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  • 1
    Electronic Resource
    Electronic Resource
    Dynamic Properties of a Model Reinforced Elastomer. Styrene-Butadiene Reinforced with Polystyrene (1970)
    s.l. : American Chemical Society
    Macromolecules 3 (1970), S. 92-96 
    Details
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/ma60013a019
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  • 2
    Electronic Resource
    Electronic Resource
    Properties of random and block copolymers of butadiene and styrene. I. Dynamic properties and glassy transition temperatures (1967)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 11 (1967), S. 1581-1591 
    Details
    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 effect of monomer sequence on physical properties was investigated for butadienestyrene solution copolymers made by organolithium initiation. The polymers varied from random copolymers of uniform composition along the polymer chain to ideal block polymers of specific block sequence arrangement and included rubbers of intermediate degrees of randomness. Uniform composition random copolymers exhibit a single glass transition temperature and a very narrow dynamic loss peak corresponding to this transition. The glass transition can be predicted from the styrene content and the microstructure of the butadiene portion of the rubber. Random copolymers in which composition varies along the polymer chain, and to some extent between molecules, exhibit a single glass transition, but the dynamic loss peak is broadened. The extent of this broadening is shown to be compatible with the sequence distribution, polymer segments of various compositions losing mobility at different temperatures. This indicates a tendency for association between segments of different temperatures. This indicates a tendency for association between segments of different chains which are similar in composition. Block copolymers display two transitions, corresponding to Tg for each type of block. The position and width of the dynamic loss peaks are related to block length and compositional purity of the blocks.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1967.070110819
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  • 3
    Electronic Resource
    Electronic Resource
    Effect of diluents on the melt viscosity of branched polybutadienes (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 305-310 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The enchanced low-shear melt viscosity of branched polybutadienes is shown to be sensitive to dilution with low molecular compounds. The viscosity of branched polymers falls more rapidly with dilution than that of linear polymers, i.e., branched polymers show increased response to plasticization. At least one instance is demonstrated in which the viscosity ratio ηbr/ηlin reverses from a value greater than unity to less than one in passing from dry polymer to rubber extended with relatively large quantities of oil.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1970.160080209
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  • 4
    Electronic Resource
    Electronic Resource
    Antioxidant properties of carbon black in unsaturated elastomers. Studies with cis-polybutadiene (1964)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 8 (1964), S. 1169-1183 
    Details
    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 thermal antioxidant behavior of carbon black was studied in vulcanized cis-polybutadiene and related to the surface chemistry of the black. Continuous and intermittent stress-relaxation and oxygen absorption measurements were employed to determine the antioxidant ability of the carbon blacks. The blacks were characterized by the surface concentrations of oxygen-containing functional groups, using methods described in the literature. Antioxidant activity was found to be highest in carbons containing relatively large amounts of bound oxygen. These carbons are also acidic and decompose peroxides by the ionic mechanism. This was demonstrated with dicumyl peroxide. However, even though the acidity and ability to decompose dicumyl peroxide to phenol and acetone could be destroyed by methylation, this treatment did not seriously impair the antioxidant activity, so that the role of acidic groups appears to be minor. Evidence is presented which suggests strongly that the antioxidant behavior of carbon blacks is due to surface quinones, possibly hydrogen-bonded with adjacent hydroxyl groups. Measurements made on samples vulcanized in peroxide and sulfur curing systems indicate that the antioxidant behavior of carbon black is independent of the method of vulcanization in the absence of other antioxidants. A characteristic feature of the antioxidant action of carbon blacks is their tendency to repress the oxidative crosslinking reactions, the relative amount of compensation of chain scission by crosslinking being smaller than in gum vulcanizates.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1964.070080311
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  • 5
    Electronic Resource
    Electronic Resource
    Rheological properties of cis-polybutadiene (1965)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 9 (1965), S. 739-755 
    Details
    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 steady-state viscosity of a number of cis-polybutadienes was determined as a function of shear rate and temperature by use of a capillary rheometer. Polymers investigated differed in molecular weight distribution and long chain branching. None of the polymers exhibited Newtonian behavior, even at the lowest shear rates attainable. Nevertheless, for polymers of similar molecular weight distribution and minimum branching, all the capillary viscometer data could be reduced to a single curve by a reduced variable treatment. The molecular weight shift function was found to be the same as for polymers exhibiting a Newtonian flow range, i.e., a 3.4th power law in weight-average molecular weight. Broadening the molecular weight distribution or increasing the degree of long-chain branching led to increasingly pronounced non-Newtonian behavior. Tensile creep experiments showed nonlinear viscoelastic behavior for all polymers studied, even at small strains. This behavior was most pronounced in the more highly branched polymers. At very low stresses some of these polymers exhibited extremely high viscosities, the strain being almost completely recoverable. Under larger stresses the viscosity of these rubbers dropped several decades and in the capillary extrusion experiments these polymers flowed readily. This is the same behavior observed previously in high molecular weight branched (multichain) narrow distribution polybutadienes. It is tentatively explained by a constraint of the branch points on the slippage of chain entanglements. The fact that all cis-polybutadienes exhibit this behavior, while linear polybutadienes made by organolithium initiation do not, suggests that all cis-polybutadienes may be branched to some extent.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1965.070090231
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  • 6
    Electronic Resource
    Electronic Resource
    Properties of random and block copolymers of butadiene and styrene. II. Melt flow (1967)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 11 (1967), S. 2121-2129 
    Details
    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: Flow curves, log (rate of shear) versus log (shear stress), as functions of temperature were obtained for several butadiene-styrene copolymers of fixed (25%) styrene content, differing in monomer sequence distribution. A random copolymer of constant composition along the polymer chain and narrow molecular weight distribution (MWD) exhibited behavior similar to linear, narrow MWD polybutadienes; the flow was Newtonian at low shear stresses, and the flow curves for various temperatures were accurately superimposable by a shift along the log (shear rate) axis. In a random copolymer varying in composition along the polymer chain, non-Newtonian behavior was more pronounced, and temperature-shear rate superposition did not succeed, a trend further perpetuated in copolymer of a single long styrene block sequence. The latter resemble branched polymers, as would be expected from association of the styrene blocks. With two styrene blocks, association produces network structures below the glass transition of polystyrene with consequent loss of flow. Disruption of these associations above Tg (styrene) imparts the greatest thermoplasticity to these elastomers. There is evidence, however, that some of the associations persist at temperatures well in excess of Tg (styrene).
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1967.070111104
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  • 7
    Electronic Resource
    Electronic Resource
    Thermal expansion, free volume, and molecular mobility in a carbon black-filled elastomer (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 571-581 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal expansion of a butadiene-styrene copolymer filled with carbon blacks differing tenfold in mean particle size (HAF and MT) was investigated. The glass transition was unaffected by MT and was raised only 0.2°C for every 10 parts per hundred by weight of polymer of HAF black added. The coefficient of expansion of the polymer component of the composite in the rubbery region was substantially unaffected by either carbon black, but decreased markedly with increasing black loading in the glassy state. These results suggest that free volume is not altered appreciably by the presence of the filler in the rubbery state, but expands with decreasing temperature below Tg. The latter effect is explained by dilatation due to stresses set up around filler particles, arising from differences in the expansion coefficients of filler and polymer, which are not relieved in the glassy state. The near invariability of Tg and of the rubbery fected by adsorption of polymer segments on the carbon black surface. A conservative rough estimate indicates that restriction of segmental motion is confined to a 30 Å layer around the particles in which Tg is elevated by only 10°C.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1970.160080408
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  • 8
    Electronic Resource
    Electronic Resource
    Inhibition of polymerization by carbon blacks (1959)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 36 (1959), S. 564-565 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1959.1203613066
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  • 9
    Electronic Resource
    Electronic Resource
    Kinetics of strain-induced crystallization of a trans-polypentenamer (1972)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2009-2024 
    Details
    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 strain-induced crystallization of a crosslinked 89% trans-polypentenamer was studied as a function of temperature and strain by using a combined birefringence - stress relaxation technique. The crystallization rate was found to be extremely sensitive to both variables and was, within experimental error, a function of the degree of undercooling alone, the increase in crystallization rate with strain being a direct consequence of the melting point elevation. From the isothermal, isometric crystallization rates, the development of crystallinity in constant-rate-of-strain experiments was calculated and related to characteristics of the stress--strain curve and of the temperature-strain rate dependence of tensile strength. These calculations allow one to estimate under what conditions sufficient crystallinity may be expected for the attainment of high strength in absence of reinforcing fillers. Crystallinities measured in this work were of the order of 10% or less. A limited x-ray diffraction study confirmed the low order of crystallinity indicated by the stress-birefringence measurements. The relatively high precision of the latter makes this technique attractive for the estimation of small straininduced crystallinities in rubbers.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1972.180101011
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  • 10
    Electronic Resource
    Electronic Resource
    Rheological properties of polybutadienes prepared by n-butyllithium initiation (1964)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A: General Papers 2 (1964), S. 797-810 
    Details
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The flow behavior of n-butyllithium-polymerized polybutadienes was investigated as a function of molecular weight, temperature, and shear rate. At low shear rates these polymers exhibit Newtonian flow up to molecular weights of several hundred thousand so that “zero shear” Newtonian viscosities can readily be determined without the risk of long extrapolation. Above 10,000 molecular weight the Newtonian viscosities obey the well-known 3.4 power dependence on weight-average molecular weight. The entanglement spacing molecular weight is estimated at 5600. The temperature dependence of viscosity is substantially independent of molecular weight and shear stress and can be represented analytically by functions proposed in the literature. The apparent activation energy for viscous flow is not constant, but decreases with rising temperature. The flow of the polymers becomes increasingly non-Newtonian with the product of shear rate, molecular weight and Newtonian viscosity. However, the departure from Newtonian behavior is apparently less than for any polymer system whose flow behavior has been described in the literature. The indications are, therefore, that sharp molecular weight distribution and freedom from long chain branching favor Newtonian flow and that the n-butyllithium initiated polybutadienes represent some of the most perfectly linear, narrow distribution polymers known.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1964.100020217
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