Particles at oil–air surfaces : powdered oil, liquid oil marbles, and oil foam

The type of material stabilized by four kinds of fluorinated particles (sericite and bentonite platelet clays and spherical zinc oxide) in air–oil mixtures has been investigated. It depends on the particle wettability and the degree of shear. Upon vigorous agitation, oil dispersions are formed in all the oils containing relatively large bentonite particles and in oils of relatively low surface tension (γla < 26 mN m⁻¹) like dodecane, 20 cS silicone, and cyclomethicone containing the other fluorinated particles. Particle-stabilized oil foams were obtained in oils having γla > 26 mN m⁻¹ where the advancing air–oil–solid contact angle θ lies between ca. 90° and 120°. Gentle shaking, however, gives oil-in-air liquid marbles with all the oil–particle systems except for cases where θ is <60°. For oils of tension >24 mN m⁻¹ with omniphobic zinc oxide and sericite particles for which advancing θ ≥ 90°, dry oil powders consisting of oil drops in air which do not leak oil could be made upon gentle agitation up to a critical oil:particle ratio (COPR). Above the COPR, catastrophic phase inversion of the dry oil powders to air-in-oil foams was observed. When sheared on a substrate, the dry oil powders containing at least 60 wt % of oil release the encapsulated oil, making these materials attractive formulations in the cosmetic and food industries

Heterogeneous Pd catalysts as emulsifiers in Pickering emulsions for integrated multistep synthesis in flow chemistry

Within the “Compartmentalised Smart Factory” approach of the ONE-FLOW project the implementation of different catalysts in “compartments” provided by Pickering emulsions and their application in continuous flow is targeted. We present here the development of heterogeneous Pd-catalysts that are ready to be used in combination with biocatalysts for catalytic cascade syntheses of active pharmaceutical ingredients (APIs). In particular, we focus on the application of the catalytic systems for Suzuki-Miyaura cross coupling reactions, which is the key step in the syntheses of the targeted APIs valsartan and sacubitril. An immobilised enzyme will accomplish the final product formation via hydrolysis. In order to create large interfacial area for the catalytic reactions and to keep the reagents separated until required, the catalyst particles are used to stabilise Pickering emulsions of oil and water. A set of Ce-Sn-Pd-oxides with the molecular formula Ce0.99-xSnxPd0.01O2-(x= 0-0.99) has been prepared utilising a simple single-step solution combustion method. The high applicability of the catalysts for different functional groups and their minimal leaching behaviour is demonstrated with various Suzuki-Miyaura cross coupling reactions in batch as well as in continuous flow employing the so-called “Plug & Play reactor”. Finally, we demonstrate the use of these particles as the sole emulsifier of oil + water emulsions for a range of oils

Two-frequency forced Faraday waves: Weakly damped modes and pattern selection

Recent experiments (Kudrolli, Pier and Gollub, 1998) on two-frequency parametrically excited surface waves exhibit an intriguing "superlattice" wave pattern near a codimension-two bifurcation point where both subharmonic and harmonic waves onset simultaneously, but with different spatial wavenumbers. The superlattice pattern is synchronous with the forcing, spatially periodic on a large hexagonal lattice, and exhibits small-scale triangular structure. Similar patterns have been shown to exist as primary solution branches of a generic 12-dimensional $D_6\dot{+}T^2$-equivariant bifurcation problem, and may be stable if the nonlinear coefficients of the bifurcation problem satisfy certain inequalities (Silber and Proctor, 1998). Here we use the spatial and temporal symmetries of the problem to argue that weakly damped harmonic waves may be critical to understanding the stabilization of this pattern in the Faraday system. We illustrate this mechanism by considering the equations developed by Zhang and Vinals (1997, J. Fluid Mech. 336) for small amplitude, weakly damped surface waves on a semi-infinite fluid layer. We compute the relevant nonlinear coefficients in the bifurcation equations describing the onset of patterns for excitation frequency ratios of 2/3 and 6/7. For the 2/3 case, we show that there is a fundamental difference in the pattern selection problems for subharmonic and harmonic instabilities near the codimension-two point. Also, we find that the 6/7 case is significantly different from the 2/3 case due to the presence of additional weakly damped harmonic modes. These additional harmonic modes can result in a stabilization of the superpatterns.Comment: 26 pages, 8 figures; minor text revisions, corrected figure 8; this version to appear in a special issue of Physica D in memory of John David Crawfor

Are block copolymer worms more effective Pickering emulsifiers than block copolymer spheres?

RAFT-mediated polymerisation-induced self-assembly (PISA) is used to prepare six types of amphiphilic block copolymer nanoparticles which were subsequently evaluated as putative Pickering emulsifiers for the stabilisation of n-dodecane-in-water emulsions. It was found that linear poly(glycerol monomethacrylate)–poly(2-hydroxypropyl methacrylate) (PGMA–PHPMA) diblock copolymer spheres and worms do not survive the high shear homogenisation conditions used for emulsification. Stable emulsions are obtained, but the copolymer acts as a polymeric surfactant; individual chains rather than particles are adsorbed at the oil–water interface. Particle dissociation during emulsification is attributed to the weakly hydrophobic character of the PHPMA block. Covalent stabilisation of these copolymer spheres or worms can be readily achieved by addition of ethylene glycol dimethacrylate (EGDMA) during the PISA synthesis. TEM studies confirm that the resulting cross-linked spherical or worm-like nanoparticles survive emulsification and produce genuine Pickering emulsions. Alternatively, stabilisation can be achieved by either replacing or supplementing the PHPMA block with the more hydrophobic poly(benzyl methacrylate) (PBzMA). The resulting linear spheres or worms also survive emulsification and produce stable n-dodecane-in-water Pickering emulsions. The intrinsic advantages of anisotropic worms over isotropic spheres for the preparation of Pickering emulsions are highlighted. The former particles are more strongly adsorbed at similar efficiencies compared to spheres and also enable smaller oil droplets to be produced for a given copolymer concentration. The scalable nature of PISA formulations augurs well for potential applications of anisotropic block copolymer nanoparticles as Pickering emulsifiers

Informed consent for research in Borderline Personality Disorder

<p>Abstract</p> <p>Background</p> <p>Previous research on informed consent for research in psychiatric patients has centered on disorders that affect comprehension and appreciation of risks. Little has been written about consent to research in those subjects with Borderline Personality Disorder, a prevalent and disabling condition.</p> <p>Discussion</p> <p>Despite apparently intact cognition and comprehension of risks, a borderline subject may deliberately choose self-harm in order to fulfill abnormal psychological needs, or due to suicidality. Alternatively, such a subject may refuse enrollment due to transference or the desire to harm him or herself. Such phenomena could be precipitated or prevented by the interpersonal dynamics of the informed consent encounter.</p> <p>Summary</p> <p>Caution should be exercised in obtaining informed consent for research from subjects with Borderline Personality Disorder. A literature review and recommendations for future research are discussed.</p

Arresting bubble coarsening: A two-bubble experiment to investigate grain growth in presence of surface elasticity

Many two-phase materials suffer from grain-growth due to the energy cost which is associated with the interface that separates both phases. While our understanding of the driving forces and the dynamics of grain growth in different materials is well advanced by now, current research efforts address the question of how this process may be slowed down, or, ideally, arrested. We use a model system of two bubbles to explore how the presence of a finite surface elasticity may interfere with the coarsening process and the final grain size distribution. Combining experiments and modelling in the analysis of the evolution of two bubbles, we show that clear relationships can be predicted between the surface tension, the surface elasticity and the initial/final size ratio of the bubbles. We rationalise these relationships by the introduction of a modified Gibbs criterion. Besides their general interest, the present results have direct implications for our understanding of foam stability

On the use of benzaldehyde to improve the storage stability of one-pot, epoxy ionic liquid formulations

A series of adducts were prepared based on the reaction of 1-ethyl-3-methylimidazolium acetate and benzal- dehyde in various stoichiometries (from equimolar reaction to benzaldehyde in 10-fold excess) and the resulting adducts were characterized using nuclear magnetic resonance spectroscopy (¹H, ¹³C, DEPT, and HQSC experi- ments). Differential scanning calorimetry was used to examine the initiating behaviour of the adducts towards mono- and di-functional epoxy resins and the data were used to determine kinetic parameters for the poly- merization. The lower temperature peak, due to carbene formation, is sensitive to adduct concentration; the residual ionic liquid in the adduct mixture contributes towards the initiation of the curing reaction. When a monofunctional epoxy and the 1:1 adduct was subjected to a 2-week period of storage at room temperature and sub-zero temperatures in the freezer, the profiles of the thermograms for the frozen samples do not change considerably over the storage period and the formulation retains a light yellow colour (rather than the viscous, dark red appearance of the formulation stored at room temperature)

Colloid-stabilized emulsions: behaviour as the interfacial tension is reduced

We present confocal microscopy studies of novel particle-stabilized emulsions. The novelty arises because the immiscible fluids have an accessible upper critical solution temperature. The emulsions have been created by beginning with particles dispersed in the single-fluid phase. On cooling, regions of the minority phase nucleate. While coarsening these nuclei become coated with particles due to the associated reduction in interfacial energy. The resulting emulsion is arrested, and the particle-coated interfaces have intriguing properties. Having made use of the binary-fluid phase diagram to create the emulsion we then make use of it to study the properties of the interfaces. As the emulsion is re-heated toward the single-fluid phase the interfacial tension falls and the volume of the dispersed phase drops. Crumpling, fracture or coalescence can follow. The results show that the elasticity of the interfaces has a controlling influence over the emulsion behaviour.Comment: Submitted for the proceedings of the 6th Liquid Matter Conference, held in Utrecht (NL) in July 200