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Many properties of materials, including their dissolution kinetics, hardness, and optical appearance, depend on their structure. Unfortunately, it is often difficult to control the structure of low molecular weight organic compounds that have a high propensity to crystallize if they are formulated from solutions wherein they have a high mobility. This limitation can be overcome by formulating these compounds within small airborne drops that rapidly dry, thereby limiting the time molecules have to arrange into the thermodynamically most stable phase. Such drops can be formed with a surface acoustic wave (SAW)-based spray-drier. In this paper, we demonstrate that the structure of a model low molecular weight compound relevant to applications in pharmacology and food, succinic acid, can be readily controlled with the supersaturation rate. Succinic acid particles preserve the metastable structure over at least 3 months if the initial succinic acid concentration is below 2% of its saturation concentration such that the supersaturation rate is high. We demonstrate that also the stability of the metastable phases against their transformation into the most stable phase increases with decreasing initial solute concentration and hence with increasing supersaturation rate of the spray-dried solution. These insights open up new opportunities to control the crystal structure and therefore properties of low molecular weight compounds that have a high propensity to crystallize.

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Protein condensates resulting from liquid-liquid phase separation have long been studied as bio-adhesives and coating materials for various applications. More recently, they are also being scrutinized as models for membraneless organelles in cells. Quantifying their interfacial mechanics and rheology at micrometer scales is vital for better understanding the physics underlying membraneless organelles in cells and for developing and improving technological applications of protein condensates. This study demonstrates how colloidal probe atomic force microscopy with an oscillating tip can be used to simultaneously investigate the interfacial mechanics and dynamic rheological properties of micro-scale protein condensates, formed via carefully controlled capillary condensation. This new approach can access oscillation frequencies ranging from 1 to 104 rad/s. By analyzing the data using an equivalent mechanical model, three characteristic frequency domains for the mechanics of micro-scale protein condensates are found: an interfacial tension-dominated domain at low frequencies, a transition domain (viscous-to-elastic crossover) at intermediate frequencies, and an elasticity-dominated domain at high frequencies, covering a broad range of time scales relevant in biology and technological applications of protein condensates.

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Acacia gum (Gum Arabic; GA) and chitosan (CTS) form complex coacervates in acidic environments, providing a polymer-rich aqueous material with interesting bio-lubricant properties. We investigate the interplay of the tribology and rheology of these coacervates, demonstrating that they dramatically reduce the friction coefficient between lubricated soft model surfaces as compared to solutions of the individual polymers. We characterize the phase separation behavior using microscopy, electrophoretic mobility and thermogravimetric analysis. The macroscopic rheological behaviour is predominantly viscous and ranges from weakly to strongly shear thinning: viscosity levels and strength of shear thinning increase with decreasing ionic strength, but no apparent yield stress or predominant elasticity were observed even in the absence of salt. Conversely, friction coefficients measured between soft and rough surfaces increase with a rise in ionic strength and can be scaled onto a Stribeck-type master curve across varying ionic strength and pH in the mixed and hydrodynamic lubrication regimes.

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Plant-based ingredients are key building blocks for future sustainable advanced materials. Functionality is typically higher for highly purified plant-based ingredients, but this is at the expense of their sustainability value. Here, a method is introduced for creating a soft functional material, with structural elements ranging from the nanometer to the millimeter scale, directly from legume flours. Globulins from soy and pea flours are extracted in their native state at acidic pH and mixed with gum arabic, resulting in liquid-liquid phase separation into a dilute phase and a viscoelastic complex coacervate. Interfacial tensions of the coacervates, determined via AFM-based probing of capillary condensation, are found to be very low (γ = 48.5 and 32.3 µN/m for, respectively, soy and pea), thus promoting the deposition of a shell of coacervate material around oil droplets. Despite the complex nature of the starting material, the dependence of interfacial tensions on salt concentrations follows a scaling law previously shown to hold for model complex coacervates. Curing of the coacervate material into a strong and purely elastic hydrogel is shown to be possible via simple heating, both in bulk and as a shell around oil droplets, thus providing proof of principle for the fabrication of precise core-shell microcapsules directly from legume flours.

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Traditionally, complex coacervates of oppositely charged biopolymers have been used to form coatings around oil droplets for encapsulation of oil-soluble payloads. However, many proteins can form coacervates by themselves under certain conditions. Here, we revisit the well-known simple coacervates of prolamins such as zein in mixed solvents to explore whether they can be used for plant-based encapsulation systems. We show that, for zein in mixed water/propylene glycol (PG) solvents, we can encapsulate limonene droplets but only under specific conditions. We illustrate that this limitation is due to the very different physical properties of the simple zein coacervates as compared to those of the more extensively studied complex coacervates. Droplets of simple coacervates of zein can carry a significant net charge, whereas complex coacervates are usually close to being charge-balanced. In particular, we demonstrate that the spreading of zein coacervates at the interface of the droplets is thermodynamically favorable due to their extremely low interfacial tensions in both the dispersed (∼0.24 mN/m) and oil phases (∼0.68 mN/m), but the kinetics of coacervate droplet deposition and the interactions among coacervate droplets that oppose coacervate droplet coalescence are highly pH-dependent, leading to a sharp pH optimum (around pH 8) for capsule formation.

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Composite polyurea/coacervate core/shell capsules are formed by coupling associative biopolymer phase separation with interfacial polymerization. They combine the excellent chemical stability of synthetic polymer barriers with the strong adhesive properties of protein-based complex coacervates, inspired by biological underwater glues. To encapsulate volatile oil droplets, a primary coacervate hydrogel capsule is formed by a protein and weak polyanion and is reinforced with a polyurea membrane synthesized in situ at the interface between the coacervate and the oil core. The polyurea layer provides an excellent permeability barrier against diffusion of small volatile molecules while the coacervate portion of the shell enhances adhesion on the targeted substrate.

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Complex coacervation is an associative liquid/liquid phase separation resulting in the formation of two liquid phases: a polymer-rich coacervate phase and a dilute continuous solvent phase. In the presence of a third liquid phase in the form of disperse oil droplets, the coacervate phase tends to wet the oil/water interface. This affinity has long been known and used for the formation of core/shell capsules. However, while encapsulation by simple or complex coacervation has been used empirically for decades, there is a lack of a thorough understanding of the three-phase wetting phenomena that control the formation of encapsulated, compound droplets and the role of the viscoelasticity of the biopolymers involved. In this contribution, we review and discuss the interplay of wetting phenomena and fluid viscoelasticity in coacervate/oil/water systems from the perspective of colloid chemistry and fluid dynamics, focusing on aspects of rheology, interfacial tension measurements at the coacervate/solvent interface, and on the formation and fragmentation of three-phase compound drops.

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We investigate the use of impinging free liquid jets as wall-free continuous microreactors. The collision of two reactant jets forming a free-standing thin liquid sheet allows us to perform rapid precipitation reactions to form colloidal particles, enhance micromixing, and master challenging reactions with very fast kinetics. To control the shape, size, and hydrodynamics of the impingement zone between the two liquid streams, it is crucial to understand the interplay among surface tension, fluid viscoelasticity, and reaction kinetics. Here, we study these aspects using model fluids, each illustrating a different physical effect of surface and bulk fluid properties. First, solutions of sodium dodecyl sulfate below, near, and above the critical micelle concentration are used to assess the role of static and dynamic surface tension. Second, we demonstrate how dilute solutions of high-molecular-weight polymers can be used to control the morphology of the free surface flow. If properly controlled, these effects can enhance the micromixing time scales to the extent that very rapid reactions can be performed with outstanding selectivity. We quantitatively assess the interplay between the free surface flow and reaction kinetics using parallel-competitive reactions and demonstrate how these results can be used to control the particle size in precipitation processes.

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This work aims at establishing a link between process conditions and resulting micromechanical properties for aminoplast core/shell microcapsules. The investigated capsules were produced by the in situ polymerization of melamine formaldehyde resins, which represents a widely used and industrially relevant approach in the field of microencapsulation. Within our study, we present a quantitative morphological analysis of the capsules' size and shell thickness. The diameter of the investigated capsules ranged from 10 to 50 µm and the shell thickness was found in a range between 50 and 200 nm. As key parameter for the control of the shell thickness, we identified the amount of amino resin per total surface area of the dispersed phase. Mechanical properties were investigated using small deformations on the order of the shell thickness by atomic force microscopy with a colloidal probe setup. The obtained capsule stiffness increased with an increasing shell thickness from 2 to 30 N/m and thus showed the same trend on the process parameters as the shell thickness. A simple analytical model was adopted to explain the relation between capsules' geometry and mechanics and to estimate the elastic modulus of the shell about 1.7 GPa. Thus, this work provides strategies for a rational design of microcapsule mechanics.

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Foams and emulsions are often exposed to strong external fields, resulting in large interface deformations far beyond the linear viscoelastic regime. Here, we investigate the nonlinear and transient interfacial rheology of adsorption layers in large-amplitude oscillatory shear flow. As a prototypical material forming soft-solid-type interfacial adsorption layers, we use Acacia gum (i.e., gum arabic), a protein/polysaccharide hybrid. We quantify its nonlinear flow properties at the oil/water interface using a biconical disk interfacial rheometer and analyze the nonlinear stress response under forced strain oscillations. From the resulting Lissajous curves, we access quantitative measures recently introduced for nonlinear viscoelasticity, including the intracycle moduli for both the maximum and zero strains and the degree of plastic energy dissipation upon interfacial yielding. We demonstrate using in situ flow visualization that the onset of nonlinear viscoelasticity coincides with shear localization at the interface. Finally, we address the nonperiodic character of this flow transition using an experimental procedure based on opposing stress pulses, allowing us to extract additional interfacial properties such as the critical interfacial stress upon yielding and the permanent deformation.

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We investigate the formation of bioactive/inorganic coprecipitates of polyphenols catechins with calcium carbonate and calcium phosphate. Extracted from the leaves of Camellia sinensis, green tea catechins are efficient free radical scavengers, but their purported benefits from the perspective of prevention, health, and nutritional physiology are accompanied by unpleasant organoleptic characteristics: they are notoriously bitter. Selective complexation of polyphenols with metal salts is a possibility to mask or inactivate bitterness and/or off-flavors. We produce such complexes using a continuous coprecipitation process. With excess calcium chloride present in the matrix we observe a correlation of the carbonate to total anions molar ratio with the catechin load. To characterize the composition and structure of the coprecipitates we combine elemental analysis, scanning electron microscopy, X-ray powder diffraction, and liquid chromatography coupled to tandem mass spectroscopy (LC/MS-MS). We quantify the release kinetics in different model environments to predict the behavior of the catechins from the coprecipitates in model media simulating the conditions during oral ingestion and storage. The dissolution data suggest that the release profile of these delivery systems can be influenced and fine-tuned via the anion composition of the mineral carrier.

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We review concepts and provide examples for the controlled structuring of biopolymer particles in hydrodynamic flow fields. The structuring concepts are grouped by the physical mechanisms governing drop deformation and shaping: (i) capillary structuring, (ii) shear and elongational structuring and (iii) confined flow methods. Non-spherical drops can be permanently structured if a solidification process, such as gelation or glass formation in the bulk or at the interface, is superimposed to the flow field. The physical and engineering properties of these processes critically depend on an elaborate balance between capillary phenomena, rheology, gel or glass formation kinetics, and bulk heat, mass and momentum transfer in multiphase fluids. This overview is motivated by the potential of non-spherical suspension particles, in particular those formed from 'natural' and 'sustainable' biopolymers, as rheology modifiers in food materials, consumer products, cosmetics or pharmaceuticals.

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Acacia gum is a hybrid polyelectrolyte containing both protein and polysaccharide subunits. We study the interfacial rheology of its adsorption layers at the oil/water interface and compare it with adsorbed layers of hydrophobically modified starch, which for economic and political reasons is often used as a substitute for Acacia gum in technological applications. Both the shear and the dilatational rheological responses of the interfaces are considered. In dilatational experiments, the viscoelastic response of the starch derivative is just slightly weaker than that for Acacia gum, whereas we found pronounced differences in shear flow: The interfaces covered with the plant gum flow like a rigid, solidlike material with large storage moduli and a linear viscoelastic regime limited to small shear deformations, above which we observe apparent yielding behavior. In contrast, the films formed by hydrophobically modified starch are predominantly viscous, and the shear moduli are only weakly dependent on the deformation. Concerning their most important technological use as emulsion stabilizers, the dynamic interfacial responses imply not only distinct interfacial dynamics but also different stabilizing mechanisms for these two biopolymers.

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The shear and dilatational rheology of condensed interfacial layers of the water-insoluble surfactant sorbitan tristearate at the air/water interface is investigated. A new interfacial shear rheometer allows measurements in both stress- and strain-controlled modes, providing comprehensive interfacial rheological information such as the interfacial dynamic shear moduli, the creep response to a stress pulse, the stress relaxation response to a strain step, or steady shear curves. Our experiments show that the interfacial films are both viscoelastic and brittle in nature and subject to fracture at small deformations, as was supported by in-situ Brewster angle microscopy performed during the rheological experiments. Although any large-deformation test is destructive to the sample, it is still possible to study the linear viscoelastic regime if the deformations involved are controlled carefully. Complementary results for the dilatational rheology in area step compression/expansion experiments are reported. The dilatational behavior is predominantly elastic throughout the frequency spectrum measured, whereas the layers exhibit generalized Maxwell behavior in shear mode within a deformation frequency regime as narrow as two decades, indicating the presence of additional relaxation mechanisms in shear as opposed to expansion/compression. If the transient rheological response from stress relaxation experiments is considered, then the data can be described well with a stretched exponential model both in the shear and dilatational deformations.

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