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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    The European physical journal 1 (1998), S. 77-86 
    ISSN: 1434-6036
    Keywords: PACS. 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 83.70.Hq Heterogeneous liquids: suspensions, dispersions, emulsions, pastes, slurries, foams, block copolymers, etc. - 61.20.Qg Structure of associated liquids: electrolytes, molten salts, etc.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract: Aqueous micellar solutions of ionic/neutral block copolymers have been studied by light scattering, small angle neutron scattering and small angle X-ray scattering. We made use of a polymer comprised of a short hydrophobic block (polyethylene-propylene) PEP and of a long polyelectrolytic block (polystyrene-sulfonate) PSSNa which has been shown previously to micellize in water. The apparent polydispersity of these micelles is studied in detail, showing the existence of a few large aggregates coexisting with the population of micelles. Solutions of micelles are found to order above some threshold in polymer concentration. The order is liquid-like, as demonstrated by the evolution with concentration of the peak observed in the structure factor ( ), and the degree of order is found to be identical over a large range of concentrations (up to 20 wt%). Consistent values of the aggregation number of the micelles are found by independent methods. The effect of salt addition on the order is found to be weak.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1292-895X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract: We report the results of small-angle neutron scattering (SANS) studies on aqueous solutions of spherical polyelectrolyte micelles formed by association of charged-neutral diblock copolymers. The neutral moieties are found to self-assemble into small dense spheres (cores of the micelles) whose sizes are independent of the polymer concentration c. In the dilute regime, c〈c *, where c* is the overlap concentration of the micelles, the conformation of the charged groups, which form the corona of the micelles, is found to be extended. A liquid-like order is observed over a wide concentration range spanning from the dilute regime to the concentrated regime. For c〉c *, polyelectrolyte correlations appear at smaller spatial scales and coexist with the liquid-like order. These results suggest that for dense brushes, above c*, the rod-like statistics of the charged chains begin to disappear due to contraction of corona arms or by interpenetration of coronae. For less dense brushes, the charged chains are found to be extended up to concentrations far above c*, before the progressive development of polyelectrolyte correlations.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical chemistry accounts 82 (1992), S. 383-396 
    ISSN: 1432-2234
    Keywords: Reptation ; Constraint release ; Viscosity ; Entanglement phenomenon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A numerical solution to the parallel processes model for combined reptation and constraint release in polymer melts is presented. The discrete chain solution to the problem exhibits an exponent of 3 in the molecular weight dependence of the viscosity, just as in the strict reptation case; the magnitude of the viscosity is overestimated and no crossover to reptation is observed, as in Graessley's independent processes model. It is shown that linear combinations of reptation and constraint release, as modeled here, cannot describe the viscosity results observed experimentally.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical chemistry accounts 82 (1992), S. 343-350 
    ISSN: 1432-2234
    Keywords: Adsorption ; Block copolymers ; Ionic solutions ; Polyelectrolytes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary We consider the adsorption of aA-B diblock copolymer on a planar hydrophobic surface in aqueous solution. The hydrophobic anchor (A) block is envisioned to avoid water and adsorbs on the solid-liquid interface in a collapsed state. The buoy block (B) is a polyelectrolyte which expands in solution and forms a brush whose structure depends strongly on the ionic strength of the solution. The minimization of the grand canonical free energy of the system gives access to the surface density (σ), the thickness of the collapsed layer (L A ) and the thickness of the external polyelectrolyte layer (L B ). These three parametersL B ,L A and σ are functions of the molecular weight of the anchored block (N A ), the molecular weight of the buoy block (N B ), the charge of the polymer (Z) and the ionic strength of the aqueous solution (∅ s ).
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Rheologica acta 19 (1980), S. 452-461 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Zusammenfassung Es wurde gefunden, daß die Diffusion von Polystyrol in die Mikroporen von porösen Packungen chromatographischer Säulen, wie sie für die Trennung von Makromolekeln verschiedener Teilchengrößen Verwendung finden, sowohl von der Fließgeschwindigkeit der Polymerlösung durch die Säule als auch von der Größe der Makromolekeln und der inneren Poren erheblich beeinflußt werden. Verdünnte Polymerlösungen (0,05 Gew.-% Polystyrol in THF) wurden kontinuierlich durch die Säulen (Dupont SEC) gepumpt. Dabei wurde die Fließgeschwindigkeit sprunghaft geändert und die Polymerkonzentration im Auslauf kontinuierlich registriert. Wenn die Durch-flußgeschwindigkeit erhöht wurde, verschob sich der Verteilungskoeffizient der Polymeren zwischen bewegter und stationärer Phase zu höheren Polymeranteilen in der Säule hin, was durch einen Konzentrationsabfall in der ausfließenden Lösung während einiger Minuten nach dem Geschwindigkeitssprung angezeigt wurde. Molekulargewicht, Porenweite und Lösungsmitteleinfluß wurden eingehend untersucht. Dabei ergab sich, daß die Polymermolekeln in die inneren Poren der Packung mit einer fließgeschwindigkeitsabhängigen Geschwindigkeit hineindiffundieren und dies in einem um so höheren Maße, je größer die Molekeln sind, vorausgesetzt, daß sie nicht aus sterischen Gründen zurückgehalten werden. Diese dynamische diffusive Verteilung ist natürlich von Bedeutung für die Trenncharakteristik einer GPC-Säule und wirft ebenso einiges Licht auf verschiedene qualitativ ähnliche Beobachtungen beim Fluten mit Polymeren zur Ausbeutesteigerung bei der Ölförderung.
    Notes: Summary We have found that diffusion of polystyrene into the micropores of packed porous chromatographic columns of a type used for size separations of macromolecules is strongly influenced by the flow rate of the polymer solution through the column and also by the macromolecular size and internal pore size of the column packing. Dilute polymer solutions (0.05 wt.% polystyrene in THF) were pumped continously through the columns (Dupont SEC). Step changes in flow rate were made and the polymer concentration in the column effluent was monitored continuously. When the flow rate was increased, the partition coefficient for polymer between mobile and stationary phase shifted toward more polymer retention in the column, as evidenced by the drop in outlet concentration for several minutes following the step change. Molecular weight, pore size and solvent effects have all been thoroughly investigated. The conclusion is that polymer molecules diffuse into the internal pores of the column packing at a flow ratedependent rate and moreover, they do so to a greater extent the larger the polymer molecule, provided they are not sterically excluded from the pores. This dynamic diffusional partitioning is clearly important in its effect on resolution characteristics of an SEC column and also sheds some light on qualitatively similar observations in polymer flooding for enhanced oil recovery.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The recently developed technique of dynamic light scattering from ternary solutions, in which the solvent and matrix polymer are isorefractive, can provide extensive information about the translational diffusion of polymers in semidilute and concentrated solutions. However, the strong molecular weight dependence of diffusion in these regimes has a substantial effect on the observed autocorrelation functions. It is demonstrated that the traditional cumulants approach is inadequate for extracting the desired decay rates, even for narrow distribution samples (i.e. Mw/Mn≅1.05). Alternative methods of analysis are proposed, and implications for other polymer diffusion experiments are discussed.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 26 (1981), S. 2067-2076 
    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 development of heterogeneous structure during the polymerization of a polyurethane system using a polyether diol of M̄n = 2000 as the soft segment and 4,4′-diphenylmethane disocyanate extended with 1,4-butanediol as the hard segment was monitored following the amount of light transmitted by the sample and the increase in viscosity of the reacting mixture. The amount of light transmitted by the reacting sample was observed to decrease sharply at a given point in the reaction. The cloud point was taken as the onset of phase separation in the system and the number average sequence at this point was found to be fairly constant at about 1.3 independent of reaction temperature and system composition. In many cases, the cloud point occurred at quite low conversion, meaning that a significant amount of subsequent polymerization occurs in a heterogeneous medium. It was also found that the viscosity of the material reached very large values at partial conversions of the monomers and presented throughout the reaction values larger than those expected from an increase in molecular weight alone. Viscosity is apparently sensitive to a different aspect of the phase separation process than the light transmission.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0887-6258
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 31 (1985), S. 1178-1186 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Gradient theory of equilibrium fluid microstructures is extended to nonequilibrium isothermal processes. The theory is applied to steady diffusion across liquid-liquid interfaces. It is shown that local equilibrium across a fluid-fluid interface is maintained even in the presence of very high diffusion fluxes and that the concept of an interface acting as an applied potential energy for a diffusing species is of limited utility. The theory is suited for practical, semiempirical calculations of structure, stress, and isothermal transport in systems containing interfaces.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 15 (1975), S. 386-393 
    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: A versatile model for ε-caprolactam polymerization is presented. A deterministic, mathematical basis for obtaining the most probable distribution of molecular weights in batch polymerization is developed. Continuous polycaproamide production has been modeled and shown to give othe than most probable distribution in many cases. The effect of adding monofunctional agents has been investigated. Results of some preliminary studies toward determining the optimal reactor configuration are presented.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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