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      Pickering emulsions stabilized by coloured organic pigment particles†

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      a , , a
      Chemical Science
      Royal Society of Chemistry

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          Abstract

          Pickering emulsions stabilised by coloured organic pigment particles.

          Abstract

          The possibility of stabilizing emulsions of water and non-polar alkane with pure, coloured organic pigment particles is explored. Seven pigment types each possessing a primary colour of the rainbow were selected. Their solubility in water or heptane was determined using a spectrophotometric method and their surface energies were derived from the contact angles of probe liquids on compressed disks of the particles. As expected, most of the pigments are relatively hydrophobic but pigment orange is quite hydrophilic. At equal volumes of oil and water, preferred emulsions were water-in-oil (w/o) for six pigment types and oil-in-water (o/w) for pigment orange. The emulsion type is in line with calculated contact angles of the particles at the oil–water interface being either side of 90°. Their stability to coalescence increases with particle concentration. Emulsions are shown to undergo limited coalescence from which the coverage of drop interfaces by particles has been determined. In a few cases, close-packed primary particles are visible around emulsion droplets. At constant particle concentration, the influence of the volume fraction of water ( φ w) on emulsions was also studied. For the most hydrophilic pigment orange, emulsions are o/w at all φ w, whereas they are w/o for the most hydrophobic pigments (red, yellow, green and blue). For pigments of intermediate hydrophobicity however (indigo and violet), catastrophic phase inversion becomes possible with emulsions inverting from w/o to o/w upon increasing φ w. For the first time, we link the pigment surface energy to the propensity of emulsions to phase invert transitionally or catastrophically.

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          Most cited references63

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          Some general features of limited coalescence in solid-stabilized emulsions.

          We produce direct and inverse emulsions stabilized by solid mineral particles. If the total amount of particles is initially insufficient to fully cover the oil-water interfaces, the emulsion droplets coalesce such that the total interfacial area between oil and water is progressively reduced. Since it is likely that the particles are irreversibly adsorbed, the degree of surface coverage by them increases until coalescence is halted. We follow the rate of droplet coalescence from the initial fragmented state to the saturated situation. Unlike surfactant-stabilized emulsions, the coalescence frequency depends on time and particle concentration. Both the transient and final droplet size distributions are relatively narrow and we obtain a linear relation between the inverse average droplet diameter and the total amount of solid particles, with a slope that depends on the mixing intensity. The phenomenology is independent of the mixing type and of the droplet volume fraction allowing the fabrication of both direct and inverse emulsion with average droplet sizes ranging from micron to millimetre.
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            Emulsions stabilised by whey protein microgel particles: towards food-grade Pickering emulsions.

            We have investigated a new class of food-grade particles, whey protein microgels, as stabilisers of triglyceride-water emulsions. The sub-micron particles stabilized oil-in-water emulsions at all pH with and without salt. All emulsions creamed but exhibited exceptional resistance to coalescence. Clear correlations exist between the properties of the microgels in aqueous dispersion and the resulting emulsion characteristics. For conditions in which the particles were uncharged, fluid emulsions with relatively large drops were stabilised, whereas emulsions stabilized by charged particles contained smaller flocculated drops. A combination of optical microscopy of the drops and spectrophotometry of the resolved aqueous phase allowed us to estimate the interfacial adsorption densities of the particles using the phenomenon of limited coalescence. We deduce two classes of particle arrangement. Complete adsorption of the particles was obtained when they were neutral or when their charges were screened by salt resulting in at least one particle monolayer at the interface. By contrast, only around 50% of the particles adsorbed when they were charged with emulsion drops being covered by less than half a monolayer. These findings were supported by direct visualization of drop interfaces using cryo-scanning electron microscopy. Uncharged particles were highly aggregated and formed a continuous 2-D network at the interface. Otherwise particles organized as individual aggregates separated by particle-free regions. In this case, we suggest that some particles spread at the interface leading to the formation of a continuous protein membrane. Charged particles displayed the ability to bridge opposing interfaces of neighbouring drops to form dense particle disks protecting drops against coalescence; this is the main reason for the flocculation and stability of emulsions containing sparsely covered drops.
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              Silica particle-stabilized emulsions of silicone oil and water: aspects of emulsification.

              A study of the emulsification of silicone oil and water in the presence of partially hydrophobic, monodisperse silica nanoparticles is described. Emulsification involves the fragmentation of bulk liquids and the resulting large drops and the coalescence of some of those drops. The influence of particle concentration, oil/water ratio, and emulsification time on the relative extents of fragmentation and coalescence during the formation of emulsions, prepared using either batch or continuous methods, has been investigated. For batch emulsions, the average drop diameter decreases with increasing particle concentration as the extent of limited coalescence is reduced. Increasing the oil volume fraction in the emulsion at fixed aqueous particle concentration results in an increase in the average drop diameter together with a dramatic lowering of the uniformity of the drop size distribution as coalescence becomes increasingly significant until catastrophic phase inversion occurs. For low oil volume fractions (phi(o)), fragmentation dominates during emulsification since the mean drop size decreases with emulsification time. For higher phi(o) close to conditions of phase inversion, coalescence becomes more prevalent and the drop size increases with time with stable multiple emulsions forming as a result.
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                Author and article information

                Journal
                Chem Sci
                Chem Sci
                Chemical Science
                Royal Society of Chemistry
                2041-6520
                2041-6539
                1 January 2017
                19 September 2016
                : 8
                : 1
                : 708-723
                Affiliations
                [a ] Department of Chemistry , University of Hull , Hull HU6 7RX , UK . Email: b.p.binks@ 123456hull.ac.uk
                Article
                c6sc03085h
                10.1039/c6sc03085h
                5465566
                28626551
                d108a6e9-6846-4f5b-bd5d-cb80ec13a347
                This journal is © The Royal Society of Chemistry 2016

                This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License ( http://creativecommons.org/licenses/by/3.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

                History
                : 13 July 2016
                : 10 September 2016
                Categories
                Chemistry

                Notes

                †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc03085h


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