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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 8786-8794 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have used composition depth profiling of polymer bilayers, based on nuclear reaction analysis, to determine miscibility, phase coexistence, and critical temperatures in mixtures of random olefinic copolymers of mean composition E1−x/EEx; here E is the ethylene group −(C4H8)−, EE is the ethylethylene group −[C2H3(C2H5)]−, and one of the copolymers is partially deuterated. The components in each binary mixture have different values x1,x2 of the EE fraction. Using a simple Flory–Huggins mixing model, our results enable us to extract an interaction parameter of the form χ(x1,x2,T)=A(x1,x2)/T, where for given x1,x2, A is a constant. Calculated binodals using this form fit our measured coexistence curves well, while allowing χ a weak composition dependence improves the fit further. Within the range of our parameters, our results suggest that in such binary polyolefin mixtures the interaction parameter increases roughly linearly with the extent of chemical mismatch expressed as the difference in degree of ethyl branching between the two components. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 8795-8806 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Using nuclear reaction analysis, we have measured the enrichment by one of the components at the surface of a binary mixture of random olefinic copolymers, with components of monomer structure E1−x1EEx1 and E1−x2EEx2. Here E and EE are the linear ethylene and branched ethylethylene groups (C4H8) and [C2H3(C2H5)], respectively, and x represents the fraction of the EE group randomly distributed on the chains. We examined 12 different couples covering a range x=0.38–0.97. The mixtures, whose thermodynamic behavior was established in our earlier paper, were cast in the form of films on both a silicon and on a gold-covered silicon surface, and were investigated in the one-phase region of the binodal in the vicinity of the critical temperature. We find that it is always the more flexible component—the one with a shorter statistical step length, corresponding to the higher ethylethylene fraction (higher x)—that is enriched at the polymer/air surface. Within our resolution neither component is enriched at the polymer/solid interface. These results show clearly that enthalpic rather than entropic factors dominate the surface potential driving the surface enrichment. For two of the mixtures we determined the excess of the surface-preferred species as a function of mixture composition along an isotherm in the one-phase region of the binodal. A consistent description of our data in terms of a mean-field model is provided by including in the surface potential a term in the mixture composition gradient at the polymer surface. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    [s.l.] : Macmillan Magazines Ltd.
    Nature 398 (1999), S. 206-207 
    ISSN: 1476-4687
    Source: Nature Archives 1869 - 2009
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
    Notes: [Auszug] Wiersma et al. have reported near-infrared optical transmission and coherent backscattering data from strongly scattering slabs of micrometre-sized semiconductor particles. Their optical transmission was much weaker, and the angular shape of their coherent backscattering more rounded, than ...
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2691-2702 
    ISSN: 0887-6266
    Keywords: surface segregation ; polyolefin copolymers ; deuterium labeling effect ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have examined the effect of deuterium labeling on surface interactions in mixtures of random olefinic copolymers [C4H8]1-x[C2H3(C2H5)]x. Based on surface segregation data we have determined a surface energy difference χs between pure blend constituents. In each binary mixture components have different fractions x1, x2 of the group C2H3(C2H5), and one component is labeled by deuterium (dx) while the other is hydrogenous (hx). The mixtures are grouped in four pairs of structurally identical blends with swapped labeled constituent (dx1/hx2, hx1/dx2). For each pair the surface energy parameter χs increases when the component with higher fraction x is deuterated, i.e., χs(dx1/hx2) 〉 χs(hx1/dx2) for x1 〉 x2. A similar pattern has been found previously for the bulk interaction parameter χ. This is explained by the solubility parameter formalism aided by the lattice theory relating the surface excess to missing-neighbor effect. χs has also an additional contribution, insensitive to deuterium swapping effect, and related to entropically driven surface enrichment in a more stiff blend component with a lower fraction x. Both enthalpic and entropic contributions to χs seem to depend on the extent of chemical mismatch between blend components. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2691-2702, 1998
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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