Elastometry of Complex Fluid Pendant Capsules.

Oil/water interfaces are ubiquitous in nature. Opposing polarities at these interfaces attract surface-active molecules, which can seed complex viscoelastic or even solid interfacial structure. Biorelevant proteins such as hydrophobin, polymers such as PNIPAM, and the asphaltenes in crude oil (CRO) are examples of some systems where such layers can occur.

Biased periodic Aztec diamond and an elliptic curve.

We study random domino tilings of the Aztec diamond with a biased periodic weight function and associate a linear flow on an elliptic curve to this model. Our main result is a double integral formula for the correlation kernel, in which the integrand is expressed in terms of this flow. For special choices of parameters the flow is periodic, and this allows us to perform a saddle point analysis for the correlation kernel.

Oil Displacement in Calcite-Coated Microfluidic Chips via Waterflooding at Elevated Temperatures and Long Times.

In microfluidic studies of improved oil recovery, mostly pore networks with uniform depth and surface chemistry are used. To better mimic the multiple porosity length scales and surface heterogeneity of carbonate reservoirs, we coated a 2.5D glass microchannel with calcite particles.

Roughness induced rotational slowdown near the colloidal glass transition.

Hypothesis: In concentrated suspensions, the dynamics of colloids are strongly influenced by the shape and topographical surface characteristics of the particles. As the particles get into close proximity, surface roughness alters the translational and rotational Brownian motions in different ways. Eventually, the rotations will get frustrated due to geometric hindrance from interacting asperities.

Ultrasensitive Detection and In Situ Imaging of Analytes on Graphene Oxide Analogues Using Enhanced Raman Spectroscopy.

We demonstrate how algorithm-improved confocal Raman microscopy (ai-CRM), in combination with chemical enhancement by two-dimensional substrates, can be used as an ultrasensitive detection method for rhodamine (R6G) molecules adsorbed from aqueous solutions. After developing a protocol for laser-induced reduction of graphene oxide, followed by noninvasive Raman imaging, a limit of detection (LOD) of 5 × 10 M R6G was achieved using ai-CRM. An equivalent subnanomolar LOD was also achieved on another graphene oxide analogue -UV/ozone-oxidized graphene.

In-situ observation of reactive wettability alteration using algorithm-improved confocal Raman microscopy.

Hypothesis: The wettability of complex fluids on surfaces usually depends on the adsorption of solutes to any of the constituting interfaces. Controlling such interfacial processes by varying the composition of a phase enables the design of smart responsive systems. Our goal is to demonstrate that 3D Confocal Raman Microscopy (CRM) can reveal the mechanistic details of such processes by allowing to simultaneously monitor the contact angle variation and redistribution of the chemical species involved.

A Periodic Hexagon Tiling Model and Non-Hermitian Orthogonal Polynomials.

We study a one-parameter family of probability measures on lozenge tilings of large regular hexagons that interpolates between the uniform measure on all possible tilings and a particular fully frozen tiling. The description of the asymptotic behavior can be separated into two regimes: the low and the high temperature regime. Our main results are the computations of the disordered regions in both regimes and the limiting densities of the different lozenges there.

Electrochemically Induced Changes in TiO and Carbon Films Studied with QCM-D.

Semi-solid fluid electrode-based battery (SSFB) and supercapacitor technologies are seen as very promising candidates for grid energy storage. However, unlike for traditional batteries, their performance can quickly get compromised by the formation of a poorly conducting solid-electrolyte interphase (SEI) on the particle surfaces. In this work we examine SEI film formation in relation to typical electrochemical conditions by combining cyclic voltammetry (CV) with quartz crystal microbalance dissipation monitoring (QCM-D).

Spherical probes for simultaneous measurement of rotational and translational diffusion in 3 dimensions.

Real time visualization and tracking of colloidal particles with 3D resolution is essential for probing the local structure and dynamics in complex fluids. Although tracking translational motion of spherical particles is well-known, accessing rotational dynamics of such particles remains a great challenge. Here, we report a novel approach of using fluorescently labeled raspberry-like colloids with an optical anisotropy to concurrently track translational and rotational dynamics in 3 dimensions.

Algorithm-improved high-speed and non-invasive confocal Raman imaging of 2D materials.

Confocal Raman microscopy is important for characterizing 2D materials, but its low throughput significantly hinders its applications. For metastable materials such as graphene oxide (GO), the low throughput is aggravated by the requirement of extremely low laser dose to avoid sample damage. Here we introduce algorithm-improved confocal Raman microscopy (ai-CRM), which increases the Raman scanning rate by one to two orders of magnitude with respect to state-of-the-art works for a variety of 2D materials.

Device for rheometry, impedance spectroscopy, and electrochemistry on fluid electrodes.

We describe the extension of a rheometer to enable in situ impedance spectroscopy and electrochemical cycling. Key advantages of this instrument over traditional flow-channel based methods for studying fluid electrodes are the possibilities to monitor the rheological properties during cycling as well as to control the mechanical history of the sample. We describe two electrochemical configurations of the instrument, allowing fluid electrodes to be studied as full and half-cells.

Cationic Hofmeister Series of Wettability Alteration in Mica-Water-Alkane Systems.

The specific interaction of ions with macromolecules and solid-liquid interfaces is of crucial importance to many processes in biochemistry, colloid science, and engineering, as first pointed out by Hofmeister in the context of (de)stabilization of protein solutions. Here, we use contact angle goniometry to demonstrate that the macroscopic contact angle of aqueous chloride salt solutions on mica immersed in ambient alkane increases from near-zero to values exceeding 10°, depending on the type and concentration of cations and pH. Our observations result in a series of increasing ability of cations to induce partial wetting in the order Na, K < Li < Rb < Cs < Ca < Mg < Ba.

Tuning Interfacial Properties and Processes by Controlling the Rheology and Structure of Poly( N-isopropylacrylamide) Particles at Air/Water Interfaces.

By combining controlled experiments on single interfaces with measurements on solitary bubbles and liquid foams, we show that poly( N-isopropylacrylamide) (PNIPAM) microgels assembled at air/water interfaces exhibit a solid to liquid transition changing the temperature, and that this is associated with the change in the interfacial microstructure of the PNIPAM particles around their volume phase transition temperature. We show that the solid behaves as a soft 2D colloidal glass, and that the existence of this solid/liquid transition offers an ideal platform to tune the permeability of air bubbles covered by PNIPAM and to control macroscopic foam properties such as drainage, stability, and foamability. PNIPAM particles on fluid interfaces allow new tunable materials, for example foam structures with variable mechanical properties upon small temperature changes.

Salinity-Dependent Contact Angle Alteration in Oil/Brine/Silicate Systems: the Critical Role of Divalent Cations.

The effectiveness of water flooding oil recovery depends to an important extent on the competitive wetting of oil and water on the solid rock matrix. Here, we use macroscopic contact angle goniometry in highly idealized model systems to evaluate how brine salinity affects the balance of wetting forces and to infer the microscopic origin of the resultant contact angle alteration. We focus, in particular, on two competing mechanisms debated in the literature, namely, double-layer expansion and divalent cation bridging.

Influence of surface roughness on silicone rubber voice prostheses on in vitro biofilm formation and clinical lifetime in laryngectomised patients.

Objectives: Evaluation of the influence of a smooth surface moulding technique of silicone rubber indwelling voice prostheses on in vitro biofilm formation and analysis of the clinical in situ lifetime.

Design: Biofilm formation on smooth and Groningen ultra low resistance (URL) prostheses was studied in an artificial throat model. The clinical lifetime of smooth voice prostheses was compared to the previous lifetime of URL by counting the number of replacements in a consecutive 6-month period in the same patient.

Mechanical History Dependence in Carbon Black Suspensions for Flow Batteries: A Rheo-Impedance Study.

We studied the effects of shear and its history on suspensions of carbon black (CB) in lithium ion battery electrolyte via simultaneous rheometry and electrical impedance spectroscopy. Ketjen black (KB) suspensions showed shear thinning and rheopexy and exhibited a yield stress. Shear step experiments revealed a two time scale response.

Design of a hybrid advective-diffusive microfluidic system with ellipsometric detection for studying adsorption.

Establishing and maintaining concentration gradients that are stable in space and time is critical for applications that require screening the adsorption behavior of organic or inorganic species onto solid surfaces for wide ranges of fluid compositions. In this work, we present a design of a simple and compact microfluidic device based on steady-state diffusion of the analyte, between two control channels where liquid is pumped through. The device generates a near-linear distribution of concentrations.

Surfactant induced autophobing.

Surfactant adsorption in a three-phase system and its influence on wetting properties are relevant in various applications. Here, we report a hitherto not observed phenomenon, namely the retraction of an aqueous drop on hydrophilic solid substrates (which we refer to as 'autophobing') in ambient oil containing water-insoluble fatty acids, caused by the deposition of these fatty acids from the ambient oil onto the solid substrate. AFM measurements confirm that the surfactant is deposited on the solid by the moving contact line.

Dynamics of colloids confined in microcylinders.

We studied both global and local effects of cylindrical confinement on the diffusive behavior of hard sphere (HS) colloids. Using confocal scanning laser microscopy (CSLM) and particle tracking, we measured the mean squared displacement (MSD) of 1 micron sized silica particles in water-glycerol. This combination of fluid and setup allowed us to measure MSDs in a 4-dimensional parameter space, defined by the HS volume fraction (Φ: 0.

High-throughput sorting of drops in microfluidic chips using electric capacitance.

We analyze a recently introduced approach for the sorting of aqueous drops with biological content immersed in oil, using a microfluidic chip that combines the functionality of electrowetting with the high throughput of two-phase flow microfluidics. In this electrostatic sorter, three co-planar electrodes covered by a thin dielectric layer are placed directly below the fluidic channel. Switching the potential of the central electrode creates an electrical guide that leads the drop to the desired outlet.

Stability Limits of Capillary Bridges: How Contact Angle Hysteresis Affects Morphology Transitions of Liquid Microstructures.

The equilibrium shape of a drop in contact with solid surfaces can undergo continuous or discontinuous transitions upon changes in either drop volume or surface energies. In many instances, such transitions involve the motion of the three-phase contact line and are thus sensitive to contact angle hysteresis. Using a combination of electrowetting-based experiments and numerical calculations, we demonstrate for a generic sphere-plate confinement geometry how contact angle hysteresis affects the mechanical stability of competing axisymmetric and nonaxisymmetric drop conformations and qualitatively changes the character of transitions between them.

Effects of shear and walls on the diffusion of colloids in microchannels.

Colloidal suspensions flowing through microchannels were studied for the effects of both the shear flow and the proximity of walls on the particles' self-diffusion. Use of hydrostatic pressure to pump micron-sized silica spheres dispersed in water-glycerol mixture through poly(dimethylsiloxane) channels with a cross section of 30×24μm(2), allowed variation in the local Peclet number (Pe) from 0.01 to 50.

Ion adsorption-induced wetting transition in oil-water-mineral systems.

The relative wettability of oil and water on solid surfaces is generally governed by a complex competition of molecular interaction forces acting in such three-phase systems. Herein, we experimentally demonstrate how the adsorption of in nature abundant divalent Ca(2+) cations to solid-liquid interfaces induces a macroscopic wetting transition from finite contact angles (≈ 10°) with to near-zero contact angles without divalent cations. We developed a quantitative model based on DLVO theory to demonstrate that this transition, which is observed on model clay surfaces, mica, but not on silica surfaces nor for monovalent K(+) and Na(+) cations is driven by charge reversal of the solid-liquid interface.

Measuring advection and diffusion of colloids in shear flow.

An analysis of the dynamics of colloids in shear flow can be challenging because of the superposition of diffusion and advection. We present a method that separates the two motions, starting from the time-dependent particle coordinates. The restriction of the tracking to flow lanes and the subtraction of estimated advective displacements are combined in an iterative scheme that eventually makes the spatial segmentation redundant.

Hard and soft colloids at fluid interfaces: Adsorption, interactions, assembly & rheology.

Soft microgel particles inherently possess qualities of both polymers as well as particles. We review the similarities and differences between soft microgel particles and stiff colloids at fluid-fluid interfaces. We compare two fundamental aspects of particle-laden interfaces namely the adsorption kinetics and the interactions between adsorbed particles.