Bijel Formation Research Articles

Formation of bijels stabilized by magnetic ellipsoidal particles in external magnetic fields.

Bicontinuous interfacially-jammed emulsion gels (bijels) are increasingly used as emulsion templates for the fabrication of functional porous materials including membranes, electrodes, and biomaterials. Control over the domain size and structure is highly desirable in these applications. For bijels stabilized by spherical particles, particle size and volume fraction are the main parameters that determine the emulsion structure. Here, we investigate the use of ellipsoidal magnetic particles and study the effect of external magnetic fields on the formation of bijels. Using hybrid Lattice Boltzmann-molecular dynamics simulations, we analyze the effect of the magnetic field on emulsion dynamics and the structural properties of the resulting bijel. We find that the formation of bijels remains robust in the presence of magnetic fields, and that the domain size and tortuosity become anisotropic when ellipsoidal particles are used. We show that the magnetic fields lead to orientational ordering of the particles which in turn leads to alignment of the interfaces. The orientational order facilitates enhanced packing of particles in the interface which leads to different jamming times in the directions parallel and perpendicular to the field. Our results highlight the potential of magnetic particles for fabrication and processing of emulsion systems with tunable properties.

Dual access to the fluid networks of colloid-stabilized bicontinuous emulsions through uninterrupted connections.

Large surface areas are important for enhancing mass and energy transfer in biological and technological processes. Bicontinuous interfacially jammed emulsion gels (bijels) increase the surface area between two fluids by intertwining them into particle stabilized networks. To facilitate efficient mass and energy exchange via the bijels' high surface area, the fluid networks need to be connected to their respective bulk phases. Here, we generate bijels between two bulk fluids and investigate the connections the bijel makes. We analyze these connections by investigating the colloidal stability, interfacial rheology and mass transfer dynamics during bijel formation. To this end, we employ confocal and electron microscopy, as well as dynamic light scattering, pendant drop analysis, electrophoretic mobility measurements and diffusion simulations. We find that the connections the bijel makes to the bulk fluid can be disrupted by severe colloidal aggregation and interruptions of the bicontinuous fluid network. However, the addition of alcohol to the bulk fluid moderates aggregation and allows undisturbed fluid network formation, facilitating open connections between bijel and bulk fluid. The unprecedented control of bijel pore connections from this research will be crucial for the application of bijels as separation membranes, electrochemical energy storage materials and chemical reactors.

Droplet-Bijel-Droplet Transition in Aqueous Two-Phase Systems Stabilized by Oppositely Charged Nanoparticles: A Simple Pathway to Fabricate Bijels.

We demonstrate a novel yet straightforward methodology of stabilizing aqueous two-phase systems (ATPS) using oppositely charged nanoparticles (OCNPs). We employ commercial-grade, Ludox, OCNPs to induce self-assembly. This self-assembly route promotes the stronger adsorption of nanoparticles at the water-water interface by triggering the formation of 2D and 3D aggregates of varying sizes and shapes. The interplay of this size and shape promotes stability due to increased Gibbs detachment energy and modulates the resulting cluster adsorption at the interface, thereby the structural state of emulsions. We demonstrate the influence of polymers' and particles' composition on the structural transformation from droplet-bijel-droplet using a phase diagram. For the first time, such a structural transition and the single pathway are reported within the domain of ATPS to produce stable bijels or colloidal capsules. It is asserted that the essential condition of three-phase contact angle (θ) = 90° to favor the formation of bijels can be established by selecting a suitable experimental condition using a phase diagram without employing any complicated surface modification procedures reported in the literature. Further, the mechanistic route favoring the formation of bijels and emulsion droplets at different experimental regimes is presented based on the empirical study using turbidity and zeta potential measurements. These studies reveal that the formation of bijels will be most favored when the parameter M (ratio of weight fraction of positively charged nanoparticles to negatively charged nanoparticles) is chosen between 0.7 and 4. It is intriguing to note the fact that, while the droplets stabilized by OCNPs have shown good resilience under high centrifugal action, the bijels produced in this way continued to remain stable for a long time, offering a facile route to prepare the bijels with a hierarchical bicontinuous network structure.

Numerical simulations of bijel morphology in thin films with complete surface wetting.

Bijels are a relatively new class of soft materials that have many potential energy and environmental applications. In this work, simulation results of bijel evolution confined within thin films with preferential surface wetting are presented. The computational approach used is a hybrid Cahn-Hilliard/Brownian dynamics method. In the absence of suspended particles, we demonstrate that the model accurately captures the rich kinetics associated with diffusion-based surface-directed spinodal decomposition, as evidenced by comparison with previous theoretical and simulation-based studies. When chemically neutral particles are included in the films, the simulations capture surface-modified bijel formation, with stabilized domain structures comparable with the experimental observations of Composto and coworkers. Namely, two basic morphologies - bicontinuous or discrete - are seen to emerge, with direct dependence on the film thickness, particle volume fraction, and particle radius.

Continuous Fabrication of Hierarchical and Asymmetric Bijel Microparticles, Fibers, and Membranes by Solvent Transfer-Induced Phase Separation (STRIPS).

Continuous generation of hierarchical and asymmetric bijels based on solvent-transfer-induced phase separation (STRIPS) is demonstrated. In STRIPS, phase separation is induced by solvent extraction from an initially homogeneous ternary mixture, and bicontinuous morphology is stabilized by inter-facial attachment of nano-particles, which are functionalized in situ. STRIPS allows stable bijel formation from a wide variety of liquids and particles.

Particle-size effects in the formation of bicontinuous Pickering emulsions.

We demonstrate that the formation of bicontinuous emulsions stabilized by interfacial particles (bijels) is more robust when nanoparticles rather than microparticles are used. Emulsification via spinodal demixing in the presence of nearly neutrally wetting particles is induced by rapid heating. Using confocal microscopy, we show that nanospheres allow successful bijel formation at heating rates two orders of magnitude slower than is possible with microspheres. In order to explain our results, we introduce the concept of mechanical leeway, i.e., nanoparticles benefit from a smaller driving force towards disruptive curvature. Finally, we suggest that leeway mechanisms may benefit any formulation in which challenges arise due to tight restrictions on a pivotal parameter, but where the restrictions can be relaxed by rationally changing the value of a more accessible parameter.

Food-grade bijels based on gelatin-maltodextrin-microbial cell composites

The concept of bijels was extended to food-grade systems by adding inactivated single-celled microorganisms (the yeast Saccharomyces cerevisiae, the bacteria Lactobacillus delbrueckii subsp. bulgaricus and the microalgae spirulina) to phase-separated gelatin-maltodextrin gels. Contrary to the control gel with its droplet-type morphology, adsorption of microbial cells to the protein-polysaccharide interface resulted in the formation of bijels that remained kinetically stable for months. The elastic modulus of the gels containing either yeast or microalgae was greater than in the control whereas incorporation of Lactobacillus bulgaricus resulted in a gel with a lower elastic modulus than the control. All gels demonstrated strain-hardening, with the presence of microbial cells shifting the fracture strain to higher values and smaller relative increases in complex modulus prior to yielding. Overall, these results demonstrated that single-celled microbes can act as structure modifiers in food-grade phase-separated gels thereby resulting in food-grade bijels.

Inversion of particle-stabilized emulsions of partially miscible liquids by mild drying of modified silica particles

Using a system of modified silica particles and mixtures of water and 2,6-lutidine to form particle-stabilized emulsions, we show that subtle alterations to the hydration of the particle surface can cause major shifts in emulsion structure. We use fluorescence confocal microscopy, solid state nuclear magnetic resonance (NMR) and thermo-gravimetric analysis (TGA) to explore this sensitivity, along with other shifts caused by modifications to the silica surface chemistry. The silica particles are prepared by a variant of the Stöber procedure and are modified by the inclusion of 3-(aminopropyl)triethoxysilane and the dye fluorescein isothiocyanate. Treatment prior to emulsification consists of gently drying the particles under carefully controlled conditions. In mixtures of water and 2,6-lutidine of critical composition, the particles stabilize droplet emulsions and bijels. Decreasing particle hydration yields an inversion of the emulsions from lutidine-in-water (L/W) to water-in-lutidine (W/L), with bijels forming around inversion. So dependent is the emulsion behavior on particle hydration that microscopic differences in drying within a particle sample can cause differences in the wetting behavior of that sample, which helps to stabilize multiple emulsions. The formation of bijels at emulsion inversion is also crucially dependent on the surface modification of the silica.

Influence of particle composition and thermal cycling on bijel formation

Colloidal particles with appropriate wetting properties can become very strongly trappedat an interface between two immiscible fluids. We have harnessed this phenomenon tocreate a new class of soft materials with intriguing and potentially useful characteristics.The material is known as a bijel: bicontinuous interfacially-jammed emulsion gel. It is acolloid-stabilized emulsion with fluid-bicontinuous domains. The potential to create thesegels was first predicted using computer simulations. Experimentally we use mixtures ofwater and 2,6-lutidine at the composition for which the system undergoes a criticaldemixing transition on warming. Colloidal silica, with appropriate surface chemistry, isdispersed while the system is in the single-fluid phase; the composite sample is then slowlywarmed well beyond the critical temperature. The liquids phase separate via spinodaldecomposition and the particles become swept up on the newly created interfaces. As thedomains coarsen the interfacial area decreases and the particles eventually becomejammed together. The resulting structures have a significant yield stress and arestable for many months. Here we begin to explore the complex wetting propertiesof fluorescently tagged silica surfaces in water–lutidine mixtures, showing howthey can be tuned to allow bijel creation. Additionally we demonstrate how theparticle properties change with time while they are immersed in the solvents.