Impact of Molecular Architecture and Adsorption Density on Adhesion of Mussel-Inspired Surface Primers with Catechol-Cation Synergy.

Marine mussels secrete proteins rich in residues containing catechols and cationic amines that displace hydration layers and adhere to charged surfaces under water via a cooperative binding effect known as catechol-cation synergy. Mussel-inspired adhesives containing paired catechol and cationic functionalities are a promising class of materials for biomedical applications, but few studies address the molecular adhesion mechanism(s) of these materials. To determine whether intramolecular adjacency of these functionalities is necessary for robust adhesion, a suite of siderophore analog surface primers was synthesized with systematic variations in intramolecular spacing between catechol and cationic functionalities. Adhesion measurements conducted with a surface forces apparatus (SFA) allow adhesive failure to be distinguished from cohesive failure and show that the failure mode depends critically on the siderophore analog adsorption density. The adhesion of these molecules to muscovite mica in an aqueous electrolyte solution demonstrates that direct intramolecular adjacency of catechol and cationic functionalities is not necessary for synergistic binding. However, we show that increasing the catechol-cation spacing by incorporating nonbinding domains results in decreased adhesion, which we attribute to a decrease in the density of catechol functionalities. A mechanism for catechol-cation synergy is proposed based on electrostatically driven adsorption and subsequent binding of catechol functionalities. This work should guide the design of new adhesives for binding to charged surfaces in saline environments

Automated Measurement of Spatially Resolved Hair-Hair Single Fiber Adhesion.

The adhesion force between individual human hair fibers in a crosshair geometry was measured by observing their natural bending and adhesive jumps out of contact, using optical video microscopy. The hair fibers' natural elastic responses, calibrated by measuring their natural resonant frequencies, were used to measure the forces. Using a custom-designed, automated apparatus to measure thousands of individual hair-hair contacts along millimeter length scales of hair, it was found that a broad, yet characteristic, spatially variant distribution in adhesion force is measured on the 1 to 1000 nN scale for both clean and conditioner-treated hair fibers. Comparison between the measured adhesion forces and adhesion forces modeled from the hairs' surface topography (measured using confocal laser profilometry) shows they have a good order-of-magnitude agreement and have similar breadth and shape. The agreement between the measurements and the model suggests, perhaps unsurprisingly, that hair-hair adhesion is governed, to a first approximation, by the unique surface structure of the hairs' cuticles and, therefore, the large distribution in local mean curvature at the various individual contact points along the hairs' lengths. We posit that haircare products could best control the surface properties (or at least the adhesive properties) between hairs by directly modifying the hair surface microstructure

Time-Dependent Physicochemical Changes of Carbonate Surfaces from SmartWater (Diluted Seawater) Flooding Processes for Improved Oil Recovery.

Over the past few decades, field- and laboratory-scale studies have shown enhancements in oil recovery when reservoirs, which contain high-salinity formation water (FW), are waterflooded with modified-salinity salt water (widely referred to as the low-salinity, dilution, or SmartWater effect for improved oil recovery). In this study, we investigated the time dependence of the physicochemical processes that occur during diluted seawater (i.e., SmartWater) waterflooding processes of specific relevance to carbonate oil reservoirs. We measured the changes to oil/water/rock wettability, surface roughness, and surface chemical composition during SmartWater flooding using 10-fold-diluted seawater under mimicked oil reservoir conditions with calcite and carbonate reservoir rocks. Distinct effects due to SmartWater flooding were observed and found to occur on two different timescales: (1) a rapid (<15 min) increase in the colloidal electrostatic double-layer repulsion between the rock and oil across the SmartWater, leading to a decreased oil/water/rock adhesion energy and thus increased water wetness and (2) slower (>12 h to complete) physicochemical changes of the calcite and carbonate reservoir rock surfaces, including surface roughening via the dissolution of rock and the reprecipitation of dissolved carbonate species after exchanging key ions (Ca2+, Mg2+, CO32-, and SO42- in carbonates) with those in the flooding SmartWater. Our experiments using crude oil from a carbonate reservoir reveal that these reservoir rock surfaces are covered with organic-ionic preadsorbed films (ad-layers), which the SmartWater removes (detaches) as flakes. Removal of the organic-ionic ad-layers by SmartWater flooding enhances oil release from the surfaces, which was found to be critical to increasing the water wetness and significantly improving oil removal from carbonates. Additionally, the increase in water wetness is further enhanced by roughening of the rock surfaces, which decreases the effective contact (interaction) area between the oil and rock interfaces. Furthermore, we found that the rate of these slower physicochemical changes to the carbonate rock surfaces increases with increasing temperature (at least up to an experimental temperature of 75 °C). Our results suggest that the effectiveness of improved oil recovery from SmartWater flooding depends strongly on the formation of the organic-ionic ad-layers. In oil reservoirs where the ad-layer is fully developed and robust, injecting SmartWater would lead to significant removal of the ad-layer and improved oil recovery

Reversible shear thickening at low shear rates of electrorheological fluids under electric fields

Shear thickening is a phenomenon of significant viscosity increase of colloidal suspensions. While electrorheological (ER) fluids can be turned into a solid-like material by applying an electric field, their shear strength is widely represented by the attractive electrostatic interaction between ER particles. By shearing ER fluids between two concentric cylinders, we show a reversible shear thickening of ER fluids above a low critical shear rate (<1 s-1) and a high critical electric field strength (>100 V/mm), which could be characterized by a modified Mason number. Shear thickening and electrostatic particle interaction-induced inter-particle friction forces is considered to be the real origin of the high shear strength of ER fluids, while the applied electric field controls the extent of shear thickening. The electric field-controlled reversible shear thickening has implications for high-performance ER/magnetorheological (MR) fluid design, clutch fluids with high friction forces triggered by applying local electric field, other field-responsive materials and intelligent systems.Comment: 29pages, 9 figure

Long-ranged attraction between disordered heterogeneous surfaces

Long-ranged attractions across water between two surfaces that are randomly covered with (mobile) positive and negative charge domains have been attributed to induced correlation of the charges (positive lining up with negative) as the surfaces approach. Here we show, by directly measuring normal forces under a rapid shear field, that these attractions may not in fact be due to such correlations. It is rather the inherent interaction-asymmetry between equally- and between oppositely-charged domains that results in the long-ranged attraction even in the complete absence of any charge correlation

Repulsive Casimir forces

We discuss repulsive Casimir forces between dielectric materials with non trivial magnetic susceptibility. It is shown that considerations based on naive pair-wise summation of Van der Waals and Casimir Polder forces may not only give an incorrect estimate of the magnitude of the total Casimir force, but even the wrong sign of the force when materials with high dielectric and magnetic response are involved. Indeed repulsive Casimir forces may be found in a large range of parameters, and we suggest that the effect may be realized in known materials. The phenomenon of repulsive Casimir forces may be of importance both for experimental study and for nanomachinery applications

Non-Equilibrium in Adsorbed Polymer Layers

High molecular weight polymer solutions have a powerful tendency to deposit adsorbed layers when exposed to even mildly attractive surfaces. The equilibrium properties of these dense interfacial layers have been extensively studied theoretically. A large body of experimental evidence, however, indicates that non-equilibrium effects are dominant whenever monomer-surface sticking energies are somewhat larger than kT, a common case. Polymer relaxation kinetics within the layer are then severely retarded, leading to non-equilibrium layers whose structure and dynamics depend on adsorption kinetics and layer ageing. Here we review experimental and theoretical work exploring these non-equilibrium effects, with emphasis on recent developments. The discussion addresses the structure and dynamics in non-equilibrium polymer layers adsorbed from dilute polymer solutions and from polymer melts and more concentrated solutions. Two distinct classes of behaviour arise, depending on whether physisorption or chemisorption is involved. A given adsorbed chain belonging to the layer has a certain fraction of its monomers bound to the surface, f, and the remainder belonging to loops making bulk excursions. A natural classification scheme for layers adsorbed from solution is the distribution of single chain f values, P(f), which may hold the key to quantifying the degree of irreversibility in adsorbed polymer layers. Here we calculate P(f) for equilibrium layers; we find its form is very different to the theoretical P(f) for non-equilibrium layers which are predicted to have infinitely many statistical classes of chain. Experimental measurements of P(f) are compared to these theoretical predictions.Comment: 29 pages, Submitted to J. Phys.: Condens. Matte