Oil-in-oil emulsions stabilised solely by solid particles

A brief review of the stabilisation of emulsions of two immiscible oils is given. We then describe the use of fumed silica particles coated with either hydrocarbon or fluorocarbon groups in acting as sole stabilisers of emulsions of various vegetable oils with linear silicone oils (PDMS) of different viscosity. Transitional phase inversion of emulsions, containing equal volumes of the two oils, from silicone-invegetable (S/V) to vegetable-in-silicone (V/S) occurs upon increasing the hydrophobicity of the particles. Close to inversion, emulsions are stable to coalescence and gravity-induced separation for at least one year. Increasing the viscosity of the silicone oil enables stable S/V emulsions to be prepared even with relatively hydrophilic particles. Predictions of emulsion type from calculated contact angles of a silica particle at the oil–oil interface are in agreement with experiment provided a small polar contribution to the surface energy of the oils is included. We also show that stable multiple emulsions of V/S/V can be prepared in a two-step procedure using two particle types of different hydrophobicity. At fixed particle concentration, catastrophic phase inversion of emulsions from V/S to S/V can be effected by increasing the volume fraction of vegetable oil. Finally, in the case of sunflower oil + 20 cS PDMS, the study is extended to particles other than silica which differ in chemical type, particle size and particle shape. Consistent with the above findings, we find that only sufficiently hydrophobic particles (clay, zinc oxide, silicone, calcium carbonate) can act as efficient V/S emulsion stabilisers

Dry oil powders and oil foams stabilised by fluorinated clay platelet particles

A series of platelet sericite particles coated to different extents with a fluorinating agent has been characterised and their behaviour in mixtures with air and oil studied. The material which forms by vigorous shaking depends on both the surface tension of the oil and the surface energy of the particles which control their degree of wetting. Oil dispersions are formed in liquids of relatively low tension (<22 mN m−1), e.g. hexane and cyclomethicone, for all particles. Particle-stabilised air-in-oil foams form in liquids of higher tension, e.g. dodecane and phenyl silicone, where the advancing three-phase contact angle θ, measured on a planar substrate composed of the particles into the liquid, lies between ca. 65° and 120°. For oils of tension above 27 mN m−1 like squalane and liquid paraffin with particles for which θ > 70°, we have discovered that dry oil powders in which oil drops stabilised by particles dispersed in air (oil-in-air) can be prepared by gentle mixing up to a critical oil : particle ratio (COPR) and do not leak oil. These powders, containing up to 80 wt% oil, release the encapsulated oil when sheared on a substrate. For many of the systems forming oil powders, stable liquid oil marbles can also be prepared. Above the COPR, catastrophic phase inversion occurs yielding an ultra-stable air-in-oil foam. We thus demonstrate the ability to disperse oil drops or air bubbles coated with particles within novel materials

Food-grade Pickering stabilisation of foams by in situ hydrophobisation of calcium carbonate particles

© 2016 Elsevier Ltd The aim of this study was to investigate the possibility of stabilising foam bubbles in water by adsorption of calcium carbonate (CaCO 3 ) particles. Because CaCO 3 is hydrophilic and not surface-active, particles were hydrophobised in situ with several emulsifiers. The used emulsifiers were food-grade and negatively charged at the pH employed. The effect of particle addition on foamability and foam stability of solutions containing either β-lactoglobulin, sodium caseinate, Quillaja, sodium dodecanoate (SD) or sodium stearoyl-2-lactylate (SSL) was studied. It was found that the ability of the emulsifiers to induce surface activity such that the particles are able to adsorb to the air-water interface is related to their structure. The structure needs to consist of a well-defined hydrophobic part and a charged part. Large emulsifiers with a complex structure, such as β-lactoglobulin, sodium caseinate and Quillaja, were able to partially hydrophobise the particles but were not able to act synergistically with the particles to increase the foam stability. Low molecular weight emulsifiers, however, consisting of a single tail with one charged group, such as SD and SSL, adsorbed at the particle surface rendering the particles partially hydrophobic such that they adsorb to the air-water interface. In a subsequent investigation, the pH was changed to a value typical for food products (pH 6–7) and the addition of milk salts on the foamability and foam stability was assessed. Based on these results, the use of food-grade CaCO 3 particles hydrophobised in situ with food-grade surfactants (SD or SSL) to prepare ultra-stable aqueous foams is demonstrated

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

The Provision of Finance to Small Businesses: Does the Banking Relationship Constrain Performance

The beneficial economic effects of entrepreneurial activity can only be realised if such activity is relatively unconstrained in both product and factor markets, finance has been widely identified as a potential constraint on entrepreneurial activity due to either debt or equity gaps. However, in terms of externally supplied finance, it is arguably the availability of debt which is of greatest signifi­cance to most entrepreneurs. Given the inevitable information problems associated with the provision of debt finance, the nature of the relationship between bank and entrepreneur can be of considerable importance in ensuring the appropriate financing decisions are made. This paper examines the link between the banking relationship and the extent to which entrepreneurs are constrained by financing arrangements. Empirical analysis of the extent to which the banking relationship constrains performance suggests that there is no significant difference between more and less successful entrepreneurs

Parametrically excited surface waves in magnetic fluids: observation of domain structures

Observations of parametrically excited surface waves in a magnetic fluid are presented. Under the influence of a magnetic field these waves have a non--monotonic dispersion relation, which leads to a richer behavior than in ordinary liquids. We report observation of three novel effects, namely: i) domain structures, ii) oscillating defects and iii) relaxational phase oscillations.Comment: to be published in Physical Review Letter

Preparation of double emulsions using hybrid polymer/silica particles: New pickering emulsifiers with adjustable surface wettability

A facile route for the preparation of water-in-oil-in-water (w/o/w) double emulsions is described for three model oils, namely, n-dodecane, isopropyl myristate, and isononyl isononanoate, using fumed silica particles coated with poly(ethylene imine) (PEI). The surface wettability of such hybrid PEI/silica particles can be systematically adjusted by (i) increasing the adsorbed amount of PEI and (ii) addition of 1-undecanal to the oil phase prior to homogenization. In the absence of this long-chain aldehyde, PEI/silica hybrid particles (PEI/silica mass ratio = 0.50) produce o/w Pickering emulsions in all cases. In the presence of 1-undecanal, this reagent reacts with the primary and secondary amine groups on the PEI chains via Schiff base chemistry, which can render the PEI/silica hybrid particles sufficiently hydrophobic to stabilize w/o Pickering emulsions at 20 °C. Gas chromatography, 1H NMR and X-ray photoelectron spectroscopy provide compelling experimental evidence for this in situ surface reaction, while a significant increase in the water contact angle indicates markedly greater hydrophobic character for the PEI/silica hybrid particles. However, when PEI/silica hybrid particles are prepared using a relatively low adsorbed amount of PEI (PEI/silica mass ratio = 0.075) only o/w Pickering emulsions are obtained, since the extent of surface modification achieved using this Schiff base chemistry is insufficient. Fluorescence microscopy and laser diffraction studies confirm that highly stable w/o/w double emulsions can be achieved for all three model oils. This is achieved by first homogenizing the relatively hydrophobic PEI/silica hybrid particles (PEI/silica mass ratio = 0.50) with an oil containing 3% 1-undecanal to form an initial w/o emulsion, followed by further homogenization using an aqueous dispersion of relatively hydrophilic PEI/silica particles (PEI/silica mass ratio = 0.075). Dye release from the internal aqueous cores into the aqueous continuous phase was monitored by visible absorption spectroscopy. These studies indicate immediate loss of 12-18% dye during the high speed homogenization that is required for double emulsion formation, but no further dye release is observed at 20 °C for at least 15 days thereafter

Baseline incidence of adverse birth outcomes and infant influenza and pertussis hospitalisations prior to the introduction of influenza and pertussis vaccination in pregnancy: a data linkage study of 78 382 mother-infant pairs, Northern Territory, Australia, 1994-2015

We conducted probabilistic data linkage of three population datasets for the Northern Territory (NT), Australia, to describe the incidence of preterm births, stillbirths, low birthweight and small for gestational age (SGA) per 1000 NT births; and influenza and pertussis hospitalisations per 1 00 000 NT births in infants <7 months of age, in a pre-maternal vaccination era. The Perinatal Trends dataset (1994–2014) formed the cohort of 78 382 births. Aboriginal mother–infant pairs (37%) had disproportionately higher average annual rates (AR) for all adverse birth outcomes compared to their non-Aboriginal counterparts; rate ratios: preterm births 2.2 (AR 142.4 vs. 64.7); stillbirths 2.3 (AR 10.8 vs. 4.6); low birthweight 2.9 (AR 54 vs. 19); and SGA 1.7 (AR 187 vs. 111). Hospitalisation (2000–2015) and Immunisation Register datasets (1994–2015), showed that influenza hospitalisations (n = 53) and rates were 42.3 times higher in Aboriginal infants (AR 254 vs. 6); and that pertussis hospitalisations (n = 37) were 7.1 times higher in Aboriginal infants (AR 142.5 vs. 20.2) compared to non-Aboriginal infants. These baseline data are essential to assess the safety and effectiveness of influenza and pertussis vaccinations in pregnant women from the NT. Remote living Aboriginal women and infants stand to benefit the most from these vaccines.This study was funded by a National Health and Medical Research Council (NHMRC) Project Grant (APP1091491). LMc was supported by an Australian Postgraduate Award scholarship provided by Charles Darwin University of the Northern Territory and an Enhanced Living scholarship provided by Menzies as part of the Doctor of Philosophy (PhD) program. TS holds a Career Development Fellowship from the NHMRC (GNT 1111657). MJB was supported by an NHMRC Early Career Fellowship (GNT1088733)

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