Core-crystalline nanoribbons of controlled length <i>via</i> diffusion-limited colloid aggregation

Schmarsow, Ruth Noemí; Ceolı́n, Marcelo; Zucchi, Ileana Alicia; Schroeder, Walter F.

doi:10.1039/c9sm00615j

Cited by 7 publications

(7 citation statements)

References 49 publications

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“…Polyethylene- b -polyethylene oxide (PE- b -PEO) with 1 : 1 ratio between blocks forms crystalline PE nanoribbons in an epoxy matrix. 5,6,19 In that case, a PEO miscible block with similar volume fraction as PE immiscible block was sufficient to stabilize the developed crystalline micelles. Analogously, polystyrene- b -polycaprolactone (PS- b -PCL) with 2 : 1 ratio between blocks (1.8 : 1 strictly) forms crystalline PCL nanoribbons in a polystyrene matrix.…”

Section: Resultsmentioning

confidence: 99%

Controlling block copolymer one-dimensional self-assembly in polymeric matrices

et al. 2023

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Section: Resultsmentioning

confidence: 99%

Controlling block copolymer one-dimensional self-assembly in polymeric matrices

et al. 2023

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“…The black line represents the experimental data, and the red line is the fitting curve using a model of elongated planar objects (homogeneous XS algorithm) with a lamellar structure factor (paracrystalline model). (b) Neat PE- b -PEO block copolymer at different temperatures (reproduced from ref . with permission from the Royal Society of Chemistry).…”

Section: Resultsmentioning

confidence: 99%

Supramolecular Networks Obtained by Block Copolymer Self-Assembly in a Polymer Matrix: Crystallization Behavior and Its Effect on the Mechanical Response

et al. 2023

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In recent years, there has been growing interest in the study of supramolecular networks obtained by self-assembly of amphiphilic molecules due to their responsive behavior to different external stimuli. The possibility of embedding supramolecular networks into polymer matrices opens access to a new generation of functional polymers with great potential for various applications. However, very little is known about how the dynamics of the supramolecular network is affected by diffusional and topological limitations imposed by the polymer matrix. In this work, we investigate the behavior of supramolecular networks embedded into a rubbery polymer. Crystallization-driven self-assembly of a poly(ethylene-block-ethylene oxide) (PE-b-PEO) diblock copolymer was used to generate supramolecular networks in dimethacrylate monomers, which were then photopolymerized at room temperature. PE-b-PEO self-assembles into nanoribbons with a semicrystalline PE core bordered by coronal chains of PEO, and the nanoribbons, in turn, bundle into lamellar aggregates with an average stacking period of around 45 nm. The nanoribbons are interconnected through crystalline nodes in a 3D network structure. Small-angle X-ray scattering experiments show that the polymer matrix preserves the structure of the supramolecular network and avoids its disintegration when the material is heated above the melting temperature of PE cores. Successive self-nucleation and annealing studies reveal that the polymer matrix does not influence the crystallization–melting processes of PE, which take place through the interconnected cores of the supramolecular network. In contrast, the matrix imposes strong effects of topological confinement on the crystallization of PEO, limiting the dimensions of the crystalline lamellae that can be formed. Mechanical tests show that the deformation capacity of these materials can be precisely tuned by programming the temperature within the melting range of the supramolecular network. This behavior was also characterized by shape memory cyclic tests.

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“…In the context of the classical nucleation theory, these nuclei will only grow if they reach a certain critical size. When this threshold is crossed, particles can grow by two main mechanisms: (1) diffusion limited coarsening, , where particles diffuse throughout the medium and grow upon collision (dynamic coalescence) or by dissolution of smaller particles and redeposition on larger particles (Ostwald ripening) and (2) reaction limited growth, which arises from the reduction of Au(I) on the surface of the particles.…”

Section: Resultsmentioning

confidence: 99%

Effect of Light Intensity on the Aggregation Behavior of Primary Particles during In Situ Photochemical Synthesis of Gold/Polymer Nanocomposites

et al. 2020

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Metal/polymer nanocomposites have attracted much attention in recent years due to their exceptional properties and wide range of potential applications. A key challenge to obtain these materials is to stabilize the metal nanoparticles in the matrix, avoiding uncontrolled aggregation processes driven by the high surface free energy of nanosized particles. Here, we investigate the aggregation mechanism of primary particles in gold−epoxy nanocomposites prepared via light-assisted in situ synthesis, under different irradiation conditions. The growth and aggregation of gold nanoparticles were monitored in situ by time-resolved small-angle X-ray scattering experiments, whereas spectroscopic measurements were performed to interpret how matrix polymerization influences the aggregation process. It was found that light intensity has a greater influence on the reduction rate than on the polymerization rate. Under irradiation, gold nanostructures evolve through five time-defined stages: nucleimass fractalssurface fractalsspherical nanoparticlesaggregates. If the maximum in the polymerization rate is reached before the aggregation step, individual primary nanoparticles will be preserved in the polymer matrix due to diffusional constraints imposed by the reaction medium. Because the light intensity has a different influence on the reduction rate than on the polymerization rate, this parameter can be used as a versatile tool to avoid aggregation of gold nanoparticles into the polymer matrix.

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Core-crystalline nanoribbons of controlled length via diffusion-limited colloid aggregation

Abstract: The mobility of the medium during crystallization-driven self-assembly plays a crucial role in the elongation process of 1D nanoribbons.

Cited by 7 publications

References 49 publications

Controlling block copolymer one-dimensional self-assembly in polymeric matrices

Controlling block copolymer one-dimensional self-assembly in polymeric matrices

Supramolecular Networks Obtained by Block Copolymer Self-Assembly in a Polymer Matrix: Crystallization Behavior and Its Effect on the Mechanical Response

Effect of Light Intensity on the Aggregation Behavior of Primary Particles during In Situ Photochemical Synthesis of Gold/Polymer Nanocomposites

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