Parametric Study of Colloidal Particle Confinement near a Surface in the Presence of DLVO and Structural Interactions Using Brownian Dynamic Simulations

Total internal reflection microscopy (TIRM) has become a crucial technique for understanding the surface interactions and dynamics of Brownian colloidal particles near a surface. However, for select colloidal systems, experimental limitations associated with TIRM can occlude exploration of nano- and submicrometer colloids dispersed in complex or structured fluids. It should be possible to use Brownian dynamic simulations to quantify, explore, or circumvent these limitations to extend the TIRM technique further. A Brownian dynamics algorithm based on the Langevin equation was utilized to identify favorable colloidal systems for conducting TIRM experiments in electrolyte and nonadsorbing polyelectrolyte solutions. In electrolyte solution, the motion of polystyrene and silica particles of nanometer- and micrometer-sized radii was simulated near a glass slide in the presence of retarded van der Waals and electric double-layer forces to develop potential energy profiles. In the case of nonadsorbing polyelectrolyte solutions, a structural force was also implemented into the simulation, and the influence of structural interactions on particle confinement was explored as a function of particle size, particle density, and polyelectrolyte concentration. In electrolyte solutions, our results were able to identify the minimum particle size required for TIRM experiments as well as insight into particle selection based on material density. For structural or oscillatory forces, our results show that prior to conducting TIRM experiments, Brownian dynamics simulation can be used to select the appropriate particle size, material, and polyelectrolyte concentration range where the colloidal particle can sample multiple structural energy wells without confinement. These results provide insight into the colloidal system suitable to experimentally study near-surface particle diffusion dynamics for a range of separations in the presence of structural interactions

Novel Characterization of Microdrops and Microbubbles in Emulsions and Foams Using Atomic Force Microscopy

The nature of the interface of drops or bubbles and the dynamic interactions between them often mediate or control macroscopic behavior in the formulation and processing of emulsions and foams in solvent extraction, froth flotation, food, personal care products, and microfluidics as well as in many biological processes. Characterization of these interfaces is often complicated due to the small size of the drops and bubbles that may range from the micrometer scale to hundreds of micrometers. We report the direct measurement of the surface or interfacial tension of drops or bubbles in aqueous solutions as a function of the concentration and type of surfactant, using atomic force microscopy (AFM) and a recently developed nanoneedle AFM cantilever. We also demonstrate the viability of imaging drops or bubbles of this size in both tapping and contact imaging modes through a systematic study of parameters, including cantilever spring constant, tip geometry, imaging force, and feedback settings as well as the AFM manufacturer. The imaging study demonstrates the viability of using AFM to visualize complex structures at the oil−water or air−water interface as well as how concentric ring artifacts observed in the literature are the result of earlier AFM instrument limitations

Effect of Orientation and Wetting Properties on the Behavior of Janus Particles at the Air–Water Interface

The adhesion force and contact angle of gold-capped silica Janus particles and plain silica particles at an air–water interface are studied via colloidal atomic force microscopy. Particles are attached to cantilevers at various orientations, and wetting properties of the gold surface are varied through modification with dodecanethiol. Thiol modification increases the hydrophobicity of the gold surface, thereby increasing the difference between the contact angles of the gold hemisphere and the silica hemisphere and, thus, increasing the degree of amphiphilicity of the Janus particle. Subsequently, the colloidal probe is pushed into a stationary bubble from the water phase followed by retraction back into the water phase. Adhesion force is found to be higher for Janus particles than isotropic silica particles, regardless of orientation of the anisotropic hemisphere. Particles with their polar half oriented toward the water and apolar half facing the air show an increase in adhesion force and contact angle as the degree of amphiphilicity of the particles increases. For particles of the reverse orientation, no significant difference is observed as wetting properties change. Both adhesion force and contact angle display an inverse relationship with a cap angle for particles with a higher degree of amphiphilicity. These results are of importance for using Janus particles to stabilize interfaces as well as for understanding the equilibrium height of Janus particles at the interface, which will impact capillary interactions and thus self-assembly

Anisotropic Particle Fabrication Using Thermal Scanning Probe Lithography

Size, shape, and chemical properties of nanoparticles are powerful tools to modulate the optical and physicochemical properties of a particle suspension. Despite having many methods to synthesize anisotropic nanoparticles, often there are challenges in terms of controlling the polydispersity, shape, size, or composition of anisotropic nanoparticles. This work has been inspired by the potential for developing a unique pathway to make different shaped monodispersed anisotropic nano- and microparticles with large flexibility in material choice. Compared to existing methods, this state-of-the-art nanolithographic method is fast, easy to prototype, and much simple in terms of its mechanical requirement. We show that this technique has been efficiently used to make a variety of anisotropic nano- and microparticles of different shapes, such as triangular prisms, ovals, disks, flowers, and stairs following the same pathway, at the same time showing the potential of being flexible with respect to the composition of the particles. The thermal scanning probe lithographic method in combination with dry reactive ion etching was used to make two-dimensional and three-dimensional templates for the fabrication of anisotropic nano- and microparticles. Deposition of different metal/metal oxides by the electron-beam evaporation method onto these templates allowed us to fabricate a range of nanomaterials according to the required functionality in potential applications. The particles were characterized by atomic force microscopy, He-ion microscopy, scanning electron microscopy, and dynamic light scattering to ensure that the developed method is reproducible, flexible, and robust in choosing the shapes for making monodispersed anisotropic nanoparticles with great control over shape and size

Structural Forces in Soft Matter Systems

Oscillating structural forces arise when nanoscale colloids are confined at high concentration between two approaching surfaces. As layers of colloid are squeezed out, changes in osmotic pressure cause alternating regions of repulsion and attraction. Here, we provide direct measurements of such oscillatory structural forces between the soft interfaces of two emulsion droplets. Quantitative comparison indicates that the deformable nature of droplets allows them to act as far more sensitive probes than solid spheres. In addition, the responsive nature of soft surfaces can give rise to unexpected behaviors not encountered in rigid systems including reversible aggregation/flocculation for emulsion droplets and, potentially, spatial ordering within concentrated emulsion phases

Bubble Colloidal AFM Probes Formed from Ultrasonically Generated Bubbles

Here we introduce a simple and effective experimental approach to measuring the interaction forces between two small bubbles (∼80−140 μm) in aqueous solution during controlled collisions on the scale of micrometers to nanometers. The colloidal probe technique using atomic force microscopy (AFM) was extended to measure interaction forces between a cantilever-attached bubble and surface-attached bubbles of various sizes. By using an ultrasonic source, we generated numerous small bubbles on a mildly hydrophobic surface of a glass slide. A single bubble picked up with a strongly hydrophobized V-shaped cantilever was used as the colloidal probe. Sample force measurements were used to evaluate the pure water bubble cleanliness and the general consistency of the measurements

Dynamic Forces between Bubbles and Surfaces and Hydrodynamic Boundary Conditions

A bubble attached to the end of an atomic force microscope cantilever and driven toward or away from a flat mica surface across an aqueous film is used to characterize the dynamic force that arises from hydrodynamic drainage and electrical double layer interactions across the nanometer thick intervening aqueous film. The hydrodynamic response of the air/water interface can range from a classical fully immobile, no-slip surface in the presence of added surfactants to a partially mobile interface in an electrolyte solution without added surfactants. A model that includes the convection and diffusion of trace surface contaminants can account for the observed behavior presented. This model predicts quantitatively different interfacial dynamics to the Navier slip model that can also be used to fit dynamic force data with a post hoc choice of a slip length

Study of Fluid and Transport Properties of Porous Anodic Aluminum Membranes by Dynamic Atomic Force Microscopy

Recent work on carbon nanotubes (CNT) has focused on their potential application in water treatment as a result of their predicted and observed enhanced flow rates. Recent work on the lesser-known porous anodic alumina membranes (PAAMs) has also shown flow enhancement, albeit at only a fraction of what has been observed in CNTs. Despite their potential applications, little research has been conducted on PAAMs’ hydrodynamic properties, and in this Article we present experimental results and theoretical models that explore the fluid flow behavior around and through these membranes. The experiments were conducted using an atomic force microscope (AFM) that pushed a solid silica particle against PAAMs that were characterized with different pore diameters. Furthermore, the PAAMs were classified as either closed or open, with the latter allowing fluid to pass through. The theoretical model developed to describe the experimental data incorporates Derjaguin–Landau–Verwey–Overbeek (DLVO) effects, cantilever drag, and hydrodynamic forces. By using the slip boundary condition for the hydrodynamic forces, we were able to fit the model to experimental findings and also demonstrate that the difference between closed and open PAAMs was negligible. The slip lengths did not correspond to any physical feature of the PAAMs, but our model does provide a simple yet effective means of describing the hydrodynamics for not only PAAMs but for membranes in general

Combined AFM−Confocal Microscopy of Oil Droplets: Absolute Separations and Forces in Nanofilms

Quantitative interpretation of the dynamic forces between micrometer-sized deformable droplets and bubbles has previously been limited by the lack of an independent measurement of their absolute separation. Here, we use in situ confocal fluorescence microscopy to directly image the position and separation of oil droplets in an atomic force microscopy experiment. Comparison with predicted force vs. separation behavior to describe the interplay of force and deformation showed excellent agreement with continuum hydrodynamic lubrication theory in aqueous films less than 30 nm thick. The combination of force measurement and 3D visualization of geometric separation and surface deformation is applicable to interactions between other deformable bodies

Influence of Surfactant Structure on Polydisperse Formulations of Alkyl Ether Sulfates and Alkyl Amidopropyl Betaines

Surfactants provide detergency, foaming, and texture in personal care formulations, yet the micellization of typical industrial primary and cosurfactants is not well understood, particularly in light of the polydisperse nature of commercial surfactants. Synergistic interactions are hypothesized to drive the formation of elongated wormlike self-assemblies in these mixed surfactant systems. Small-angle neutron scattering, rheology, and pendant drop tensiometry are used to examine surface adsorption, viscoelasticity, and self-assembly structure for wormlike micellar formulations comprising cocoamidopropyl betaine, and its two major components laurylamidopropyl betaine and oleylamidopropyl betaine, with sodium alkyl ethoxy sulfates. The tail length of sodium alkyl ethoxy sulfates was related to their ability to form wormlike micelles in electrolyte solutions, indicating that a tail length greater than 10 carbons is required to form wormlike micelles in NaCl solutions, with the decyl homologue unable to form elongated micelles and maintaining a low viscosity even at 20 wt % surfactant loading with 4 wt % NaCl present. For these systems, the incorporation of a disperse ethoxylate linker does not enable shorter chain surfactants to elongate into wormlike micelles for single-component systems; however, it could increase the interactions between surfactants in mixed surfactant systems. For synergy in surfactant mixing, the nonideal regular solution theory is used to study the sulfate/betaine mixtures. Tail mismatch appears to drive lower critical micelle concentrations, although tail matching improves synergy with larger relative reductions in critical micelle concentrations and greater micelle elongation, as seen by both tensiometric and scattering measurements