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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 24 (1991), S. 5226-5229 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 25 (1992), S. 2470-2473 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 26 (1993), S. 1120-1136 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
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  • 4
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 27 (1994), S. 7079-7084 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
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  • 5
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We derive a Landau free energy functional for polymeric mixtures containing components with different sequence statistics. We then apply this general field theory to two mixtures that belong to the Ising universality class: mixtures of two different linear random copolymers, and ternary systems of linear random copolymers and two homopolymers. We discuss the instability conditions for the homogeneous state of these mixtures, and calculate the structure factors for different components in the homogeneous state. The structure factors show interesting features which can directly be compared with scattering experiments carried out with selectively deuterated samples. We also work out the eigenmodes representing the least stable concentration fluctuations for these mixtures. The nature of these concentration fluctuations provides information regarding the ordered phases and the kinetic pathways that lead to them. We find various demixing modes for different characteristics of the two mixtures (e.g., average compositions, statistical correlation lengths, and volume fractions). © 2000 American Institute of Physics.
    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 115 (2001), S. 3387-3400 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study microphase ordering of molten randomly grafted copolymers (RGCs) by using a mean field theory and the replica method to calculate the quenched average. Our results illustrate that in the weak segregation limit (WSI), the optimal wave vector q* of the lamellar phase formed by molten RGCs, has a temperature dependence different from either linear random copolymers (LRCs) or diblock copolymers (DCPs): when close, but below the microphase separation transition (MST) temperature, q* increases sharply with decreasing temperature; then q* gradually acquires an asymptotic value determined by the length of the branch and the average distance between branch points on the backbone. Our results are compared with recent experiments, and the effects of chain architecture on the microphase separation characteristics of RGCs are delineated. Our results suggest a new method for controlling the microphase spacing by exploiting quenched disorder. © 2001 American Institute of Physics.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 112 (2000), S. 1598-1605 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We use a Landau theory to study the instability of the homogeneous state of a mixture of linear random copolymers and diblock copolymers. Interesting features of the calculated structure factors for different components of the mixture are found, which can be directly compared with scattering experiments with selectively deuterated samples. We also investigate the least stable concentration fluctuations and find four different types of segregation modes at the spinodal depending upon the characteristics of the mixture (e.g., average compositions, statistical correlation lengths and volume fractions). The different segregation modes are also indicative of the kinetic pathways leading to the formation of ordered microstructures. Experiments probing these pathways are suggested. © 2000 American Institute of Physics.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 3401-3405 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study the microphase segregation of molten randomly grafted copolymers (RGCs) using a Landau field theory. Under one wave number approximation, we find three equilibrium ordered microphases: lamellar phase (LAM), hexagonal cylinder phase (HEX), and bcc sphere phase (BCC). The stability of these phases strongly depends on the architectural parameters describing the RGC chains (e.g., the backbone length, the branch length, and the number of branches). Our calculation reveals that RGCs with high average composition of backbone monomers or with low branching density tend to form LAM microstructures. For a small average composition of backbone monomers, HEX and BCC microphases appear in turn with increasing branching density. Independent of the architectural parameters and composition, the disorder to order transition for molten RGCs is always from the disordered phase to the LAM microphase. The physical reasons underlying this behavior and experimentally testable predictions are discussed. © 2001 American Institute of Physics.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 10074-10091 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Motivated by practical issues that pertain to polymer adhesion, we consider the equilibrium behavior of a dilute solution of ideal A–B random block copolymers confined between two solid surfaces. We develop a general theory for the situation wherein the A–A, B–B, and A–B intersegment interactions are different, and furthermore, the A and B segments interact differently with the solid surfaces. Random block copolymers constitute a class of materials wherein a quenched disorder (the sequence distribution) is carried by the fluid whose statistical properties are of interest. In our theory, we perform quenched disorder averages using the replica trick. The nonlocal terms in our action functional are decoupled by introducing a set of random fields. The resulting equations for the propagator are analyzed within the framework of eigenfunction expansions. Since we consider long chains in confined geometries, we invoke the ground state approximation. We also carry out the functional integrals over the random fields using saddle points.Our theory does not treat the segment–surface interactions within a mean field approximation. Our analysis leads to a set of nonlinear self-consistent-field equations. We have solved our general equations numerically for a particular problem. In order to isolate and highlight the effects of dissimilar segment–surface interactions, we consider a case wherein the intersegment interactions are all alike (of the excluded volume type), while the A segments are attracted to the solid surfaces and the B units are repelled. For this specific problem we find that, above a threshold value of the fraction of attractive segments, significant microphase ordering is induced by the surface. This leads to damped oscillations in the composition profile. This onset of significant surface-induced composition fluctuations is accompanied by an "adsorption–desorption transition'' which corresponds to a qualitative change in the shape of the total segment density profile. These and other results are discussed and the experimentally testable consequences of our predictions are elucidated. Our results are in agreement with recent simulation studies. We suggest specific experiments that may shed further light on the physical phenomena revealed by our calculations. © 1994 American Institute of Physics.
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 1528-1541 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We consider the diffusion of ionic species in technologically relevant materials such as zeolites. These materials are characterized by a disordered density distribution of charged sites that couple with the diffusing species. We present a model for ion diffusion in a specific form of charged disorder. This is a primitive model for ion diffusion in charged or acidic zeolites. The theory relies on a path integral representation of the propagator, and a Gaussian field theory for the effects of the disorder. We use the Feynman–Bogoliubov variational method to treat the model, and calculate the diffusion coefficient for ions in a medium characterized by randomly located charges. Numerical solution of our equations, and asymptotic analyses of the same, show that in our theory there is a crossover from diffusive to subdiffusive behavior beyond a threshold value for the average density of the disorder. This threshold coincides with the actual diffusion changing from processes well approximated by Gaussian paths to those involving escapes from deep potential wells and barrier crossings. These results are discussed in the context of recent field-theoretic and renormalization group approaches to the problem of diffusion in random media. Our approach to diffusion in random media appears reasonably general and should be applicable to many technologically relevant problems, and is not compute intensive.
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