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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 9122-9132 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    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 92 (1990), S. 6255-6270 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The thermodynamic and dynamic properties of a partially deuterated poly(ethylene-propylene)–poly(ethylethylene)(PEP–PEE) diblock copolymer containing 55% by volume PEP were characterized above and below the order–disorder transition (ODT) by small-angle neutron scattering (SANS) and rheological measurements, respectively. Both experimental techniques produced unambiguous evidence of composition fluctuations well above TODT(T−TODT(approximately-less-than)50 °C) in the disordered state, which increase in magnitude as the weak first-order transition is approached. Based on the SANS results, which are nearly predicted by a recent fluctuation theory, we conclude that the (equilibrium) instantaneous morphology in the disordered state closely resembles a spinodally decomposed binary mixture. Below TODT, long-range order can be obtained by the application of a shear field as evidenced by the resulting highly anisotropic (one-dimensional) SANS pattern. As the ODT is approached in the shear-oriented ordered state, an isotropic scattering component develops (evident at wavevectors transverse to the principle line of reflections) in qualitative agreement with the fluctuation theory. We speculate that the (equilibrium) ordered morphology can be represented by the superposition of a static lamellar structure with a fluctuating spinodal pattern. Temperature quenching into the ordered region from the disordered state in the absence of an external field produces a macroscopically isotropic (nonequilibrium) material with a complex, poorly defined morphology. Associated with each of these different morphologies and phase states are gross differences in the low-frequency rheological properties that we have interpreted based on the SANS results and fluctuation theory.
    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 96 (1992), S. 8605-8615 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The microstructure of thin films of nearly symmetric poly(ethylene–propylene)–poly(ethylethylene) (PEP-PEE) diblock copolymers (f=0.55, where f is the volume fraction of PEP) was characterized by neutron reflectometry (NR). A symmetric film structure in which the PEE block segregates preferentially to both interfaces is observed above and below the bulk order–disorder transition (ODT). Measurements at room temperature for several chain lengths, N, provide a real-space picture of the change in interdomain interfacial profiles associated with the crossover between the strong and weak segregation limits. The polymer/air and substrate/polymer interfaces are observed to induce an ordered microstructure even when the center of the film is disordered. The characteristic dimension of this near surface microstructure is larger than the corresponding bulk value for values of χN lying between those of the bulk Gaussian-to-stretched-coil and order–disorder transitions, where χ is the segment–segment interaction parameter. This behavior is attributed to the correlation of large amplitude composition fluctuations in the film with the interfaces. A mean-field behavior prevails for χN〈(χN)GST,bulk, where some preferential segregation occurs at the interfaces, but the characteristic dimension once again matches that in the bulk.
    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 91 (1989), S. 3258-3274 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A nearly symmetric critical mixture (φc=0.486) of perdeuterated and protonated 1,4-polybutadiene exhibiting an upper critical solution temperature Tc=61.5±1.5 °C has been quenched from the homogeneous state ((approximately-equal-to)75 °C) to various temperatures between 25 and 57.5 °C. Light scattering measurements document the subsequent spinodal decomposition process which we describe based on a four-stage model: early, intermediate, transition, and final. The early stage is accounted for by the Cahn theory, yielding initial correlation lengths and effective diffusion coefficients in quantitative agreement with mean-field predictions. Nonlinear effects mark the beginning of the intermediate stage, which exhibits a simple power-law growth of heterogeneity length Lm(t)∼tneff, but with a temperature dependent exponent neff. As the composition fluctuation amplitude approaches the equilibrium values, the spinodal decomposition process enters the transition stage, characterized by a decreasing interfacial thickness and an increasing Lm(t). Once the interfacial profile equilibrates, a crossover to the final stage occurs. Subsequent growth of L(t) leaves the morphology unaffected as evidenced by a universal structure factor. These findings are discussed in the context of the current theory and are compared with prior studies involving polymer–polymer and simple liquid mixtures.
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  • 5
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Review of Scientific Instruments 66 (1995), S. 1090-1095 
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: "Living'' anionic polymerization offers a readily feasible preparation of very well-controlled homo- or copolymers in a wide range of molar masses and chemical structures. Such samples are vital in experimental polymer physics and the technique presented here offers self-sufficiency with such samples. The technique of anionic polymerization performed under inert atmosphere is presented here. The components of the setup are described in detail. Purification procedures for glassware and chemicals for specific polymerizations are given. Illustrative examples and results are presented. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 16 (1983), S. 1013-1015 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 17 (1984), S. 1987-1993 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 18 (1985), S. 2478-2486 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    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 100 (1994), S. 6813-6817 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Allowance is made for harmonic corrections within mean-field theory for weakly segregated block copolymers. The theory of Marques and Cates [C. M. Marques and M. E. Cates, Europhys. Lett. 13, 267 (1990)] for the stability of phases near the ordering transition is applied to diblock copolymer melts. A wave-vector dependence of the coefficients in the Landau mean-field free energy is included. We find that the face centered cubic (fcc) and square phases predicted by Marques and Cates to be stable near the ordering transition depending on the structure factor for the system are not stable for diblock copolymers. In addition, hexagonal close packed (hcp) and ordered bicontinuous double diamond (OBDD) structures are found to be unstable with respect to the classical lamellar, cylinder, and body centered cubic phases. The hexagonal intermediate phases and complex bicontinuous structures recently observed near the order–disorder transition are not accounted for in this theory.
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