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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2961-2968 
    ISSN: 0887-6266
    Keywords: anchored coils ; hydrodynamic thickness ; surface forces apparatus ; interfacial rheology ; interface ; viscosity ; theta solvent ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We study the drainage of a near-theta solvent through densely grafted polymer layers and compare to recent notions that these layers display little permeability to solvent flow at surface separations less than a “hydrodynamic thickness.” The solvent is trans-decalin (a near-theta solvent at the experimental temperature of 24°C). The polymer is polystyrene (PS) end-attached to two opposed mica surfaces via the selective adsorption of the polyvinylpyridine (PVP) block of a PS-PVP diblock copolymer. The experimental probe was a surface forces apparatus modified to apply small-amplitude oscillatory displacements in the normal direction. Out-of-phase responses reflected viscous flow of solvent alone - the PS chains did not appear to contribute to dissipation over the oscillation frequencies studied. The value of the hydrodynamic thickness (RH) was less than the coil thickness (Lo) measured independently from the onset of surface-surface interactions in the force-distance profile, implying significant penetration of the velocity field into the polymer layer. As the surface-surface separation was reduced from 3Lo to 0.3Lo, the apparent hydrodynamic thickness (RH*) decreased monotonically to values RH* ≪ RH. Physically, this indicates that the “slip plane” moved progressively closer to the solid surfaces with decreasing surface-surface separation. This was accompanied by augmentation of the effective viscosity by a factor of up to approximately 5, indicating somewhat diminished permeability of solvent through the overlapping polymer layers. Similar results hold for the flow through surface-anchored polymers in a good solvent. It is interesting to note the strong stretching of densely end-grafted polymers in a theta solvent. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2961-2968, 1997
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 33 (1995), S. 2429-2437 
    ISSN: 0887-6266
    Keywords: surface ; adsorption ; exchange ; FTIR-ATR ; histogram ; hydrogen-bond ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polarized infrared spectroscopy in attenuated total reflection was used to investigate the adsorption of PMMA (polymethylmethacrylate) onto PS (polystyrene) that was previously adsorbed onto oxidized silicon from dilute solution in carbon tetrachloride at 30°C. The carbonyl group of PMMA forms hydrogen bonds with surface silanol groups, giving segment-surface interaction energy of 4 kT as against 1 kT for PS (k is the Boltzmann constant, T the absolute temperature). The formation of hydrogen-bonding by PMMA was unaffected, in rate or amount, by preadsorbed PS, but a lesser total amount of PMMA adsorbed onto PS, resulting in a higher average bound fraction. The histogram of the mass adsorbed, attributable to subpopulations of chains with different bound fractions, was inferred by subtracting infrared spectra acquired at successive times. Whereas this histogram was broad and bimodal for adsorption onto bare surface, it was narrower and unimodal for adsorption onto preadsorbed PS. © 1995 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 37 (1989), S. 2767-2772 
    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: Self-assembled films of Octadecyltrichlorosilane (OTS) have been deposited on freshly cleaved mica. A combination of argon plasma pretreatment, long adsorption times in solution, and a posttreatment at a moderate temperature (60°C) were required to form homogeneous OTS layers exhibiting good adherence to the mica. This process is more complex than the procedure required to form similar layers on glass. Advancing contact angles of water droplets ranged from 113 to 116°, with receding angles of 107 to 110°.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 28 (1983), S. 1717-1728 
    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: Stress-relaxation measurements in uniaxial extension, in the terminal zone, were made of sulfonated ethylene-propylene terpolymer (EPDM), neutralized with zinc cation. The sulfonation levels were 15 to 20 meq/100 g polymer (0.47 and 0.62 mol %), and for each level the effect of the ionic plasticizer, zinc stearate, was investigated. For all the polymers, the decay of the modulus with elapsed time was gradual and featureless, reflecting a broad distribution of relaxation times. Sensitivity of the ionomers' structures to thermal history before an experiment was suggested by irreproducibility in the magnitudes, but not the distribution, of relaxation times at a given temperature. For polymers containing zinc stearate measured at 80°C, the amount of permanent set was low for relaxation up to about 20h, but increased rapidly with additional hours of stretch. Time-temperature superposition did not apply. Composite curves were constructed by matching the stress-relaxation response at short times; moduli measured at long times fell above the composite curve. The shapes of the composite curves were similar, regardless of the level of EPDM sulfonation or the presence of zinc stearate. The apparent Arrhenius activation energy for short-time relaxation at similar levels of the modulus was about 35 kcal/mol at 140°C for the unplasticized polymers and about 70 kcal/mol at 90°C for the polymers containing zinc stearate, in contrast to the usual effect of plasticizer on the rate of relaxation of amorphous polymers except near the glass transition temperature.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stress relaxation in uniaxial extension and dynamic shear moduli G′ and G″ have been studied in networks of vinyl-terminated poly(dimethyl siloxane) (PDMS) of five different molecular weights (Mn from 1800 to 29,200) crosslinked with cis-dichlorobis (diethyl sulfide) platinum (II) and containing 10 and 15 wt % of two samples of high-molecular-weight unattached linear hydroxyl-terminated PDMS (Mw 700,000 and 950,000). The Mw/Mn ratio of both the network prepolymers and the unattached linear species was approximately 2. In stress relaxation the stretch ratio was 1.25 or less and the shear relaxation modulus was calculated from the neo-Hookean stress-strain relation. In the dynamic measurements, the strain amplitude was 15% or less; after conversion to the timedependent shear relaxation modulus G(t) the two sets of measurements were combined and the contribution of the unattached species G1(t) was calculated by difference. After multiplication by (1 - v22)-1G0N/Ge, where v2 is the volume fraction of network, G0N is the plateau modulus of the uncrosslinked polymer, and Ge is the equilibrium modulus of the network containing unattached molecules, G1(t) was compared with G11(t), the relaxation modulus was essentially the same in both environments. The relaxation was slower in the networks than in the uncrosslinked polymer by 1 to 2 orders of magnitude, and it increased gradually with increasing Ge, which is a measure of total to pological obstacles represented by crosslinks plus trapped entanglements. A similar but less striking difference between relaxation in a network and in the homologous environment of a linear polymer was previously observed in end-linked polybutadiene networks and the butadiene phase of a styrene-butadiene-styrene block copolymer. It appears that, in these systems where the topology of the obstacles is fixed, the reptation is severely restricted or else alternative modes of configurational rearrangement which contribute to relaxation in the uncrosslinked polymer are suppressed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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