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Pickering Emulsion and Derived Materials

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A special issue of Materials (ISSN 1996-1944).

Deadline for manuscript submissions: closed (30 June 2016) | Viewed by 82981

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Special Issue Editors

Prof. Dr. To Ngai

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Guest Editor

Department of Chemistry, The Chinese University of Hong Kong, Hong Kong 999077, China
Interests: colloidal particle; interfacial science; polymer and soft materials
Special Issues, Collections and Topics in MDPI journals

Dr. Syuji Fujii

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Co-Guest Editor

Department of Applied Chemistry, Faculty of Engineering Osaka Institute of Technology 5-16-1, Omiya, Asahi-ku, Osaka 535-8585, Japan
Interests: synthesis and characterization of polymer-based colloidal particles; particle at interface; particle-stabilized soft dispersed systems (emulsion, foam, liquid marble and dry liquid); design and synthesis of functional materials based on biomimetic technology; synthesis of element-block polymer materials

Special Issue Information

Dear Colleagues,

Particle-stabilized emulsions, today referred to as Pickering/Ramsden emulsions, are vital in many fields, including personal care products, foods, pharmaceuticals, and oil recovery. The exploitation of these Pickering emulsions for the manufacture of new functional materials has also recently become the subject of intense investigation. While much progress has been made over the past decade, Pickering emulsion still remains a rich topic since many aspects of their behavior have yet to be investigated. The present “Pickering Emulsion and Derived Materials” Special Issue aims to bring together research and review papers pertaining to the recent developments in the design, fabrication, and application of Pickering emulsions. The themes include, but are not limited to:

1. Interactions of colloidal particles confined at fluid interfaces

2. Pickering emulsion-based polymerization

3. Interfacial assembly and emulsion stabilization

4. Rheology of particle laden interfaces and Pickering emulsions

5. Functional materials templated from Pickering emulsions

We believe this Special Issue will serve as a platform for researchers to share their exciting works and, in the long run this will attract further attention and interest in the innovative development of this important and promising area.

It is our great pleasure to invite you to submit a manuscript for this Special Issue. Full papers, short communication, and review are welcome.

Dr. To Ngai
Dr. Syuji Fujii
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Materials is an international peer-reviewed open access semimonthly journal published by MDPI.

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Keywords

Particle-stabilized emulsions
Particle interaction at the interface
Pickering emulsion-based polymerization
Emulsion stabilization
Interfacial assembly
Rheology of interfacial particles and Pickering emulsions
Functional materials

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Published Papers (10 papers)

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Research

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14 pages, 5681 KiB

Open AccessArticle

Pickering Particles Prepared from Food Waste

by Joanne Gould, Guillermo Garcia-Garcia and Bettina Wolf

Materials 2016, 9(9), 791; https://doi.org/10.3390/ma9090791 - 21 Sep 2016

Cited by 42 | Viewed by 8888

Abstract

In this paper, we demonstrate the functionality and functionalisation of waste particles as an emulsifier for oil-in-water (o/w) and water-in-oil (w/o) emulsions. Ground coffee waste was chosen as a candidate waste material due to its naturally high content of lignin, a chemical component imparting emulsifying ability. The waste coffee particles readily stabilised o/w emulsions and following hydrothermal treatment adapted from the bioenergy field they also stabilised w/o emulsions. The hydrothermal treatment relocated the lignin component of the cell walls within the coffee particles onto the particle surface thereby increasing the surface hydrophobicity of the particles as demonstrated by an emulsion assay. Emulsion droplet sizes were comparable to those found in processed foods in the case of hydrophilic waste coffee particles stabilizing o/w emulsions. These emulsions were stable against coalescence for at least 12 weeks, flocculated but stable against coalescence in shear and stable to pasteurisation conditions (10 min at 80 °C). Emulsion droplet size was also insensitive to pH of the aqueous phase during preparation (pH 3–pH 9). Stable against coalescence, the water droplets in w/o emulsions prepared with hydrothermally treated waste coffee particles were considerably larger and microscopic examination showed evidence of arrested coalescence indicative of particle jamming at the surface of the emulsion droplets. Refinement of the hydrothermal treatment and broadening out to other lignin-rich plant or plant based food waste material are promising routes to bring closer the development of commercially relevant lignin based food Pickering particles applicable to emulsion based processed foods ranging from fat continuous spreads and fillings to salad dressings. Full article

(This article belongs to the Special Issue Pickering Emulsion and Derived Materials)

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10 pages, 3295 KiB

Open AccessCommunication

High-Surface-Area, Emulsion-Templated Carbon Foams by Activation of polyHIPEs Derived from Pickering Emulsions

by Robert T. Woodward, François De Luca, Aled D. Roberts and Alexander Bismarck

Materials 2016, 9(9), 776; https://doi.org/10.3390/ma9090776 - 14 Sep 2016

Cited by 29 | Viewed by 8104

Abstract

Carbon foams displaying hierarchical porosity and excellent surface areas of >1400 m²/g can be produced by the activation of macroporous poly(divinylbenzene). Poly(divinylbenzene) was synthesized from the polymerization of the continuous, but minority, phase of a simple high internal phase Pickering emulsion. By the addition of KOH, chemical activation of the materials is induced during carbonization, producing Pickering-emulsion-templated carbon foams, or carboHIPEs, with tailorable macropore diameters and surface areas almost triple that of those previously reported. The retention of the customizable, macroporous open-cell structure of the poly(divinylbenzene) precursor and the production of a large degree of microporosity during activation leads to tailorable carboHIPEs with excellent surface areas. Full article

(This article belongs to the Special Issue Pickering Emulsion and Derived Materials)

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13 pages, 3897 KiB

Open AccessArticle

Preparation and Application of Water-in-Oil Emulsions Stabilized by Modified Graphene Oxide

by Xiaoma Fei, Lei Xia, Mingqing Chen, Wei Wei, Jing Luo and Xiaoya Liu

Materials 2016, 9(9), 731; https://doi.org/10.3390/ma9090731 - 26 Aug 2016

Cited by 23 | Viewed by 7187

Abstract

A series of alkyl chain modified graphene oxides (AmGO) with different alkyl chain length and content was fabricated using a reducing reaction between graphene oxide (GO) and alkyl amine. Then AmGO was used as a graphene-based particle emulsifier to stabilize Pickering emulsion. Compared with the emulsion stabilized by GO, which was oil-in-water type, all the emulsions stabilized by AmGO were water-in-oil type. The effects of alkyl chain length and alkyl chain content on the emulsion properties of AmGO were investigated. The emulsions stabilized by AmGO showed good stability within a wide range of pH (from pH = 1 to pH = 13) and salt concentrations (from 0.1 to 1000 mM). In addition, the application of water-in-oil emulsions stabilized by AmGO was investigated. AmGO/polyaniline nanocomposite (AmGO/PANi) was prepared through an emulsion approach, and its supercapacitor performance was investigated. This research broadens the application of AmGO as a water-in-oil type emulsion stabilizer and in preparing graphene-based functional materials. Full article

(This article belongs to the Special Issue Pickering Emulsion and Derived Materials)

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8 pages, 4372 KiB

Open AccessCommunication

Assembly and Rearrangement of Particles Confined at a Surface of a Droplet, and Intruder Motion in Electro-Shaken Particle Films

by Zbigniew Rozynek, Milena Kaczmarek-Klinowska and Agnieszka Magdziarz

Materials 2016, 9(8), 679; https://doi.org/10.3390/ma9080679 - 10 Aug 2016

Cited by 15 | Viewed by 5210

Abstract

Manipulation of particles at the surface of a droplet can lead to the formation of structures with heterogeneous surfaces, including patchy colloidal capsules or patchy particles. Here, we study the assembly and rearrangement of microparticles confined at the surface of oil droplets. These processes are driven by electric-field-induced hydrodynamic flows and by ‘electro-shaking’ the colloidal particles. We also investigate the motion of an intruder particle in the particle film and present the possibility of segregating the surface particles. The results are expected to be relevant for understanding the mechanism for particle segregation and, eventually, lead to the formation of new patchy structures. Full article

(This article belongs to the Special Issue Pickering Emulsion and Derived Materials)

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11 pages, 5371 KiB

Open AccessArticle

Effect of Geometric and Chemical Anisotropy of Janus Ellipsoids on Janus Boundary Mismatch at the Fluid–Fluid Interface

by Dong Woo Kang, Woong Ko, Bomsock Lee and Bum Jun Park

Materials 2016, 9(8), 664; https://doi.org/10.3390/ma9080664 - 6 Aug 2016

Cited by 18 | Viewed by 5534

Abstract

We investigated the geometric and chemical factors of nonspherical Janus particles (i.e., Janus ellipsoids) with regard to the pinning and unpinning behaviors of the Janus boundary at the oil–water interface using attachment energy numerical calculations. The geometric factors were characterized by aspect ratio (AR) and location of the Janus boundary (α) separating the polar and apolar regions of the particle. The chemical factor indicated the supplementary wettability (β) of the two sides of the particle with identical deviations of apolarity and polarity from neutral wetting. These two factors competed with each other to determine particle configurations at the interface. In general, the critical value of β (β_c) required to preserve the pinned configuration was inversely proportional to the values of α and AR. From the numerical calculations, the empirical relationship of the parameter values of Janus ellipsoids was found; that is,

λ = Δ β_{c} / Δ α \approx 0.61 A R - 1.61

. Particularly for the Janus ellipsoids with AR > 1, the β_c value is consistent with the boundary between the tilted only and the tilted equilibrium/upright metastable region in their configuration phase diagram. We believe that this work performed at the single particle level offers a fundamental understanding of the manipulation of interparticle interactions and control of the rheological properties of particle-laden interfaces when particles are used as solid surfactants. Full article

(This article belongs to the Special Issue Pickering Emulsion and Derived Materials)

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16 pages, 2518 KiB

Open AccessFeature PaperArticle

Quaternized Cellulose Hydrogels as Sorbent Materials and Pickering Emulsion Stabilizing Agents

by Inimfon A. Udoetok, Lee D. Wilson and John V. Headley

Materials 2016, 9(8), 645; https://doi.org/10.3390/ma9080645 - 30 Jul 2016

Cited by 40 | Viewed by 7781

Abstract

Quaternized (QC) and cross-linked/quaternized (CQC) cellulose hydrogels were prepared by cross-linking native cellulose with epichlorohydrin (ECH), with subsequent grafting of glycidyl trimethyl ammonium chloride (GTMAC). Materials characterization via carbon, hydrogen and nitrogen (CHN) analysis, thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR)/¹³C solid state NMR spectroscopy provided supportive evidence of the hydrogel synthesis. Enhanced thermal stability of the hydrogels was observed relative to native cellulose. Colloidal stability of octanol and water mixtures revealed that QC induces greater stabilization over CQC, as evidenced by the formation of a hexane–water Pickering emulsion system. Equilibrium sorption studies with naphthenates from oil sands process water (OSPW) and 2-naphthoxy acetic acid (NAA) in aqueous solution revealed that CQC possess higher affinity relative to QC with the naphthenates. According to the Langmuir isotherm model, the sorption capacity of CQC for OSPW naphthenates was 33.0 mg/g and NAA was 69.5 mg/g. CQC displays similar affinity for the various OSPW naphthenate component species in aqueous solution. Kinetic uptake of NAA at variable temperature, pH and adsorbent dosage showed that increased temperature favoured the uptake process at 303 K, where Q_m = 76.7 mg/g. Solution conditions at pH 3 or 9 had a minor effect on the sorption process, while equilibrium was achieved in a shorter time at lower dosage (ca. three-fold lower) of hydrogel (100 mg vs. 30 mg). The estimated activation parameters are based on temperature dependent rate constants, k₁, which reveal contributions from enthalpy-driven electrostatic interactions. The kinetic results indicate an ion-based associative sorption mechanism. This study contributes to a greater understanding of the adsorption and physicochemical properties of cellulose-based hydrogels. Full article

(This article belongs to the Special Issue Pickering Emulsion and Derived Materials)

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9 pages, 2259 KiB

Open AccessFeature PaperArticle

Pickering Emulsion-Based Marbles for Cellular Capsules

by Guangzhao Zhang and Chaoyang Wang

Materials 2016, 9(7), 572; https://doi.org/10.3390/ma9070572 - 14 Jul 2016

Cited by 10 | Viewed by 7103

Abstract

The biodegradable cellular capsule, being prepared from simple vaporization of liquid marbles, is an ideal vehicle for the potential application of drug encapsulation and release. This paper reports the fabrication of cellular capsules via facile vaporization of Pickering emulsion marbles in an ambient atmosphere. Stable Pickering emulsion (water in oil) was prepared while utilizing dichloromethane (containing poly(l-lactic acid)) and partially hydrophobic silica particles as oil phase and stabilizing agents respectively. Then, the Pickering emulsion marbles were formed by dropping emulsion into a petri dish containing silica particles with a syringe followed by rolling. The cellular capsules were finally obtained after the complete vaporization of both oil and water phases. The technique of scanning electron microscope (SEM) was employed to research the microstructure and surface morphology of the prepared capsules and the results showed the cellular structure as expected. An in vitro drug release test was implemented which showed a sustained release property of the prepared cellular capsules. In addition, the use of biodegradable poly(l-lactic acid) and the biocompatible silica particles also made the fabricated cellular capsules of great potential in the application of sustained drug release. Full article

(This article belongs to the Special Issue Pickering Emulsion and Derived Materials)

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13 pages, 5242 KiB

Open AccessArticle

Transition Behaviors of Configurations of Colloidal Particles at a Curved Oil-Water Interface

by Mina Lee, Ming Xia and Bum Jun Park

Materials 2016, 9(3), 138; https://doi.org/10.3390/ma9030138 - 26 Feb 2016

Cited by 14 | Viewed by 5706

Abstract

We studied the transition behaviors of colloidal arrangements confined at a centro-symmetrically curved oil-water interface. We found that assemblies composed of several colloidal particles at the curved interface exhibit at least two unique patterns that can be attributed to two factors: heterogeneity of single-colloid self-potential and assembly kinetics. The presence of the two assembly structures indicates that an essential energy barrier between the two structures exists and that one of the structures is kinetically stable. This energy barrier can be overcome via external stimuli (e.g., convection and an optical force), leading to dynamic transitions of the assembly patterns. Full article

(This article belongs to the Special Issue Pickering Emulsion and Derived Materials)

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25 pages, 10664 KiB

Open AccessFeature PaperReview

Tuning Amphiphilicity of Particles for Controllable Pickering Emulsion

by Zhen Wang and Yapei Wang

Materials 2016, 9(11), 903; https://doi.org/10.3390/ma9110903 - 8 Nov 2016

Cited by 76 | Viewed by 14667

Abstract

Pickering emulsions with the use of particles as emulsifiers have been extensively used in scientific research and industrial production due to their edge in biocompatibility and stability compared with traditional emulsions. The control over Pickering emulsion stability and type plays a significant role in these applications. Among the present methods to build controllable Pickering emulsions, tuning the amphiphilicity of particles is comparatively effective and has attracted enormous attention. In this review, we highlight some recent advances in tuning the amphiphilicity of particles for controlling the stability and type of Pickering emulsions. The amphiphilicity of three types of particles including rigid particles, soft particles, and Janus particles are tailored by means of different mechanisms and discussed here in detail. The stabilization-destabilization interconversion and phase inversion of Pickering emulsions have been successfully achieved by changing the surface properties of these particles. This article provides a comprehensive review of controllable Pickering emulsions, which is expected to stimulate inspiration for designing and preparing novel Pickering emulsions, and ultimately directing the preparation of functional materials. Full article

(This article belongs to the Special Issue Pickering Emulsion and Derived Materials)

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22 pages, 2703 KiB

Open AccessReview

Controlling Pickering Emulsion Destabilisation: A Route to Fabricating New Materials by Phase Inversion

by Catherine P. Whitby and Erica J. Wanless

Materials 2016, 9(8), 626; https://doi.org/10.3390/ma9080626 - 27 Jul 2016

Cited by 66 | Viewed by 10570

Abstract

The aim of this paper is to review the key findings about how particle-stabilised (or Pickering) emulsions respond to stress and break down. Over the last ten years, new insights have been gained into how particles attached to droplet (and bubble) surfaces alter the destabilisation mechanisms in emulsions. The conditions under which chemical demulsifiers displace, or detach, particles from the interface were established. Mass transfer between drops and the continuous phase was shown to disrupt the layers of particles attached to drop surfaces. The criteria for causing coalescence by applying physical stress (shear or compression) to Pickering emulsions were characterised. These findings are being used to design the structures of materials formed by breaking Pickering emulsions. Full article

(This article belongs to the Special Issue Pickering Emulsion and Derived Materials)

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