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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Prospective Application, Mechanism, and Deficiency of Lithium Bis(oxalate)Borate as the Electrolyte Additive for Lithium-Batteries

Lithium bis(oxalate)borate (LiBOB) is one of the most common film-forming electrolyte additives used in lithium ion batteries (LIBs), since it can form a dense boron-containing polymer as a solid electrolyte interlayer (or cathode electrolyte interlayer) in order to isolate the electrode material from the electrolyte and prevent side reactions. LiBOB can serve as HF scavenger to maintain the structural integrity of electrodes via avoiding the transition metal dissolution caused by HF attack. Additionally, LiBOB also can react with LiPF 6 to generate lithium difluoro (oxalate)borate (LiDFOB) that can be further used as a clean-up agent for reactive oxygen radicals. This article lists the application of LiBOB in high capacity and high voltage cathode materials, and also reviews the working mechanisms of LiBOB used in these materials to improve the performance of LIBs. Finally, it presents the current shortcomings of LiBOB and strategies to overcome these. This article is expected to provide useful insights for employing LiBOB as a feasible method of dealing with the difficulty of running high capacity LIBs stably under high voltage.

25 ENERGY STORAGE↗
DOE OSTI2026

Supramolecular Arene‐Perfluoroarene Assembly Enhances Photoiniferter Polymerization Kinetics

Ultra-high-molecular-weight (UHMW, >106 Da) polymers have unique thermomechanical properties due to their large number of physical entanglements. Producing UHMW styrenic polymers is challenging because of their prohibitively slow homopolymerization kinetics. In this report, we show that alternating photoiniferter copolymerization between methoxy-functionalized styrenic monomers and pentafluorostyrene can circumvent this limitation under conditions where arene–perfluoroarene (AP) interactions contribute to favorable monomer association and accelerate copolymerization. Increasing methoxy substitution on the styrene arene ring leads to pronounced rate enhancements that correlate with electronic complementarity between the styrenic comonomers. Density functional theory calculations reveal increasingly favorable AP interaction energies across the series, consistent with monomer association contributing to faster propagation. The result is up to 2000% enhancement in propagation rate in copolymerizations compared to styrene homopolymerization. Despite these rate enhancements, the resulting materials retain broadly similar glass-transition temperatures and network-like thermomechanical behavior, with only modest softening across the series. Here, we then leverage the approach to produce UHMW trialkoxystyrene copolymers bearing sterically encumbered pendants, which are ultrasoft (Young's modulus of 8 kPa) and highly extensible (560%). These results establish that designed supramolecular association between styrenics is a powerful tool for controlling reactivity in radical polymerization and generating otherwise difficult-to-obtain materials.

Marquez, Joshua D. [University of Florida, Gainesv↗
DOE OSTI2021

Controlled n –Doping of Naphthalene Diimide–Based Two–Dimensional Polymers

Two-dimensional polymers (2DPs) are promising as structurally well-defined, permanently porous, organic semiconductors. However, 2DPs are nearly always isolated as closed shell organic species with limited charge carriers, which leads to low bulk conductivities. Here, we enhance the bulk conductivity of two naphthalene diimide (NDI)-containing 2DP semiconductors by controllably n-doping the NDI units using cobaltocene (CoCp 2 ). Optical and transient microwave spectroscopy reveals that both as-prepared NDI-containing 2DPs are semiconducting with sub-2 eV optical bandgaps and photoexcited charge-carrier lifetimes of tens of nanoseconds. Following reduction with CoCp 2 , both 2DPs largely retain their periodic structures and exhibit optical and electron-spin resonance spectroscopic features consistent with the presence of NDI-radical anions. Here, while the native NDI-based 2DPs are electronically insulating, maximum bulk conductivities of >10 –4 S cm –1 are achieved by substoichiometric levels of n-doping. Density functional theory calculations show that the strongest electronic couplings in these 2DPs exist in the out-of-plane (π-stacking) crystallographic directions, which indicates that cross-plane electronic transport through NDI stacks is primarily responsible for the observed electronic conductivity. Taken together, this study underlines that controlled molecular doping is a useful approach to access structurally well-defined, paramagnetic, 2DP n-type semiconductors with measurable bulk electronic conductivities of interest for electronic or spintronic devices.

2D polymers↗
DOE OSTI2022

Probing the Kinetic Origin of Varying Oxidative Stability of Ethyl- vs. Propyl-spaced Amines for Direct Air Capture

Amine-based adsorbents are promising for direct air capture of CO 2 , yet oxidative degradation remains a key unmitigated risk hindering wide-scale deployment. Borrowing wisdom from the basic auto-oxidation scheme, insights are gained into the underlying degradation mechanisms of polyamines by quantum chemical, advanced sampling simulations, adsorbent synthesis, and accelerated degradation experiments. The reaction kinetics of polyamines are contrasted with that of typical aliphatic polymers and they elucidate for the first time the critical role of aminoalkyl hydroperoxide decomposition in the oxidative degradation of amino-oligomers. The experimentally observed variation in oxidative stability of polyamines with different backbone structures is explained by the relationship between the local chemical structure and the free energy barrier of aminoalkyl hydroperoxide decomposition, suggesting that its energetics can be used as a descriptor to screen and design new polyamines with improved stability. In conclusion, the developed computational capability sheds light on radical-induced degradation chemistry of other organic functional materials.

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

Defining Reactivity–Deconstructability Relationships for Copolymerizations Involving Cleavable Comonomer Additives

The incorporation of cleavable comonomers as additives into polymers can imbue traditional polymers with controlled deconstructability and expanded end-of-life options. The efficiency with which cleavable comonomer additives (CCAs) can enable deconstruction is sensitive to their local distribution within a copolymer backbone, which is dictated by their copolymerization behavior. While qualitative heuristics exist that describe deconstructability, comprehensive quantitative connections between CCA loadings, reactivity ratios, polymerization mechanisms, and deconstruction reactions on the deconstruction efficiency of copolymers containing CCAs have not been established. Here, in this work, we broadly define these relationships using stochastic simulations characterizing various polymerization mechanisms (e.g., controlled/living, free-radical, and reversible ring-opening polymerizations), reactivity ratio pairs (spanning 2 orders of magnitude between 0.01 and 100), CCA loadings (2.5% to 20%), and deconstruction reactions (e.g., comonomer sequence-dependent deconstruction behavior). We show general agreement between simulated and experimentally observed deconstruction fragment sizes from the literature, demonstrating the predictive power of the methods used herein. These results will guide the development of more efficient CCAs and inform the formulation of deconstructable materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Improved Fuel Cell Chemical Durability of an Heteropoly Acid Functionalized Perfluorinated Terpolymer-Perfluorosulfonic Acid Composite Membrane

Commercial proton exchange membrane heavy-duty fuel cell vehicles will require a five-fold increase in durability compared to current state-of-the art light-duty fuel cell vehicles. We describe a new composite membrane that incorporates silicotungstic heteroply acid (HPA), α -K 8 SiW 11 O 40 ▪13H 2 O, a radical decomposition catalyst and when acid-exchanged can potentially conduct protons. The HPA was covalently bound to a terpolymer of tetrafluoroethylene, vinylidene fluoride, and sulfonyl fluoride containing monomer (1,1,2,2,3,3,4,4-octafluoro-4-((1,2,2-trifluorovinyl)oxy)butane-1-sulfonyl fluoride) by dehydrofluorination followed by addition of diethyl (4-hydroxyphenyl) phosphonate, giving a perfluorosulfonic acid-vinylidene fluoride-heteropoly acid (PFSA-VDF-HPA). A composite membrane was fabricated using a blend of the PFSA-VDF-HPA and the 800EW 3M perfluoro sulfonic acid polymer. The bottom liner-side of the membrane tended to have a higher proportion of HPA moieties compared to the air-side as gravity caused the higher mass density PFSA-VDF-HPA to settle. The composite membrane was shown to have less swelling, more hydrophobic properties, and higher crystallinity than the pure PFSA membrane. The proton conductivity of the membrane was 0.130 ± 0.03 S cm −1 at 80 °C and 95% RH. Impressively, when the membrane with HPA-rich side was facing the anode, the membrane survived more than 800 h under accelerated stress test conditions of open-circuit voltage, 90 °C and 30% RH.

08 HYDROGEN↗
DOE OSTI2021

4D-STEM of Beam-Sensitive Materials

We report that a scanning electron nanobeam diffraction, or 4D-STEM (four-dimensional scanning transmission electron microscopy), is a flexible and powerful approach to elucidate structure from "soft" materials that are challenging to image in the transmission electron microscope because their structure is easily damaged by the electron beam. In a 4D-STEM experiment, a converged electron beam is scanned across the sample, and a pixelated camera records a diffraction pattern at each scan position. This four-dimensional data set can be mined for various analyses, producing maps of local crystal orientation, structural distortions, crystallinity, or different structural classes. Holding the sample at cryogenic temperatures minimizes diffusion of radicals and the resulting damage and disorder caused by the electron beam. The total fluence of incident electrons can easily be controlled during 4D-STEM experiments by careful use of the beam blanker, steering of the localized electron dose, and by minimizing the fluence in the convergent beam thus minimizing beam damage. This technique can be applied to both organic and inorganic materials that are known to be beam-sensitive; they can be highly crystalline, semicrystalline, mixed phase, or amorphous. One common example is the case for many organic materials that have a π-π stacking of polymer chains or rings on the order of 3.4-4.2 Å separation. If these chains or rings are aligned in some regions, they will produce distinct diffraction spots (as would other crystalline spacings in this range), though they may be weak or diffuse for disordered or weakly scattering materials. We can reconstruct the orientation of the π-π stacking, the degree of π-π stacking in the sample, and the domain size of the aligned regions. This Account summarizes illumination conditions and experimental parameters for 4D-STEM experiments with the goal of producing images of structural features for materials that are beam-sensitive. We will discuss experimental parameters including sample cooling, probe size and shape, fluence, and cameras. 4D-STEM has been applied to a variety of materials, not only as an advanced technique for model systems, but as a technique for the beginning microscopist to answer materials science questions. It is noteworthy that the experimental data acquisition does not require an aberration-corrected TEM but can be produced on a variety of instruments with the right attention to experimental parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Latent Catalysis as a Platform for Accessing Diverse Material Properties in Vat Photopolymerization 3D Printing

Vat photopolymerization (VP) 3D printing is an attractive strategy to manufacture customized polymer parts. The properties of printed materials are limited by the need to employ a low viscosity liquid resin and achieve rapid polymerization kinetics. To circumvent this limitation, dual‐cure methods have been developed using reagents embedded in the liquid resin formulation; however, the reagent‐based approach requires the discovery and optimization of new chemistry for each desired material. Here, in this work, we demonstrate a catalytic, dual‐cure platform that enables access to both Nylon‐6 and polyester interpenetrating networks through VP 3D printing under a universal approach. Structure–reactivity relationships of the latent NHC catalysts led to the identification of a magnesium chloride–NHC adduct as a latent catalyst that is orthogonal to radical polymerization and can be unmasked at elevated temperatures post‐printing to initiate ring‐opening polymerization of lactones and lactams. This strategy results in access to semicrystalline materials, which are a challenging morphology to access via VP 3D printing, that have attractive mechanical properties and can be printed at high resolution. This work represents the first photochemical‐based 3D printing of Nylon‐based materials and demonstrates the value of catalytic approaches to access new material properties in VP 3D printing.

Colliver, Cali N. [University of North Carolina, C↗
DOE OSTI2024

Polymer Macrocycles: A novel topology to control dynamics of rubbery materials (Final Report)

One of the current challenges in polymer physics and engineering is to understand the behavior of circular macromolecules. Though such molecules have been made by dilute solution ring closure methods in the past, such procedures have been limited to relatively small, unentangled rings as well as to small sample quantities. Initial studies were also hampered by issues surrounding purity of the rings, though this problem has been somewhat overcome by the use of liquid chromatography at critical conditions (LCCC) methods that separate rings and linear chains. Furthermore, in spite of the continued progress a full understanding of ring dynamics remains elusive. The present work has addressed multiple aspects of the behavior of ring molecules by using a novel synthetic route: reversible radical recombination redox polymerization (R3P) to produce poly(3,6-dioxa-1,8-octanedithiol) (PolyDODT) molecules. The synthesis conditions were chosen to produce linear (LDODT), cyclic (RDODT) and linear-cyclic mixtures (LRDODT) in order to investigate dilute solution and rheological responses of the materials. Importantly, the R3P synthesis makes larger quantities and higher molecular weights than do the dilute solution ring closure methods and also has the potential to be scaled to industrial quantities, thus becoming commercializable. We emphasize two important outcomes of the work. The first is that the rheological investigation shows that very large molecular weight the PolyDODT rings permitted the investigation of ring dynamics from glassy towards terminal flow for molecular sizes corresponding to approximately 300 entanglements of the linear counterpart. At the same time, these very large sized rings could be diluted in a solvent in order to reduce the molecular entanglement density to less than unity. The results demonstrate that ring viscosity follows a Rouse-like linear dependence on molecular weight or entanglement number to approximately 15 entanglements. This range of "Rouse-like" response is greater than what was achieved in all prior works where synthesis conditions have limited the molecular sizes achievable. After the entanglement number $Z_w$ increases beyond approximately 15, we find that the viscosity-molecular weight scaling undergoes a rapid change from the Rouse-like $η\sim{Z}^1_w$ to a very strong power-law scaling that is approximately $η\sim{Z}^{5.8}_w$. This aspect of the work strongly suggests that prior investigations on highly pure rings have invariably been performed on unentangled systems simply because ring molecules have very high entanglement thresholds. The results are further supported by plateau modulus measurements that show that in the "Rouse-like" viscosity regime, for the RDODT samples there is a corresponding lack of a rubbery entanglement plateau and once entanglement coupling is seen, the rubbery plateau also appears in the dynamic modulus data. Furthermore, upon appropriate scaling, we show that the unentangled polyDODT rings (i.e., the diluted high molecular weight rings) show virtually identical dynamics (upon appropriate scaling to account for the chain dilutions) to the dynamics of similarly unentangled LCCC fractionated polystyrene rings.

36 MATERIALS SCIENCE↗
DOE OSTI2022

On the Mechanism of the Steady-State Gamma Radiolysis-Induced Scissions of the Phenyl-Vinyl Polyester-Based Resins

The major societal problem of polymeric waste necessitates new approaches to break down especially challenging discarded waste streams. Gamma radiation was utilized in conjunction with varying solvent environments in an attempt to discern the efficacy of radiolysis as a tool for the deliberate degradation of model network polyesters. Our EPR results demonstrated that gamma radiolysis of neat resin and in the presence of four widely used solvents induces glycosidic scissions on the backbone of the polyester chains. EPR results clearly show the formation of alkoxy radicals and C-centered radicals as primary intermediate radiolytic products. Despite the protective role of the phenyl groups on the backbone of the radiation-induced polyester chains, the radiolytic-glycosidic scissions predominate. Among the following three solvents used in this study (water, isopropyl alcohol, and dichloromethane), the highest radiolytic yield of glycosidic scission was achieved using water. The •OH radicals produced in the radiolysis of phenyl unsaturated polyester aqueous suspensions very rapidly abstract H atoms from the methylene group, which is followed by a very rapid glycosidic scission. The lowest glycosidic yield was found in the dichloromethane solutions of these polyester resins due to scavenging by the fast electron capture reactions.

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

Elucidating the modes of incorporation of the ferulic acid amides feruloyltyramine and feruloyloctopamine into the lignin-suberin fraction of potato periderms

Ferulic acid amides are naturally present in the cell walls of potato (Solanum tuberosum) periderms. In this study, we investigated their modes of incorporation into the periderm cell wall polymers. A lignin/suberin-enriched fraction was isolated and analyzed by GPC, DFRC, and 2D-NMR. The analyses revealed that the lignin domain of this fraction was predominantly composed of G-lignin units, with an H:G:S ratio of 2:70:28 (S/G ratio of 0.40). More importantly, the data also indicated the presence of two ferulic acid amides, feruloyltyramine and feruloyloctopamine, that are incorporated into the lignin/suberin structure of potato periderms through a variety of linkages, including 8-O-4' and 4-O-beta' ether linkages, as well as 8-5' linkages forming a phenylcoumaran structure involving the ferulate moiety. Although the phenolic groups of the tyramine and octopamine moieties could theoretically undergo oxidation, potentially creating additional sites for radical coupling, our research indicates that these groups remain predominantly as free phenolic entities that do not participate in radical coupling. On the other hand, all the phenolic groups of the ferulate moieties are bound through ether linkages reinforcing the conclusion that the feruloyltyramine and feruloyloctopamine moieties are linked to lignin/suberin within the cell wall via radical coupling reactions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

A new approach to zip–lignin: 3,4–dihydroxybenzoate is compatible with lignification

Renewed interests in the development of bioenergy, biochemicals, and biomaterials have elicited new strategies for engineering the lignin of biomass feedstock plants. Furthermore, this study shows, for the first time, that 3,4-dihydroxybenzoate (DHB) is compatible with the radical coupling reactions that assemble polymeric lignin in plants. We introduced a bacterial 3-dehydroshikimate dehydratase into hybrid poplar (Populus alba × grandidentata) to divert carbon flux away from the shikimate pathway, which lies upstream of lignin biosynthesis. Transgenic poplar wood had up to 33% less lignin with p-hydroxyphenyl units comprising as much as 10% of the lignin. Mild alkaline hydrolysis of transgenic wood released fewer ester-linked p-hydroxybenzoate groups than control trees, and revealed the novel incorporation of cell-wall-bound DHB, as well as glycosides of 3,4-dihydroxybenzoic acid (DHBA). Two-dimensional nuclear magnetic resonance (2D-NMR) analysis uncovered DHBA-derived benzodioxane structures suggesting that DHB moieties were integrated into the lignin polymer backbone. In addition, up to 40% more glucose was released from transgenic wood following ionic liquid pretreatment and enzymatic hydrolysis. This work highlights the potential of diverting carbon flux from the shikimate pathway for lignin engineering and describes a new type of ‘zip-lignin’ derived from the incorporation of DHB into poplar lignin.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Electricity-driven recycling of ester plastics using one-electron electro-organocatalysis

Here, we report the catalytic use of electrochemically generated one-electron reducing agents to produce ester anion radicals that can decompose to acids and alcohols in the presence of oxygen. Through this approach, we demonstrate that molecular analogs of polyethylene terephthalate (PET) can be deconstructed into their molecular components. We additionally show efficient reductive scission of ester bonds in PET plastic using catalytically regenerated reducing agents based on benzimidazolium cations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Probing the limits of genetic recoding using multi-omics-guided evolution

Engineering the genetic code—by reassigning multiple of the 64 natural codons—enables making organisms resistant to all viruses, preventing genetic information exchange, and allowing the biosynthesis of genetically encoded unnatural polymers. However, synonymous codon replacement—recoding—is frequently lethal, and how recoding impacts fitness remains poorly explored. Here, we explore these effects using genome synthesis, directed evolution, and genome-transcriptome-translatome-proteome co-profiling on multiple synthetic Escherichia coli genomes. We construct six partially recoded E. coli strains bearing up to 45.8% of a synthetic genome with a deleterious 57-codon genetic code. As our analyses revealed widespread defects—including unassigned codons in Syn61 and Syn57—we apply multi-omics to revise our genome design and mitigate defects. Using multi-omics, we show that recoding induces transcriptional and translational changes leading to fitness defects under hundreds of conditions. Finally, we develop a multi-omics-guided evolution strategy that rapidly restores fitness, enabling genome synthesis with radical changes.

Nyerges, Akos [Harvard Medical School, Boston, MA ↗
DOE OSTI2023

C–H Functionalization of Polyolefins to Access Reprocessable Polyolefin Thermosets

Upcycling plastic waste into reprocessable materials with performance-advantaged properties would contribute to the development of a circular plastics economy. Here, we modify branched polyolefins and postconsumer polyethylene through a versatile C–H functionalization approach using thiosulfonates as a privileged radical group transfer functionality. Cross-linking the functionalized polyolefins with polytopic amines provided dynamically cross-linked polyolefin networks enabled by associative bond exchange of diketoenamine functionality. A combination of resonant soft X-ray scattering and grazing incidence X-ray scattering revealed hierarchical phase morphology in which diketoenamine-rich microdomains phase-separate within amorphous regions between polyolefin crystallites. The combination of dynamic covalent cross-links and microphase separation results in useful and improved mechanical properties, including a ~4.5-fold increase in toughness, a reduction in creep deformation at temperatures relevant to use, and high-temperature structural stability compared to the parent polyolefin. The dynamic nature of diketoenamine cross-links provides stress relaxation at elevated temperatures, which enabled iterative reprocessing of the dynamic covalent polymer network with little cycle-to-cycle property fade. Finally, the ability to convert polyolefin waste into a reprocessable thermoformable material with attractive thermomechanical properties provides additional optionality for upcycling to enable future circularity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Design Trade-Offs in Composite Fuel Cell Membranes: Effects of Reinforcement and Chemical Additives

Perfluorosulfonic acid (PFSA) membranes are critical components in proton exchange membrane fuel cells, where performance depends on balancing ionic conductivity, mechanical durability, and chemical stability. This study characterizes a composite membrane (NC700) featuring PFSA-impregnated expanded polytetrafluoroethylene (ePTFE) reinforcement and cerium-based radical scavengers, benchmarked against unreinforced NR211. Complementary techniques, including electron microscopy, X-ray scattering, infrared spectroscopy, thermogravimetric analysis, and dynamic mechanical analysis, identify the structural and compositional strategies employed in NC700. Water sorption isotherms reveal lower water uptake for NC700 across all conditions, attributed to reinforcement and cerium incorporation. Reinforcement reduces in-plane swelling from 11% to 2.1% at 90% RH, confirming strong swelling anisotropy, while maintaining mechanical properties at elevated temperatures. While the ionic conductivity of NC700 is approximately 10% lower than that of NR211, the reduced thickness yields a 40% decrease in calculated area-specific resistance, suggesting the composite architecture can favorably shift the conductivity-stability trade-off. The composite structure also reduces gas permeability, indicating potential for improved separator function alongside favorable transport properties. Systematic deconvolution of reinforcement and additive contributions shows that conductivity losses from cerium incorporation are largely offset by gains from the lower equivalent-weight polymer, providing quantitative relationships that may guide composite membrane design for fuel cells and other electrochemical applications.

25 ENERGY STORAGE↗
DOE OSTI2023

Investigation of the Effect of Atmospheric Plasma Treatment in Nanofiber and Nanocomposite Membranes for Piezoelectric Applications

In this work, we report the effect of steady-state atmospheric plasma (Corona discharge) in nanofibers and nanocomposite membranes for piezoelectric applications. The investigation was performed in PVDF (Poly vinylidene fluoride) nanofibers, CNT (Carbon Nanotubes)-reinforced PVDF nanocomposites, and PAN (Poly acrylonitrile) nanofiber membranes. Steady-state plasma was generated with a high voltage power source with 1 mA discharge current output and 6 kV discharge voltage, and the gap between tip and the material was maintained to be 1 cm. For the fabrication of nanofibers and nanocomposite membranes, an electrospinning method was used. The electrospinning parameters, such as flow rate and voltage, were optimally tuned for obtaining uniform nanofibers and nanomembranes. Along with the plasma treatment, heat treatment above the glass transition temperature was also conducted on the nanofiber membranes. Using a Scanning Electron Microscope (SEM), the morphology of the nanofibers was observed. X-ray Diffraction (XRD) demonstrated the polycrystallinity of the nanofibers. Fourier Transform Infrared Spectroscopy (FTIR) analysis of the PVDF nanofibers shows a peak at 796 cm−1 representing α-phase (C-H rocking) in the control sample which is absent in the treated samples. Raman spectroscopy of PVDF nanofibers identifies a Raman shift from 873 cm−1 to 877 cm−1 (denoting β-phase) for plasma-treated samples only. Electron Paramagnetic Resonance (EPR) concludes that the intensity of the free radicals increases from 1.37 to 1.46 (a.u.) after plasma treatment. Then, sensors were fabricated from the PVDF nanofibers, MWCNT-reinforced PVDF nanofibers, and PAN nanofibers to characterize their piezoelectric properties. The impact test results showed that the atmospheric plasma and heat-treated samples had 86%, 277%, and 92% increases of the d33 value (piezoelectric coefficient) in the case of PVDF nanofibers, MWCNT-reinforced nanofibers, and PAN nanofibers, respectively. It was also observed that the capacitance of the nanofiber membranes has increased due to the plasma treatment.

Biochemistry & Molecular Biology↗
DOE OSTI2024

Organic nanoparticles with tunable size and rigidity by hyperbranching and cross-linking using microemulsion ATRP

Unlike inorganic nanoparticles, organic nanoparticles (oNPs) offer the advantage of “interior tailorability,” thereby enabling the controlled variation of physicochemical characteristics and functionalities, for example, by incorporation of diverse functional small molecules. In this study, a unique inimer-based microemulsion approach is presented to realize oNPs with enhanced control of chemical and mechanical properties by deliberate variation of the degree of hyperbranching or cross-linking. The use of anionic cosurfactants led to oNPs with superior uniformity. Benefitting from the high initiator concentration from inimer and preserved chain-end functionality during atom transfer radical polymerization (ATRP), the capability of oNPs as a multifunctional macroinitiator for the subsequent surface-initiated ATRP was demonstrated. This facilitated the synthesis of densely tethered poly(methyl methacrylate) brush oNPs. Detailed analysis revealed that exceptionally high grafting densities (~1 nm −2 ) were attributable to multilayer surface grafting from oNPs due to the hyperbranched macromolecular architecture. The ability to control functional attributes along with elastic properties renders this “bottom-up” synthetic strategy of macroinitiator-type oNPs a unique platform for realizing functional materials with a broad spectrum of applications.

ATRP↗