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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. 2228-2235 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We highlight here the symmetry breaking which occurs as rodlike particles are adsorbed onto a planar surface. A spin-1 Ising-variable Hamiltonian is defined which includes both bilinear and biquadratic interaction terms. Nearest-neighbor couplings are also introduced which distinguish between parallel pairs of particles having different orientations with respect to the surface normal; finally, a single-particle term describes the anisotropy in adsorption energy. By solving for the thermodynamics of this Hamiltonian in both mean-field and renormalization-group approximation, we establish the necessary conditions for the appearance of two successive fluid–fluid phase transitions.
    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 95 (1991), S. 6112-6123 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The influence of surface constraints on the conformations of a flexible polymer are investigated. The polymer is modeled as a Gaussian chain, and the influence of repulsive polymer–polymer excluded volume interactions is investigated using renormalization group methods. Various measures of the polymer mean dimensions are computed for chains terminally attached to mutually orthogonal surfaces and for a wide range of polymer excluded volume interactions. Two limiting cases of the polymer–surface interaction are considered—the absorbing boundary condition corresponding to a "repelling'' surface and the reflecting boundary condition associated with the "adsorption theta point,'' where surface attractions fall just short of adsorbing the polymer.
    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 92 (1990), S. 1427-1434 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We describe an extension of the generalized regular solution model of a liquid supported monolayer of long chain amphiphile molecules in which chain–chain interactions outside the surface layer are included as well as the effects of chain flexibility in the surface and in the space above the surface layer. Self-consistent equations for the distribution of molecular configurations and the surface density and pressure are derived by using a model free energy expression. Two first order fluid–fluid phase transitions are predicted for three different models for the chain–chain interactions outside the surface. These transitions are identified as the observed gas-to-"liquid-expanded'' and liquid-expanded-to-"liquid-condensed'' phase transitions in a monolayer, the first to be associated with the condensation of the in-surface portions of the amphiphile chains and the second to be associated with the condensation of the out of surface portions of the amphiphile chains. This interpretation comes from the observation of the different distributions of the molecular configurations in the coexistence regions for the two transitions and is reinforced by the analysis of the sensitivity of the equation of state to the parameters used in the model. The theory leads to a simple and qualitative but accurate physical picture of the successive fluid-fluid transitions of the monolayer.
    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 94 (1991), S. 679-687 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study the curvature elastic properties of monolayers of diblock copolymers adsorbed at the interface of two incompatible solvents which are also selective solvents for the two blocks. At saturation, the interfacial free energy is minimized with respect to contributions from the chain conformation free energy, the interfacial tension, and the two-dimensional translational entropy of the chains. For a curved interface, this minimization leads naturally to curvature elasticity. The three elastic coefficients, the spontaneous radius of curvature, the bending modulus, and the Gaussian bending modulus, as functions of the molecular weights, the interfacial tension, the interaction parameters, etc., are obtained for a number of cases. Our study employs the theory for grafted chains recently developed by Milner et al. to obtain the chain conformation free energy which takes into account the nonuniformity of the chain-end distribution. This improvement not only affects the overall prefactor of the free energy but it changes the relative values of the three elastic coefficients as well. We consider the cases of both a swollen monolayer and a monolayer consisting of a melt of copolymer chains, as well as an interesting case where one of the blocks is in the swollen condition and the other block is in the melt condition. Because the chains in the melt and the swollen conditions have distinctively different scaling behaviors, the mixed case displays some features that are different from either the swollen and the melt cases.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 9128-9141 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Using a statistical-thermodynamic formulation, we investigate the failure of ideal and almost-ideal solids at finite temperature. We propose that the onset of failure in a defect-free crystal is associated with the loss of a metastable minimum in the free energy at a critical value of the applied tensile force. Using a mean-field approximation, we estimate the free energy of the two-dimensional Lennard-Jones crystal under stress and derive the temperature dependence of its ideal strength and other properties. These results are compared to Monte Carlo simulations of this system, and the mean-field estimate of the ideal strength is shown to be an upper bound to the values observed via simulation. We also show that atomic-scale defects such as vacancies and substitutional impurities significantly reduce the crystal's strength as a result of stress enhancement effects. While the overall strength of a defective crystal depends strongly on both temperature and the nature of the defects, the maximum local stress that the crystal can sustain without failure is essentially independent of these factors.
    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 99 (1993), S. 4191-4200 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We present a theoretical study of spatially modulated phases in self-assembled monolayers of mixed surfactants. We propose two models which are appropriate, respectively, for monolayers at a fluid–fluid interface and monolayers on a solid substrate. We show that in both cases, the molecular shape asymmetry, coupled with the local composition variation, can lead to spontaneous formation of periodic structures. In the case of liquid-supported monolayers, the molecular shape asymmetry is manifested as a spontaneous curvature of each component of the film, which induces periodic variations both in the composition of the amphiphiles and in the height profile of the interface (ripples). In the case of solid-supported monolayers, the shape asymmetry is reflected in the spontaneous splay of the orientation of the amphiphiles, and the spatial modulation involves the composition as well as the orientation of the amphiphilic molecules. We analyze these models in some detail near the critical region, where we highlight the roles played by various length scales in determining the critical wavelength. We show that gravity has some very subtle and nontrivial effects for a liquid-supported, tension-free monolayer. We also present some preliminary results for the low temperature cases.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Woodbury, NY : American Institute of Physics (AIP)
    Applied Physics Letters 64 (1994), S. 2034-2036 
    ISSN: 1077-3118
    Source: AIP Digital Archive
    Topics: Physics
    Notes: NbN/AlN/NbN tunnel junctions are fabricated at ambient temperature on MgO substrates, and a critical current density of 8 kA/cm2 is obtained in junctions with 1.5–nm–thick AlN barriers. Even though the NbN/AlN/NbN trilayers are deposited without intentional heating, the junctions show a large gap voltage (Vg=5 mV), sharp quasiparticle current rise (ΔVg=0.16 mV), and small subgap leakage current (Vm=25 mV and Rsg/RN=9). This report shows that high-quality NbN/AlN/NbN tunnel junctions can be made at ambient substrate temperature.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Langmuir 6 (1990), S. 928-934 
    ISSN: 1520-5827
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    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 100 (1994), S. 2298-2309 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study the quasistatic behavior of the lamellar phase of diblock copolymers under uniaxial compression and tension along the normal direction of the layers, in both the weak segregation limit (WSL) and the strong segregation limit (SSL). In the SSL, we derive a (nonlinear) continuum free energy description of the system in terms of local displacement of the lamellar layers, and use this free energy to study the mechanical behaviors. While compression induces the usual Hookian elastic response (for strains or stresses that are not too large), tension leads to square-lattice wave undulations in the transverse directions when the strain exceeds a critical value. In the WSL close to the order–disorder transition temperature, compression can "melt'' the lamellar phase to the isotropic phase; such a melting can take the form of three types of instabilities, a quasithermodynamic instability, a spinodal at controlled strain, and a mechanical instability at controlled stress. It is shown that the third instability always precedes the second one under controlled-stress conditions. For a weakly first-order transition, the quasithermodynamic instability precedes the mechanical instability; but for a (hypothetical) second-order transition, the mechanical instability appears first as the stress is increased. In the case of tension, a transverse square-lattice wave deformation again develops at a critical strain. This deformation can be followed by a subsequent melting of types similar to the compressional case, upon further increase of the stress or strain. In both the SSL and WSL, the modulus undergoes an abrupt decrease when layer undulation develops, to a value 7/15 of that before the onset of undulation. Because the critical strain for the onset of undulation is usually very small, the modulus for tension will appear different from the modulus for compression, the former being 7/15 of the latter. As a result of this decrease in the modulus, melting of the lamellar phase in the WSL will occur at larger strains under tension than under compression.
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  • 10
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 97 (1993), S. 1237-1242 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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