Urs T. Gonzenbach

Stabilization of Oil-in-Water Emulsions by Colloidal Particles Modified with Short Amphiphiles

Emulsions stabilized through the adsorption of colloidal particles at the liquid-liquid interface have long been used and investigated in a number of different applications. The interfacial adsorption of particles can be induced by adjusting the particle wetting behavior in the liquid media. Here, we report a new approach to prepare stable oil-in-water emulsions by tailoring the wetting behavior of colloidal particles in water using short amphiphilic molecules. We illustrate the method using hydrophilic metal oxide particles initially dispersed in the aqueous phase. The wettability of such particles in water is reduced by an in situ surface hydrophobization that induces particle adsorption at oil-water interfaces. We evaluate the conditions required for particle adsorption at the liquid-liquid interface and discuss the effect of the emulsion initial composition on the final microstructure of oil-water mixtures containing high concentrations of alumina particles modified with short carboxylic acids. This new approach for emulsion preparation can be easily applied to a variety of other metal oxide particles.

Materials from foams and emulsions stabilized by colloidal particles

Foams and emulsions stabilized by colloidal particles can lead to new materials with unique structures and properties. In this Highlight article, we describe the underlying mechanisms of this new enabling technology, highlighting some of the processing routes to obtain capsules and porous structures for a variety of applications.

Designing macroporous polymers from particle-stabilized foams

Particle-stabilized liquid foams provide a general route for producing low-density macroporous materials from melt-processable and intractable thermoplastic polymers. In this paper, we demonstrate how these liquid foams can be used to design macroporous polymers with tailored microstructures and properties by adjusting the various processing parameters. By varying the size, concentration, and wettability of the particles in the colloidal suspensions and controlling the frothing, drying, and sintering conditions, macroporous materials with porosities between 33 and 95% and median pore sizes (D50) between 13 and 634 μm were obtained. This foaming process is applicable to a wide range of hydrophobic materials and is demonstrated here on commercially available polymeric powders of poly(tetrafluoroethylene) (PTFE), poly(vinylidene fluoride) (PVDF), poly(ether imide) (PEI), and poly(ether ether ketone) (PEEK).

Covalent cell surface functionalization of human fetal osteoblasts for tissue engineering

The chemical functionalization of cell-surface proteins of human primary fetal bone cells with hydrophilic bioorthogonal intermediates was investigated. Toward this goal, chemical pathways were developed for click reaction-mediated coupling of alkyne derivatives with cellular azido-expressing proteins. The incorporation via a tetraethylene glycol linker of a dipeptide and a reporter biotin allowed the proof of concept for the introduction of cell-specific peptide ligands and allowed us to follow the reaction in living cells. Tuning the conditions of the click reaction resulted in chemical functionalization of living human fetal osteoblasts with excellent cell survival.

Metallic foams from nanoparticle-stabilized wet foams and emulsions

We present a method to prepare metallic foams with a unique architecture of small pores and thin struts using wet foams and emulsions stabilized by metallic nanoparticles as templates.

Unifying Model for the Electrokinetic and Phase Behavior of Aqueous Suspensions Containing Short and Long Amphiphiles

Aqueous suspensions containing oppositely charged colloidal particles and amphiphilic molecules can form fluid dispersions, foams, and percolating gel networks, depending on the initial concentration of amphiphiles. While models have been proposed to explain the electrokinetic and flotation behavior of particles in the presence of long amphiphilic molecules, the effect of amphiphiles with less than six carbons in the hydrocarbon tail on the electrokinetic, rheological, and foaming behavior of aqueous suspensions remains unclear. Unlike conventional long amphiphiles (≥10 carbons), short amphiphiles do not exhibit increased adsorption on the particle surface when the number of carbons in the molecule tail is increased. On the basis of classical electrical double layer theory and the formerly proposed hemimicelle concept, we put forward a new predictive model that reconciles the adsorption and electrokinetic behavior of colloidal particles in the presence of long and short amphiphiles. By introducing in the classical Gouy-Chapman theory an energy term associated with hydrophobic interactions between the amphiphile hydrocarbon tails, we show that amphiphilic electrolytes lead to a stronger compression of the diffuse part of the electrical double layer in comparison to hydrophilic electrolytes. Scaling relationships derived from this model provide a quantitative description of the rich phase behavior of the investigated suspensions, correctly accounting for the effect of the alkyl chain length of short and long amphiphiles on the electrokinetics of such colloidal systems. The proposed model contributes to our understanding of the stabilization mechanisms of particle-stabilized foams and emulsions and might provide new insights into the physicochemical processes involved in mineral flotation.

Surface functionalization of alumina ceramic foams with organic ligands.

Different anchoring groups have been studied with the aim of covalently binding organic linkers to the surface of alumina ceramic foams. The results suggested that a higher degree of functionalization was achieved with a pyrogallol derivative--as compared to its catechol analogue--based on the XPS analysis of the ceramic surface. The conjugation of organic ligands to the surface of these alumina materials was corroborated by DNP-MAS NMR measurements.

Functionalization of microstructured open-porous bioceramic scaffolds with human fetal bone cells.

Bone substitute materials allowing trans-scaffold migration and in-scaffold survival of human bone-derived cells are mandatory for development of cell-engineered permanent implants to repair bone defects. In this study, we evaluated the influence on human bone-derived cells of the material composition and microstructure of foam scaffolds of calcium aluminate. The scaffolds were prepared using a direct foaming method allowing wide-range tailoring of the microstructure for pore size and pore openings. Human fetal osteoblasts (osteo-progenitors) attached to the scaffolds, migrated across the entire bioceramic depending on the scaffold pore size, colonized, and survived in the porous material for at least 6 weeks. The long-term biocompatibility of the scaffold material for human bone-derived cells was evidenced by in-scaffold determination of cell metabolic activity using a modified MTT assay, a repeated WST-1 assay, and scanning electron microscopy. Finally, we demonstrated that the osteo-progenitors can be covalently bound to the scaffolds using biocompatible click chemistry, thus enhancing the rapid adhesion of the cells to the scaffolds. Therefore, the different microstructures of the foams influenced the migratory potential of the cells, but not cell viability. Scaffolds allow covalent biocompatible chemical binding of the cells to the materials, either localized or widespread integration of the scaffolds for cell-engineered implants.

Ceramic Spheres—A Novel Solution to Deep Sea Buoyancy Modules

Ceramic-based hollow spheres are considered a great driving force for many applications such as offshore buoyancy modules due to their large diameter to wall thickness ratio and uniform wall thickness geometric features. We have developed such thin-walled hollow spheres made of alumina using slip casting and sintering processes. A diameter as large as 50 mm with a wall thickness of 0.5–1.0 mm has been successfully achieved in these spheres. Their material and structural properties were examined by a series of characterization tools. Particularly, the feasibility of these spheres was investigated with respect to its application for deep sea (>3000 m) buoyancy modules. These spheres, sintered at 1600 °C and with 1.0 mm of wall thickness, have achieved buoyancy of more than 54%. As the sphere’s wall thickness was reduced (e.g., 0.5 mm), their buoyancy reached 72%. The mechanical performance of such spheres has shown a hydrostatic failure pressure above 150 MPa, corresponding to a rating depth below sea level of 5000 m considering a safety factor of 3. The developed alumina-based ceramic spheres are feasible for low cost and scaled-up production and show great potential at depths greater than those achievable by the current deep-sea buoyancy module technologies.

Hollow calcium aluminate microcapsules with porous shell microstructure and unique mechanical properties

Since the mid-1970s, microencapsulation has become increasingly popular in food, detergent, cosmetic and pharmaceutical industries to protect active agents from degradation or facilitate their controlled release or targeted delivery. Here we report on a synthesis route of a novel class of hollow inorganic microcapsules with unique microstructural and mechanical properties. The method is based on the adsorption of calcium aluminate particles at the interface of water droplets of an oil-continuous emulsion. Upon contact with water, these particles hydrate and form a mechanically stable, porous capsule shell. After solvent evaporation, hollow microcapsules can be harvested with diameters between 30 and 200 μm and yields of up to 75%. The mechanical characterization of entire capsules is accomplished using a uniaxial, micromechanical compression setup installed in a scanning electron microscope. We show that these inorganic calcium aluminate microcapsules are highly crack tolerant owing to their porous shell microstructure. Such a behavior is in strong contrast to the one of hollow aluminosilicate cenospheres, which feature dense shells and show therefore brittle failure in our compression tests.