Interfacial layering in a three-component polymer system

We study theoretically the temporal evolution and the spatial structure of the interface between two polymer melts involving three different species (A, A* and B). The first melt is composed of two different polymer species A and A* which are fairly indifferent to one another (Flory parameter chi_AA* ~ 0). The second melt is made of a pure polymer B which is strongly attracted to species A (chi_AB 0). We then show that, due to these contradictory tendencies, interesting properties arise during the evolution of the interface after the melts are put into contact: as diffusion proceeds, the interface structures into several adjacent "compartments", or layers, of differing chemical compositions, and in addition, the central mixing layer grows in a very asymmetric fashion. Such unusual behaviour might lead to interesting mechanical properties, and demonstrates on a specific case the potential richness of multi-component polymer interfaces (as compared to conventional two-component interfaces) for various applications.Comment: Revised version, to appear in Macromolecule

Stripes of Partially Fluorinated Alkyl Chains: Dipolar Langmuir Monolayers

Stripe-like domains of Langmuir monolayers formed by surfactants with partially fluorinated lipid anchors (F-alkyl lipids) are observed at the gas-liquid phase coexistence. The average periodicity of the stripes, measured by fluorescence microscopy, is in the micrometer range, varying between 2 and 8 microns. The observed stripe-like patterns are stabilized due to dipole-dipole interactions between terminal -CF3 groups. These interactions are particularly strong as compared with non-fluorinated lipids due to the low dielectric constant of the surrounding media (air). These long-range dipolar interactions tend to elongate the domains, in contrast to the line tension that tends to minimize the length of the domain boundary. This behavior should be compared with that of the lipid monolayer having alkyl chains, and which form spherical micro-domains (bubbles) at the gas-liquid coexistence. The measured stripe periodicity agrees quantitatively with a theoretical model. Moreover, the reduction in line tension by adding traces (0.1 mol fraction) of cholesterol results, as expected, in a decrease in the domain periodicity.Comment: 20 pages, 4 fig

Contact line motion for partially wetting fluids

We study the flow close to an advancing contact line in the limit of small capillary number. To take into account wetting effects, both long and short-ranged contributions to the disjoining pressure are taken into account. In front of the contact line, there is a microscopic film corresponding to a minimum of the interaction potential. We compute the parameters of the contact line solution relevant to the matching to a macroscopic problem, for example a spreading droplet. The result closely resembles previous results obtained with a slip model

Generic morphologies of viscoelastic dewetting fronts

A simple model is put forward which accounts for the occurrence of certain generic dewetting morphologies in thin liquid coatings. It demonstrates that by taking into account the elastic properties of the coating, a morphological phase diagram may be derived which describes the observed structures of dewetting fronts. It is demonstrated that dewetting morphologies may also serve to determine nanoscale rheological properties of liquids.Comment: 4 pages, 2 figure

Liquid-liquid coexistence in the phase diagram of a fluid confined in fractal porous materials

Multicanonical ensemble sampling simulations have been performed to calculate the phase diagram of a Lennard-Jones fluid embedded in a fractal random matrix generated through diffusion limited cluster aggregation. The study of the system at increasing size and constant porosity shows that the results are independent from the matrix realization but not from the size effects. A gas-liquid transition shifted with respect to bulk is found. On growing the size of the system on the high density side of the gas-liquid coexistence curve it appears a second coexistence region between two liquid phases. These two phases are characterized by a different behaviour of the local density inside the interconnected porous structure at the same temperature and chemical potential.Comment: 5 pages, 4 figures. To be published in Europhys. Letter

Monomer dynamics of a wormlike chain

We derive the stochastic equations of motion for a tracer that is tightly attached to a semiflexible polymer and confined or agitated by an externally controlled potential. The generalised Langevin equation, the power spectrum, and the mean-square displacement for the tracer dynamics are explicitly constructed from the microscopic equations of motion for a weakly bending wormlike chain by a systematic coarse-graining procedure. Our accurate analytical expressions should provide a convenient starting point for further theoretical developments and for the analysis of various single-molecule experiments and of protein shape fluctuations.Comment: 6 pages, 4 figure

A diaphragmatic electrical activity-based optimization strategy during pressure support ventilation improves synchronization but does not impact work of breathing.

Poor patient-ventilator synchronization is often observed during pressure support ventilation (PSV) and has been associated with prolonged duration of mechanical ventilation and poor outcome. Diaphragmatic electrical activity (Eadi) recorded using specialized nasogastric tubes is a surrogate of respiratory brain stem output. This study aimed at testing whether adapting ventilator settings during PSV using a protocolized Eadi-based optimization strategy, or Eadi-triggered and -cycled assisted pressure ventilation (or PSVN) could (1) improve patient-ventilator interaction and (2) reduce or normalize patient respiratory effort as estimated by the work of breathing (WOB) and the pressure time product (PTP). This was a prospective cross-over study. Patients with a known chronic pulmonary obstructive or restrictive disease, asynchronies or suspected intrinsic positive end-expiratory pressure (PEEP) who were ventilated using PSV were enrolled in the study. Four different ventilator settings were sequentially applied for 15 minutes (step 1: baseline PSV as set by the clinician, step 2: Eadi-optimized PSV to adjust PS level, inspiratory trigger, and cycling settings, step 3: step 2 + PEEP adjustment, step 4: PSVN). The same settings as step 3 were applied again after step 4 to rule out a potential effect of time. Breathing pattern, trigger delay (Td), inspiratory time in excess (Tiex), pressure-time product (PTP), and work of breathing (WOB) were measured at the end of each step. Eleven patients were enrolled in the study. Eadi-optimized PSV reduced Td without altering Tiex in comparison with baseline PSV. PSVN reduced Td and Tiex in comparison with baseline and Eadi-optimized PSV. Respiratory pattern did not change during the four steps. The improvement in patient-ventilator interaction did not lead to changes in WOB or PTP. Eadi-optimized PSV allows improving patient ventilator interaction but does not alter patient effort in patients with mild asynchrony. Clinicaltrials.gov identifier: NCT 02067403 . Registered 7 February 2014

Theoretical study of dislocation nucleation from simple surface defects in semiconductors

Large-scale atomistic calculations, using empirical potentials for modeling semiconductors, have been performed on a stressed system with linear surface defects like steps. Although the elastic limits of systems with surface defects remain close to the theoretical strength, the results show that these defects weaken the atomic structure, initializing plastic deformations, in particular dislocations. The character of the dislocation nucleated can be predicted considering both the resolved shear stress related to the applied stress orientation and the Peierls stress. At low temperature, only glide events in the shuffle set planes are observed. Then they progressively disappear and are replaced by amorphization/melting zones at a temperature higher than 900 K