ABSTRACT
When a swollen, thermoresponsive polymer gel is heated in a solvent bath, it expels solvent and deswells. When this heating is slow, deswelling proceeds homogeneously, as observed in a toroid-shaped gel that changes volume while maintaining its toroidal shape. By contrast, if the gel is heated quickly, an impermeable layer of collapsed polymer forms and traps solvent within the gel, arresting the volume change. The ensuing evolution of the gel then happens at fixed volume, leading to phase separation and the development of inhomogeneous stress that deforms the toroidal shape. We observe that this stress can cause the torus to buckle out of the plane, via a mechanism analogous to the bending of bimetallic strips upon heating. Our results demonstrate that thermodynamic instabilities, i.e., phase transitions, can be used to actuate mechanical deformation in an extreme thermodynamics of materials.
ABSTRACT
In this paper we revisit the derivation of a nonlocal interfacial Hamiltonian model for systems with short-ranged intermolecular forces. Starting from a microscopic Landau-Ginzburg-Wilson Hamiltonian with a double-parabola potential, we reformulate the derivation of the interfacial model using a rigorous boundary integral approach. This is done for three scenarios: a single fluid phase in contact with a nonplanar substrate (i.e., wall); a free interface separating coexisting fluid phases (say, liquid and gas); and finally a liquid-gas interface in contact with a nonplanar confining wall, as is applicable to wetting phenomena. For the first two cases our approaches identifies the correct form of the curvature corrections to the free energy and, for the case of a free interface, it allows us to recast these as an interfacial self-interaction as conjectured previously in the literature. When the interface is in contact with a substrate our approach similarly identifies curvature corrections to the nonlocal binding potential, describing the interaction of the interface and wall, for which we propose a generalized and improved diagrammatic formulation.
ABSTRACT
We use experiment and computational modeling to understand the defect structure and director configuration in a nematic liquid crystal capillary bridge confined between two parallel plates. We find that tuning of the aspect ratio of the bridge drives a transition between a ring defect and a point defect. This transition exhibits hysteresis, due to the metastability of the point-defect structure. In addition, we see that the shape of the capillary-bridge surface determines whether the defect is hyperbolic or radial, with waistlike bridges containing hyperbolic defects and barrel-like bridges containing radial defects.
ABSTRACT
We study a liquid of zigzagging two-dimensional directed polymers with bending rigidity, i.e., polymers whose conformations follow checkerboard paths. In the continuum limit the statistics of such polymers obey the Dirac equation for particles of imaginary mass. We exploit this observation to investigate a liquid of these polymers via a quantum many-fermion analogy. A self-consistent approximation predicts a phase of tilted order, in which the polymers may develop a preference to zig rather than zag. We compute the phase diagram and key response functions for the polymer liquid, and comment on the role played by fluctuations.
ABSTRACT
Macroscopic properties of suspensions, such as those composed of globular particles (e.g., colloidal or macromolecular), can be tuned by controlling the equilibrium aggregation of the particles. We examine how aggregation - and, hence, macroscopic properties - can be controlled in a system composed of both globular particles and long, flexible polymer chains that reversibly bind to one another. We base this on a minimal statistical mechanical model of a single aggregate in which the polymer chain is treated either as ideal or self-avoiding, and, in addition, the globular particles are taken to interact with one another via excluded volume repulsion. Furthermore, each of the globular particles is taken to have one single site to which at most one polymer segment may bind. Within the context of this model, we examine the statistics of the equilibrium size of an aggregate and, thence, the structure of dilute and semidilute suspensions of these aggregates. We apply the model to biologically relevant aggregates, specifically those composed of macromolecular proteoglycan globules and long hyaluronan polymer chains. These aggregates are especially relevant to the materials properties of cartilage and the structure-function properties of perineuronal nets in brain tissue, as well as the pericellular coats of mammalian cells.
Subject(s)
Polymers/chemistry , Hyaluronic Acid/chemistry , Proteoglycans/chemistry , ThermodynamicsABSTRACT
We present measurements of the superconducting transition temperature, Tc, for arrays of mesoscopic Nb islands patterned on Au films, for large island spacings d. We show that Tc â¼ 1/d(2), and explain this dependence in terms of the quasiclassical prediction that the Thouless energy, rather than the superconducting gap, governs the inter-island coupling at large spacings. We also find that the temperature dependence of the critical current, Ic(T), in our arrays is similar to that of single SNS junctions. However, our results deviate from the quasiclassical theory in that Tc is sensitive to island height, because the islands are mesoscopic.
ABSTRACT
The impact of impenetrable obstacles on the energetics and equilibrium structure of strongly repulsive directed polymers is investigated. As a result of the strong interactions, regions of severe polymer depletion and excess are found in the vicinity of the obstacle, and the associated free-energy cost is found to scale quadratically with the average polymer density. The polymer-polymer interactions are accounted for via a sequence of transformations: from the 3D line liquid to a 2D fluid of Bose particles to a 2D composite fermion fluid and, finally, to a 2D one-component plasma. The results presented here are applicable to a range of systems consisting of noncrossing directed lines.
ABSTRACT
We consider the impact of the elastomer network on the nematic structure and fluctuations in isotropic-genesis nematic elastomers, via a phenomenological model that underscores the role of network compliance. The model contains a network-mediated nonlocal interaction as well as a new kind of random field that reflects the memory of the nematic order present at network formation and also encodes local anisotropy due to localized nematogenic polymers. This model enables us to predict regimes of short-ranged oscillatory spatial correlations (thermal and glassy) in the nematic alignment.
ABSTRACT
Recent experiments on the conductance of thin, narrow superconducting strips have found periodic fluctuations, as a function of the perpendicular magnetic field, with a period corresponding to approximately two flux quanta per strip area [A. Johansson et al., Phys. Rev. Lett. 95, 116805 (2005)]. We argue that the low-energy degrees of freedom responsible for dissipation correspond to vortex motion. Using vortex-charge duality, we show that the superconducting strip behaves as the dual of a quantum dot, with the vortices, magnetic field, and bias current respectively playing the roles of the electrons, gate voltage, and source-drain voltage. In the bias-current versus magnetic-field plane, the strip conductance displays regions of small vortex conductance (i.e., small electrical resistance) that we term "Weber blockade" diamonds, which are dual to Coulomb blockade diamonds in quantum dots.
ABSTRACT
We show that the effective spin-spin interaction between three-level atoms confined in a multimode optical cavity is long-ranged and sign changing, like the RKKY interaction; therefore, ensembles of such atoms subject to frozen-in positional randomness can realize spin systems having disordered and frustrated interactions. We argue that, whenever the atoms couple to sufficiently many cavity modes, the cavity-mediated interactions give rise to a spin glass. In addition, we show that the quantum dynamics of cavity-confined spin systems is that of a Bose-Hubbard model with strongly disordered hopping but no on-site disorder; this model exhibits a random-singlet glass phase, absent in conventional optical-lattice realizations. We briefly discuss experimental signatures of the realizable phases.
ABSTRACT
We show that layered quenched randomness in planar magnets leads to an unusual intermediate phase between the conventional ferromagnetic low-temperature and paramagnetic high-temperature phases. In this intermediate phase, which is part of the Griffiths region, the spin-wave stiffness perpendicular to the random layers displays anomalous scaling behavior, with a continuously variable anomalous exponent, while the magnetization and the stiffness parallel to the layers both remain finite. Analogous results hold for superfluids and superconductors. We study the two phase transitions into the anomalous elastic phase, and we discuss the universality of these results, and implications of finite sample size as well as possible experiments.
ABSTRACT
The application of single molecules as templates for nanodevices is a promising direction for nanotechnology. We use suspended deoxyribonucleic acid molecules or single-walled carbon nanotubes as templates for fabricating superconducting devices and then study these devices at cryogenic temperatures. Because the resulting nanowires are extremely thin, comparable in diameter to the templating molecule itself, their electronic state is highly susceptible to thermal fluctuations. The most important family of these fluctuations are the collective ones, which take the form of Little's phase slips or ruptures of the many-electron organization. These phase slips break the quantum coherence of the superconducting condensate and render the wire slightly resistive (i.e., not fully superconducting), even at temperatures substantially lower than the critical temperature of the superconducting transition. At low temperatures, for which the thermal fluctuations are weak, we observe the effects of quantum fluctuations, which lead to the phenomenon of macroscopic quantum tunneling. The modern fabrication method of molecular templating, reviewed here, can be readily implemented to synthesize nanowires from other materials, such as normal metals, ferromagnetic alloys, and semiconductors.
Subject(s)
Nanowires/chemistry , DNA/chemistry , Electron Transport , Quantum Theory , Silicon/chemistryABSTRACT
Spatial heterogeneity in the elastic properties of soft random solids is examined via vulcanization theory. The spatial heterogeneity in the structure of soft random solids is a result of the fluctuations locked-in at their synthesis, which also brings heterogeneity in their elastic properties. Vulcanization theory studies semimicroscopic models of random-solid-forming systems and applies replica field theory to deal with their quenched disorder and thermal fluctuations. The elastic deformations of soft random solids are argued to be described by the Goldstone sector of fluctuations contained in vulcanization theory, associated with a subtle form of spontaneous symmetry breaking that is associated with the liquid-to-random-solid transition. The resulting free energy of this Goldstone sector can be reinterpreted as arising from a phenomenological description of an elastic medium with quenched disorder. Through this comparison, we arrive at the statistics of the quenched disorder of the elasticity of soft random solids in terms of residual stress and Lamé-coefficient fields. In particular, there are large residual stresses in the equilibrium reference state, and the disorder correlators involving the residual stress are found to be long ranged and governed by a universal parameter that also gives the mean shear modulus.
ABSTRACT
We study the stochastic dynamics of superconductive-resistive switching in hysteretic current-biased superconducting nanowires undergoing phase-slip fluctuations. We evaluate the mean switching time using the master-equation formalism, and hence obtain the distribution of switching currents. We find that as the temperature is reduced this distribution initially broadens; only at lower temperatures does it show the narrowing with cooling naively expected for phase slips that are thermally activated. We also find that although several phase-slip events are generally necessary to induce switching, there is an experimentally accessible regime of temperatures and currents for which just one single phase-slip event is sufficient to induce switching, via the local heating it causes.
Subject(s)
Nanowires/chemistry , Cold Temperature , DNA/chemistry , Electric Conductivity , Electric Impedance , Models, Chemical , Nanotubes, Carbon/chemistry , Stochastic ProcessesABSTRACT
A Landau theory is constructed for the gelation transition in cross-linked polymer systems possessing spontaneous nematic ordering, based on symmetry principles and the concept of an order parameter for the amorphous solid state. This theory is substantiated with help of a simple microscopic model of cross-linked dimers. Minimization of the Landau free energy in the presence of nematic order yields the neoclassical theory of the elasticity of nematic elastomers and, in the isotropic limit, the classical theory of isotropic elasticity. These phenomenological theories of elasticity are thereby derived from a microscopic model, and it is furthermore demonstrated that they are universal mean-field descriptions of the elasticity for all chemical gels and vulcanized media.
ABSTRACT
The effects of thermal elastic fluctuations in rubbery materials are examined. It is shown that, due to their interplay with the incompressibility constraint, these fluctuations qualitatively modify the large-deformation stress-strain relation, compared to that of classical rubber elasticity. To leading order, this mechanism provides a simple and generic explanation for the peak structure of Mooney-Rivlin stress-strain relation and shows good agreement with experiments. It also leads to the prediction of a phonon correlation function that depends on the external deformation.
ABSTRACT
We consider a microscopic model of a polymer blend that is prone to phase separation. Permanent cross-links are introduced between randomly chosen pairs of monomers, drawn from the Deam-Edwards distribution. Thereby, not only density but also concentration fluctuations of the melt are quenched-in in the gel state, which emerge upon sufficient cross-linking. We derive a Landau expansion in terms of the order parameters for gelation and phase separation, and analyze it on the mean-field level, including Gaussian fluctuations. The mixed gel is characterized by thermal as well as time-persistent (glassy) concentration fluctuations. Whereas the former are independent of the preparation state, the latter reflect the concentration fluctuations at the instant of cross-linking, provided the mesh size is smaller than the correlation length of phase separation. The mixed gel becomes unstable to microphase separation upon lowering the temperature in the gel phase. Whereas the length scale of microphase separation is given by the mesh size, at least close to the transition, the emergent microstructure depends on the composition and compressibility of the melt. Hexagonal structures, as well as lamellas or random structures with a unique wavelength, can be energetically favorable.
ABSTRACT
Starting from the assumption that the normal solid to supersolid (NS-SS) phase transition is continuous, we develop a phenomenological Landau theory of the transition in which superfluidity is coupled to the elasticity of the crystalline lattice. We find that the elasticity does not affect the universal properties of the superfluid transition, so that in an unstressed crystal the well-known anomaly in the heat capacity of the superfluid transition should also appear at the NS-SS transition. We also find that the onset of supersolidity leads to anomalies in the elastic moduli and thermal expansion coefficients near the transition and, conversely, that inhomogeneous lattice strains can induce local variations of the superfluid transition temperature, leading to a broadened transition.
ABSTRACT
The cavity approach is used to address the physical properties of random solids in equilibrium. Particular attention is paid to the fraction of localized particles and the distribution of localization lengths characterizing their thermal motion. This approach is of relevance to a wide class of random solids, including rubbery media (formed via the vulcanization of polymer fluids) and chemical gels (formed by the random covalent bonding of fluids of atoms or small molecules). The cavity approach confirms results that have been obtained previously via replica mean-field theory, doing so in a way that sheds new light on their physical origin.
Subject(s)
Biophysics/methods , Gels , Hydrogen Bonding , Macromolecular Substances , Models, Statistical , Models, Theoretical , Polymers/chemistry , Probability , ThermodynamicsABSTRACT
The application of single molecules as templates for nanodevices is a promising direction for nanotechnology. We used a pair of suspended DNA molecules as templates for superconducting two-nanowire devices. Because the resulting wires are very thin, comparable to the DNA molecules themselves, they are susceptible to thermal fluctuations typical for one-dimensional superconductors and exhibit a nonzero resistance over a broad temperature range. We observed resistance oscillations in these two-nanowire structures that are different from the usual Little-Parks oscillations. Here, we provide a quantitative explanation for the observed quantum interference phenomenon, which takes into account strong phase gradients created in the leads by the applied magnetic field.