Controlling orientational order in block copolymers using low-intensity magnetic fields.

The interaction of fields with condensed matter during phase transitions produces a rich variety of physical phenomena. Self-assembly of liquid crystalline block copolymers (LC BCPs) in the presence of a magnetic field, for example, can result in highly oriented microstructures due to the LC BCP's anisotropic magnetic susceptibility. We show that such oriented mesophases can be produced using low-intensity fields (<0.5 T) that are accessible using permanent magnets, in contrast to the high fields (>4 T) and superconducting magnets required to date. Low-intensity field alignment is enabled by the addition of labile mesogens that coassemble with the system's nematic and smectic A mesophases. The alignment saturation field strength and alignment kinetics have pronounced dependences on the free mesogen concentration. Highly aligned states with orientation distribution coefficients close to unity were obtained at fields as small as 0.2 T. This remarkable field response originates in an enhancement of alignment kinetics due to a reduction in viscosity, and increased magnetostatic energy due to increases in grain size, in the presence of labile mesogens. These developments provide routes for controlling structural order in BCPs, including the possibility of producing nontrivial textures and patterns of alignment by locally screening fields using magnetic nanoparticles.

High Performance Nanofiltration Membrane for Effective Removal of Perfluoroalkyl Substances at High Water Recovery.

We demonstrate the fabrication of a loose, negatively charged nanofiltration (NF) membrane with tailored selectivity for the removal of perfluoroalkyl substances with reduced scaling potential. A selective polyamide layer was fabricated on top of a poly(ether sulfone) support via interfacial polymerization of trimesoyl chloride and a mixture of piperazine and bipiperidine. Incorporating high molecular weight bipiperidine during the interfacial polymerization enables the formation of a loose, nanoporous selective layer structure. The fabricated NF membrane possessed a negative surface charge and had a pore diameter of ∼1.2 nm, much larger than a widely used commercial NF membrane (i.e., NF270 with pore diameter of ∼0.8 nm). We evaluated the performance of the fabricated NF membrane for the rejection of different salts (i.e., NaCl, CaCl2, and Na2SO4) and perfluorooctanoic acid (PFOA). The fabricated NF membrane exhibited a high retention of PFOA (∼90%) while allowing high passage of scale-forming cations (i.e., calcium). We further performed gypsum scaling experiments to demonstrate lower scaling potential of the fabricated loose porous NF membrane compared to NF membranes having a dense selective layer under solution conditions simulating high water recovery. Our results demonstrate that properly designed NF membranes are a critical component of a high recovery NF system, which provide an efficient and sustainable solution for remediation of groundwater contaminated with perfluoroalkyl substances.

Janus Graft Block Copolymers: Design of a Polymer Architecture for Independently Tuned Nanostructures and Polymer Properties.

The graft-through synthesis of Janus graft block copolymers (GBCPs) from branched macromonomers composed of various combinations of homopolymers is presented. Self-assembly of GBCPs resulted in ordered nanostructures with ultra-small domain sizes down to 2.8 nm (half-pitch). The grafted architecture introduces an additional parameter, the backbone length, which enables control over the thermomechanical properties and processability of the GBCPs independently of their self-assembled nanostructures. The simple synthetic route to GBCPs and the possibility of using a variety of polymer combinations contribute to the universality of this technique.

Flat Drops, Elastic Sheets, and Microcapsules by Interfacial Assembly of a Bacterial Biofilm Protein, BslA.

Protein adsorption and assembly at interfaces provide a potentially versatile route to create useful constructs for fluid compartmentalization. In this context, we consider the interfacial assembly of a bacterial biofilm protein, BslA, at air-water and oil-water interfaces. Densely packed, high modulus monolayers form at air-water interfaces, leading to the formation of flattened sessile water drops. BslA forms elastic sheets at oil-water interfaces, leading to the production of stable monodisperse oil-in-water microcapsules. By contrast, water-in-oil microcapsules are unstable but display arrested rather than full coalescence on contact. The disparity in stability likely originates from a low areal density of BslA hydrophobic caps on the exterior surface of water-in-oil microcapsules, relative to the inverse case. In direct analogy with small molecule surfactants, the lack of stability of individual water-in-oil microcapsules is consistent with the large value of the hydrophilic-lipophilic balance (HLB number) calculated based on the BslA crystal structure. The occurrence of arrested coalescence indicates that the surface activity of BslA is similar to that of colloidal particles that produce Pickering emulsions, with the stability of partially coalesced structures ensured by interfacial jamming. Micropipette aspiration and flow in tapered capillaries experiments reveal intriguing reversible and nonreversible modes of mechanical deformation, respectively. The mechanical robustness of the microcapsules and the ability to engineer their shape and to design highly specific binding responses through protein engineering suggest that these microcapsules may be useful for biomedical applications.

Highly stiff yet elastic microcapsules incorporating cellulose nanofibrils.

Microcapsules with high mechanical stability and elasticity are desirable in a variety of contexts. We report a single-step method to fabricate such microcapsules by microfluidic interfacial complexation between high stiffness cellulose nanofibrils (CNF) and an oil-soluble cationic random copolymer. Single-capsule compression measurements reveal an elastic modulus of 53 MPa for the CNF-based capsule shell with complete recovery of deformation from strains as large as 19%. We demonstrate the ability to manipulate the shell modulus by the use of polyacrylic acid (PAA) as a binder material, and observe a direct relationship between the shell modulus and the PAA concentration, with moduli as large as 0.5 GPa attained. These results demonstrate that CNF incorporation provides a facile route for producing strong yet flexible microcapsule shells.

Physical Continuity and Vertical Alignment of Block Copolymer Domains by Kinetically Controlled Electrospray Deposition.

The fabrication of block copolymer (BCP) thin films is reported with vertically aligned cylindrical domains using continuous electrospray deposition onto bare wafer surfaces. The out-of-plane orientation of hexagonally packed styrene cylinders is achieved in the "fast-wet" deposition regime in which rapid evaporation of the solvent in deposited droplets of polymer solution drives the vertical alignment of the self-assembled structure. Thermally activated crosslinking of the polybutadiene matrix provides kinetic control of the morphology, freezing the vertical alignment and preventing relaxation of the system to its preferred parallel orientation on the nontreated substrate. Physically continuous vertically oriented domains can be achieved over several micrometers of film thickness. The ability of electrospray deposition to fabricate well-ordered and aligned BCP films on nontreated substrates, the low amount of material used relative to spin-coating, and the continuous nature of the deposition may open up new opportunities for BCP thin films.

Order-disorder transition and alignment dynamics of a block copolymer under high magnetic fields by in situ x-ray scattering.

We examine the influence of magnetic fields on the order-disorder transition (ODT) in a liquid crystalline block copolymer. This is motivated by a desire to understand the dynamics of microstructure alignment during field annealing as potentially dictated by selective destabilization of nonaligned material. Temperature resolved scattering across the ODT and time-resolved measurements during isothermal field annealing at sub-ODT temperatures were performed in situ. Strongly textured mesophases resulted in each case but no measurable field-induced shift in T(ODT) was observed. This suggests that selective melting does not play a discernable role in the system's field response. Our data indicate instead that alignment occurs by slow grain rotation within the mesophase. We identify an optimum subcooling that maximizes alignment during isothermal field annealing. This is corroborated by a simple model incorporating the competing effects of an exponentially decreasing mobility and divergent, increasing magnetic anisotropy on cooling below T(ODT). The absence of measurable field effects on T(ODT) is consistent with estimates based on the relative magnitudes of the field interaction energy and the enthalpy associated with the ODT.

Laser-based three-dimensional manufacturing technologies for rechargeable batteries.

Laser three-dimensional (3D) manufacturing technologies have gained substantial attention to fabricate 3D structured electrochemical rechargeable batteries. Laser 3D manufacturing techniques offer excellent 3D microstructure controllability, good design flexibility, process simplicity, and high energy and cost efficiencies, which are beneficial for rechargeable battery cell manufacturing. In this review, notable progress in development of the rechargeable battery cells via laser 3D manufacturing techniques is introduced and discussed. The basic concepts and remarkable achievements of four representative laser 3D manufacturing techniques such as selective laser sintering (or melting) techniques, direct laser writing for graphene-based electrodes, laser-induced forward transfer technique and laser ablation subtractive manufacturing are highlighted. Finally, major challenges and prospects of the laser 3D manufacturing technologies for battery cell manufacturing will be provided.

Chemically Cross-Linked Graphene Oxide as a Selective Layer on Electrospun Polyvinyl Alcohol Nanofiber Membrane for Nanofiltration Application.

Graphene oxide (GO) nanosheets were utilized as a selective layer on a highly porous polyvinyl alcohol (PVA) nanofiber support via a pressure-assisted self-assembly technique to synthesize composite nanofiltration membranes. The GO layer was rendered stable by cross-linking the nanosheets (GO-to-GO) and by linking them onto the support surface (GO-to-PVA) using glutaraldehyde (GA). The amounts of GO and GA deposited on the PVA substrate were varied to determine the optimum nanofiltration membrane both in terms of water flux and salt rejection performances. The successful GA cross-linking of GO interlayers and GO-PVA via acetalization was confirmed by FTIR and XPS analyses, which corroborated with other characterization results from contact angle and zeta potential measurements. Morphologies of the most effective membrane (CGOPVA-50) featured a defect-free GA cross-linked GO layer with a thickness of ~67 nm. The best solute rejections of the CGOPVA-50 membrane were 91.01% for Na2SO4 (20 mM), 98.12% for Eosin Y (10 mg/L), 76.92% for Methylene blue (10 mg/L), and 49.62% for NaCl (20 mM). These findings may provide one of the promising approaches in synthesizing mechanically stable GO-based thin-film composite membranes that are effective for solute separation via nanofiltration.

Sustainable manufacturing of sensors onto soft systems using self-coagulating conductive Pickering emulsions.

Compliant sensors based on composite materials are necessary components for geometrically complex systems such as wearable devices or soft robots. Composite materials consisting of polymer matrices and conductive fillers have facilitated the manufacture of compliant sensors due to their potential to be scaled in printing processes. Printing composite materials generally entails the use of solvents, such as toluene or cyclohexane, to dissolve the polymer resin and thin down the material to a printable viscosity. However, such solvents cause swelling and decomposition of most polymer substrates, limiting the utility of the composite materials. Moreover, many such conventional solvents are toxic or otherwise present health hazards. Here, sustainable manufacturing of sensors is reported, which uses an ethanol-based Pickering emulsion that spontaneously coagulates and forms a conductive composite. The Pickering emulsion consists of emulsified polymer precursors stabilized by conductive nanoparticles in an ethanol carrier. Upon evaporation of the ethanol, the precursors are released, which then coalesce amid nanoparticle networks and spontaneously polymerize in contact with the atmospheric moisture. We printed the self-coagulating conductive Pickering emulsion onto a variety of soft polymeric systems, including all-soft actuators and conventional textiles, to sensitize these systems. The resulting compliant sensors exhibit high strain sensitivity with negligible hysteresis, making them suitable for wearable and robotic applications.

Miscible Polyether/Poly(ether-acetal) Electrolyte Blends.

This study shows that it is possible to obtain homogeneous mixtures of two chemically distinct polymers with a lithium salt for electrolytic applications. This approach is motivated by the success of using mixtures of organic solvents in modern lithium-ion batteries. The properties of mixtures of a polyether, poly(ethylene oxide) (PEO), a poly(ether-acetal), poly(1,3,6-trioxocane) (P(2EO-MO)), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were studied by small-angle neutron scattering (SANS) and electrochemical characterization in symmetric cells. The SANS data are used to determine the miscibility window and quantify the effect of added salt on the thermodynamic interactions between the polymers. In the absence of salt, PEO/P(2EO-MO) blends are homogeneous and characterized by attractive interactions, i.e., a negative Flory-Huggins interaction parameter, χ. The addition of small amounts of salt results in a positive effective Flory-Huggins interaction parameter, χ eff, and macrophase separation. Surprisingly, miscible blends and negative χ eff parameters are obtained when the salt concentration is increased beyond a critical value. The electrochemical properties of PEO/P(2EO-MO)/LiTFSI blends at a given salt concentration were close to those obtained in PEO/LiTFSI electrolytes at the same salt concentration. This suggests that in the presence of PEO the electrochemical properties exhibited by P(2EO-MO) chains are similar to those of PEO chains. This work opens the door to a new direction for creating new and improved polymer electrolytes either by combining existing polymers and salt or by synthesizing new polymers with the specific aim of including them in miscible polymer blend electrolytes.

Pathway-engineering for highly-aligned block copolymer arrays.

While the ultimate driving force in self-assembly is energy minimization and the corresponding evolution towards equilibrium, kinetic effects can also play a very strong role. These kinetic effects, such as trapping in metastable states, slow coarsening kinetics, and pathway-dependent assembly, are often viewed as complications to be overcome. Here, we instead exploit these effects to engineer a desired final nano-structure in a block copolymer thin film, by selecting a particular ordering pathway through the self-assembly energy landscape. In particular, we combine photothermal shearing with high-temperature annealing to yield hexagonal arrays of block copolymer cylinders that are aligned in a single prescribed direction over macroscopic sample dimensions. Photothermal shearing is first used to generate a highly-aligned horizontal cylinder state, with subsequent thermal processing used to reorient the morphology to the vertical cylinder state in a templated manner. Finally, we demonstrate the successful transfer of engineered morphologies into inorganic replicas.

Strong Orientational Coupling of Block Copolymer Microdomains to Smectic Layering Revealed by Magnetic Field Alignment.

We elucidate the roles of the isotropic-nematic (I-N) and nematic-smectic A (N-SmA) transitions in the magnetic field directed self-assembly of a liquid crystalline block copolymer (BCP), using in situ X-ray scattering. Cooling into the nematic from the disordered melt yields poorly ordered and weakly aligned BCP microdomains. Continued cooling into the SmA, however, results in an abrupt increase in BCP orientational order with microdomain alignment tightly coupled to the translational order parameter of the smectic layers. These results underscore the significance of the N-SmA transition in generating highly aligned states under magnetic fields in these hierarchically ordered materials.

Isomeric Effect Enabled Thermally Driven Self-Assembly of Hydroxystyrene-Based Block Copolymers.

We demonstrate through isomeric effect the modulation of thermal properties of poly(hydroxystyrene) (PHS)-based block copolymers (BCPs). A minimal structural change of substituting 3HS for 4HS in the BCP results in a drastic decrease in Tg, which in turn enables the thin film assembly of the BCP via thermal annealing. We synthesized a series of poly(3-hydroxystyrene-b-tert-butylstyrene) [P(3HS-b-tBuSt)] and poly(4-hydroxystyrene-b-tert-butylstyrene) [P(4HS-b-tBuSt)] BCPs by sequential anionic polymerization of protected 3HS/4HS monomer and tBuSt followed by deprotection. Measured Tg of P(3HS) was ∼20-30 °C lower than P(4HS) of comparable molecular weights. As a result, thermally driven self-assembly of P(3HS-b-tBuSt) BCPs in both bulk and thin film is demonstrated. For P(4HS-b-tBuSt) thermal annealing in thin-film at high temperatures results in poorly developed morphology due to cross-linking reaction of the 4HS block. The smallest periodicity observed for P(3HS-b-tBuSt) was 8.8 nm in lamellar and 11.5 nm in cylindrical morphologies. The functionality of the 3HS block was exploited to incorporate vapor phase metal oxide precursors to generate sub-10 nm alumina nanowires.

Elements Provide a Clue: Nanoscale Characterization of Thin-Film Composite Polyamide Membranes.

In this study, we exploit the nitrogen-sulfur elemental contrast of thin-film composite (TFC) polyamide membranes and present, for the first time, the application of two elemental analysis techniques, scanning transmission electron microscopy-energy-dispersive X-ray spectroscopy (STEM-EDX) and X-ray photoelectron spectroscopy (XPS) C60+ ion-beam sputtering, to elucidate the nanoscale structure and chemical composition of the polyamide-polysulfone interface. Although STEM-EDX elemental mapping depicts the presence of a dense polyamide layer at the interface, it is incapable of resolving the elemental contrast at nanoscale resolution at the interfacial zone. Depth-resolved XPS C60+ ion-beam sputtering enabled nanoscale characterization of the polyamide-polysulfone interface and revealed the presence of a heterogeneous layer that contains both polyamide and polysulfone signatures. Our results have important implications for future studies to elucidate the structure-property-performance relationship of TFC membranes.

Thermally switchable aligned nanopores by magnetic-field directed self-assembly of block copolymers.

A scalable approach for developing large area polymer films, with stimuli responsive vertically aligned nanopores is reported. Magnetic fields are used to create highly aligned hexagonally packed block copolymer cylindrical microdomains with order parameters exceeding 0.95. Selective etch removal of material yields nanoporous films which demonstrate reversible pore closure on heating.

Molecular Design of Liquid Crystalline Brush-Like Block Copolymers for Magnetic Field Directed Self-Assembly: A Platform for Functional Materials.

We report on the development of a liquid crystalline block copolymer with brush-type architecture as a platform for creating functional materials by magnetic-field-directed self-assembly. Ring-opening metathesis of n-alkyloxy cyanobiphenyl and polylactide (PLA) functionalized norbornene monomers provides efficient polymerization yielding low polydispersity block copolymers. The mesogenic species, spacer length, monomer functionality, brush-chain length, and overall molecular weight were chosen and optimized to produce hexagonally packed cylindrical PLA domains which self-assemble and align parallel to an applied magnetic field. The PLA domains can be selectively removed by hydrolytic degradation resulting in the production of nanoporous films. The polymers described here provide a versatile platform for scalable fabrication of aligned nanoporous materials and other functional materials based on such templates.

Scalable fabrication of polymer membranes with vertically aligned 1 nm pores by magnetic field directed self-assembly.

There is long-standing interest in developing membranes possessing uniform pores with dimensions in the range of 1 nm and physical continuity in the macroscopic transport direction to meet the needs of challenging small molecule and ionic separations. Here we report facile, scalabe fabrication of polymer membranes with vertically (i.e., along the through-plane direction) aligned 1 nm pores by magnetic-field alignment and subsequent cross-linking of a liquid crystalline mesophase. We utilize a wedge-shaped amphiphilic species as the building block of a thermotropic columnar mesophase with 1 nm ionic nanochannels, and leverage the magnetic anisotropy of the amphiphile to control the alignment of these pores with a magnetic field. In situ X-ray scattering and subsequent optical microscopy reveal the formation of highly ordered nanostructured mesophases and cross-linked polymer films with orientational order parameters of ca. 0.95. High-resolution transmission electron microscopy (TEM) imaging provides direct visualization of long-range persistence of vertically aligned, hexagonally packed nanopores in unprecedented detail, demonstrating high-fidelity retention of structure and alignment after photo-cross-linking. Ionic conductivity measurements on the aligned membranes show a remarkable 85-fold enhancement of conductivity over nonaligned samples. These results provide a path to achieving the large area control of morphology and related enhancement of properties required for high-performance membranes and other applications.