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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

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↗
DOE OSTI2021

Controllable growth of interpenetrating or random copolymer networks

Interpenetrating and random copolymer networks are vital in a number of industrial applications, including the fabrication of automotive parts, damping materials, and tissue engineering scaffolds. We develop a theoretical model for a process that enables the controlled growth of interpenetrating network (IPNs), or a random copolymer network (RCN) of specified size and mechanical properties. In this process, a primary gel “seed” is immersed into a solution containing the secondary monomer and crosslinkers. After the latter species are absorbed into the primary network, the absorbed monomers are polymerized to form the secondary polymer chains, which then can undergo further crosslinking to form an IPN, or undergo inter-chain exchange with the existing network to form a RCN. The swelling and elastic properties of the IPN and RCN networks can be tailored by modifying the monomer and crosslinker concentrations in the surrounding solution, or by tuning the enthalpic interactions between the primary polymer, secondary monomer and solvent through a proper choice of chemistry. This process can be used repeatedly to fabricate gels with a range of mechanical properties from stiff, rigid materials to soft, flexible networks, allowing the method to meet the materials requirements of a variety of applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Disulfonated Poly(arylene ether sulfone) Random Copolymers Containing Hierarchical Iptycene Units for Proton Exchange Membranes

Two series of disulfonated iptycene-based poly(arylene ether sulfone) random copolymers, i.e., TRP-BP (triptycene-based) and PENT-BP (pentiptycene-based), were synthesized via condensation polymerization from disulfonated monomer and comonomers to prepare proton exchange membranes (PEMs) for potential applications in electrochemical devices such as fuel cell. To investigate the effect of iptycene units on membrane performance, these copolymers were systematically varied in composition (i.e., iptycene content) and the degree of sulfonation (i.e., 30–50%), which were characterized comprehensively in terms of water uptake, swelling ratio, oxidative stability, thermal and mechanical properties, and proton conductivity at various temperatures. Comparing to copolymers without iptycene units, TRP-BP and PENT-BP ionomers showed greatly enhanced thermal and oxidative stabilities due to strong intra- and inter-molecular supramolecular interactions induced by hierarchical iptycene units. In addition, the introduction of iptycene units in general provides PEMs with exceptional dimensional stability of low volume swelling ratio at high water uptakes, which is ascribed to the supramolecularly interlocked structure as well as high fractional free volume of iptycene-based polymers. It is demonstrated that the combination of high proton conductivity and good membrane dimension stability is the result of the synergistic effects of multiple factors including free volume (iptycene content), sulfonation degree, hydrophobicity, and swelling behavior (supramolecular interactions).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Synthesis and Characterization of Methacrylamide-Based Block Random Copolymers via Amine Functionalization of Polystyrene- Block -Poly(Pentafluorophenyl Methacrylate) Toward Enhanced Amenability to Manufacturing Criteria in Nanolithography

Recent interest in manipulating the chemistry of block copolymers (BCPs) to manage the covarying properties necessary to meet manufacturing criteria in nanolithography has resulted in the development and expansion of the A-block-(B-random-C) BCP architecture, where the random block allows for the decoupling of thermodynamic and wetting properties. Previous reports of such BCPs have used click chemistry to create the desired random block, but all such instances possess additional functional groups that are susceptible to undesirable side reactions upon annealing, such as cross-linking and surface grafting. This study reports the substitution reaction of polystyrene-block-poly(pentafluorophenyl methacrylate) (PS-b-PPFMA) with primary amines. The resulting methacrylamide structure of the functionalized random block has only an amide linkage between the attached functional group and the polymer backbone, thereby omitting any sources of side reactions within the BCP. The outcomes of this report also demonstrate the enhanced thermal stability of these materials by virtue of their stable amide bonds. A range of random copolymer compositions is assessed to develop BCPs in which the random block has approximately the same surface energy as the PS block. These BCPs can self-assemble into perpendicular lamellae and are therefore promising candidates for directed self-assembly.

block copolymers↗
DOE OSTI2023

Quaternized Polynorbornene Random Copolymers for Fuel Cell Devices

Quaternized polymers are critical components for various energy devices. Vinyl-addition polynorbornenes provide high mechanical strength, high ion conductivity, and chemical stability in a wide range of pH environments due to the all-C–C bond backbone. In this paper, we present the synthesis of a series of quaternized polynorbornene random copolymers via vinyl addition polymerization and elucidate the impact of polymer composition on their properties. The quaternary ammonium alkyl tether length and the ratio of n-hexylnorbornene to unsubstituted norbornene are systemically tailored. A copolymer of 5-(3-bromopropyl)-2-norbornene and norbornene with pendant trimethylammonium groups achieved hydroxide conductivity of 109 mS/cm at 80 °C with a modest water uptake of 72%. The addition of n-hexylnorbornene to the copolymer, to make a terpolymer, allows for the polymer composition to be tailored for properties, including a decrease in water uptake and higher processability, despite a slightly decreased hydroxide conductivity. Moreover, the developed membranes are chemically robust and highly mechanically stable, enabling thin membranes to be easily fabricated. This study provides insight into important design parameters for quaternized polynorbornenes for a variety of energy storage and conversion devices, especially fuel cells.

25 ENERGY STORAGE↗
DOE OSTI2021

Morphological Studies of Solution-Crystallized Thermoplastic Elastomers with Polyethylene Endblocks and a Random-Copolymer Midblock

Styrenic thermoplastic elastomers (TPEs) in the form of triblock copolymers possessing glassy endblocks and a rubbery midblock account for the largest global market of TPEs worldwide, and typically rely on microphase separation of the endblocks and the subsequent formation of rigid microdomains to ensure satisfactory network stabilization. In this work, the morphological characteristics of a relatively new family of crystallizable TPEs that instead consist of polyethylene endblocks and a random-copolymer midblock composed of styrene and (ethylene-co-butylene) moieties are investigated. Copolymer solutions prepared at logarithmic concentrations in a slightly endblock-selective solvent are subjected to crystallization under different time and temperature conditions to ascertain if copolymer self-assembly is directed by endblock crystallization or vice versa. According to transmission electron microscopy, semicrystalline aggregates develop at the lowest solution concentration examined (0.01 wt%), and the size and population of crystals, which dominate the copolymer morphologies, are observed to increase with increasing aging time. Real-space results are correlated with small- and wide-angle X-ray scattering to elucidate the concurrent roles of endblock crystallization and self-assembly of these unique TPEs in solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Random copolymer of poly(polyethylene glycol methyl ether)methacrylate as tunable transition temperature solid-solid phase change material for thermal energy storage

Polymer based phase change materials (PCM) for thermal energy storage (TES) applications have gained some attention recently due to their high stability and potential solid to solid phase transition. In this work, we are the first to utilize a simple copolymerization strategy for static tunability transition temperature (T t ) of polymeric PCM. The copolymerization between short and long side chain polyethylene glycol based methacrylate polymers was designed to tune T t with minimum impact on their energy density. Polarized optical microscope and x-ray techniques were also used to understand the relationship between crystal structure and T t of different copolymer composition which was discussed in the context. The solid to solid transition polymeric PCM were successfully developed with tunable T t ranged from 18 °C to 35 °C which is suitable toward building envelop applications.

14 SOLAR ENERGY↗
DOE OSTI2023

Quaternary Ammonium-Functionalized Poly(Arylene Ether Sulfone) Random Copolymers for Direct Air Capture

Direct air capture (DAC) is a promising tool for reducing CO 2 concentrations in the atmosphere and fighting climate change. We synthesized a series of quaternary ammonium (QA) functionalized poly(arylene ether sulfone) copolymers with varying mole fractions of charge content and demonstrated their potential as sorbents for DAC. Molecular weight analysis determined high monomer conversion was achieved in <6 h and relatively high molecular weights for all copolymer compositions. Thermal analysis revealed all polymers had degradation temperatures >240 °C and a single glass transition temperature (T g ); the T g decreased with an increase in ion exchange capacity (IEC). Fractional free volume and water uptake percentage increased and water contact angle decreased with the number of QA sites when compared to a neutral, commercially available polysulfone (Udel® P-1700 PSU). Next, the novel series of ammonium-functionalized copolymers exhibited a moisture-mediated capture and release of atmospheric CO 2 . When exposed to air containing 30% relative humidity the polymers captured CO 2 and the capacity increased with the IEC. When the relative humidity was increased to 95% the samples released the CO 2 . This study demonstrates a promising CO 2 DAC sorbent and highlights the possibility for continuous DAC with purpose-built free-standing membranes.

42 ENGINEERING↗
DOE OSTI2023

Wetting Behavior of A -block- (B- random -C) Copolymers with Equal Block Surface Energies on Surfaces Functionalized with B- random -C Copolymers

To form nanopatterns with self-assembled block copolymers (BCPs), it is desirable to have through-film domains that are oriented perpendicular to the substrate. The domain orientation is determined by the interfacial interactions of the BCP domains with the substrate and with the free surface. Here, we use thin films of two different sets of BCPs with A-block-(B-random-C) architecture matched with a corresponding B-random-C copolymer nanocoating on the substrate to demonstrate two distinct wetting behaviors. The two sets of A-b-(B-r-C) BCPs are made by using thiol–epoxy click chemistry to functionalize polystyrene-block-poly(glycidyl methacrylate) with trifluoroethanethiol (TFET) and either 2-mercaptopyridine (2MP) or methyl thioglycolate (MTG). For each set of BCPs, the composition ratio of the two thiols in the BCP (φ 1 ) is found that results in the two blocks of the modified BCP having equal surface energies (Δγ air = 0). The corresponding B-r-C random copolymers were synthesized and used to modify the substrate, and the composition ratio (φ 2 ) values that resulted in the two blocks of the BCP having equal interfacial energy with the substrate (Δγ sub = 0) were determined with scanning electron microscopy. The correlation between each block’s γ sub value and the interaction parameter, χ, is employed to explain the different wetting behaviors of the two sets of BCPs. For the thiol pair 2MP and TFET, the values of φ 1 and φ 2 that lead to Δγ air = 0 and Δγ sub = 0, respectively, are significantly different. A similar difference was observed between the φ 1 and φ 2 values that lead to Δγ air = 0 and Δγ sub = 0 for the BCPs made with the thiol pair MTG and TFET. In the latter case, for Δγ sub = 0 two windows of φ 2 are identified, which can be explained by the thermodynamic interactions of the specific thiol pair and the A-b-(B-r-C) architecture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Interconnected Nanoporous Polysulfone by the Self-Assembly of Randomly Linked Copolymer Networks and Linear Multiblocks

Porous materials have attracted considerable attention due to their versatile applications, especially in water purification. Interconnected nanoporous structures are distinguished by their high degree of porosity and resistance to clogging, as well as their insensitivity to nanostructural orientation. Previous works on randomly linked copolymer systems have shown that they can effectively produce disordered cocontinuous nanostructures, which upon removal of one component yield interconnected nanoporous materials. However, the cocontinuous nanomaterials previously developed using polystyrene (PS) and poly(d,l-lactic acid) (PLA) strands, and the resulting interconnected nanoporous PS monoliths, were far too brittle to enable practical use as membranes. Here, we study the self-assembly of randomly linked copolymer networks prepared using blocks of the engineering polymer polysulfone (PSU). A wide cocontinuous regime (spanning 40 wt %) was found for randomly end-linked copolymer networks (RECNs) constructed from PSU and PLA strands, via a combination of mechanical testing, gravimetry, small-angle X-ray scattering, and scanning electron microscopy. The PSU/PLA cocontinuous nanomaterial with symmetric composition showed 2.4 times higher Young’s modulus and ~100 times greater toughness than the corresponding PS/PLA sample. The interconnected nanoporous PSU fabricated after etching of PLA even exhibited 1.6 times greater toughness than PS/PLA prior to PLA removal. To facilitate the production of thin films of cocontinuous nanomaterials, we applied solution-processable randomly linked linear PSU/PLA multiblock polymers onto ultrafiltration membranes. Here, the interconnected nanoporous PSU thin film generated by etching PLA was found to effectively reject 50 nm diameter particles without significantly compromising permeability. This discovery presents a valuable addition to the existing techniques used to fabricate PSU membranes. In contrast to traditional methods, which are sensitive to processing conditions, produce a wide range of pore sizes, and offer limited adjustability of pore size, the current technique is anticipated to enable interconnected PSU membranes with more uniform and tailorable porosity.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Nanocomposites Based on Coil-Comb Diblock Copolymers

The polymer chain architecture is an important factor determining the phase behavior of nanoparticle (NP) assembly in polymer matrices. Block copolymers (BCPs) containing a random copolymer (RCP) block present a convenient variation on traditional BCPs to tune the interaction parameters between the polymer blocks and the nanofillers as well as to evaluate the effect of the chain architecture on the NP arrangements within BCP microdomains. Here, we synthesized BCPs with a coil polystyrene (PS) block and a comb RCP block through reversible addition-fragmentation chain transfer polymerization. The RCP block consists of methyl- and lauryl acrylates, the latter of which confers a long-chain alkyl moiety to favorably interact with alkyl-passivated NPs. BCPs showing lamellar, cylindrical, and mixed morphologies were obtained by varying the volume fractions of the RCP block (f RCP ). In comparison to coil-coil BCP, the coil-comb BCPs show highly asymmetric phase behavior with respect to fRCP, where lamellar morphologies were observed at fRCP from 0.31 to 0.51. NPs in the size of 4-5 nm were successfully incorporated in the RCP block of the BCPs with periodicities of 30-60 nm. An order-to-order phase transition from lamellae to PS cylinders was observed after the addition of only 1-2 vol % 5 nm NPs into the BCP with a periodicity of 25 nm and f RCP of 0.51. Self-consistent field theory-density functional theory simulations qualitatively described the observed morphologies and phase transitions in the nanocomposites. Here, the current study presents a platform to fabricate nanocomposites with NP assemblies in coil-comb BCPs that contain a random copolymer block and provides insight into how polymer chain architectures can affect the phase behavior of BCPs and nanocomposites.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Assembly of Disordered Cocontinuous Morphologies by Multiblock Copolymers with Random Block Sequence and Length Dispersity

Among the wide variety of nanostructures accessible by self-assembly of block copolymers, cocontinuous morphologies are of great interest for separations, catalysis, sensing, and energy storage due to their ability to integrate distinct properties of the constituent polymers. Furthermore, we investigate the tendency to form disordered cocontinuous phases of multiblock copolymers (MBCs) with random block sequence and length dispersity prepared by step-growth polymerization of pre-made telechelic polymers, specifically using thiol-Michael addition between diacrylate functionalized polystyrene (PS) and poly (D,L - lactide) (PLA) chains and a small molecule dithiol. In the phase diagram so established, disordered cocontinuous nanostructures occupy a wide window (≈ 25 % vol) at a modest segregation strength of χN = 15, close to the critical value for microphase separation. At a higher segregation strength of χN = 30, only a moderately wide (≈ 10 vol %) cocontinuous window is found, with MBCs instead tending to form ordered nanostructures. Although the breadth of the cocontinuous widow is less than that found in prior work on analogous randomly end-linked copolymer networks (RECNs), the MBC architecture offers offsetting advantages in terms of solution and melt processability.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Block copolymer self-assembly to pattern gold nanodots for site-specific placement of DNA origami and attachment of nanomaterials

Directed placement of DNA origami could play a key role in future integrated nanoelectronic devices. Here we demonstrated the site-selective attachment of DNA origami on gold dots formed using a pattern transfer method through block copolymer self-assembly. First, a random copolymer brush layer is grafted on the Si surface and then poly (styrene-b-methylmethacrylate) block copolymer is spin-coated to give a hexagonal nanoarray after annealing. UV irradiation followed by acetic acid etching is used to remove the PMMA, creating cylindrical holes and then oxygen plasma etching removes the random copolymer layer inside those holes. Next, metal evaporation, followed by lift-off creates a gold dot array. We evaluated different ligand functionalization of Au dots, as well as DNA hybridization to attach DNA origami to the nanodots. DNA-coated Au nanorods are assembled on the DNA origami as a step towards creating nanowires and to facilitate electron microscopy characterization of the attachment of DNA origami on these Au nanodots. The DNA hybridization approach showed better DNA attachment to Au nanodots than localization by electrostatic interaction. Here, this work contributes to the understanding of DNA-templated assembly, nanomaterials, and block copolymer nanolithography. Furthermore, the work shows potential for creating DNA-templated nanodevices and their placement in ordered arrays in future nanoelectronics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Reversible Photoswitching in Poly(2-oxazoline) Nanoreactors

This contribution reports light responsive catalytic nanoreactors based on poly(2-oxazoline) diblock copolymers. The hydrophobic block of the copolymer is a random copolymer consisting of a spiropyran functionalized 2-oxazoline (SPOx) and 2-(but-3-yn-1-yl)-4,5-dihydrooxazole (ButynOx), while the hydrophilic block is based on 2-methyl-2-oxazoline (MeOx). The block copolymer is terminated with tris(2-aminoethyl) amine (TREN) that serves as catalyst in a Knoevenagel condensation. Four block copolymers with different ButynOx/SPOx and hydrophilic/hydrophobic ratios are synthesized and self-assembled through solvent exchange. Micelles and vesicles of various sizes are observed by TEM, which undergo morphological and size changes in response to irradiation with UV light. We hypothesize that these transformations in the nanostructures are caused by increases in the hydrophilicity of the hydrophobic block when spiropyran (SP) isomerizes to merocyanine (MC) in the presence of UV light. The reversible transition from micellar to vesicular nanoreactors resulted in increased reaction kinetics through improved substrate accessibility to the catalytic site, or termination of the catalytic reaction due to polymer precipitation. Furthermore, these nanoreactors present a promising platform towards photoregulating reaction outcomes based on changes in nanostructure morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Janus bottlebrush compatibilizers

Bottlebrush random copolymers (BRCPs), consisting of a random distribution of two homopolymer chains along a backbone, can segregate to the interface between two immiscible homopolymers. BRCPs undergo a reconfiguration, where each block segregates to one of the homopolymer phases, adopting a Janus-type structure, reducing the interfacial tension and promoting adhesion between the two homopolymers, thereby serving as a Janus bottlebrush copolymer (JBCP) compatibilizer. Here, we synthesized a series of JBCPs by copolymerizing deuterated or hydrogenated polystyrene (DPS/PS) and poly(tert-butyl acrylate) (PtBA) macromonomers using ruthenium benzylidene-initiated ring-opening metathesis polymerization (ROMP). Subsequent acid-catalyzed hydrolysis converted the PtBA brushes to poly(acrylic acid) (PAA). The JBCPs were then placed at the interface between DPS/PS homopolymers and poly(2-vinyl pyridine) (P2VP) homopolymers, where the degree of polymerization of the backbone (N BB ) and the grafting density (GD) of the JBCPs were varied. Neutron reflectivity (NR) was used to determine the interfacial width and segmental density distributions (including PS homopolymer, PS block, PAA block and P2VP homopolymer) across the polymer-polymer interface. Our findings indicate that the star-like JBCP with N BB = 6 produces the largest interfacial broadening. Increasing N BB to 100 (rod-like shape) and 250 (worm-like shape) reduced the interfacial broadening due to a decrease in the interactions between blocks and homopolymers by stretching of blocks. Decreasing the GD from 100% to 80% at N BB = 100 caused an increase the interfacial width, yet further decreasing the GD to 50% and 20% reduced the interfacial width, as 80% of GD may efficiently increase the flexibility of blocks and promote interactions between homopolymers, while maintaining relatively high number of blocks attached to one molecule. The interfacial conformation of JBCPs was further translated into compatibilization efficiency. Thin film morphology studies showed that only the lower N BB values (N BB = 6 and N BB = 24) and the 80% GD of N BB = 100 had bicontinuous morphologies, due to a sufficient binding energy that arrested phase separation, supported by mechanical testing using asymmetric double cantilever beam (ADCB) tests. These provide fundamental insights into the assembly behavior of JBCPs compatibilizers at homopolymer interfaces, opening strategies for the design of new BCP compatibilizers.

36 MATERIALS SCIENCE↗