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  • 1
    Unknown
    Cambridge, UK ; New York : Cambridge University Press
    Keywords: Monte Carlo method. ; Statistical physics.
    Pages: xv, 432 p.
    Edition: 2nd ed
    ISBN: 0-511-13098-8
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 7726-7740 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The bond fluctuation model on the simple cubic lattice is studied by Monte Carlo simulations on a multitransputer array, for polymer volume fractions φ in the range 0.025≤φ≤0.500 and chain lengths N in the range 20≤N≤200. Extensive data are presented on the dynamics of monomer displacements, center-of-gravity displacements, and relaxation times. This study is complementary to previous work, in which the crossover scaling properties of the chain linear dimensions, structure factor, and self-diffusion constant were tested for the same athermal model. The simulation technique takes both excluded volume interactions and entanglement constraints into account, but ignores hydrodynamic forces. Our results describe the crossover from Rouse behavior of swollen chains (τ∼N1+2ν, ν being the exponent describing the radius R of the chains, R∼Nν ) to reptation, τ∼N3. Since the excluded volume screening length is found to be smaller than the tube diameter by a factor of about 3, the rescaled times Wτ/N1+2ν decrease first as a function of the scaled chain length N˜∼Nφ1/(3ν−1), before they increase due to the onset of reptation. Additional evidence for reptative behavior is found by identifying the several successive crossovers in the time-dependent displacements predicted by de Gennes.
    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 91 (1989), S. 7265-7275 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A theory is presented to describe the nucleation and subsequent growth of weakly inhomogeneous lamellar phases from a supercooled disordered phase. Detailed calculations are performed for the case of near-symmetric diblock copolymer melts, although the results have relevance for other physical systems in the Brazovskii "universality class.'' Nucleation phenomena in such systems are particularly interesting because the bulk phase transitions have a very weak, fluctuation-induced first order character. We find unusually small nucleation barriers and critically slowed growth kinetics. For a diblock copolymer melt with degree of polymerization N and undercooling δ∝(Tt−T)/Tt(very-much-less-than)1, the barrier is of order ΔF*/kBT∼N−1/3δ−2. Our estimate for the completion time of the nucleation and growth processes is θc ∼N1/12 δ−3/4 τd exp(ΔF*/4kBT), where τd is the copolymer terminal relaxation time.
    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 97 (1992), S. 586-595 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Grafted polymer layers under variable solvent conditions are studied by Monte Carlo simulations using the bond fluctuation model. Structural information such as monomer density profiles, brush thickness, mean-square displacement of monomers, and positions of the monomers along the chain are obtained for temperatures above, at, and below the aitch-theta point. In particular, the scaling of the brush thickness is formulated and verified by the simulation data. At the aitch-theta point, more extensive simulations are performed to investigate the structural and dynamical properties. While the brush thickness at the aitch-theta point agrees very well with the scaling and self-consistent field predictions, the latter deviate from our results for the monomer density profile and the distribution function of the free chain ends. It is not clear whether these deviations result from our chains being too short or from a basic inadequacy of the theory. For the dynamics at the aitch-theta point, both the relaxation of the chain configurations and the mean-square time displacement of the chains are studied. The relaxation time τ for a polymer brush of chain length N and surface coverage σ are found to behave as τ∼N3σb with an apparent exponent b(approximately-equal-to)1.6. For poor solvent conditions below the aitch-theta point, we find that the layer (with randomly fixed grafting sites) develops considerable lateral inhomogenity in its density, which has not been predicted by previous theories.
    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 96 (1992), S. 6291-6306 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The glass transition of a two-dimensional melt of lattice polymers is discussed. The glass temperature Tg is determined by the free volume approach, by the isothermal compressibility as well as by other methods. The decay of the bond autocorrelation function displays typical glasslike behavior. The time temperature superposition law detected in the dynamical polymer structure factor and in orientational autocorrelation functions can be explained by simple dynamical scaling arguments. Mean square displacements observed over more than five decades in time yield very precise diffusion constants as a function of temperature.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 5459-5473 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The behavior of monomer density profiles of a star polymer in a d-dimensional good solvent, which was predicted in an earlier paper using scaling arguments, is now derived by using the renormalization group ε=4−d expansion method. Both the case of a free star in the bulk and of a center-adsorbed star at a free surface are considered. In the latter case of a semi-infinite problem, a distinction is made between repulsive walls, attractive walls—where for large arm length l, the configuration of the star is quasi-(d−1)-dimensional—and "marginal walls,'' where for l→∞ the transition from d-dimensional to (d−1)-dimensional structure occurs. For free stars, ρ(r) behaves as r−d+1/ν for small r, where ν is the exponent describing the linear dimensions of the star, e.g., the gyration radius Rgyr∼lν. For center-adsorbed stars at repulsive or marginal walls, ρ(r(parallel),z) behaves as ρ(r(parallel),0)∼r−d+λ( f )(parallel) and ρ(0,z)∼z−d+1/ν, where r(parallel) and z denote the distances parallel and perpendicular to the surface, respectively; the new exponent λ( f ) depends explicitly on the number of arms f in general. We calculate this exponent λ( f ) to first order in ε=4−d; then λ( f ) is obtained to be (f−1)ε/4+O(ε2) for repulsive walls and 2−ε/4+O(ε2) for marginal walls.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 5444-5458 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Monomer density profiles ρ(r) and center–end distribution functions g(rCE) of star polymers are analyzed by using a scaling theory in arbitrary dimensions d, considering dilute solutions and the good solvent limit. Both the case of a free star in the bulk and of a center-adsorbed star at a free surface are considered. In the latter case of a semi-infinite problem, a distinction is made between repulsive walls, attractive walls—where for large arm length l the configuration of the star is quasi-(d−1) dimensional—, and "marginal walls'' where for l→∞ the transition from d-dimensional structure occurs. For free stars, ρ(r) behaves as r−d+1/ν for small r, where ν is the exponent describing the linear dimensions of the star, e.g., the gyration radius Rgyr∼lν. For center-adsorbed stars at repulsive or marginal walls, ρ(r(parallel),z) behaves as ρ(r(parallel),0) ∼r−d+λ( f )(parallel) and ρ(0,z)∼z−d+1/ν, where r(parallel) and z denote the distances parallel and perpendicular to the surface, respectively; the new exponent λ( f ) depends explicitly on the number of arms f in general. For center-adsorbed stars at attractive walls, ρ(r(parallel),z) behaves as ρ(r(parallel),0)∼r−(d−1)+1/ν(d−1)(parallel), ν(d−1) being the exponent describing (d−1)-dimensional stars, while ρ(0,z) decays exponentially.On the other hand, the center–end distribution function at short distances is described by nontrivial exponents. For free stars with f arms, g(rCE)∼(rCE)θ( f ) for small rCE, where θ( f ) is expressed in terms of the configuration-number exponent γ( f ) and the exponent γ of linear polymers as θ( f ) =[γ−γ( f+1) +γ( f )−1]/ν. For center-adsorbed stars, at repulsive or marginal walls gs(rCE(parallel),ze) behaves as gs(rCE(parallel),0) ∼(rCE(parallel))θ(parallel)( f ), gs(0,zE) ∼(zE)θ⊥( f ) with θ(parallel)( f ) =[γ1−γs( f+1) +γs( f )−1]/ν and θ⊥( f ) =[γ−γs( f+1) +γs( f )−1]/ν, γ1 being the exponent of a linear polymer with one end at the surface. The scaling theory of general polymer networks at the adsorption transition is also presented.The configuration-number exponent γG for a polymer network G with nh h functional units in the bulk, n'h h-functional units at the surface and totally composed of f linear polymers with the same length is given by γSBG =α−1−f+ν +∑∞h=1[nhΔh +nhΔSBh]. Δh and ΔSBh are related, respectively, to the exponents of star polymers as γ( f )=α−1+(γ−α)f/2+Δf and γSBs( f ) =α−1+ν+(γ−α)f/2 +ΔSBf, with α given by α=2−νd. The exponent γSBs( f ) is evaluated by means of the renormalization-group ε=4−d expansion to the first order.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 9288-9299 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The bond fluctuation model of polymer chains on lattices is used to study layers of polymers anchored with one end at a hard wall, assuming good solvent conditions and repulsive interactions between the monomers and the wall. Chain lengths from N=10 to N=80 and grafting densities σ from 0.025 to 0.20 are considered, both for the "quenched'' case, where the anchor points are kept fixed at randomly chosen surface sites, and the "annealed'' case, where lateral diffusion of the anchored ends at the wall is considered. Profiles of monomer density and free end density, chain linear dimensions parallel and perpendicular to the wall, as well as corresponding mean square displacements of inner and end monomers are studied and discussed in the light of current theoretical predictions, and it is shown that most of these properties can be understood in terms of appropriate scaling concepts. Both the relaxation of the total chain configurations and the time dependence of monomer mean square displacements are studied. In the annealed case the lateral diffusion constant D is found to behave as D∼σ−qN−p, where q=2/3 and p crosses over from p≈1 at small σ to p≈2 at large σ. The results for the relaxation time τ are consistent with the recent scaling prediction τ∼σbNa with a=3 and b=2/3.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 8537-8541 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Wetting transitions of binary polymer mixtures in contact with a wall were studied using lattice models by the method of Monte Carlo simulation. First-order wetting transitions were found below the critical temperature but at a moderately high volume fraction of the polymer type favored by the wall. The transitions appear to be second order at low temperatures or for short chain lengths.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 4786-4798 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A recently introduced bead-spring type model of polymer chains with purely repulsive interactions between the beads is modified to allow for attractive forces at intermediate distances. This new model is suitable for the study of thermal properties of three-dimensional polymer solutions and melts and can be efficiently simulated with Link–Cell Monte Carlo methods. As a first step, the single chain lengths up to N=128 beads are studied and the theta temperature θ is located. It is shown that the data are compatible with the theoretically predicted crossover scaling behavior, and that the properties of collapsed chains can be studied for reasonably low temperatures T〈θ. In addition to static properties (chain radii, polymer density inside the coil, internal energy, specific heat) also dynamic properties are obtained, namely various mean square displacements and relaxation times and the self diffusion constant. While for T=θ (and long enough chains), there is reasonable agreement with the Rouse model, a different behavior occurs for collapsed chains. As a second step, the behavior of the polymer solution at T=θ is studied as function of concentration. There is a clear increase of the chain gyration radii with concentration φ, although the values of 〈Rg2〉T=aitch-theta in the highly concentrated regime (melts) are still smaller than their counterparts for the corresponding "athermal'' model (with purely repulsive interactions) at melt densities. Thus one cannot identify the chain linear dimensions at the θ point with the chain dimensions in melts quantitatively. For the chain lengths studied (N≤64) the dynamic properties are compatible with Rouse behavior at all concentrations.
    Type of Medium: Electronic Resource
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