pH-Dependent Solution Micellar Structure of Amphoteric Polypeptoid Block Copolymers with Positionally Controlled Ionizable Sites
Not Available
59 BASIC BIOLOGICAL SCIENCES↗
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Late Stage Domain Coarsening Dynamics of Lamellar Block Copolymers
Block copolymer (BCP) phase separation dynamics can be expected to differ significantly from that of the polymer blends due to the constraint of chain connectivity. BCP phase separation dynamics has been studied theoretically, but there has been little experimental evidence to confirm the BCP domain growth scaling laws put forward theoretically. Here, we investigate the dynamics of late-stage lamellar BCP domain coarsening and find that the scaling exponent for lamellar domain growth is ≈1/6 (0.17), irrespective of the annealing temperature, a value close to the scaling exponent of 0.2 predicted by theoretical studies. Furthermore, we show that the prefactors in the domain coarsening equation show Arrhenius dependence on temperature, indicating that the BCP domain growth dynamics is Arrhenius over the temperature range investigated.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Intrinsic Ion Transport Properties of Block Copolymer Electrolytes
Knowledge of intrinsic properties is of central importance for materials design and assessing suitability for specific applications. Self-assembling block copolymer electrolytes (BCEs) are of great interest for applications in solid-state energy storage devices. A fundamental understanding of ion transport properties, however, is hindered by the difficulty in deconvoluting extrinsic factors, such as defects, from intrinsic factors, such as the presence of interfaces between the domains. Here, we quantify the intrinsic ion transport properties of a model BCE system consisting of poly(styrene-block-ethylene oxide) (SEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt using a generalizable strategy of depositing thin films on interdigitated electrodes and self-assembling fully connected parallel lamellar structures throughout the films. Comparison between conductivity in homopolymer poly(ethylene oxide) (PEO)-LiTFSI electrolytes and the analogous conducting material in SEO over a range of salt concentrations (r, molar ratio of lithium ion to ethylene oxide repeat units) and temperatures reveals that between 20% and 50% of the PEO in SEO is inactive. Using mean-field theory calculations of the domain structure and monomer concentration profiles at domain interfaces-both of which vary substantially with salt concentration-the fraction of inactive PEO in the SEO, as derived from conductivity measurements, can be quantitatively reconciled with the fraction of PEO that is mixed with greater than a few volume percent of polystyrene. Despite the detrimental interfacial effects for ion transport in BCEs, the intrinsic conductivity of the SEO studied here (ca. 10 -3 S/cm at 90 degrees C, r = 0.085) is an order of magnitude higher than reported values from bulk samples of similar molecular weight SEO (ca. 10 -4 S/cm at 90 degrees C, r = 0.085). Finally, this work provides motivation and methods for pursuing improved BCE chemical design, interfacial engineering, and processing.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Low Weight, High Strength Coal-Based Building Materials for Infrastructure Products (Rev.A)
Semplastics has developed, tested, and proven the viability of a new class of composite infrastructure components that use coal as the primary component. Phase I resulted in the production of brick and block components, called X-BRIX and X-BLOX, with dimensions comparable to commercially available bricks and concrete blocks, but with superior mechanical strength, lower weight, greater hardness, improved toughness, greater abrasion resistance, and greater chemical resistance than concrete. Multiple samples of full-size (16” × 8” × 8”) X-BLOX and full-size (8” × 4” × 2.5”) X-BRIX were made to demonstrate the technology, and to support the development of mortar or joining techniques. Phase I moved the coal-based composite materials technology from a current Technology Readiness Level (TRL) of 3 to TRL 5. Semplastics’ coal-based composite materials exhibit a number of high-performance characteristics, including high strength (five times the flexure strength of the best commercial brick, and more than twice the compressive strength of construction-grade concrete block), lower density (by 37 to 41%), improved mechanical durability and abrasion resistance, and resistance to chemicals, acids, salts, and chemical wastewater. These properties offer significant improvements over conventional bricks, concrete blocks, and pavers. The coal particles are completely encapsulated and bonded using a specially formulated polymer-derived ceramic (PDC) that is cured to form an “aggregate” of coal and PDC resin. This aggregate can be further processed and lightly pressed (at 10 to 50 psi) to produce a brick. After pyrolyzing (similar to the processing used to make standard clay bricks), the finished coal-based brick is significantly harder and more abrasion-resistant than regular bricks. We have produced prototype X-BRIX and X-BLOX that contain at least 55% coal by weight (71% carbon by weight, due to the controlled carbon content of the PDC) and showed their superior mechanical properties through in-house and contracted testing.
01 COAL, LIGNITE, AND PEAT↗
Polymer membrane with vertically aligned pore channels and controlled pore surface chemistry
A nanoporous polymer membrane with vertically aligned pore channels can be synthesized through self-assembly of amphiphilic block copolymers on a supporting substrate. The pore surface chemistry can be functionalized for selective anion transport.
Fan, Hongyou↗
Lithium Phosphorus Sulfide Chloride–Polymer Composite via the Solution–Precipitation Process for Improving Stability toward Dendrite Formation of Li-Ion Solid Electrolyte
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
How the Size and Density of Charge-Transfer Excitons Depend on Heterojunction’s Architecture
We have characterized the size, intensity, density, and distribution of charge-transfer (CT) excitons as a function of the acceptor–donor architecture of prototypical organic interfaces. This characterization was done by computational analysis of 17 models of varying numbers, positions, and orientations of the donor and acceptor molecules. The models’ building blocks were phenyl-C61-butyric acid methyl ester (PCBM) fullerene acceptors and dual-band donor polymers composed of thiophene, benzothiadiazole, and benzotriazole subunits. The electronic structure of the donor–acceptor complexes was computed with the time-dependent long-range-corrected density-functional tight-binding method and analyzed with the fragment-based one-electron transition density matrix. In all models, the complexes with edge-on orientation have denser spectra of low-energy CT states lying below the absorption bands compared to the complexes with face-on orientation. This CT-state distribution in edge-on complexes provides a gate to efficiently populate cold CT excitons. Moreover, the cold CT excitons have a higher degree of charge separation in the edge-on than in the face-on complexes. The CT amount and the CT exciton size generally increase with the energy of the CT states, although the electron remains localized on a single molecule in cold CT states. Delocalization over two PCBM molecules was observed for high-energy CT states. The exciton size also depends on the orientation. Larger excitons are produced by the delocalization of the electrons perpendicularly to the interface. When the delocalization is parallel, the smaller electron–hole distances yield moderately sized CT excitons.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Heterogenous catalysis for oxygen tolerant photoredox atom transfer radical polymerization and small-molecule dehalogenation
Heterogeneous photocatalysts (PCs) have garnered attention for their sustainability and cost-effectiveness. Despite the existence of various types of these PCs, their synthesis often involves complex, multi-step procedures and laborious purification. Herein, we propose a simple method for attaching small-molecule photocatalytic species onto crosslinked 3-D polymer networks as insoluble scaffolds to create robust heterogeneous PCs. The highly swellable poly(ethylene glycol)-based ChemMatrix (CM) resin, known for its amphiphilic properties and high functional group loading, facilitated the covalent immobilization of the photoredox dye Eosin Y (EY), but also streamlined functionalization with Ir( III ) complexes. The resulting heterogeneous CM-EY demonstrated efficient photocatalytic performance in open-to-air dual photoredox catalysis of atom transfer radical polymerization (photo-ATRP) under green light. This was confirmed by the well-controlled synthesis of polymers with molecular masses ranging from 20 kDa to 300 kDa and low dispersities. Furthermore, CM-EY exhibited excellent photostability and recyclability over multiple cycles of ATRP. The heterogeneous catalysis of photo-ATRP provided high temporal control and enabled benign conditions for synthesizing protein-polymer hybrids (PPH). When combined with the initiator-modified CM (CM-BIB), CM-EY facilitated the solid-phase synthesis of homopolymers and block copolymers with recyclable performance. However, the coordinatively bound Ir@CM showed decreased catalytic activity and efficiency toward photoredox dehalogenation due to the leaching of active species during recycling. This study highlights the advantages of the covalent linking of catalysts to solid supports over non-covalent interactions, underscoring the potential of functionalized polymer resin as a promising scaffold. Such an approach offers customization and tunability, presenting opportunities for innovation in green chemistry.
Kapil, Kriti↗
Poly(norbornene) anion conductive membranes: homopolymer, block copolymer and random copolymer properties and performance
It has previously been shown that phase-separated block copolymers with non-ion conducting (hydrophobic) blocks and ion conducting (hydrophilic) blocks can form efficient ion conducting channels with high ionic mobility and conductivity. Block copolymers can provide a means for phase segregation and ion channel formation while homopolymers and random copolymers have been shown to have lower ion mobility. In this study, the properties of poly(norbornene) based anion exchange membranes (AEMs) comprising homopolymers, block copolymers, and random copolymers with high ion-exchange capacity (IEC) (3.48–4.55 meq. g -1 ) have been investigated and compared. The polymers were cross-linked with N,N,N',N'-tetramethyl-1,6-hexanediamine before casting the membranes to avoid excessive water swelling due to high water uptake. It was shown that high ionic conductivity can be achieved in both random copolymers and homopolymers even in the absence of microphase-separated structures. For example, the conductivity of a random copolymer was 194 mS cm -1 at 80 °C, which was comparable to the block copolymer, 201 mS cm -1 at 80 °C. The H 2 /O 2 fuel cell performance of random copolymer composite membranes showed a peak power density of 3.05 W cm -2 and peak current density of 7.85 A cm -2 at 80 °C compared to block copolymer membranes (peak power density of 3.21 W cm -2 and peak current density of 8.27 A cm -2 at 80 °C). It is more critical that high water transport be achieved in AEMs than achieving a phase-segregated morphology. Finally, the homopolymer, block copolymer, and random copolymer membranes showed <1.35% degradation after aging in 1 M NaOH at 80 °C for 1000 h.
08 HYDROGEN↗
Polymerizations of 2-(Trimethylsilyl)ethanesulfonyl-activated aziridines
A novel N-sulfonyl aziridine, N-((2-(trimethylsilyl)ethyl)sulfonyl)-2-methyl-aziridine (SES-MeAz) was synthesized, and its controlled anionic ring-opening polymerization to form poly(SES-MeAz) studied. The desulfonylation of poly(SES-MeAz)s can be achieved under mild conditions, with tetrabutylammonium fluoride (TBAF) to form polypropylene imine (PPI), although purification of the PPI was not completely successful. The block copolymer p(pTs-MeAz)-b-p(SES-MeAz), (pTs-MeAz = N-para-tosyl-2-methyl-aziridine) was prepared by a sequential polymerization. The desulfonylation of the block copolymer is the first example of the selective removal of a sulfonyl protecting group from a poly(sulfonylazirdine) block copolymer and this is the first formation of a polysufonylaziridine-block-polypropylene imine copolymer. Three-armed star-shaped poly(SES-MeAz)s were also successfully synthesized and exhibited improved solubility compared with linear poly(SES-MeAz)s.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Direct synthesis of ordered mesoporous materials from thermoplastic elastomers
Abstract The ability to manufacture ordered mesoporous materials using low-cost precursors and scalable processes is essential for unlocking their enormous potential to enable advancement in nanotechnology. While templating-based methods play a central role in the development of mesoporous materials, several limitations exist in conventional system design, including cost, volatile solvent consumption, and attainable pore sizes from commercial templating agents. This work pioneers a new manufacturing platform for producing ordered mesoporous materials through direct pyrolysis of crosslinked thermoplastic elastomer-based block copolymers. Specifically, olefinic majority phases are selectively crosslinked through sulfonation reactions and subsequently converted to carbon, while the minority block can be decomposed to form ordered mesopores. We demonstrate that this process can be extended to different polymer precursors for synthesizing mesoporous polymer, carbon, and silica. Furthermore, the obtained carbons possess large mesopores, sulfur-doped carbon framework, with tailorable pore textures upon varying the precursor identities.
36 MATERIALS SCIENCE↗
Confinement and Processing Can Alter the Morphology and Periodicity of Bottlebrush Block Copolymers in Thin Films
Bottlebrush block copolymers (BBCPs) are intriguing architectural variations on linear BCPs with highly tunable structure. Confinement can have a significant impact on polymer assembly, giving rise to changes in morphology, assembly kinetics, and properties like the glass transition. Given that confinement leads to significant changes in the persistence length of bottlebrush homopolymers, it is reasonable to expect that BBCPs will see significant changes in their structure and periodicity relative to the bulk morphology. Understanding how confinement influences assembly will be important for designing BBCPs for thin film applications including membranes, integrated photonic structures, and potentially BCP lithography. In this work, in order to study the effects of confinement on BBCP conformation and morphology, a blade coating was used to prepare films with continuous variation in film thickness. Unlike thin films of linear BCPs, islands/holes were not observed, and instead mixtures of parallel and perpendicular morphologies emerge after annealing. The lamellar periodicity ($L_0$) of the morphologies is found to be thickness dependent, increasing $L_0$ with decreasing film thickness for blade coated films. Films coated out of tetrahydrofuran (THF) resulted in a single well-defined lamellar periodicity, verified through atomic force microscopy (AFM) and grazing incidence small-angle X-ray scattering (GISAXS), which increases dramatically from the bulk value (30.6 nm) and continues to increase as the film thickness decreases. The largest observed $L_0$ was 65.5 nm, and this closely approaches the estimated upper limit of 67 nm corresponding to a fully extended backbone in a bilayer arrangement. Films coated out of propylene glycol methyl ether acetate (PGMEA) resulted in a mixture of perpendicular lamellae and a smaller, likely cylindrical morphology. The lamellar portion of the film shows the same thickness dependence as the lamellae observed in the THF coated films. The scaling of the lamellar $L_0$ with respect to film thickness follows predictions for confined semiflexible polymers with weak excluded volume interactions and can be related to models for confinement of DNA. Spin coated films shows the same reduction in periodicity, although at very different film thicknesses. This result suggests that the material has shallow free-energy barriers to transitioning between different $L_0$ and morphologies, a property that could be taken advantage of for patterning diverse structures with a single material.
36 MATERIALS SCIENCE↗
Self‐Assembled Membranes for High Ion Selectivity and Proton Blocking in Electrochemical Applications
Anion-exchange membranes (AEMs) with high anion/cation selectivity and exceptional proton-blocking ability are critical for applications such as bipolar membrane electrodialysis and electrochemical acid recovery. However, existing AEMs are constrained by a trade-off between ionic conductivity and selectivity, largely due to the intrinsic coupling between charge density and water content, and they suffer from excessive proton leakage facilitated by the Grotthuss hopping mechanism. In this work, poly(vinylimidazolium) membranes functionalized with long alkyl side chains that self-assemble into well-defined microphase-separated morphologies stabilized by hydrophobic and electrostatic interactions are reported. These unique structures localize the charge density along the polymer backbone to promote fast and selective ion transport. As a result, these membranes exhibit ionic conductivities and counter-ion diffusivities surpassing those of conventional homogeneous membranes, along with unprecedented counter-ion/co-ion selectivity and proton-blocking ability. These results establish a new design paradigm for high-performance, phase separated charged polymer membranes that overcome the limitations of homogeneous membranes, with broad implications for advanced electrochemical technologies.
36 MATERIALS SCIENCE↗
Experimental Investigation of Polymer-Induced Fouling of Heater Tubes in the First-Ever Polymer Flood on Alaska North Slope Part II
A polymer flood pilot has been ongoing in the Schrader Bluff viscous oil reservoir at Milne Point on the Alaska North Slope. The results from the pilot are encouraging. However, a major concern of the operator is the influence of polymer on the production system after breakthrough, especially the fouling in heat exchangers. This work applies a multiexperimental approach to study the severity of polymer-induced fouling in both dynamic and static states of produced fluids to determine safe operating conditions. Dynamic scale loop (DSL) tests were conducted to study fouling due to polymer at different skin temperatures (165–350°F) in a dynamic state of fluid flow where the fluids’ flow mimics the residence time of fluids in the heat exchanger of the field pilot. Static deposit tests were also conducted at similar skin temperatures of 165–250°F using a novel experimental apparatus designed and built in-house. It was found that at higher skin temperatures of 250–350°F, tube blocking was observed in the DSL tests, whereas the tests at 165–200°F did not show any tube blocking, even in a more extended test period. The deposit test showed that the deposit rate generally increases with skin temperature, and the presence of polymer aggravates the fouling. The copper tube performs best when the skin temperatures are 165–200°F, while the stainless steel tube performs best at a skin temperature of 250°F. These experiments also manifested the influence of the cloudpoint of the solution as the deposit rate increased significantly when the skin temperature was higher than the solution cloudpoint. The study provides a source of practical guidance to the field operations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Generating forces in confinement via polymerization
Understanding how to produce forces using biomolecular building blocks is essential for the development of adaptive synthetic cells and living materials. Here we ask whether a dynamic polymer system can generate deformation forces in soft shells by pure self-assembly, motivated by the fact that biological polymer networks like the cytoskeleton can exert forces, move objects, and deform membranes by simply growing, even in the absence of molecular motors. We address this question by investigating polymer force generation by varying the release rate, the structure, and the interactions of self-assembling monomers. First, we develop a toy computational model of polymerization in a soft elastic shell that reveals the emergence of spontaneous bundling which enhances shell deformation. We then extend our model to account more explicitly for monomer binding dynamics. We find that the rate at which monomers are released into the interior of the shell is a crucial parameter for achieving deformation through polymer growth. Lastly, we demonstrate that the introduction of multivalent particles that can join polymers can either improve or impede polymer performance, depending on the amount and on the structure of the multivalent particles. Our results provide guidance for the experimental realization of polymer systems that can perform work at the nanoscale, for example through rationally designed self-assembling proteins or nucleic acids.
Osmanović, Dino [University of California at Los A↗
Complex Functional Materials
The Complex Functional Materials (CFM) area of leadership focuses on the identification and development of materials comprised of multiple components or building blocks that are integrated or chemically bound together to achieve a desired function or response. Soft materials, such as polymers, as well as structural properties at the meso- and micro-scale that control materials function are particularly emphasized in this leadership area. Further, complex functional materials are generally developed to satisfy multiple materials design criteria all of which are essential to the overall application. CFM supports applications that are aligned with all three Los Alamos National Laboratory mission areas. These mission areas are: materials for nuclear deterrence, materials for energy security, and materials for global security
36 MATERIALS SCIENCE↗