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.
more »
« less
Current status and future directions of self-assembled block copolymer membranes for molecular separations
One of the most efficient and promising separation alternatives to thermal methods such as distillation is the use of polymeric membranes that separate mixtures based on molecular size or chemical affinity. Self-assembled block copolymer membranes have gained considerable attention within the membrane field due to precise control over nanoscale structure, pore size, and chemical versatility. Despite the rapid progress and excitement, a significant hurdle in using block copolymer membranes for nanometer and sub-nanometer separations such as nanofiltration and reverse osmosis is the lower limit on domain size features. Strategies such as polymer post-functionalization, self-assembly of oligomers, liquid crystals, and random copolymers, or incorporation of artificial/natural channels within block copolymer materials are future directions with the potential to overcome current limitations with respect to separation size.
more »
« less
- NSF-PAR ID:
- 10352943
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 17
- Issue:
- 46
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 10405 to 10415
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Porous polymer-derived membranes are useful for applications ranging from filtration and separation technologies to energy storage and conversion. Combining block copolymer (BCP) self-assembly with the industrially scalable, non-equilibrium phase inversion technique (SNIPS) yields membranes comprising periodically ordered top surface structures supported by asymmetric, hierarchical substructures that together overcome performance tradeoffs typically faced by materials derived from equilibrium approaches. This review first reports on recent advances in understanding the top surface structural evolution of a model SNIPS-derived system during standard membrane formation. Subsequently, the application of SNIPS to multicomponent systems is described, enabling pore size modulation, chemical modification, and transformation to non-polymeric materials classes without compromising the structural features that define SNIPS membranes. Perspectives on future directions of both single-component and multicomponent membrane materials are provided. This points to a rich and fertile ground for the study of fundamental as well as applied problems using non-equilibrium-derived asymmetric porous materials with tunable chemistry, composition, and structure.more » « less
-
more » « less
Abstract Mesoporous inorganic particles and hollow spheres are of increasing interest for a broad range of applications, but synthesis approaches are typically material specific, complex, or lack control over desired structures. Here it is reported how combining mesoscale block copolymer (BCP) directed inorganic materials self‐assembly and macroscale spinodal decomposition can be employed in multicomponent BCP/hydrophilic inorganic precursor blends with homopolymers to prepare mesoporous inorganic particles with controlled meso‐ and macrostructures. The homogeneous multicomponent blend solution undergoes dual phase separation upon solvent evaporation. Microphase‐separated (BCP/inorganic precursor)‐domains are confined within the macrophase‐separated majority homopolymer matrix, being self‐organized toward particle shapes that minimize the total interfacial area/energy. The pore orientation and particle shape (solid spheres, oblate ellipsoids, hollow spheres) are tailored by changing the kind of homopolymer matrix and associated enthalpic interactions. Furthermore, the sizes of particle and hollow inner cavity are tailored by changing the relative amount of homopolymer matrix and the rates of solvent evaporation. Pyrolysis yields discrete mesoporous inorganic particles and hollow spheres. The present approach enables a high degree of control over pore structure, orientation, and size (15–44 nm), particle shape, particle size (0.6–3 µm), inner cavity size (120–700 nm), and chemical composition (e.g., aluminosilicates, carbon, and metal oxides).
-
The separation of oil from water and filtration of aqueous solutions and dispersions are critical issues in the processing of waste and contaminated water treatment. Membrane-based technology has been proven as an effective method for the separation of oil from water. In this research, novel vertical nanopores membrane, via oriented cylindrical block copolymer (BCP) films, suitable for oil/water filtration has been designed, fabricated and tested. We used a ∼100 nm thick model poly(styrene- block -methymethacrylate) (PS- b -PMMA) BCP as the active top nanofiltration layer, processed using a roll-to-roll (R2R) method of cold zone annealing (CZA) to obtain vertical orientation, followed by ultraviolet (UV) irradiation selective etch of PMMA cylinders to form vertically oriented nanopores as a novel feature compared to meandering nanopores in other reported BCP systems. The cylindrical nanochannels are hydrophilic, and have a uniform pore size (∼23 nm), a narrow pore size distribution and a high nanopore density (∼420 per sq. micron). The bottom supporting layer is a conventional microporous polyethersulfone (PES) membrane. The created asymmetric membrane is demonstrated to be effective for oil/water extraction with a modestly high throughput rate comparable to other RO/NF membranes. The molecular weight dependent filtration of a water soluble polymer, PEO, demonstrates the broader applications of such membranes.more » « less
-
more » « less
Abstract Surface segregation in blended polymer films has attracted much interest in fundamental research as well as for practical applications. A variety of methodologies have been proposed for controlling surface segregation. They often require long annealing times, however, to achieve thermodynamic equilibrium. Here, a strategy and proof‐of‐principle experiments are described to control surface segregation of thin block‐copolymer (BCP) layers on top of a homopolymer in a single casting step from blended BCP/homopolymer solutions. The surface coverage by the minor constituent BCP (2–10 wt%) is accomplished despite almost identical surface energies of BCP and homopolymer constituents. Immersing this casted solution into water for nonsolvent induced phase separation (NIPS), a nonequilibrium process, affords solidified bilayer ultrafiltration membranes composed of a thin porous surface layer of self‐assembled BCP atop an asymmetric porous homopolymer substructure. Key to successful BCP surface segregation is the choice of a binary solvent system based on careful considerations of solvent surface energies and polymer‐solvent interaction parameters. Furthermore, stabilizing the BCP micellar structure by a divalent metal additive is also essential. The approach provides a cost‐effective method for fabricating bilayer‐type asymmetric ultrafiltration membranes with uniform BCP self‐assembly based selective top surface pore layers in a single casting step.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1SM01368H
