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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. 9142-9153 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We provide a mathematical formalism for a self-consistent mean field treatment of long chain molecules. The formalism is applied to the case of a neutral polymer under the excluded volume interaction. Upon scaling the problem in the N→∞ limit we find the natural scaling length RN, of the polymer, which is made up of (N+1) monomers or beads, is RN∼N3/5, the well known Flory result. The asymptotics of the problem is dominated by the neighborhood of the turning point, so that a uniformly valid Green's function solution of the differential equations is necessary. In the neighborhood of a point y* the scaled polymer density fN(x), is found to decay sharply. If we let x denote the scaled distance from one end of the chain to a point in space we obtain, for y*−x(approximately-greater-than)O(N−2/15), a closed form expression for the polymer density viz., fN(x)∼{1/2x2[fN(x)−fN(y*)]1/2} while for x−y*(approximately-greater-than)O(N−2/15) the density is shown to be, to leading order, zero. Although our results imply the rate of decay of the density at y* is O(N1/5) we are unable to verify this explicitly by calculating fN′(y*). We believe this is due to the inability of the WKB theory to correctly approximate solutions in regions of rapid variation. We suggest remedies for this, so that a complete self-consistent solution may be obtained. © 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. 5294-5303 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We investigate the problem of wetting transitions in polymer blends confined to a slitlike adsorbing capillary of thickness H by Monte Carlo methods. Two paths for capillary wetting are considered, either along a path of increasing temperature, T, or increasing surface chemical potential, μ1. We find that H can be thought of as an additional thermodynamic parameter which controls the nature of the transitions. We find that there exists a capillary critical separation, Hc. For separations less than Hc the blend falls in the one phase region of the phase diagram. Above Hc there exists a separation Hbulk, where the polymer blend begins to show bulk behavior. Hbulk is shown to separate regions of first order transitions (H〈Hbulk) from critical wetting transitions (H≥Hbulk). Along a path of constant T and increasing μ1 we find for 2ξ〈H1〈H2〈Hbulk that the first-order transitions between the two separations is shifted according to μc1(H2)−μc1(H1)∝1/H1−1/H2. We discuss the implications of these results for the case of H→∞ and compare them with theoretical results. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 106 (1997), S. 4282-4290 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Prewetting transitions in polymer blends near a hard surface which favors one of the phases in the blend are studied by both mean-field and Monte Carlo methods. The mean-field results predict for systems that have a first-order wetting transition at a bulk density of (ρ∞)W, there exists first-order prewetting transitions for (ρ∞)W≤ρ∞〈(ρ∞)PW. For ρ∞〉(ρ∞)PW there exist second-order transitions so that (ρ∞)PW may be identified as the prewetting critical point. Monte Carlo simulations of the bond fluctuation model on a simple cubic lattice between two hard walls H lattice spacings apart are performed and qualitative agreement is found with the mean-field predictions. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 105 (1996), S. 3849-3858 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We investigate the problem of wetting transitions in polymer blends near a hard surface or wall by using a Monte Carlo technique to study the wetting transition along a path of increasing surface chemical potential. We introduce a parameter εs which describes the monomer–monomer interactions in the layer adjacent to the wall. This parameter is shown to behave similarly to the parameter g, used in mean field theory to describe the change in monomer–monomer interactions due to the wall. We identify a wetting tricritical point which may be defined either with respect to εs or the bulk density. For bulk densities less than the tricritical bulk density we obtain first-order transitions while for bulk densities greater than the tricritical bulk density we obtain critical wetting transitions, in accordance with mean-field theory. We also show how the molecular weight of the polymer can be varied to obtain first-order or critical wetting, as desired. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 3740-3741 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We consider the order of wetting transitions in polymer mixtures with particular reference to the recent self-consistent mean field calculation of Genzer and Composto [J. Genzer and R. J. Composto, J. Chem. Phys. 106, 1257 (1997)]. We discuss anomalies between these results and the simulation results of Pereira and Wang, and suggest a possible reason for the discrepancies. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
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