Block copolymers self-assemble on nanometer length scales, making them ideal for emerging nanotechnologies. Many applications (e.g., templating, membranes) require the use of block in thin film geometries (∼100 nm thickness), where self-assembly is strongly influenced by surface energetics. In this review, we discuss roles and interfacial effects self-assembly, with a specific focus confinement, substrate modification, thermal solvent annealing conditions. Finally, comment novel techniques...

ABSTRACT Ion‐conducting block copolymers (BCPs) have attracted significant interest as conducting materials in solid‐state lithium batteries. BCP self‐assembly offers promise for designing ordered with nanoscale domains. Such nanostructures provide a facile method introducing sufficient mechanical stability into polymer electrolyte membranes, while maintaining the ionic conductivity at levels similar to corresponding solvent‐free homopolymer electrolytes. This ability simultaneously control...

Block copolymers have garnered significant attention in the past few decades due to their ability self-assemble into nanoscale structures (∼10–100 nm), making them ideal for emerging nanotechnologies, such as nanolithography, nanotemplating, nanoporous membranes, and ultrahigh-density storage media. Many of these applications require thin film geometries, which block form well-ordered nanostructures and/or precisely controlled domain orientations. In this Perspective, we discuss recent...

In this report, we merge block copolymers with vitrimers in an effort to realize the prospect of higher-order, nanoscale control over associative cross-link exchange and flow. We show use controlled polymerization as a vital tool understand fundamental structure–property effects through precise polymer architecture molecular weight. Vitrimers derived from self-assembling exhibit superior resistance macroscopic deformation comparison their analogs generated statistical copolymers. Our results...

We present characterization data for linear poly(isoprene-b-styrene-b-ethylene oxide) (PI−PS−PEO) triblock copolymers containing equal volume fractions of PI and PS (fPI = fPS) varying amounts PEO, 0 ≤ fPEO 1/3. Detailed by TEM, SAXS, dynamic mechanical spectroscopy, static birefringence, DSC indicates three distinct morphologies: two-domain lamellae, a three-domain noncubic triply periodic network structure, lamellae with increasing PEO content. This phase behavior is in striking contrast...

The equilibrium phase behavior of 43 linear poly(isoprene-b-styrene-b-ethylene oxide) (ISO) triblock copolymer melts, with molecular weights that place these materials near the order−disorder transition, is reported. Ordered morphologies were characterized using small-angle X-ray scattering, transmission electron microscopy, dynamic mechanical spectroscopy, and static birefringence measurements. Interpretation results was aided by a modeling technique facilitates resolution reciprocal...

The phase behavior of lithium salt-doped poly(styrene-b-ethylene oxide) (PS−PEO) was studied as a function salt concentration, (Li) counterion (X), and annealing temperature. Three LiX salts were employed in this work: LiClO4, LiCF3SO3, LiAsF6. Increasing the doping ratio ([EO]:[Li]) from 48:1 to 3:1 led morphological changes hexagonally packed cylinders lamellar morphologies; however, comparison between small-angle X-ray scattering (SAXS) transmission electron microscopy (TEM) results shows...

Thickness is a governing factor in the behavior of films and coatings. To enable high-throughput analysis this parameter polymer systems, we detail design operation “flow coater” device for fabricating continuous libraries film thickness over tailored ranges. Focusing on production model polystyrene libraries, thoroughly outline performance flow coating by varying critical factors including geometry, motion, solution parameters.

In this perspective, we survey recent advances in the synthesis and characterization of block copolymers, discuss several key materials opportunities enabled by highlight some challenges that currently limit further realization copolymers promising nanoscale applications. One significant challenge, especially as complexity functionality designer macromolecules increases, is requirement multiple complementary techniques to fully characterize resultant polymers materials. Thus, select...

We explored the relationship between ionic conductivities and morphology in a lithium perchlorate-doped poly(styrene-b-ethylene oxide) (PS–PEO) system using ac impedance spectroscopy, situ small-angle X-ray scattering, transmission electron microscopy. To aid morphological analysis, flow alignment technique was used to orient nanoscale domains order facilitate characterization of nanostructures such as hexagonally perforated lamellae (HPL), packed cylinders (HEX), (LAM). Over PEO volume...

Softwood (guaiacylic) lignin-based methacrylate polymers (LBMPs) that exhibit excellent glass transition temperatures (Tg's), desirable thermal stabilities (greater than 100 °C above Tg), and intermediate shear-flow resistances, in comparison to polystyrene poly(methyl methacrylate), are reported herein. Different R-groups (p-position hydrogen, methyl, ethyl, formyl groups) otherwise homologous LBMPs impart distinct characteristics the flow behavior properties of these bio-based polymers,...

We report a new and robust strategy toward the development of high-performance pressure sensitive adhesives (PSAs) from chemicals directly obtained raw biomass deconstruction. A particularly unique translatable aspect this work was use monomer real biomass, as opposed to model compound or lignin-mimic, generate well-defined nanostructure-forming polymers. Herein, poplar wood depolymerization followed by minimal purification steps (filtration extraction) produced two aromatic compounds,...

We report a versatile scheme for the synthesis of renewable homopolymers and block copolymers (BCPs) via functionalization subsequent controlled reversible addition–fragmentation chain transfer (RAFT) polymerization vanillin, possible lignin derivative. The vanillin-based exhibit glass transition temperatures (120 °C) degradation (≥300 comparable to polystyrene, indicating that these similar polymers may serve as suitable alternatives petroleum-based materials. Additionally, by employing...

Sustainable polymers from lignocellulosic biomass have the potential to reduce environmental impact of commercial plastics while also offering significant performance and cost benefits relative petrochemical-derived macromolecules. However, most currently available biobased are hampered by insufficient thermomechanical properties, low economic feasibility (e.g., high cost), reduced scalability in comparison petroleum-based incumbents. Future materials must overcome these limitations be...

Nanoscale self-assembly of block copolymer thin films has garnered significant research interest for nanotemplate design and membrane applications. To fulfill these roles, control film morphology orientation is critical. Solvent vapor annealing (SVA) treatments can be used to kinetically trap morphologies in not achievable by traditional thermal treatments, but many variables affect the outcome SVA, including solvent choice, total concentration/swollen thickness, removal rate. In this work,...

Membranes are a critical component of redox flow batteries (RFBs), and their major purpose is to keep the redox-active species in two half cells separate allow passage charge-balancing ions. Despite significant performance enhancements RFB membranes, further developments still needed that holistically consider conductivity, selectivity, stability, sustainability, cost. In this Focus Review, structure–property relationships have led advances membranes for various types (vanadium, zinc, iron,...

We report the use of solvent vapor swelling ultrathin polymer films to determine Flory–Huggins solvent–polymer and polymer–polymer interaction parameters (χi–j) for poly(3-hexylthiophene) (P3HT) polystyrene (PS) over a wide composition range. From calculated parameters, we constructed polymer/polymer/solvent phase diagram that was validated experimentally. χtetrahydrofuran–P3HT (1.04 ± 0.04) χCHCl3–P3HT (0.99 0.01) were determined through P3HT films. Similar experiments using PS gave...

N-Heterocyclic carbene (NHC)-mediated ring-opening polymerization of N-decyl-N-carboxylanhydride monomer (De-NCA) has been shown to occur in a controlled manner, yielding cyclic poly(N-decylglycine)s (c-PNDGs) with polymer molecular weights (MW) between 4.8 and 31 kg mol–1 narrow weight distributions (PDI < 1.15). The reaction exhibits pseudo-first-order kinetics respect concentration. MW increases linearly conversion, consistent living polymerization. ESI MS SEC analyses confirm the...