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  • 1
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The changes that are observed under magnification when a single polyvinyl chloride particle is immersed in a drop of diluent and slowly heated have been explained on the basis of a three-dimensional network system in which the polymer crystallites act as junction points for the network. The existence of a temperature at which a sharp gel-to-sol transformation is observed has been attributed to the melting of the polymer crystallites. The temperature at which this transformation occurs was found to be rate-independent, reproducible, and characteristic for each polyvinyl chloride-diluent system. At this apparent melting temperature, the volume fraction of the diluent in the swollen particle was shown to approach unity. These findings made it possible, for the first time, to apply to polyvinyl chloride-diluent systems Flory's treatment of the effect of diluents on the crystal melting temperature of semicrystalline polymers. The apparent melting temperatures of polyvinyl chloride with 27 diluents were determined by the above method. The interaction parameter χ for each of the diluents used had been previously reported by Doty and Zable. A linear relationship was obtained when the reciprocal melting temperature was plotted against (1-χ)/V1 for all of the above polyvinyl chloride-diluent systems (V1 is the molar volume of the diluent at the melting temperature). From this plot the values for the extrapolated melting temperature of pure polyvinyl chloride and for the average heat of fusion were calculated and found to be 176°C. and 656 cal./mole, respectively. Based on these findings a micromethod has been developed which can be used to determine the parameter χ of a diluent with polyvinyl chloride from a single determination of this apparent melting temperature. This method also yields the value for the energy of interaction parameter B.
    Additional Material: 7 Ill.
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  • 2
    ISSN: 0095-9898
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 43 (1960), S. 101-116 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polarized infrared spectra of crab chitin crystallites, blowfly larval cuticle, lobster tendon, and partially deacetylated lobster chitin have been studied. In addition, the spectra of amorphous deacetylated chitin, deuterated lobster chitin and crystalline N-acetylated chitohexaose were obtained and analyzed. Band assignments have been made with the aid of previous work on celluloses and other related molecules. The complete intermolecular C=O----H—N hydrogen bonding scheme, orginally proposed by Carlstrom from x-ray studies, is in agreement with the infrared data. With the aid of a scale model of the chitin unit cell, a number of hydrogen-bonding schemes involving the primary hydroxyl group have been examined and are discussed.
    Additional Material: 8 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 43 (1960), S. 71-84 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The infrared spectra of doubly oriented films of mercerized ramie and Fortisan crystallites were observed over the 650-3600 cm. -1 frequency range. Polarization properties of the bands were determined. The CH2 symmetric bending frequency was found to be parallel polarized, from which it was concluded that the C6 hydroxyl groups are not engaged in intramolecular hydrogen bonds. The perpendicular bands in the OH stretching region are associated with intermolecular hydrogen bonds most probably in the 101 plane. The two bands showing strong parallel dichroism in the OH stretching region are associated with O3 → O′5 intramolecular hydrogen bonds. The observed data allowed a critical evaluation of the various hydrogen bonding schemes which have been proposed for cellulose II. Alternate schemes which are in better agreement with the infrared data are considered.
    Additional Material: 8 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 46 (1960), S. 3-17 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A viscometric polydispersity index may be calculated by forming the ratio of the viscosity-average molecular weights of a polymer in a relatively good solvent and in a relatively poor solvent and subtracting 1. This index has been examined by measuring dilute solution viscosities of a polydisperse polystyrene and a polydisperse methyl methacrylate in a variety of solvents, calculating viscosity-average molecular weights using Mark-Staudinger-Houwink equations, and forming the viscometric polydispersity indices. These are compared to Schulz parameters, weight-average-number-average molecular weight ratios minus 1, determined from osmotic pressure and light scattering. Viscometric polydispersity indices are more sensitive to polydispersities than expected when compared to Schulz parameters if account is taken of the differences in the powers of molecular weight in the various molecular weight sums. Viscometric polydispersity indices are examined for other polymers, including an almost monodisperse polystyrene. From these measurements it is concluded that the viscometric polydispersity index is valuable for characterizing the polydispersity of polydisperse linear polymers and rough fractions. The weight-average-viscosity-average polydispersity index is more sensitive than the viscometric polydispersity index and may be used to characterize relatively monodisperse linear polymers.
    Additional Material: 2 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 42 (1960), S. 383-390 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymerization of the dichlorophosphinic nitride trimer, catalyzed by benzoic acid, ether, ethanol, or methanol, is first order in the trimer. With methanol and benzoic acid as catalysts, but not with ether, the first-order rate constants increase linearly with catalyst concentration. Solution polymerization in benzene is somewhat slower than bulk polymerization.
    Additional Material: 5 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 44 (1960), S. 549-551 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 8
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polarized infrared spectra of polypropylene, poly(propylene-1,1-d2), poly(propylene-2-d), and poly(propylene-3,3,3-d3) in the carbon - hydrogen and carbon - deuterium stretching regions were observed and interpreted. The A and E components of each stretching mode were found to be at the same frequency. The polarization of both CH2 and CD2 symmetric stretching bands was observed to be weakly parallel. This observation would probably imply that the bisector of the HCH or DCD angle makes an angle somewhat less than 54° 44′ with the helical axis. The tertiary CH stretching frequency was found at about 2920 cm. - 1. The two antisymmetric CH3 (or CD3) stretching frequencies were resolved in the polarized spectra of the polymers. From this infrared study, it is suspected that poly(propylene-3,3,3-d3) may have a different structure than the other polypropylenes used in this work.
    Additional Material: 4 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 44 (1960), S. 195-211 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Free radicals as well as peroxides are formed when irradiation of polyethylene is accomplished with the use of cobalt-60 or a Van de Graaff electron accelerator, as radiation sources, even in the presence of air. The free radicals are able to induce graft copolymerization under low temperatures, in which peroxide grafting cannot occur. When the irradiated polymer is stored in air, the trapped free radicals disappear monomolecularly, probably combining with oxygen. The activation energy for this reaction is 20 kcal./mole. In graft copolymerization by free radicals, the percent grafting is proportional to the square root of the free radical content, and the higher the grafting temperature, the faster the initial rate of graft copolymerization. There occurs, however, a saturation phenomenon of the per cent grafting with a grafting time, especially in high temperatures, and the higher the grafting temperature, the smaller the saturation value. It is believed that the kinetic theory of vinyl polymerization in a homogeneous system is applicable for graft reaction in spite of its apparent heterogeneous character.
    Additional Material: 19 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 45 (1960), S. 289-303 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polycondensation of ethylene dichloride and 3,3′-iminobis(propylamine) resulted in high molecular weight soluble polymers or insoluble gels, depending on the ratio of the reactants and the extent of reaction. It is shown that the functionality of a polyfunctional compound containing groups of unequal reactivities can be determined experimentally. The effective functionality of 3,3′-iminobis(propylamine) was found to be 2.9 from gelation studies and 3.5 based on the relative reaction rates of the primary and secondary amino groups. By using the effective functionality value, the reaction kinetics can be treated in a simple manner. A typical soluble polymer formed has a low intrinsic viscosity and a very high M̄w/M̄n ratio. Condensations of other alkylene dichlorides and alkylene polyamines demonstrated the validity of Carothers' rule that high polymers will not result if formation of 5- or 6-membered rings is possible.
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