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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 88 (1984), S. 6613-6617 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , 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 99 (1993), S. 4804-4820 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Although the lattice cluster theory (LCT) incorporates many features which are essential in describing real polymer blends, such as compressibility, monomer structures, local correlations, chain connectivity, and polymer–polymer interactions, it still remains a mean field theory and is therefore not applicable in the vicinity of the critical point where critical fluctuations become large. The LCT, however, permits formulating the Ginzburg criterion, which roughly specifies the temperature range in which mean field applies. The present treatment abandons the conventional assumptions of incompressibility and of composition and the molecular weight independent effective interaction parameter χeff upon which all prior analyses of the Ginzburg criterion are based. Blend compressibility, monomer structure, and local correlations are found to exert profound influences on the blend phase diagram and other critical properties and, thus, exhibit a significant impact on the estimate of the size of the nonclassical region. The LCT is also used to test various methods which employ available experimental data in computations of the Ginzburg number Gi. The reduced temperature τ=||T−Tc||/T defining the range of the validity of mean field theory (τ(approximately-greater-than)τMF) and the onset of the Ising-type scaling regime (τ(approximately-greater-than)τcrit) are quite different, and renormalization group estimates of τMF and τcrit are presented as a function of Gi to more precisely specify these scaling regimes.
    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 105 (1996), S. 4798-4811 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The segmental concentration profile ρ of end-tethered flexible polymer chains is calculated for comparison with recent measurements on polymer layers having a low surface grafting density σ. Moments of ρ are also calculated as these quantities, rather than the full concentration profiles, are usually measured experimentally. Exact calculations of ρ are summarized for ideal flexible chains with an arbitrary short-range polymer–surface interaction. Though technical difficulties restrict our renormalization group (RG) calculations for swollen chains to limiting values of the polymer–surface interaction, our analysis indicates that the relatively simple, closed-form, Gaussian-chain expression for ρ provides a good approximation to the RG results if the average size of the Gaussian chain is replaced by its swollen-chain analog. This approximate concentration profile for chains with excluded volume and variable polymer–surface interaction should prove useful when interpreting experimental results for low-grafting-density polymer layers formed in good solvents. Recent measurements [Kent et al., J. Chem. Phys. 103, 2320 (1995)] of the second moment of ρ in the limit σ→0 agree well with our RG calculations, and the measured concentration profile ρ, whose determination by neutron reflection is somewhat uncertain, agrees qualitatively with our theoretical predictions. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 18 (1985), S. 821-823 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 20 (1987), S. 543-551 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 17 (1984), S. 1854-1870 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    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 104 (1996), S. 1589-1599 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The effect of shear on the ordering temperature of a triblock copolymer melt of polystyrene-polybutadiene-polystyrene (SBS) is examined by in situ small angle neutron scattering (SANS). Results obtained by SANS are compared to the rheologically determined order–disorder transition temperature, TRODT=115±5 °C. The SANS measurements from a Couette geometry shear cell are then used to construct a "dynamical phase diagram'' based on characteristic changes in the scattering with temperature and shear rate, γ(overdot). A shear rate dependent ordering temperature, Tord(γ(overdot)), is identified as the system is sheared isothermally from the disordered state. The scattering behavior is shown to be highly strain dependent. We compare our findings on the shear rate dependence of the ordering transition in triblock materials with previous observations on diblock copolymer materials and theoretical expectations for the shear rate dependence of the order–disorder transition temperature. A simple scaling argument leads to a good description of the shear rate dependence of Tord(γ(overdot)) in both diblock and triblock copolymer measurements over the range of shear rates examined. © 1996 American Institute of Physics.
    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 100 (1994), S. 3821-3826 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: An algorithm originally devised for calculating the diffusion-controlled reaction rate toward an arbitrarily shaped object is adapted to calculate the scalar translational hydrodynamic friction and the electrostatic capacitance of the object. In this algorithm Brownian particles are launched from a spherical surface enclosing the object. Each particle is propagated until it either hits the enclosed object or crosses the starting surface. In the latter case the particle is allowed to escape to infinity with an analytically known probability. If the particle does not escape to infinity, it is put back on the starting surface with the correct distribution density and the process is repeated. The scalar friction or capacitance of the "probed'' object is proportional to the fraction of particles that hit the object. This algorithm is illustrated on a dumbbell made of two equal-size spheres, a cube, and a phantom spherical shell having random distributed beads embedded in its surface.
    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 87 (1987), S. 1346-1354 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The renormalization group method is employed in conjunction with the Kirkwood–Riseman and two-parameter models to study the double crossover dependence of the hydrodynamic radius of flexible polymers on both hydrodynamic and excluded volume interactions. An exact second order in ε crossover analysis is derived for the limiting cases of Gaussian and self-avoiding chains and for free-draining and nondraining chains. Our calculations show that the excluded volume and hydrodynamic interactions act competitively to affect the dynamical measures of the molecular dimensions, so that an increase in the excluded volume interaction produces a decrease in the strength of the effective hydrodynamic interaction. This coupling of the hydrodynamic and excluded volume interactions can provide an explanation of why dynamical measures of polymer dimensions are often found to scale with lower exponents than equilibrium measures, and methods are described for experimentally testing such an explanation.
    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 86 (1987), S. 4280-4293 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Gell-Mann–Low style renormalization group is applied to the two-parameter type model of block copolymers and mixtures. These systems have multiple excluded volume interaction variables between like and unlike chemical species in addition to variables characterizing the lengths of the substituent blocks. This leads to a five parameter model for monodisperse binary polymer mixtures and diblock copolymers. We derive the full crossover dependence of dilute solution block copolymer and mixture properties on all five parameters by calculating effective exponents in the crossover region to second order in ε=4−d and the prefactors to order ε. The multiparameter renormalization group equation is solved to first order in ε, and a simplifying approximation is introduced to derive closed analytic forms charcterizing average polymer dimensions. Specific radial observables of block copolymers, such as the radius of gyration and the mean square end-to-end vector distance of di- and triblock copolymers as a whole and of the individual blocks, are evaluated in order to compare with Monte Carlo calculations in the avoiding block limit. An important component of this comparison involves the use of a physical reference state to replace the nonexistent theta state for blocks and mixtures. Good agreement is found between the Monte Carlo data and the renormalization group predictions. Moreover, the renormalization group calculations cover a much larger domain of the parameter space of variable excluded volume interaction and composition than explored in previous Monte Carlo studies. Our calculations also provide the basic input parameters for a renormalization group description of semidilute solutions of block copolymers and mixtures.
    Type of Medium: Electronic Resource
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