Living systems are composed of a select number of biopolymers and minerals yet exhibit an immense diversity in materials properties. The wide-ranging characteristics, such as enhanced mechanical properties of skin and bone, or responsive optical properties derived from structural coloration, are a result of the multiscale, hierarchical structure of the materials. The fields of materials and polymer chemistry have leveraged equilibrium concepts in an effort to mimic the structure complex materials seen in nature. However, realizing the remarkable properties in natural systems requires moving beyond an equilibrium perspective. An alternative method to create materials with multiscale structures is to approach the issue from a kinetic perspective and utilize chemical processes to drive phase transitions.
This Account features an active area of research in our group, reaction-induced phase transitions (RIPT), which uses chemical reactions such as polymerizations to induce structural changes in soft material systems. Depending on the type of phase transition (e.g., microphase versus macrophase separation), the resulting change in state will occur at different length scales (e.g., nm – μm), thus dictating the structure of the material. For example, the in situ formation of either a block copolymer or a homopolymer initially in a monomer mixture during a polymerization will drive nanoscale or macroscale transitions, respectively. Specifically, three different examples utilizing reaction-driven phase changes will be discussed: 1) in situ polymer grafting from block copolymers, 2) multiscale polymer nanocomposites, and 3) Lewis adduct-driven phase transitions. All three areas highlight how chemical changes via polymerizations or specific chemical binding result in phase transitions that lead to nanostructural and multiscale changes.
Harnessing kinetic chemical processes to promote and control material structure, as opposed to organizing pre-synthesized molecules, polymers, or nanoparticles within a thermodynamic framework, is a growing area of interest. Trapping nonequilibrium states in polymer materials has been primarily focused from a polymer chain conformation viewpoint in which synthesized polymers are subjected to different thermal and processing conditions. The impact of reaction kinetics and polymerization rate on final polymer material structure is starting to be recognized as a new way to access different morphologies not available through thermodynamic means. Furthermore, kinetic control of polymer material structure is not specific to polymerizations and encompasses any chemical reaction that induce morphology transitions. Kinetically driven processes to dictate material structure directly impact a broad range of areas including separation membranes, biomolecular condensates, cell mobility, and the self-assembly of polymers and colloids. Advancing polymer material syntheses using kinetic principles such as RIPT opens new possibilities for dictating material structure and properties beyond what is currently available with traditional self-assembly techniques.
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This content will become publicly available on May 9, 2024
Gas-phase microactuation using kinetically controlled surface states of ultrathin catalytic sheets
Biological systems convert chemical energy into mechanical work by using protein catalysts that assume kinetically controlled conformational states. Synthetic chemomechanical systems using chemical catalysis have been reported, but they are slow, require high temperatures to operate, or indirectly perform work by harnessing reaction products in liquids (e.g., heat or protons). Here, we introduce a bioinspired chemical strategy for gas-phase chemomechanical transduction that sequences the elementary steps of catalytic reactions on ultrathin (<10 nm) platinum sheets to generate surface stresses that directly drive microactuation (bending radii of 700 nm) at ambient conditions (T = 20 °C; P total = 1 atm). When fueled by hydrogen gas and either oxygen or ozone gas, we show how kinetically controlled surface states of the catalyst can be exploited to achieve fast actuation (600 ms/cycle) at 20 °C. We also show that the approach can integrate photochemically controlled reactions and can be used to drive the reconfiguration of microhinges and complex origami- and kirigami-based microstructures.
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- Award ID(s):
- 1719875
- NSF-PAR ID:
- 10411280
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 120
- Issue:
- 19
- ISSN:
- 0027-8424
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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