins interaction parameters χ for three poly(styrene-co-butadiene) + solvent systems at 25°C are reported. For Philprene 1502 + benzene: χ = 0.379-0.297 v22; for Philprene 1502 + n-heptane: χ = 0.595 + 0.030 v2 for Solprene 1204 + benzene: χ = 0.516-0.026 v2. The volume for fractions of polymer v2 range from ca. 0.4 to 0.9.
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  • 160
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 245-263 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intrinsic viscosity [η] and the translational friction coefficient f of polymer molecules in solution are calculated on the basis of the porous sphere model. The only information needed to predict [η] and f is the polymer molecular weight, the radius of gyration in the solvent, and the permeability as a function of position in the “porous sphere.” For systems for which this information is available there is satisfactory agreement between predicated and directly measured values of [η] and f. No adjustment of parameters is required. The influence of solvent quality is more complex than is suggested by the experimentally verified Flory-Fox relation for [η]; the simple form of this relation stems from the fact that two quite large effects of solvent quality approximately compensate each other. The complete flow pattern of the solvent around and through the polymer coil can be calculated. Contrary to what is usually believed the solvent flow in the polymer coil is not “effectively blocked”, even at the center. The connection between the present treatment and the microscopic theory of Kirkwood and Riseman is investigated.
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  • 161
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 29-36 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The birefringence change occuring upon stretching a rubber containing spherical isotropic filler particles is calculated as a function of the volume fraction of the filler. The stress concentration arising from the presence of the filler particles leads to an enhanced birefringence of the rubber. From a consideration of the detailed birefringence pattern about a spherical particle within a stretched rubber, the enhancement of the retardation is calculated as a function of the volume fraction of the filler particles.
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  • 162
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 59-80 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic mechanical and dielectric properties of substituted polypentenamers with phosphonate side groups and their hydrogenated derivatives have been studied. Methyl esters, acids, and salts were investigated at two concentrations, 6.5 and 11.1 mole percent. In the unhydrogenated derivatives, one principal relaxation, labeled β, is observed mechanically in the temperature range from -160 to 100°C. This β relaxation arises from micro-Brownian segmental motion accompanying the glass transition. Its temperature is substantially affected by the substituent concentration while its breadth is affected by the chemical nature of the substituent. An extended “rubbery plateau” region exists in the acid and salt derivatives. The dielectric results generally reinforce the mechanical assignments. In the hydrogenated derivatives, three relaxations labeled α, β, and γ in order of decreasing temperature occur mechanically in this temperature range. The temperatures at which the α and β relaxations occur depend greatly on the chemical nature of the substituents, the substituent concentration, and the thermal history of the sample; while the γ relaxation appears to be independent of these variables. Suggested assignments for the relaxations observed in these polymers, based on the dual glass transition theory of Boyer for semicrystalline polymers, have been proposed. The dielectric results are consistent with the proposed assignments.
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  • 163
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 121-130 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The elastic component of the solvent chemical potential in isotropically swollen polymer networks is investigated as a function of the degree of dilation. The experimental method is similar to one employed by Gee, Herbert, and Roberts; the differential solvent vapor sorption by crosslinked and uncrosslinked polymers is measured as a function of solvent activity. Three systems have been investigated: poly(dimethylsiloxane) + benzene, poly(styrene-co-butadiene) + benzene, and poly(styrene-co-butadiene) + n-heptane. The same vulcanizate was used for the latter two series of measurements. The qualitative behavior found for all three systems is in general agreement with the results of Gee et al. on natural rubber + benzene. The data suggest that the elastic and mixing free energies are not separable.
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  • 164
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 689-694 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A quantitative model for the pressure dependence of the thermal conductivity K in glassy polymers is presented. By extending the hole theory of liquids to temperatures below the glass transition temperature, an equation of state is obtained and an expression for the pressure dependence of the thermal conductivity is then formulated from a consideration of the anharmonicity associated with the segmental vibrations. The resulting equation ΔK/K = γGf0[1-exp(-p/B*)], where γG is the Grüneisen parameter, f0 is the fractional free volume, and B* = kTg/V0, is compared with experimental results for the poly(alkyl methacrylates).
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  • 165
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 717-723 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: New elastomeric ionene polymers containing poly(tetramethylene oxide) chain units were synthesized. The electrical conductivities of the salts of these polymers with (the anion radical of tetracyanoquinodimethane) (simple salt) and with neutral TCNQ added (doped salt) were investigated. Each cationic site in the polycationic polymer chain is separated by a long elastic chain unit, and consequently, moieties in the simple salt are expected to be well separated. Unexpectedly, doping with neutral TCNQ caused a marked decrease in the specific resistivity and the activation energy. Although the simple salt is elastic, doping with neutral TCNQ increased the stiffness of the material. The room-temperature specific resistivity of the doped salts was in the range of 103 to 104 Ω cm. The marked change of electrical and mechanical properties brought about by doping with neutral TCNQ is discussed in terms of a structural model in which phase separation of the ionic part from the nonionic elastic units has been assumed.
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  • 166
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1261-1275 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pressure-volume-temperature (PVT) properties of a commercial polysulfone derived from bisphenol A and 4,4′-dichlorodiphenylsulfone are studied experimentally and theoretically in the temperature range 30-370°C and for pressures to 2000 kg/cm2. PVT surfaces are determined for an annealed glass, formed under zero pressure, and for the melt. Two glass-transition lines must be distinguished: T*g(P) which is the intersection of the glass and melt PVT surfaces, and Tg(P), which is obtained by pressurizing the melt isothermally. The application of Ehrenfest-type equations to these transitions are discussed. The Prigogine-Defay ratio r = ΔkΔCp/T*gV*g(Δα)2 at P = 0 is found to be equal to 0.95 (±20%), using ΔCp data determined on identical samples. The melt data is compared with the Simha-Somcynski hole theory, using the reducing parameters V* = 0.788 cm3/g, T* = 12,560°K, P* = 10,875 bar. The hole fraction appearing in the theory is found to be constant along T*g(P), but the glass PVT relationship cannot be reproduced by using the Simha-Somcynsky theory together with the assumption that the hole fraction remains constant in the glass. At P = 0 the hole fraction must be allowed to decrease with decreasing temperature, but at a slower rate than in the melt.
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  • 167
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 143-157 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study has been made of the dynamic and steady shear melt theology of an ethylene-methacrylic acid copolymer, its methyl ester, and 70% neutralized sodium salt. Measurements were made with a Rheometrics mechanical spectrometer using the eccentric rotating disks and cone-and-plate geometries over a temperature range of 120-180°C and frequency range of 10-3 to 102 rad/sec. Correspondence was found between steady shear viscosity and the complex dynamic viscosity for the ester and acid materials. Over the temperature and frequency range studied the time-temperature superposition principle was applicable to G′ data for each of the derivatives and a supermaster curve could be constructed from the three individual master curves. Time-temperature superposition was found not applicable to G″ data for the sodium salt. Differences in rheological response between the ester and acid copolymers are explained by differences in Tg. It is suggested that differences in temperature shifts ΔT required to produce G′ superposition between the three derivatives reflect differences in ΔH for interchain interactions. A mechanism for flow of clustered ionomers is consisting of an initiation and a propagation step.
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  • 168
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 189-200 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The extinction coefficient for acoustic branch, second-order (two-phonon) Raman scattering from a zigzag chain, using force constants and polarizabilities appropriate to polyethylene is computed. As a consequence of the computation, we propose identification of a line at 890 cm-1 in the published Raman spectrum of polyethylene as a second-order Raman line.
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  • 169
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 231-244 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Energy migration and intramolecular excimer formation have been studied in a series of copolymers comprising 1-vinylnaphthalene, 2-vinylnaphthalene, and styrene with methyl methacrylate. The technique of fluorescence depolarization was used to characterize energy migration in glassy solutions of the copolymers. The extent of energy migration in these copolymers is determined by the mean sequence length of aromatic species l̄a. Assuming that excimer formation occurs as a result of nearest-neighbor interactions, the concentration of excimer sites in the macromolecule will be proportional to the fraction of links between aromatic species faa. It is proposed that these sites are populated via energy migration from the site of absorption. Proportionality between the ratio of excimer to monomer emission intensities and the function l̄a·faa was predicted. Good agreement with this relationship was obtained in each of the copolymer systems studied. Reactivity ratios of methyl methacrylate (rm) in copolymerization at 70°C with the aromatic monomers (ra) were determined as: 1-vinylnaphthalene - rm = 0.43, ra = 1.71: 2-vinylnaphthalene - rm = 0.37, ra = 4.46; styrene-rm = 0.45, ra = 0.58.
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  • 170
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 271-288 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relationship between the crystalline superstructure of polymer films and molecular orientation was studied in cold-drawn poly(chlorotrifluoroethylene) films by wide-angle x-ray diffraction, birefringence, and depolarized light scattering. By changing crystallization conditions, specimens with almost identical crystallinity but different crystalline superstructures were obtained; i.e., (1) a structure having a random array of crystallites, (2) a superstructure having a rod-like orientation correlation of the chains (a prespherulitic and sheaf-like superstructure), and (3) spherulitic superstructure. Upon stretching of specimens, crystallites initially randomly arranged orient with their chain axes along the stretching direction in accord with simple affine deformation. The amorphous chains also orient along the stretching direction. The orientation behavior of the specimens having the rod-like superstructure is similar to that of the specimens with a random array of crystallites, indicating that the interaction between the crystallites in the superstructure is relatively weak. The molecular orientation behavior of the spherulitic specimens, however, strongly deviates from simple affine deformation owing to strong interaction of the crystallites in the spherulites. The deviation can be interpreted in terms of spherulite deformation and of internal reorientation of chains within deformed spherulites.
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  • 171
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 341-347 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Proton spin-lattice relaxation times T1 were measured for two samples of polydimethylsiloxane (PDMS), one with weight-average molecular weight Mw = 77,400 and the other with Mw = 609,000. Two T1 minima and a T1 discontinuity were observed for each compound. The high-temperature T1 minima were attributed to a stretching and flexing motion of the PDMS chain. Quantitative comparison of the relaxation data with a theoretical model developed for this motion allowed the activation energy, 2.3 kcal/mole, and the maximum angular displacement of the methyl group symmetry axis to be determined. The latter was found to be 31°, independent of sample molecular weight. The low-temperature minima were ascribed to methyl reorientation with an activation energy of 1.6 kcal/mole. The T1 discontinuities were attributed to melting and allowed the degree of crystallinity to be estimated.
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  • 172
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 375-377 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 173
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 395-405 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An assessment of the possible collapse mechanisms for solution-grown pyramidal polymer crystals is made, taking into account electron microscope observations and the mechanics of the loading situation. That comprehensive collapse always occurs is shown not to be as self-evident as is normally assumed, even though the more exacting criteria for its establishment are indeed usually met. Bending of lamellar crystals is found to account for many observations, although an alternative means of tilting molecular chains, the “differential shear tilt model” is also considered.
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  • 174
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 443-455 
    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 polarized fluorescence is developed for uniaxial physical systems in which micro-Brownian motion is not negligible. All experimental information is shown to reduce, with reasonable assumptions, to four quantities characterizing molecular orientation and reorientational molecular mobility. The geometrical properties of the mobility in uniaxial systems are studied and methods are given for correcting for the effects of the birefringence and for a possible delocalization of the fluorescence transition moments.
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  • 175
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 467-484 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The decay kinetics of the chain allyl free radical has been studied in the following morphological forms of polyethylene (PE): Marlex bulk film, hydrogenated PE, and extended-chain PE. Coupled with previous work on single-crystalline PE it can be seen that the decay rate is greater the more amorphous the sample. In the Marlex bulk film and hydrogenated PE the decay can be interpreted in terms of a simultaneous fast and slow decay process by means of our Q-function equation, but with rising temperature the decay approximates a single rate process. With extended-chain PE the allyl decay rate does not become appreciable until the melting range is approached. The fraction of allyl radicals decaying by the slow process is 2 to 10 times greater than the fraction of fast decaying radicals. The ratio of the fast decay rate constant to that of the slow rate constant is greater for the bulk Marlex film than for the hydrogenated PE. All ratios decrease with rising temperature. For times up to about 150 min the allyl decay in the extended-chain PE accurately follows a single second-order decay law with a time-independent diffusion controlled reaction rate constant.
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  • 176
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 565-565 
    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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  • 177
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 627-639 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An excluded-volume theory of polyelectrolytes is presented based on the concept of a Kuhn statiscal segment depending on the concentration of added salt. The polyion is viewed as a wormlike chain bearing charges which interact according to a Debye-Hückel potential. It is shown that it is consistent to split up the screened Coulomb potential into two parts: a short-range interaction giving rise to a so-called electrostatic persistence length which depends on the Debye-Hückel radius, and a long-range interaction denoting the excluded-volume effect. The mean-square radius of the polyelectrolyte is derived, and this deviates markedly from expressions based on a constant Kuhnsegment length. Furthermore, certain polyelectrolytes exhibit negligible excluded-volume effects and behave as wormlike chains with a persistence length equal to the sum of the bare persistence length and the electrostatic persistence length. In addition, an expression for the polyion-polyion contribution to the second virial coefficient is obtained.
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  • 178
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 679-688 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Drawing of oxidized high-density polyethylene (HDPE) and subsequent annealing greatly reduce the low-temperature dielectric loss when the electric field is applied perpendicular to the draw direction. This supports our model (J. Polym. Sci. Polym. Phys. Ed., 15, 43 (1977)) of the proton moving parallel to the c axis of the PE crystal. A particular antioxidant (Ionox 330) in unoxidized HDPE induces a dielectric loss with a frequency and temperature dependence which differs from that for the loss in oxidized HDPE. The antioxidant loss seems to be an overlapping of tunneling and a thermal activation process. The possibility that the hydroperoxide group in the PE crystal is the origin of the loss in oxidized HDPE was theoretically examined in a manner similar to that used for the hydroxyl group in the previous paper. Results suggest that the hydroperoxide group is less probable than hydroxyl as the origin of the low-frequency loss in HDPE.
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  • 179
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 703-716 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The degree of swelling and attendant reduction in the glass transition temperature have been determined for a 70% styrene-30% acrylonitrile copolymer in a large number of organic liquids. The critical strain ∊c for crazing or cracking has been determined also in air and in each agent. Limited crazing data have been obtained also on a dicyano bisphenol polycarbonate in which the CN groups take the place of the methyl groups in bisphenol A (BPA) polycarbonate. The two resins are compared with polystyrene and BPA polycarbonate, respectively, in terms of crazing resistance, swelling, and other properties. In both systems CN incorporation raises ∊c (air) and reduces susceptibility to liquids of low solubility parameter δ; Tg and shear yield stress are raised in the polycarbonate but not in the styrene system. The volume efficiency of CN in raising ∊c (air) is greater in the polycarbonate system than the styrene system; for the rise in polymer solubility parameter, CN efficiency is apparently reversed. These changes are discussed in terms of the differences in molecular architecture of the two systems. For glassy polymers, ∊c (air) is shown to depend in semiquantitative fashion on polymer Tg, δ, and resistance to shear deformation.
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  • 180
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 753-758 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 181
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 775-792 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology of surfaces produced during peel experiments was studied to increase the understanding of peel phenomena. Thin films of polystyrenes of narrow molecular-weight distribution and a polydisperse polyester on flexible supports were peeled from rigid substrates at temperatures above their glass transitions with equipment that also permitted quenching and preservation of the peeled surfaces which then could be studied by scanning electron microscopy. The results show many types of cavitation including foams and the coalescence of cavities to form fibers. Cavitation occurred throughout and beyond the region of transition from cohesive to interfacial failure where peel force decreased abruptly; however, cavity growth was abruptly restricted as the failure mode changed. The master curves and shift factors obtained in this work provided strong evidence that the quenching used to preserve the peeled surfaces did not introduce large perturbations in the results. The reason was that failure occurred at or close to the heated substrate.
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  • 182
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 833-839 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ribbon-like lamellar single crystals of cellulose II are grown from dilute aqueous solution of cellulose triacetate (number-average degree of polymerization (DP)-15) by deacetylation and consequent precipitation. The best results are obtained with methylamine as the deacetylation reagent at 90°C. Electron diffraction indicates the (110) planes to be the growth face. Twin growth occurs frequently with (110) as the twinning plane.
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  • 183
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 859-881 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Results are presented for the thermal, ultraviolet, and γ-ray polymerization of 2,4-hexadiyne-1,6-diol bis-(p-toluene sulfonate) (PTS). Monomer extraction is used to obtain polymer conversion-vs.-time curves at 30, 50, and 80°C. In agreement with previous work over a narrower temperature range, the curves all display a dramatic autocatalytic effect with an onset at about 10% conversion to polymer. Although the polymerization rate undergoes a 200-fold change over this temperature range, the shape of the conversion curves does not change. These data yield an activation energy (Etha) of 22.2 ± 0.4 kcal/mole when interpreted in terms of the time required to reach 50% polymer. An annealing technique is used to provide a closer look at the autocatalytic region. In that case, Etha = 22.5 ± 0.8 kcal/mole is determined from measurements of the time required to go from 10 to 50% polymer at temperatures ranging from 23 to 80°C (a 500-fold change in rate). Thermal polymerization rates measured in the low-conversion limit using a spectroscopic method based on diffuse reflectance yield Etha = 22.8 ± 0.6 kcal/mole. Thus Etha is independent of polymer conversion and the autocatalytic effect can be best understood as arising from a large increase in the propagation length of the polymer chains. The autocatalytic effect is shown to be present in both UV and γ-ray polymerization. In the case of γ-ray polymerization, conversion-vs.-time and spectroscopic measurements are consistent with inhomogeneities in the polymer concentration caused by particle tracks. Activation energies for UV and γ-ray polymerization are quite low (2-3 kcal/mole) and confirm that the chain initiation event makes the major energetic contribution to Etha. The polymerization mechanism is discussed in detail. The photopolymerization experiments can be consistently interpreted with a model based on the triplet excited state of the diacetylene monomer as the chain initiation species.
    Additional Material: 11 Ill.
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  • 184
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 915-919 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The strain history of the combined test is formed by a constant strain rate during the period 0 〈t 〈 t1 followed by a constant strain for t 〉 t1. This test includes as limiting cases the relaxation test (t1 → 0), the constant strain rate or stress growth experiment (t1 → ∞), and the stress relaxation after cessation of constant strain rate flow (t1 sufficiently large). The constant t1 can be chosen arbitrarily such that the test conditions of the combined test can be adjusted according to the problem investigated and to the capability of the testing device. From this, practical advantages follow for linear viscoelastic studies of polymeric solids and liquids, e.g., the zero shear viscosity η0 for unstable polymer melts can be determined at least approximately. In order to obtain linear viscoelastic material functions from the measured stress record, a simple procedure is given which avoids the difficulties with the “factor-of-10 rule” for short relaxation times.
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  • 185
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 921-934 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Precise melting and crystallization temperatures of extended-chain and folded-chain crystals of form I and folded-chain crystals of form II poly(vinylidene fluoride) under high pressure have been obtained by microdifferential thermal analysis (DTA). Upon heating at pressures above 4000 kg/cm2, the micro-DTA thermogram of form II crystallized from the melt at atmospheric pressure shows melting of the form II structure and the melting of the folded-chain and extended-chain crystals of form I, formed through recrystallization processes. These features were clarified by supplemental methods. The bandwidth seen in electron micrographs of the extended-chain crystal of form I obtained by crystallization under high pressure was in the range of 1500 to 2000 Å. At atmospheric pressure, the extended-chain crystal of form I melted at 207°C, approximately 17°C higher than the folded-chain crystal of form I and 31°C higher than the folded-chain crystal of form II.
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  • 186
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 959-965 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The elegant approach of Eshelby, developed for dilute dispersions, is generalized to include the interaction of filler with filler. It is then utilized to determine the five elastic moduli of filled polymer containing aligned ellipsoidal particles at finite concentrations ϕ. The anisotropic particle shape is characterized by an aspect ratio ρ of an ellipsoid. The present theory compares well with available experiments in the literature. The experimentally verified Kerner equation for spherical particles and rule of mixtures for the longitudinal Young's modulus at ρ → ∞ are special cases of our new results.
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  • 187
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1085-1100 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The creep curves of poly(chlorotrifluoroethylene) (PCTFE) and poly(methyl methacrylate) (PMMA) were measured at temperatures near 78°K in nitrogen environments so that practically all the creep strain was produced by crazing. Data were obtained over a range of temperatures, stresses, and partial pressures of the nitrogen. It was found that all creep curves had the form, ε1/3 = ε1/30 + st, where ε0 is the initial strain (∼10-4) and s is a constant which depends on the conditions of the test. The microparameters such as number, dimensions, and velocity of the crazes were measured in each speciman. A theoretical creep equation was derived in terms of these microparameters. There was good quantitative agreement between theory and the experiments.
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  • 188
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The densities of aqueous solutions of some poly(ethylene glycols) (mono-, di-, tri-, and tetraethylene glycol, and four carbowaxes with a mean molecular weight ranging from 600 to 15,000), and of di-, tri-, and tetraethylene glycol dimethyl ether have been determined at 25°C, in the concentration range 5-100 g/liter. From these data, the limiting partial specific and/or molar volume of the solute has been calculated. A value of 37.0 ml/monomole has been evaluated for the partial molar volume of the repeating unit —CH2CH2O—, and has been found independent of both terminal groups and chain length. The results suggest that the ethylene units in higher polymers are accessible to the solvent as easily as in oligomers, and support an “open” or extended conformation of the poly(ethylene glycol) chain in aqueous dilute solution. This interpretation has been confirmed by a comparison of the experimental values of partial molar volume with the values calculated by semiempirical models.
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  • 189
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1139-1154 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Heat effects and structural transformations in amorphous crystallizable poly(ethylene terephthalate) (PET) during uniaxial stretching accompanied by neck formation, have been investigated by calorimetric and x-ray methods over a wide range of temperatures and deformation rates. At small deformation (not exceeding 1-2%) and at temperatures below the glass transition temperature of the polymer, PET behaves as an elastic body. Upon stretching at a constant rate, constant heat power is absorbed, heat effects during loading and unloading coincide completely, and no hysteresis is observed. At large deformations (of the order of 50%), cold drawing develops in this temperature range. The internal energy change in cold drawing is zero within experimental error. A periodic heat release during the self-oscillation regime of drawing PET corresponds to periodic changes in stress, in the rate of the neck formation, and in the appearance of the sample. The temperature limits of the region where crystallization resulting from an uniaxial drawing of the polymer is possible, have been determined, and the heat effect of this phase transition has been measured. Orientation crystallization develops only from 70 to 94°C. These limits are insensitive to changes in deformation rate within one decimal order. The structure of PET in this temperature range has been investigated. The heat of phase transition of orientation crystallization of PET has been determined from the relationship between the measured values of the internal energy change during this process and the limiting degree of crystallinity for the stretched samples. This heat proves to be 5.5 ± 0.1 cal/g.
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  • 190
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1227-1252 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Conformational energy calculations are used to investigate molecular motions in polyethylene crystals. From these a model is derived for the motion that accomplishes the net rotation translation that is believed to underlie the nuclear magnetic resonance (NMR) and dielectric α processes in polyethylenes and paraffins (and their dipole decorated derivatives). The resulting model is found to incorporate features of a number of previous models but differs significantly from all of them. The rotation is accomplished by means of a twisted (by 180°) region that propagates smoothly along the chain across the crystal. It differs from previous rotational models in that the twisted region is found to be rather localized (to ∼12 CH2 units). A dependence of activation energy on chain length (paraffins) or crystal thickness (polyethylenes), with the activation energy becoming independent of thickness in thick crystals, results not from the rotational lattice mismatch of the twisted region per se but from the translational lattice mismatch induced by the 180° rotation of one stem relative to the other. The twist differs from a stable point-defect twist previously proposed (Reneker defect) in that the chain torsion is relatively uniform through the twist and there is no shortening of the chain accompanying it. Further, the twist propagates smoothly without local barriers to its advance. Thus the propagating twist is to be through of as a transition state rather than a hopping defect. Detailed atomistic conformational energy calculations on C22H46 crystals were combined with a simplified elastic theory for translational stem mismatch in longer chains. From the combined calculations the activation parameters for twist propagation as a function of chain length or crystal thickness could be calculated. The results were compared with experiment for the dielectric α relaxation in paraffins containing dissolved ketones and polyethylenes containing carbonyl groups. The agreement is quite good, especially considering the paucity of adjustable parameters in the model. There is only some slight uncertainty in the calculated entropy of activation and a scattering correction was made a posteriori to account for a slow continued drop-off in relaxation rate in very thick crystals.
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  • 191
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1321-1323 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 192
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1355-1364 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal properties of 2,4-hexadiynyl-1,6-bis(p-toluenesulfonate) have been explored by program temperature and isothermal differential calorimetry. The heat of fusion for the rapidly heated pure solid was 8254 cal/mole (34,540 J/mole) at 367.1°K (93.8°C). This amounts to an entropy change of 22.5 cal/mole °K (94.1 J/mole °K). The energy of activation for the thermal polymerizations was 18.97 kcal/mole (79.37 kJ/mole). The thermal polymerization appears to follow a solid-solid phase transition which proceeds by random homogeneous nucleation throughout the process. The kinetics were simple first order over 70% of the reaction. Programmed temperature studies indicate that during the first 10% of the polymerization a new high temperature (mp 375.4°K) solid phase is formed which acts as the monomer form during the bulk of the reaction.
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  • 193
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    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1399-1407 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffusion coefficient of butane in linear polyethylene at room temperature as a function of the vapor pressure of butane was measured by the spin-echo method with a pulsed magnetic field gradient. For the Special morphology of randomly oriented stacks of parallel lamellas the detour factor is 1/3. As long as the blocking factor and migration through the lamellas can be neglected, the local diffusion coefficient Da of the small molecules through the amorphous layers in the direction parallel to the lamellas is three times the apparent diffusion coefficient D derived from the decay of the amplitude of the spin echo under the assumption of an infinitely extended homogeneous medium. The diffusion coefficient and the spin-spin relaxation time both increase exponentially with increasing pressure, i.e., butane concentration in the polymer, while the spin-lattice relaxation time is pressure independent and seems to be determined by interaction with the amorphous polyethylene matrix.
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  • 194
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    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 41-48 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of chlorophosphines (phosphorus trichloride, dichlorophenylphosphine, chlorodiphenylphosphine) on the radical polymerization of methyl methacrylate was investigated in benzene solution. The polymerization was carried out at 50°C by the standard solution method, α,α′-azobisisobutyronitrile being used as an initiator. These chlorophosphines accelerated the polymerization of methyl methacrylate but did not affect the rate of decomposition of α,α′-azobisisobutyronitrile. Ultraviolet and infrared spectral data suggested that the acceleration effect was due to the complex formation of methyl methacrylate with each chlorophosphine. From the result of a copolymerization with styrene, it was found that the reactivity of methyl methacrylate monomer increased in the presence of dichlorophenylphosphine.
    Additional Material: 6 Ill.
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  • 195
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    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 71-76 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of ferrocene-containing polymers by chemical modification of chlorinated polyethylenes, polyvinyl chloride (PVC), and other halogenated polymers, under Friedel-Crafts conditions, is described. The effect of reaction conditions on the structure and composition of the products obtained with various substrates was investigated. Soluble polymers of up to 62% ferrocene content were obtained. In most cases, substitution was accompanied by dehydrohalogenation. The ferrocene-to-vinylene ratio was higher in the reaction products of chlorinated polyethylenes than in those of PVC.
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  • 196
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polydispersity of diallyl phthalate prepolymers was determined by gel-permeation chromatography (GPC). The measurements were carried out in tetrahydrofuran and chloroform on Mexel 2000, Poragel, and Styragel polystyrene gels. The influence of the polymerization conditions, initiator, and type of transfer agent on the molecular weight distribution of the prepolymers is shown. Other correlations of interest, such as molecular weight distribution of Dapon 35 and Dapon 201, are also presented.
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  • 197
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    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 129-136 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerizations of l-menthyl vinyl ether (l-MVE) with styrene (St) and N-phenylmaleimide (N-PMI) as comonomers were carried out in benzene with azobisisobutyronitrile (AIBN) as an initiator to give optically active copolymers. After the removal of the optically active menthyl group by use of hydrogen bromide gas, the ether-cloven l-MVE-N-PMI copolymer (VA-N-PMI) was still optically active. On the other hand, the optical activity of l-MVE-St copolymer disappeared after ether cleavage. It is thought that asymmetric induction took place in the polymer main chains. The optical rotatory dispersion and circular dichroism of the original and ether-cloven copolymers were measured in order to confirm the asymmetric induction.
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  • 198
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    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 77-87 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction between polyelectrolytes and Acridine Orange (AO) has been investigated in the case of poly(acrylic acid) (PAA), poly(methacrylic acid) (PMA), and a polycondensate between 1,3-benzene disulfonyl chloride and L-lysine (PLL) by visible absorption and fluorescence spectroscopy. The influence of both polymer ionization and polymer/dye ratio (P/D) on the spectral behavior of the bound dye has been studied. The stacking tendency of AO is found lower in the presence of PLL under compact conformation (in an ionization range depending on the nature of the counterion) with correlated enhancement of the green fluorescence of the monomeric species of the bound dye. The disappearance of the green fluorescence and the dimerization of bound AO are directly related to the increased flexibility of polyion chains upon ionization. Some analogy is found between the behavior of bound AO in the presence of very compact PLL chains and that reported for AO in the presence of native DNA, which might be due to specific interactions responsible for a kind of “intercalation” of the monomeric bound dye.
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  • 199
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    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 155-162 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel phenylated polyamides having inherent viscosities in the range of 0.2-0.4 were prepared by the ring-opening polyaddition of 2,2′-p-phenylenebis(4,4-diphenyl-5-oxazolone) with aliphatic diamines in polar aprotic solvents. Similarly, unsubstituted polyamides were obtained from 2,2′-p-phenylenebis-5-oxazolone and both aliphatic and aromatic diamines. The phenylated polyamides were highly soluble in a wide range of solvents including tetrahydrofuran and dioxane, while the unsubstituted polymers showed limited solubility in the solvents. No marked differences in thermal stability between the phenylated and unsubstituted polyamides were noted, and all the polyamides began to decompose at around 250°C in both air and nitrogen.
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  • 200
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    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 197-212 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alkylene-linked aromatic polyimides were prepared from a family of new dianhydride monomers and aromatic diamines. The dianhydrides were synthesized by Friedel-Crafts catalysis of the condensation of ditertiary alcohols with o-xylene, subsequent oxidation of the aryl methyl groups to carboxy, and finally, dehydration of the ortho-carboxy substituents to anhydride groups. Alkylene-linked aromatic polyimides, with up to 8 methylene groups in the polymer chain, are stable to 400°C in air and can be extruded or compression-molded at 300°C. In addition, these polymers are soluble in solvents within the solubility parameter range of 10.4 ± 1.2.
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