Phase behaviour in 2D assemblies of dumbbell-shaped colloids generated under geometrical confinement

Stuckert, Rouven; Lüders, Anton; Wittemann, Alexander; Nielaba, Peter

doi:10.1039/d1sm00635e

Cited by 10 publications

(5 citation statements)

References 57 publications

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“…In addition, small amounts of a charged comonomer (NaSS) were added to stabilize the polymer lobes grown from the monomer protrusions. Although the synthesis route was established for dumbbell particles with two polystyrene lobes of similar sizes [3,16], it has turned out that the concept can be extended to the synthesis of dumbbell particles with lobes made from two different materials. For this purpose, a second seeded polymerization was performed to obtain dumbbell-shaped hybrid particles.…”

Section: Dumbbell Particles With Similar and Dissimilar Lobes Obtaine...mentioning

confidence: 99%

“…It is thus to be expected that their proportion will be even larger during the actual dumbbell synthesis carried out at 70 °C [3]. This is reflected by the fact that only dumbbell particles were obtained after complete conversion of the monomer at this elevated temperature [16]. Ethane at its freezing point is often used as the cryogen of choice.…”

Section: Effect Of Higher Temperature On Protrusion Formationmentioning

confidence: 99%

“…Their particular shape, configuration and symmetry is responsible for a rich phase behavior with regard to superstructures built from those anisotropic particles [14,15]. Their assembly has recently been investigated in some detail [16].…”

Section: Introductionmentioning

confidence: 99%

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Cryogenic transmission electron microscopy for observation of monomer protrusions that emerge during formation of dumbbell-shaped polymer colloids

2022

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Anisotropic particles exhibit directional interactions resulting in a rich phase behavior. Considerable efforts have thus been invested in guiding particle synthesis into an anisotropic direction. Dumbbell-shaped polymer particles are one of the most remarkable examples. They result from phase separation during seeded polymerization. The underlying mechanism and thermodynamic principles are understood from its proximal end. Segregation of monomer and seed particle results in a monomer protrusion attached to the seed. Polymerization of the protrusion finally yields particles with two bulb-shaped halves. Little attention has been paid to an investigation of transient states, namely the formation of liquid protrusions grown from monomer-swollen seeds. This study demonstrates that cryogenic transmission electron microscopy is an excellent tool for mapping transient states within colloidal objects. Swelling of polymer particles and formation of liquid protrusions mediated by a surface coating on the seeds is explored for styrene and methyl-methacrylate at different temperatures and monomer-to-seed volume ratios.

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Section: Dumbbell Particles With Similar and Dissimilar Lobes Obtaine...mentioning

confidence: 99%

Section: Effect Of Higher Temperature On Protrusion Formationmentioning

confidence: 99%

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Cryogenic transmission electron microscopy for observation of monomer protrusions that emerge during formation of dumbbell-shaped polymer colloids

2022

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“…For the 2D assembly of colloidal dimers or dumbbells, the computational simulation predicted that they may be self‐assembled into (disordered) plastic crystals, herringbone or orientated crystalline films, [ 18,57 ] which were also observed experimentally. [ 57–59 ] However, because of the small free energy difference between their degenerate structures, it still remains a challenge to obtain large‐area mono‐crystalline structures in bulk. [ 60 ]…”

Section: Colloidal Superstructures Of Colloidal Clustersmentioning

confidence: 99%

“…For the 2D assembly of colloidal dimers or dumbbells, the computational simulation predicted that they may be self-assembled into (disordered) plastic crystals, herringbone or orientated crystalline films, [18,57] which were also observed experimentally. [57][58][59] However, because of the small free energy difference between their degenerate structures, it still remains a challenge to obtain large-area mono-crystalline structures in bulk. [60] For 3D assembly, dimers or triangular trimers similarly form thermodynamically stable aperiodic or degenerate crystal phases, in which spheres in dimers or trimers are arranged in the fcc lattice in the Monte Carlo simulation.…”

Section: Colloidal Superstructures Of Colloidal Clustersmentioning

confidence: 99%

Advances in Colloidal Building Blocks: Toward Patchy Colloidal Clusters

et al. 2022

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The scalable synthetic route to colloidal atoms has significantly advanced over the past two decades. Recently, colloidal clusters with DNA‐coated cores called “patchy colloidal clusters” have been developed, providing a directional bonding with specific angle of rotation due to the shape complementarity between colloidal clusters. Through a DNA‐mediated interlocking process, they are directly assembled into low‐coordination colloidal structures, such as cubic diamond lattices. Herein, the significant progress in recent years in the synthesis of patchy colloidal clusters and their assembly in experiments and simulations is reviewed. Furthermore, an outlook is given on the emerging approaches to the patchy colloidal clusters and their potential applications in photonic crystals, metamaterials, topological photonic insulators, and separation membranes.

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Linear growth of colloidal dumbbells into three-lobed polymer nanoparticles mediated by a gradient in surface wettability

Monteiro

Wittemann

2023

Colloid Polym Sci

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Anisotropy is a deciding factor in determining the hydrodynamics and self-assembly of colloidal particles. Linking particle morphology to said behaviors promoted the development of strategies to obtain anisotropic particles exhibiting defined shapes and symmetries. Dumbbell-shaped polymer particles made by phase separation during seeded polymerization are prominent examples. Phase separation among monomer and seed particle yields a liquid protrusion of monomer on the seed. This protrusion is then polymerized, becoming solid and yielding a solid spherical lobe. When this process is performed with spherical seeds, two-lobed particles, known as colloidal dumbbells, are obtained. Repeating this process of lobe formation one or more times could pave the way to tailored particle morphologies. Given the higher degree of anisotropy, multi-lobed particles can expand the rich phase behavior already found for dumbbells. We propose a new route in making anisotropic polymer particles by directing phase separation in a linear direction, thus permitting linear growth. Colloidal particles composed of three individual polymer lobes with the potential for site-specific modifications are obtained. Triggering of the phase separation is done complementary to prior efforts in fabricating three-lobed polymer particles based on cross-linked precursor particles. We will show that tailored surface properties of anisotropic seed particles can prove as an effective tool not only to promote the monomer-polymer phase separation, but also to guide it in a linear direction. Such gradients in surface functionalization open perspectives for making polymer colloids on a large scale in whose custom-tailored shapes their phase behavior and superstructure formation are already established. Graphical Abstract

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Phase behaviour in 2D assemblies of dumbbell-shaped colloids generated under geometrical confinement

Abstract: Structure formation in experimental monolayers of dumbbell particles is explored and compared to Brownian dynamics simulations. Probability densities of shape factors found in Voronoi tessellations allow for an in-depth analysis of structural motifs.

Cited by 10 publications

References 57 publications

Cryogenic transmission electron microscopy for observation of monomer protrusions that emerge during formation of dumbbell-shaped polymer colloids

Cryogenic transmission electron microscopy for observation of monomer protrusions that emerge during formation of dumbbell-shaped polymer colloids

Advances in Colloidal Building Blocks: Toward Patchy Colloidal Clusters

Linear growth of colloidal dumbbells into three-lobed polymer nanoparticles mediated by a gradient in surface wettability

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