Transient Interfacial Pattern Formation in Block Copolymer Thin Films via Sequential Thermal and Solvent Immersion Annealing

A variety of structures encountered in nature only arise in materials under highly nonequilibrium conditions, suggesting to us that the scope for creating new functional block copolymer (BCP) structures might be significantly enlarged by embracing complex processing histories that allow for the fabrication of structures quite unlike those created under “near-equilibrium” conditions. The present work examines the creation of polymer film structures in which highly nonequilibrium processing conditions allow for the creation of entirely new types of transient BCP morphologies achieved by transitioning between different ordered states. Most previous studies of BCP materials have emphasized ordering them from their disordered state obtained from a solution film casting process, followed by a slow thermal annealing (TA) process at elevated temperatures normally well above room temperature. We have previously shown that achieving the equilibrium TA state can be accelerated by a direct solvent immersion annealing (DIA) preordering step that creates nascent ordered microstructures, followed by TA. In the present work, we examine the reverse nonequilibrium sequential processing in which we first thermally anneal the BCP film to different levels of partial (lamellar) order and then subject it to DIA to swell the lamellae. This sequential processing rapidly leads to a swelling-induced wrinkle pattern that initially grows with immersion time and can be quenched by solvent evaporation into its corresponding glassy state morphology. The article demonstrates the formation of wrinkling “defect” patterns in entangled BCP films by this sequential annealing that does not form under ordinary TA conditions. At long DIA times, these highly “defective” film structures evolve in favor of the equilibrium morphology of parallel lamellae observed with DIA alone. In conjunction with our previous study of sequential DIA + TA, the present TA + DIA study demonstrates that switching the order of these processing methods for block copolymer films gives the same final state morphology in the limit of long time as any one method alone, but with drastically different intermediate transient state morphologies. These transient morphologies could have many applications

Transient Interfacial Pattern Formation in Block Copolymer Thin Films via Sequential Thermal and Solvent Immersion Annealing

A variety of structures encountered in nature only arise in materials under highly nonequilibrium conditions, suggesting to us that the scope for creating new functional block copolymer (BCP) structures might be significantly enlarged by embracing complex processing histories that allow for the fabrication of structures quite unlike those created under “near-equilibrium” conditions. The present work examines the creation of polymer film structures in which highly nonequilibrium processing conditions allow for the creation of entirely new types of transient BCP morphologies achieved by transitioning between different ordered states. Most previous studies of BCP materials have emphasized ordering them from their disordered state obtained from a solution film casting process, followed by a slow thermal annealing (TA) process at elevated temperatures normally well above room temperature. We have previously shown that achieving the equilibrium TA state can be accelerated by a direct solvent immersion annealing (DIA) preordering step that creates nascent ordered microstructures, followed by TA. In the present work, we examine the reverse nonequilibrium sequential processing in which we first thermally anneal the BCP film to different levels of partial (lamellar) order and then subject it to DIA to swell the lamellae. This sequential processing rapidly leads to a swelling-induced wrinkle pattern that initially grows with immersion time and can be quenched by solvent evaporation into its corresponding glassy state morphology. The article demonstrates the formation of wrinkling “defect” patterns in entangled BCP films by this sequential annealing that does not form under ordinary TA conditions. At long DIA times, these highly “defective” film structures evolve in favor of the equilibrium morphology of parallel lamellae observed with DIA alone. In conjunction with our previous study of sequential DIA + TA, the present TA + DIA study demonstrates that switching the order of these processing methods for block copolymer films gives the same final state morphology in the limit of long time as any one method alone, but with drastically different intermediate transient state morphologies. These transient morphologies could have many applications

Transient Interfacial Pattern Formation in Block Copolymer Thin Films via Sequential Thermal and Solvent Immersion Annealing

A variety of structures encountered in nature only arise in materials under highly nonequilibrium conditions, suggesting to us that the scope for creating new functional block copolymer (BCP) structures might be significantly enlarged by embracing complex processing histories that allow for the fabrication of structures quite unlike those created under “near-equilibrium” conditions. The present work examines the creation of polymer film structures in which highly nonequilibrium processing conditions allow for the creation of entirely new types of transient BCP morphologies achieved by transitioning between different ordered states. Most previous studies of BCP materials have emphasized ordering them from their disordered state obtained from a solution film casting process, followed by a slow thermal annealing (TA) process at elevated temperatures normally well above room temperature. We have previously shown that achieving the equilibrium TA state can be accelerated by a direct solvent immersion annealing (DIA) preordering step that creates nascent ordered microstructures, followed by TA. In the present work, we examine the reverse nonequilibrium sequential processing in which we first thermally anneal the BCP film to different levels of partial (lamellar) order and then subject it to DIA to swell the lamellae. This sequential processing rapidly leads to a swelling-induced wrinkle pattern that initially grows with immersion time and can be quenched by solvent evaporation into its corresponding glassy state morphology. The article demonstrates the formation of wrinkling “defect” patterns in entangled BCP films by this sequential annealing that does not form under ordinary TA conditions. At long DIA times, these highly “defective” film structures evolve in favor of the equilibrium morphology of parallel lamellae observed with DIA alone. In conjunction with our previous study of sequential DIA + TA, the present TA + DIA study demonstrates that switching the order of these processing methods for block copolymer films gives the same final state morphology in the limit of long time as any one method alone, but with drastically different intermediate transient state morphologies. These transient morphologies could have many applications

Transient Interfacial Pattern Formation in Block Copolymer Thin Films via Sequential Thermal and Solvent Immersion Annealing

A variety of structures encountered in nature only arise in materials under highly nonequilibrium conditions, suggesting to us that the scope for creating new functional block copolymer (BCP) structures might be significantly enlarged by embracing complex processing histories that allow for the fabrication of structures quite unlike those created under “near-equilibrium” conditions. The present work examines the creation of polymer film structures in which highly nonequilibrium processing conditions allow for the creation of entirely new types of transient BCP morphologies achieved by transitioning between different ordered states. Most previous studies of BCP materials have emphasized ordering them from their disordered state obtained from a solution film casting process, followed by a slow thermal annealing (TA) process at elevated temperatures normally well above room temperature. We have previously shown that achieving the equilibrium TA state can be accelerated by a direct solvent immersion annealing (DIA) preordering step that creates nascent ordered microstructures, followed by TA. In the present work, we examine the reverse nonequilibrium sequential processing in which we first thermally anneal the BCP film to different levels of partial (lamellar) order and then subject it to DIA to swell the lamellae. This sequential processing rapidly leads to a swelling-induced wrinkle pattern that initially grows with immersion time and can be quenched by solvent evaporation into its corresponding glassy state morphology. The article demonstrates the formation of wrinkling “defect” patterns in entangled BCP films by this sequential annealing that does not form under ordinary TA conditions. At long DIA times, these highly “defective” film structures evolve in favor of the equilibrium morphology of parallel lamellae observed with DIA alone. In conjunction with our previous study of sequential DIA + TA, the present TA + DIA study demonstrates that switching the order of these processing methods for block copolymer films gives the same final state morphology in the limit of long time as any one method alone, but with drastically different intermediate transient state morphologies. These transient morphologies could have many applications

Self-Cross-Linking of MXene-Intercalated Graphene Oxide Membranes with Antiswelling Properties for Dye and Salt Rejection

Membrane-based water purification is poised to play an important role in tackling the potable water crisis for safe and clean water access for the general population. Several studies have focused on near two-dimensional membranes for this purpose, which is based on an ion rejection technique. However, membrane swelling in these materials has emerged as a significant challenge because it leads to the loss of function. Herein, we report a self-cross-linked MXene-intercalated graphene oxide (GO) membrane that retains ion and dye rejection properties because the physical cross-linking interaction between Ti–O–Ti and neighboring nanosheets effectively suppresses the swelling of the membrane. In addition to the associative Ti–O–Ti bonds, C–O–C, OC–O, and C–OH bonds are also formed, which are important for inhibiting the swelling of the membrane. To ensure the longevity of these membranes in a service context, they were subjected to heat pressurization and subsequent thermal annealing. The membrane subjected to this novel processing history exhibits minimal swelling upon immersion in solutions and retains function, rejecting salt and dyes over a wide range of salt and dye concentrations. Furthermore, these membranes successfully rejected dye and salt over a period of 72 h without a degradation of function, suggesting that these membranes have the requisite durability for water filtration applications

Polymer-Grafted Nanoparticles with Variable Grafting Densities for High Energy Density Polymeric Nanocomposite Dielectric Capacitors

Designing high energy density dielectric capacitors for advanced energy storage systems needs nanocomposite-based dielectric materials, which can utilize the properties of both inorganic and polymeric materials. Polymer-grafted nanoparticle (PGNP)-based nanocomposites alleviate the problems of poor nanocomposite properties by providing synergistic control over nanoparticle and polymer properties. Here, we synthesize “core–shell” barium titanate–poly(methyl methacrylate) (BaTiO3–PMMA) grafted PGNPs using surface-initiated atom transfer polymerization (SI-ATRP) with variable grafting densities of (0.303 to 0.929) chains/nm2 and high molecular masses (97700 g/mL to 130000 g/mol) and observe that low grafted density and high molecular mass based PGNP show high permittivity, high dielectric strength, and hence higher energy densities (≈ 5.2 J/cm3) as compared to the higher grafted density PGNPs, presumably due to their “star-polymer”-like conformations with higher chain-end densities that are known to enhance breakdown. Nonetheless, these energy densities are an order of magnitude higher than their nanocomposite blend counterparts. We expect that these PGNPs can be readily used as commercial dielectric capacitors, and these findings can serve as guiding principles for developing tunable high energy density energy storage devices using PGNP systems

Nanobrick Wall Multilayer Thin Films with High Dielectric Breakdown Strength

Current thermally conductive and electrically insulating insulation systems are struggling to meet the needs of modern electronics due to increasing heat generation and power densities. Little research has focused on creating insulation systems that excel at both dissipating heat and withstanding high voltages (i.e., have both high thermal conductivity and a high breakdown strength). Herein, a polyelectrolyte-based multilayer nanocomposite is demonstrated to be a thermally conductive high-voltage insulation. Through inclusion of both boehmite and vermiculite clay, the breakdown strength of the nanocomposite was increased by ≈115%. It was also found that this unique nanocomposite has an increase in its breakdown strength, modulus, and hydrophobicity when exposed to elevated temperatures. This readily scalable insulation exhibits a remarkable combination of breakdown strength (250 kV/mm) and thermal conductivity (0.16 W m–1 K–1) for a polyelectrolyte-based nanocomposite. This dual clay insulation is a step toward meeting the needs of the next generation of high-performance insulation systems

Nanobrick Wall Multilayer Thin Films with High Dielectric Breakdown Strength

Current thermally conductive and electrically insulating insulation systems are struggling to meet the needs of modern electronics due to increasing heat generation and power densities. Little research has focused on creating insulation systems that excel at both dissipating heat and withstanding high voltages (i.e., have both high thermal conductivity and a high breakdown strength). Herein, a polyelectrolyte-based multilayer nanocomposite is demonstrated to be a thermally conductive high-voltage insulation. Through inclusion of both boehmite and vermiculite clay, the breakdown strength of the nanocomposite was increased by ≈115%. It was also found that this unique nanocomposite has an increase in its breakdown strength, modulus, and hydrophobicity when exposed to elevated temperatures. This readily scalable insulation exhibits a remarkable combination of breakdown strength (250 kV/mm) and thermal conductivity (0.16 W m–1 K–1) for a polyelectrolyte-based nanocomposite. This dual clay insulation is a step toward meeting the needs of the next generation of high-performance insulation systems

Facile Entropy-Driven Segregation of Imprinted Polymer-Grafted Nanoparticle Brush Blends by Solvent Vapor Annealing Soft Lithography

Polymer-grafted nanoparticles (PGNPs) have attracted extensive research interest due to their potential for enhancing mechanical and electrical properties of both bulk polymer composite materials, as well as thin polymer films incorporating these nanoparticles (NPs). In previous studies, we have shown that an entropic driving force serves to organize low-molecular-mass PGNPs in imprinted blend films of PGNPs with low-molecular-mass homopolymers. In this work, we developed a novel solvent vapor annealing soft lithography (SVA-SL) method to overcome the technical difficulties in processing the high-molecular-mass PGNP blends due to the intrinsically sluggish melt annealing kinetics found in the phase separation of these blend PGNP materials. In particular, we utilized SVA-SL to create nanopatterns in blends of PGNPs having relatively high-molecular-mass-grafted layers but with cores of NPs having greatly different sizes. The minimization of the entropic free energy in the present system corresponded to larger PGNPs partitioning almost exclusively into the “mesa” regions of the imprinted PGNP blend films, as quantified by the estimation of the partition coefficient, Kp. The use of the SVA-SL processing method is important because it allows facile imprint patterning of PGNP materials and large-scale organization of the PGNPs even when the grafted chain lengths are long enough for the chains to be highly entangled, allowing enhanced thermo-mechanical property enhancements of the resulting films and a corresponding extended range of potential nanotech applications