Water-in-Water Emulsions Stabilized by Nanoplates

Vis, Mark; Opdam, Joeri; Oor, Ingo S. J. van ’t; Soligno, Giuseppe; Roij, René van; Tromp, R. Hans; Erné, Ben H.

doi:10.1021/acsmacrolett.5b00480

Cited by 125 publications

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“…The bonding potential is usually strong enough to allow stable monolayers of particles. Since a pioneering study by Pieranski [3], a lot of interest has been devoted to these quasi-2D systems, which have many applications, e.g., emulsions [4][5][6][7][8][9], coatings [10,11], optics [12], and new material development [13]. Because of the contact angle constraint imposed by Young's Law, an adsorbed particle in general induces deformations in the shape of the fluid-fluid interface.…”

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confidence: 99%

“…[25,26], where both hexagonal and honeycomb lattices of truncated nanocubes were observed. For cubes with L ¼ 1 μm, instead, a much lower tension γ ≈ 0.2 − 0.5 μN=m is needed to obtain the h phase, which could, however, possibly be achieved in the extreme case of, e.g., water-water interfaces [9]. In our analysis, we did not include other kinds of particle-particle interactions, e.g., van der Waals which appear to become relevant only in the limit of nanosized particles at nearcontact distances (see Ref.…”

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Self-Assembly of Cubes into 2D Hexagonal and Honeycomb Lattices by Hexapolar Capillary Interactions

2016

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Particles adsorbed at a fluid-fluid interface induce capillary deformations that determine their orientations and generate mutual capillary interactions which drive them to assemble into 2D ordered structures. We numerically calculate, by energy minimization, the capillary deformations induced by adsorbed cubes for various Young's contact angles. First, we show that capillarity is crucial not only for quantitative, but also for qualitative predictions of equilibrium configurations of a single cube. For a Young's contact angle close to 90°, we show that a single-adsorbed cube generates a hexapolar interface deformation with three rises and three depressions. Thanks to the threefold symmetry of this hexapole, strongly directional capillary interactions drive the cubes to self-assemble into hexagonal or graphenelike honeycomb lattices. By a simple free-energy model, we predict a density-temperature phase diagram in which both the honeycomb and hexagonal lattice phases are present as stable states. DOI: 10.1103/PhysRevLett.116.258001 Over a century ago, it had already been observed that submm sized particles strongly adsorb at fluid-fluid interfaces [1,2]. Indeed, a fluid-fluid interface of area A and surface tension γ has a free energy cost γA, and particles can reduce A by adsorbing at the interface. The bonding potential is usually strong enough to allow stable monolayers of particles. Since a pioneering study by Pieranski [3], a lot of interest has been devoted to these quasi-2D systems, which have many applications, e.g., emulsions [4][5][6][7][8][9], coatings [10,11], optics [12], and new material development [13]. Because of the contact angle constraint imposed by Young's Law, an adsorbed particle in general induces deformations in the shape of the fluid-fluid interface. These so-called capillary deformations are responsible for capillary interactions between the adsorbed particles [14,15], which regulate the particle self-assembly at the interface [16][17][18]. These interactions can be tuned by varying, e.g., the particle shape and chemistry [10,[19][20][21], or the curvature of the fluidfluid interface [22][23][24]. Very recent experiments [25][26][27] have shown that adsorbed nanocubes with truncated corners can assemble into graphenelike honeycomb and hexagonal lattices. The origin of these structures is unknown, although ligand adsorption and van der Waals forces between specific facets of the truncated cubes have been suggested [25]. In this Letter, however, we show that generic cubes with homogeneous surface properties generate hexapolar capillary deformations which are largely responsible for the observed structures. Cubes of other materials or dimensions could, therefore, form similar structures.A primary step for understanding adsorbedparticle systems is the study of an isolated particle at a macroscopically flat fluid-fluid interface. Important issues are the equilibrium configuration of the particle at the interface [28][29][30][31] and the adsorption energy [32-34] which depend on the particl...

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Self-Assembly of Cubes into 2D Hexagonal and Honeycomb Lattices by Hexapolar Capillary Interactions

2016

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“…In addition to dextran/PEO w/w emulsions, other polymer combinations were investigated as well. The system dextran and gelatin in water was investigated by Erné and co‐workers . Gibbsite nanoplates were used as Pickering stabilizer that proved to be very efficient due to the 2D structure.…”

Section: Aqueous Multiphase Systemsmentioning

confidence: 99%

“…In order to assemble giant vesicles high polymer concentrations above 10 wt% were employed leading to giant vesicles with sizes from 2 to 20 µm that were visualized via optical microscopy ( Figure ). The requirement of large concentrations for the generation of giant vesicles was explained with the extended interfacial structure (tens of nm) of DHBC self‐assembly systems . Therefore, larger amounts of polymers are needed to allow the formation of hollow structures.…”

Section: Double Hydrophilic Block Copolymer Systems For Self‐assemblymentioning

confidence: 99%

“…The system dextran and gelatin in water was investigated by Erné and co-workers. [77] Gibbsite nanoplates were used as Pickering stabilizer that proved to be very efficient due to the 2D structure. In such a way, the interface between droplet and surrounding medium can be covered efficiently, while the weight of the droplet keeps low, which avoids settling and destabilization of the emulsion.…”

Section: Aqueous Multiphase Systemsmentioning

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Double Hydrophilic Block Copolymer Self‐Assembly in Aqueous Solution

Schmidt

2018

Macro Chemistry & Physics

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Self‐assembly of double hydrophilic block copolymers (DHBCs) in water is an emerging area of research. The self‐assembly process can be derived from aqueous two‐phase systems that are composed of hydrophilic homopolymers at elevated concentration. Consecutively, DHBCs form self‐assembled structures like micelles, vesicles, or particles at high concentrations in water and without the use of external triggers that would change solubility of individual blocks. Careful choice of the two hydrophilic blocks and design of the polymer structure allows formation of self‐assembled structures with high efficiency. The present contribution highlights recent research in the area of DHBC self‐assembly, including the polymer types employed and strategies for crosslinking of the self‐assembled structures. Moreover, an overview of aqueous multiphase systems and theoretical considerations of DHBC self‐assembly are presented, as well as an outlook regarding potential future applications in areas such as the biomedical field.

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