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  • 11
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 19 (1986), S. 369-372 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 19 (1986), S. 502-502 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 19 (1986), S. 502-502 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 14
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 15
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 18 (1985), S. 2545-2555 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 16
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 30 (1985), S. 3189-3223 
    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: Oxygen injection has been proposed as an effective control measure for limiting the rate of heat release and altering the rate of polymerization in emulsion processes. A detailed mathematical model is developed to describe the system behavior with and without oxygen injection. Because of the rapid penetration of dissolved oxygen into the polymer particles, growing radical chains are terminated prematurely, lowering product molecular weights. Moderate oxygen flows and moderate set point temperatures are found to give the optimal response without significant lowering of the final molecular weight.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 30 (1985), S. 3707-3749 
    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: Several control strategies for the free-radical polymerization of methyl methacrylate are analyzed with a detailed constitutive model incorporating the gel and glass effects. Optimal temperature history, photoinitiation intensity variation, and programmed monomer and solvent additions, employed alone and in combination, represent cases simulated by this model. Solvent addition is selected for further experimental studies, due to some attractive features. The product molecular weight distribution is narrowed, while the molecular weight averages are maintained high. Model predictions of the solvent injection history exhibit a strong sensitivity to the constitutive equations for describing the gel and glass effects.
    Additional Material: 26 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 30 (1985), S. 3825-3840 
    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: Programmed solvent injection was previously proposed and analyzed in the first part of this two-paper series as a viable alternative for controlling the average molecular weight and narrowing the polydispersity of products from a free-radical polymerization process with an inherent tendency to exhibit strong gel and glass effects. Here, methyl methacrylate is chosen for experimental verification of this idea. The product molecular weight distribution is indeed narrowed.
    Additional Material: 10 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 22 (1982), S. 673-683 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Measurements were made of linear viscoelastic properties and nonlinear stress-strain properties of phase-separated styrene-butadiene-styrene (SBS) copolymers and their blends with several homopolymer polystyrenes (PS) and one random copolymer (SBR). Torsion pendulum testing yielded shear moduli G′, G″, and Rheovibron experiments produced tensile moduli E′, E″, over a 220°K range of temperature, both at low frequencies. For pure copolymers and their PS blends, G′ and E′ correlated quite well with the total PS content, but G″ and E″ were more sensitive to how the additive was distributed. Results suggest that a PS additive whose molecular weight (M) is less than that of the copolymer PS-block (Ms) causes expansion of both the interphase and the homogeneous PS-rich phase, while an additive with M 〉 Ms mixes less well with these phases (probably forming separate domains of pure PS) and is less effective in enhancing the linear moduli. The blending with SBB produced reduction in G′ but a broad midrange peak in G″, suggesting that SBR was localized almost entirely within an expanded interphase. Tensile stress-strain data were obtained with an Material Testing System at room temperature. For PS blends, properties did not correlate well with the total PS content, the blends being always weaker than the SBS of the same overall composition. The amount of set also increased with PS content in the blends. Cyclic tests to increasing strain showed progressive structural alterations (as for the host SBS), with blend behavior resembling host properties more closely with each new cycle. When SBR was the additive, amounts as small as 1 percent reduced the curves by 15 percent. The yield stress was eliminated entirely with an addition of 10 percent SBR, but for all cases the set was the same. Results are discussed in terms of interphase force barriers to chain flow.
    Additional Material: 8 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 25 (1985), S. 232-244 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Free-radical polymerization of methyl methacrylate in a tubular reactor has been conducted at above-Tg temperatures. A salient feature of these experiments is the very efficient control of reactor temperature by vapor-liquid equilibrium of the polymerizing mixture via monomer evaporation. The system pressure thus provides a powerful control variable, restricting the temperature in the entire reactor by changing the monomer evaporation rate. In the range of our experimental conditions, the temperature and pressure in the reactor follow the Antoine equation closely. High temperature runs also reduce the length requirement of the reactor. However, molecular weight averages of the products are not impressive, unless slow-burning initiators are used. Modeling of above-Tg reactions has been attempted at two-levels of sophistication. A plug-flow model gives predictions in good agreement with our experimental temperatures and conversion data. The predicted molecular weights are also consistent with the experimentally observed values. However, the more elaborate rheokinctic model suggests that the superficial agreement between model and experiment is due to initiator burn-out, which limits the final conversion to within 40 percent. The liquid layer next to the reactor wall can never be so viscous as to form a stagnant deposit, due to this conversion limitation. The velocity profiles are thus not very much distorted, and a plug-flow model is adequate. With a slow-burning initiator and a sufficiently long reactor, skewing of velocity profile and reactor channeling will eventually emerge. Hence, the rheokinetic model must be evoked to model the system under such conditions.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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