Single polymer adsorption in shear: flattening versus hydrodynamic lift and corrugation effects

The adsorption of a single polymer to a flat surface in shear is investigated using Brownian hydrodynamics simulations and scaling arguments. Competing effects are disentangled: in the absence of hydrodynamic interactions, shear drag flattens the chain and thus enhances adsorption. Hydrodynamic lift on the other hand gives rise to long-ranged repulsion from the surface which preempts the surface-adsorbed state via a discontinuous desorption transition, in agreement with theoretical arguments. Chain flattening is dominated by hydrodynamic lift, so overall, shear flow weakens the adsorption of flexible polymers. Surface friction due to small-wavelength surface potential corrugations is argued to weaken the surface attraction as well.Comment: 6 pages, 4 figure

Mesoscale simulations of polymer dynamics in microchannel flows

The non-equilibrium structural and dynamical properties of flexible polymers confined in a square microchannel and exposed to a Poiseuille flow are investigated by mesoscale simulations. The chain length and the flow strength are systematically varied. Two transport regimes are identified, corresponding to weak and strong confinement. For strong confinement, the transport properties are independent of polymer length. The analysis of the long-time tumbling dynamics of short polymers yields non-periodic motion with a sublinear dependence on the flow strength. We find distinct differences for conformational as well as dynamical properties from results obtained for simple shear flow

Water slippage versus contact angle: a quasiuniversal relationship

Using molecular dynamics simulations of an atomistic water model, we study the interfacial hydrodynamic slippage of water at various hydrophobic surfaces, both organic (silane monolayers) and inorganic (diamondlike and Lennard-Jones models). The measured slip lengths range from nanometers to tens of nanometers. Slip lengths on different surfaces are found to collapse nearly onto a single curve as a function of the static contact angle characterizing the surface wettability, thereby suggesting a quasiuniversal relationship. This dependence is rationalized on the basis of a simple scaling description of the fluid-solid friction at the microscopic level. The link between slippage and water depletion at hydrophobic surfaces is clarified. These results shed light on the controversy over experimental measurements of the slip length at smooth hydrophobic surfaces.David M. Huang, Christian Sendner, Dominik Horinek, Roland R. Netz and Lydéric Bocque

Water Infiltration in Methylammonium Lead Iodide Perovskite: Fast and Inconspicuous

While the susceptibility of CH3NH3PbI3 to water is well documented, water influence on device performance is not well understood. Herein we use infrared spectroscopy to show that water infiltration into CH3NH3PbI3 occurs much faster and at much lower humidity than previously thought. We propose a molecular model where water molecules have a strong effect on the hydrogen bonding between the methylammonium cations and the Pb-I cage. Furthermore, the exposure of CH3NH3PbI3 to ambient environment increases the photocurrent of films in lateral devices by more than one order of magnitude. The observed slow component in the photocurrent buildup indicates that the effect is associated with enhanced proton conduction when light is combined with water and oxygen exposure.C.M. and M.S. acknowledge support by the Heidelberg Graduate School of Fundamental Physics. A.A.B. is a Royal Society University Research Fellow.This is the author accepted manuscript. The final version is available from the American Chemical Society via http://dx.doi.org/10.1021/acs.chemmater.5b0388

Semiflexible polymer conformation, distribution and migration in microcapillary flows

The flow behavior of a semiflexible polymer in microchannels is studied using Multiparticle Collision Dynamics (MPC), a particle-based hydrodynamic simulation technique. Conformations, distributions, and radial cross-streamline migration are investigated for various bending rigidities, with persistence lengths Lp in the range 0.5 < Lp/Lr < 30. The flow behavior is governed by the competition between a hydrodynamic lift force and steric wall-repulsion, which lead to migration away from the wall, and a locally varying flow-induced orientation, which drives polymer away from the channel center and towards the wall. The different dependencies of these effects on the polymer bending rigidity and the flow velocity results in a complex dynamical behavior. However, a generic effect is the appearance of a maximum in the monomer and the center-of-mass distributions, which occurs in the channel center for small flow velocities, but moves off-center at higher velocities.Comment: in press at J. Phys. Condens. Matte

Surface nanobubbles as a function of gas type

We experimentally investigate the nucleation of surface nanobubbles on PFDTS-coated silicon as a function of the specific gas dissolved in the water. In each case we restrict ourselves to equilibrium conditions ($c=100$, $T_{liquid} = T_{substrate}$). Not only is nanobubble nucleation a strong function of gas type, but there also exists an optimal system temperature of $\sim 35-40\mathrm{^oC}$ where nucleation is maximized, which is weakly dependent on gas type. We also find that contact angle is a function of nanobubble radius of curvature for all gas types investigated. Fitting this data allows us to describe a line tension which is dependent on the type of gas, indicating that the nanobubbles are sat on top of adsorbed gas molecules. The average line tension was $\tau \sim -0.8 \mathrm{nN}$

Anisotropic diffusion of water molecules in hydroxyapatite nanopores

Funded by EPSRC Grant EP/K000128/1

Scaling behaviour for the water transport in nanoconfined geometries

The transport of water in nanoconfined geometries is different from bulk phase and has tremendous implications in nanotechnology and biotechnology. Here molecular dynamics is used to compute the self-diffusion coefficient D of water within nanopores, around nanoparticles, carbon nanotubes and proteins. For almost 60 different cases, D is found to scale linearly with the sole parameter theta as D(theta)=DB[1+(DC/DB-1)theta], with DB and DC the bulk and totally confined diffusion of water, respectively. The parameter theta is primarily influenced by geometry and represents the ratio between the confined and total water volumes. The D(theta) relationship is interpreted within the thermodynamics of supercooled water. As an example, such relationship is shown to accurately predict the relaxometric response of contrast agents for magnetic resonance imaging. The D(theta) relationship can help in interpreting the transport of water molecules under nanoconfined conditions and tailoring nanostructures with precise modulation of water mobility

Inversion symmetry and bulk Rashba effect in methylammonium lead iodide perovskite single crystals

Methylammonium lead iodide perovskite (MAPbI_3) exhibits long charge carrier lifetimes that are linked to its high efficiency in solar cells. Yet, the mechanisms governing these unusual carrier dynamics are not completely understood. A leading hypothesis—disproved in this work—is that a large, static bulk Rashba effect slows down carrier recombination. Here, using second harmonic generation rotational anisotropy measurements on MAPbI_3 crystals, we demonstrate that the bulk structure of tetragonal MAPbI_3 is centrosymmetric with I4/mcmspace group. Our calculations show that a significant Rashba splitting in the bandstructure requires a non-centrosymmetric lead iodide framework, and that incorrect structural relaxations are responsible for the previously predicted large Rashba effect. The small Rashba splitting allows us to compute effective masses in excellent agreement with experiment. Our findings rule out the presence of a large static Rashba effect in bulk MAPbI_3, and our measurements find no evidence of dynamic Rashba effects