Polymerized ionic liquid (POIL) block copolymers represent a unique class of materials for fundamental studies single ion conduction as function morphology in microphase-separated polymer electrolytes energy storage and conversion applications. We describe the synthesis series poly(styrene-b-4-vinylbenzylalkylimidazolium bis(trifluoromethanesulfonyl)imide) (PS-b-PVBn(alkyl)ImTFSI; alkyl = CH3 (Me), n-C4H9 (Bu), n-C6H13 (Hex)) diblock (2.7–17.0 mol % POIL) via exhaustive functionalization...

Controlled/"living" polymerizations and tandem polymerization methodologies offer enticing opportunities to enchain a wide variety of monomers into new, functional block copolymer materials with unusual physical properties. However, the use these synthetic methods often introduces nontrivial molecular weight polydispersities, type chain length heterogeneity, one or more blocks. While self-assembly behavior monodisperse AB diblock ABA triblock copolymers is both experimentally theoretically...

Significance Surfactants (“soaps”) spontaneously self-assemble into spherical micelles in water, which pack ordered crystalline states. Such soft particles have long been assumed to adopt the same closest-packed configurations observed with hard spheres (e.g., billiard balls). Here, we show that surfactant also form complex, tetrahedrally Frank–Kasper (FK) phases. Surprisingly, low-symmetry unit cells of these structures comprise multiple particle types discrete size distributions. We...

This study uses first-principles methods to model Li transport, resistivity and overpotential of lithium-ion battery cathode coating materials.

A symmetric, acyclic olefin possessing trithiocarbonate moieties, available in two synthetic steps from commercially starting materials, is demonstrated to act as a chain transfer agent (CTA) ring opening metathesis polymerizations (ROMP). The efficiency of the ruthenium-catalyzed ROMP 1,5-cyclooctadiene presence this new CTA investigated means producing telechelic polybutadienes bearing endgroups. Telechelic polymers thus synthesized are macromolecular agents reversible addition...

Electrolyte decomposition reactions on Li-ion battery electrodes contribute to the formation of solid electrolyte interphase (SEI) layers. These SEI layers are one known causes for loss in voltage and capacity over repeated charge/discharge cycles. In this work, density functional theory (DFT)-based ab initio calculations applied study initial steps organic component ethylene carbonate (EC) (101̅4) surface a layered Li(Nix,Mny,Co1-x-y)O2 (NMC) cathode crystal, which is commonly used...

Surface-adsorbed polar molecules can significantly alter the ferroelectric properties of oxide thin films. Thus, fundamental understanding and controlling effect surface adsorbates are crucial for implementation film devices, such as tunnel junctions. Herein, we report an imprint control BaTiO3 (BTO) films by chemically induced polarization pinning in top few atomic layers water-exposed BTO Our studies based on synchrotron X-ray scattering coherent Bragg rod analysis demonstrate that is not...

Concentration-dependent supramolecular self-assembly of amphiphilic molecules in water furnishes a variety nanostructured lyotropic liquid crystals (LLCs), which typically display high symmetry bicontinuous network and discontinuous micellar morphologies. Aqueous dispersions soft spherical micelles derived from small molecule amphiphile hydration pack into exemplary body-centered cubic closest-packed LLCs. However, investigations hydrated mixtures the ionic surfactant tetramethylammonium...

The observation of complex, Frank-Kasper (FK) particle packings in diblock polymer melts has until recently been limited to low molecular weight, conformationally asymmetric polymers. We report temperature-dependent small-angle X-ray scattering (SAXS) studies blends a sphere-forming poly(styrene-block-1,4-butadiene) (SB) (Mn = 33.3 kg/mol, Đ Mw/Mn 1.08, fB 0.18) with two different poly(1,4-butadiene) (B) homopolymer additives. When the B additive Mn is same as that core-forming segment,...

Aqueous lyotropic liquid crystal (LLC) assemblies with bicontinuous cubic morphologies (Q-phases) have shown promise in applications ranging from selective chemical separations to ion transporting media, yet universal design criteria for amphiphiles that adopt these unique structures remain elusive. Recent reports demonstrated cationic gemini surfactants exhibit a tendency form LLCs as compared single-tail amphiphiles; however, the universality of this surfactant motif stabilizing Q-phases...

Abstract Polymerized ionic liquids (PILs) are a platform for fundamental studies of structure‐property relationships in single ion conductors, with potential applications energy storage and conversion. The synthesis, thermal properties, conductivities homologous, narrow dispersity styrenic PILs described. Hydrophilic poly(4‐vinylbenzyl alkylimidazolium chloride) (PVBn(alkyl)ImCl) homopolymers constant average degrees polymerization were synthesized by post‐synthetic functionalization ( M n =...

Inverse lyotropic liquid crystal phases comprising spatially-limited aqueous nanodomains have potentially wide-ranging applications, including the encapsulation and selective delivery of small molecules as nanoreactors for molecular catalysis. We report self-assembly two homologous, zwitterionic bis(alkyltriazolium sulfobetaine) gemini surfactants into previously unknown inverse cubic micellar with Pmn symmetry (space group #223). Using temperature-dependent X-ray scattering, we demonstrate...

Metal oxide coatings can improve the electrochemical stability of cathodes and hence, their cycle-life in rechargeable batteries. However, such often impose an additional electrical ionic transport resistance to cathode surfaces leading poor charge–discharge capacity at high C-rates. Here, a mixed (Al2O3)1–x(Ga2O3)x alloy coating, prepared via atomic layer deposition (ALD), on Li[Ni0.5Mn0.3Co0.2]O2 (NMC) is developed that has increased electron conductivity demonstrated improved rate...

Phenylhydrazine is an effective modifier for conventional ATRP syntheses, providing systematic control over the dispersity of polymers with unimodal molecular weight distributions.

Small-angle X-ray scattering analyses reveal that the hydrated diblock oligomer n-C16H23(OCH2CH2)20-OH (C16E20 or Brij 58) forms lyotropic liquid crystals (LLCs) exhibiting face-centered cubic (FCC), body-centered (BCC), Frank-Kasper (FK) A15, and cylindrical (HI) morphologies over concentration range 30-65 wt % amphiphile. Heating LLCs comprising 54-59 C16E20 drives temperature-dependent phase transition sequence: A15 → BCC HI. However, rapidly quenching resulting HI from 70 to 25 °C...

Discoveries of Frank–Kasper phases and closely related dodecagonal quasicrystals (DDQCs) in soft, mesoscopic systems have galvanized efforts to unveil the fundamental mechanisms that drive formation these remarkably complex micellar packings. Toward this end, we report temperature-dependent small-angle X-ray scattering analyses a crystalline–amorphous poly(ethylene oxide)-block-poly(2-ethyl hexylacrylate) (OA) diblock copolymer with Mn = 8300 g/mol, Đ Mw/Mn 1.10, volume composition fO 0.21....

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTTitanium-Mediated Syndiospecific Styrene Polymerizations: Role of Oxidation StateMahesh K. Mahanthappa and Robert M. WaymouthView Author Information Department Chemistry, Stanford University Stanford, California 94305-5080 Cite this: J. Am. Chem. Soc. 2001, 123, 48, 12093–12094Publication Date (Web):November 9, 2001Publication History Received29 June 2001Published online9 November inissue 1 December...

Comb block copolymers are a relatively new architecture of polymer whose assembly into ordered morphologies in the solid state is largely unexplored. Thirty-two comb with molecular weights from 168 to 4200 kg mol−1 were synthesized and assembled domain sizes as large 138 nm. The individual structures these polymers studied by atomic force microscopy scanning electron identify their shapes. solid-state imaged small-angle X-ray scattering when permissible. Four phase maps plotted 32 data...

ADVERTISEMENT RETURN TO ISSUEPREVCommunication to the...Communication the EditorNEXTPolydispersity-Induced Stabilization of a Disordered Bicontinuous Morphology in ABA Triblock CopolymersJoan M. Widin, Adam K. Schmitt, Kyuhyun Im, Andrew L. and Mahesh Mahanthappa*View Author Information Department Chemistry, University Wisconsin−Madison, 1101 Avenue, Madison, Wisconsin 53706*Corresponding author. E-mail: [email protected]Cite this: Macromolecules 2010, 43, 19, 7913–7915Publication Date...

We describe the morphological implications of broad molecular weight dispersity on bulk and thin film self-assembly behavior seven model poly(styrene-block-methyl methacrylate) (SM) diblock copolymers. Derived from sequential nitroxide-mediated polymerizations, these unimodal copolymers are comprised narrow S blocks (Đ ≤ 1.14) M ∼ 1.7) with total weights Mn,total = 29.2–42.9 kg/mol volume fractions fM 0.35–0.63. Small-angle X-ray scattering (SAXS) transmission electron microscopy (TEM)...

We report the synthesis and characterization of a series 13 strongly segregated poly(lactide-b-1,4-butadiene-b-lactide) (LBL) triblock copolymers, in which broad dispersity center B segment (Đ = Mw/Mn ∼ 1.7–1.9) is embedded between two narrow L end blocks ≤ 1.20). Derived from chain transfer ring-opening metathesis polymerization (ROMP-CT) 1,5,9-cyclododecatriene presence 1,4-diacetoxy-2-butene, α,ω-dihydroxytelechelic poly(1,4-butadienes) serve as transesterification (ROTEP) macroinitiators...

The water-driven self-assembly of homologous dianionic surfactants into lyotropic liquid crystals (LLCs) is investigated, with a focus on understanding how surfactant headgroup and counterion identities guide supramolecular spherical mesophase selection. Using temperature-dependent small-angle X-ray scattering (SAXS), we demonstrate that 2-alkylmalonate (CnMal-M2) n = 8 (octyl) or 10 (decyl) M K+, Cs+, (CH3)4N+ form both simple complex micelle packings. Observed morphologies include...

The successful development of tablet formulations many active pharmaceutical ingredients (APIs) is challenged by their poor manufacturability (e.g., flowability, tabletability) and dissolution characteristics. Here, we report a novel quasi-emulsion solvent diffusion cocrystallization (QESD-CC) method as an integrated crystal particle engineering approach for generation spherical cocrystal agglomerates the poorly soluble drug indomethacin (IMC) sweet agent saccharin (SAC). QESD-CC process...

Microstructure of and mechanical properties a series symmetric EPE (E = poly(ethylene-co-1-butene) P poly(ethylene-alt-propylene)) triblock copolymers with Mn 27−372 kg/mol have been investigated in the solid state. Microphase separation originates from either (i) chemical incompatibility-induced microphase melt before crystallization at high overall molecular weights or (ii) crystallization-induced homogeneous low weights. Small-angle X-ray scattering demonstrates that these EPEs (fE ≈ fP...

The self-assembly behavior of gemini (dimeric or twin-tail) dicarboxylate disodium surfactants is studied using molecular dynamics simulations. A united atom model employed for the with fully atomistic counterions and water. This architecture, in which two single tailed are joined through a flexible hydrophobic linker, has been shown to exhibit concentration-dependent aqueous into lyotropic phases including hexagonal, gyroid, lamellar morphologies. Our simulations reproduce experimentally...