A decade of innovation and progress in understanding the morphology and structure of heterogeneous polymers in rigid confinement

Ok, Salim; Vayer, Marylène; Sinturel, Christophe

doi:10.1039/d1sm00522g

Cited by 9 publications

(9 citation statements)

References 171 publications

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“…Because this is an imaging technique, promising future applications may include the determination of the relative degree of polymerization in different regions of the same sample of inhomogeneous polymer networks and films. [67][68][69][70][71][72][73] The FLRAP/FRAP autofluorescence approach developed here may be amenable to monitoring additional chemical systems with viscosity changes, including diverse synthetic polymerization systems that were previously overlooked for lack of obvious fluorescence handles.…”

Section: Discussionmentioning

confidence: 99%

A General Autofluorescence Method to Characterize Polymerization Progress

2023

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An autofluorescence technique to characterize polymerization progress in real time/in line was developed, which functioned in the absence of typical fluorogenic groups on the monomer or polymer. The monomer dicyclopentadiene and polymer polydicyclopentadiene are hydrocarbons that lack traditional functional groups for fluorescence spectroscopy. Here, the autofluorescence of formulations containing this monomer and polymer during ruthenium-catalyzed ring-opening metathesis polymerization (ROMP) was harnessed for reaction monitoring. The methods fluorescence recovery after photobleaching (FRAP) and here-developed fluorescence lifetime recovery after photobleaching (FLRAP) characterized polymerization progress in these native systems-without requiring exogenous fluorophore. (Auto)fluorescence lifetime recovery changes during polymerization correlated linearly to degree of cure, providing a quantitative link with reaction progress. These changing signals also provided relative rates of background polymerization, enabling comparison of 10 different catalyst-inhibitor-stabilized formulations. Multiple-well analysis demonstrated suitability for future high-throughput evaluation of formulations for thermosets. The central concept of the combined autofluorescence and FLRAP/FRAP method may be extendable to monitoring other polymerization reactions previously overlooked for lack of an obvious fluorescence handle.

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Section: Discussionmentioning

confidence: 99%

A General Autofluorescence Method to Characterize Polymerization Progress

2023

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“…238,239 An interplay between surface wetting effects and selective swelling of amphiphilic BCP domains in the binary mixture of two solvent vapors has been exploited to tune the morphology of PS-b-PEO diblock confined in porous template. 240 More information on the formation of 3D polymer structures, especially in anodic aluminum oxide (AAO) templates, can be found in the recent comprehensive review by Ok et al 241 Solvent-induced soft shearing. The application of tangential mechanical stress transduced by an elastomeric PDMS pad to an underlying BCP film has been originally proposed by Angelescu et al as an effective way of aligning BCP morphologies.…”

Section: Hybrid Methodsmentioning

confidence: 99%

Section: Review Of Solvent-assisted Self-assembly Of Bcp Filmsmentioning

confidence: 99%

Solvent-assisted self-assembly of block copolymer thin films

2022

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“…Block copolymers can self-assemble into phase-separated periodic nanostructures, such as lamellae, gyroid, cylinders, spheres, and have attracted much scientific interest due to the potential application of these structures in various areas, − such as in nanolithography and material science . Confinement can be used to break the symmetry of structures formed in the self-assembly of block copolymers and hence generate novel structures that cannot be obtained in bulk. ,, In general, confinement can be classified into one-dimensional (1D) planar confinement, ,− two-dimensional (2D) cylindrical confinement, ,− and three-dimensional (3D) spherical confinement ,− based on the confining geometries. Previous extensive studies showed that frustration induced by 1D confinement of block copolymers in thin films can lead to different orientations and adjustable periods of structures depending on the surface–block interactions and film thickness, , while 2D cylindrical confinement and 3D spherical confinement could induce frustration and distortions that cannot be observed in bulk or 1D confinement due to the curvature of the confining pore.…”

Section: Introductionmentioning

confidence: 99%

Nanospheres with Patches Arranged in Polyhedrons from Self-Assembly of Solution-State Diblock Copolymers under Spherical Confinement

Wang

et al. 2022

Macromolecules

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Self-assembly of sphere-forming solution-state amphiphilic diblock copolymers under spherical nanopore confinement is investigated using a simulated annealing technique. For two types of cases of different pore−surface/copolymer interactions, sequences of self-assembled patchy nanospheres are obtained, and phase diagrams are constructed. Self-assembled patchy nanospheres with 1−21 solvophobic domains are observed. The outermost solvophobic domains (patches) are packed into various polyhedrons when their number is larger than 3, where three Platonic solids of a regular tetrahedron, an octahedron, and an icosahedron and seven Johnson solids of J12, J13, J17, J50, J51, J86, and J87 are identified. In addition, another Johnson solid of J84 is identified in a structure with two categories of B-domains. These polyhedrons have all or most of their faces in a triangular shape, and hence, they are closer to spherical in shape, which may relieve the chain stretching. Nanospheres with 1, 4, 6, 9, and 12 numbers of patches occur in relatively large windows in the phase diagrams of both types of cases. In one of the two types of cases, all nanospheres with any number of 1−14 patches occur in the phase diagram, whereas in the other type of cases, nanospheres with 2, 3, 5, 11, and 13 numbers of patches are absent in the phase diagram. Furthermore, at a given pore size, the number of patches changes nonmonotonically or is unchanged with an increase in the strength of the pore−surface/copolymer interactions for one type or the other type of case, respectively. Quantitative calculations are performed to elucidate mechanisms of the window size in the phase diagrams of nanospheres with different numbers of patches and structure details. All the observed phase behaviors can be well-explained based on the structure frustration, the conclusion being that the systems tend to avoid forming polyhedral structures with uneven distribution of solvophobic domains, and the differences between the two types of cases. Our results may provide a fundamental understanding of the relationship among confinement conditions, solvent conditions, and self-assembled structures.

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A decade of innovation and progress in understanding the morphology and structure of heterogeneous polymers in rigid confinement

Abstract: When confined into nanoscale domains, polymers generally encounter changes of their structural, thermodynamics and dynamics properties compared to those in bulk, due to the high amount of polymer/walls interfaces and...

Cited by 9 publications

References 171 publications

A General Autofluorescence Method to Characterize Polymerization Progress

A General Autofluorescence Method to Characterize Polymerization Progress

Solvent-assisted self-assembly of block copolymer thin films

Nanospheres with Patches Arranged in Polyhedrons from Self-Assembly of Solution-State Diblock Copolymers under Spherical Confinement

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