Nanofibers Produced by Electrospinning of Ultrarigid Polymer Rods Made from Designed Peptide Bundlemers
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Materials Science↗
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Results for “Polymer Science”
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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Hydroesterification of Polycyclooctene to Access Linear Ethylene Ethyl Acrylate Copolymers as a Step Toward Polyolefin Functionalization
To advance a strategy of polymer-to-polymer upcycling of waste polyolefin by dehydrogenation then functionalization, we report successful hydroesterification of polycyclooctene (PCOE), an analogue for partially unsaturated polyethylene. Here, we convert PCOE to a linear analog for poly(ethylene-co-ethyl acrylate) (EEA) across a range of ethyl acrylate incorporations (0 to 18 mol % of ethylene units). The ester incorporation was well controlled by reaction time, and the remaining C=C bonds were subsequently hydrogenated. Here, the bulky ethyl acrylate groups did not incorporate into orthorhombic PE crystals, decreasing the crystallinity, crystallite size, and melting temperature with increasing functionalization. Additionally, hydroesterification tuned the dynamic mechanical properties, decreasing both the glass transition temperature and the storage modulus in the rubbery regime with greater functionalization. The linear EEA analogs reported here achieve remarkable extensibility (strain > 4000%) and high toughness, comparable to commercial random and branched EEA. Ultimately, we demonstrate successful conversion of an analogue to dehydrogenated PE to a linear EEA with favorable mechanical properties.
36 MATERIALS SCIENCE↗
Report on ISR-1 High-Altitude Balloon Flight
To test small technologies at lower cost for space science applications, LANL has developed a small high altitude balloon payload that could, in the future, be regularly and inexpensively launched from LANL. A neutron detector, NEMO, was integrated to evaluate its performance in a space-like mixed-radiation environment and collect neutron data in the atmosphere. In collaboration with EES-14, a high-altitude balloon payload was launched from LANL Technical Area 51 on February 27, 2023 and April 17, 2023. For real-time geolocation, a SAM-M8Q M8 GNSS module was used to get position and time, and an Iridium RockBLOCK 9603 was used to communicate with the ground using the Iridium satellite fleet. These modules were all controlled using an Iteaduino Mega microcontroller board. Finally, a High Altitude Science Eagle Flight Computer with a temperature pressure sensor ran independently, writing data to an SD card. All of these modules were powered by a 5 mAh lithium polymer battery. The battery was attached to the bottom of the payload while the remaining electronics were embedded in the underside of the top of the payload. These modules were wired as seen in Figure 1-2. The Iteaduino Mega microcontroller board was programmed to use the RockBLOCK to send a message once every 10 minutes containing neutron and GPS data read off the NEMO and SAM M8Q, respectively. Once the message send attempt finished, the RockBLOCK would be slept for the rest of the 10 minute interval. The Eagle Flight Computer ran continuously throughout the flight, taking data every 6 seconds. The RockBLOCK message data was set up to be delivered from the Iridium satellite fleet to a website, where it was stored and parsed to create live maps and plots for analysis and balloon retrieval. The RockBLOCK message data was additionally configured to be sent to an email as a fail-safe. The payload was ground-tested successfully for over 50 hours, with multiple revisions occurring to best prepare for conditions at altitude and improve the software and firmware to fix any issues that cropped up with the data pipeline. Additional to the balloon payload, the flight had an attached iMet-4 radiosonde and Garmin T5 GPS Dog Collar. The radiosonde provided GPS and meteorological data. The T5 dog collar is used along with a Garmin Astro 430 to track the balloon at a range of up to 9 miles for retrieval. The balloon itself was initially a 1600 g meteorological balloon with an attached High Altitude Science parachute, both of which can be seen in Figure 1-3. After the first flight, the EES team swapped to a Rocketman parachute.
42 ENGINEERING↗
Revisiting the activity of two poly(vinyl chloride)- and polyethylene-degrading enzymes
Biocatalytic degradation of non-hydrolyzable plastics is a rapidly growing field of research, driven by the global accumulation of waste. Enzymes capable of cleaving the carbon-carbon bonds in synthetic polymers are highly sought-after as they may provide tools for environmentally friendly plastic recycling. Despite some reports of oxidative enzymes acting on non-hydrolyzable plastics, including polyethylene or poly(vinyl chloride), the notion that these materials are susceptible to efficient enzymatic degradation remains controversial, partly driven by a general lack of studies independently reproducing previous observations. Here, we attempt to replicate two recent studies reporting that deconstruction of polyethylene and poly(vinyl chloride) can be achieved using an insect hexamerin from Galleria mellonella (so-called “Ceres”) or a bacterial catalase-peroxidase from Klebsiella sp., respectively. Reproducing previously described experiments, we do not observe any activity on plastics using multiple reaction conditions and multiple substrate types. Digging deeper into the discrepancies between the previous data and our observations, we show how and why the original experimental results may have been misinterpreted.
36 MATERIALS SCIENCE↗
Development of Antimicrobial PLA Composites for Fused Filament Fabrication
In addition to possessing the desirable properties of being a biodegradable and biocompatible polymer fabricated from renewable resources, poly (lactic acid) (PLA) has useful mechanical and thermal attributes that has enabled it to be one of the most widely-used plastics for medicine, manufacturing, and agriculture. Yet, PLA composites have not been heavily explored for use in 3D-printing applications, and the range of feasible materials for the technology is limited, which inhibits its potential growth and industry adoption. In this study, tunable, multifunctional antimicrobial PLA composite filaments for 3D-printing have been fabricated and tested via chemical, thermal, mechanical, and antimicrobial experiments. Thermally stable antimicrobial ceramics, ZnO and TiO2, were used as fillers up to 30 wt%, and poly (ethylene glycol) (PEG) was used as a plasticizer to tune the physical material properties. Results demonstrate that the PLA composite filaments exhibit the thermal phase behaviors and thermal stability suitable for 3D-printing. Additionally, PEG can be used to tune the mechanical properties while not affecting the antimicrobial efficacy that ZnO and TiO2 imbue.
TiO2↗
Pyrolysis Vacuum-Assisted Plasma Ionization Ion Mobility–Mass Spectrometry for Insoluble Polymer Analysis
Wire-based metal additive manufacturing utilizes the ability of additive manufacturing to fabricate complex geometries with high deposition rates (above 7 kg/h), thus finding applications in the fabrication of large-scale components, such as stamping dies. Traditionally, the workhorse materials for stamping dies have been martensitic steels. However, the complex thermal gyrations induced during additive manufacturing can cause the evolution of an inhomogeneous microstructure, which leads to a significant scatter in the mechanical properties, especially the toughness. Therefore, to understand these phenomena, arc-based additive AISI 410 samples were fabricated using robotic gas metal arc welding (GMAW) and were subjected to a detailed characterization campaign. The results show significant scatter in the tensile properties as well as Charpy V-notch impact toughness data, which was then correlated to the microstructural heterogeneity and delta (δ) ferrite formation. Post-processing (austenitizing and tempering) treatments were developed and an ~70% reduction in the scatter of tensile data and a four-times improvement in the toughness were obtained. The changes in mechanical properties were rationalized based on the microstructure evolution during additive manufacturing. Based on these, an outline to tailor the composition of “printable” steels for tooling with isotropic and uniform mechanical properties is presented and discussed.
36 MATERIALS SCIENCE↗
Confusion-Driven Machine Learning of Structural Phases of a Flexible, Magnetic Stockmayer Polymer
We use a semisupervised, neural-network-based machine learning technique, the confusion method, to investigate structural transitions in magnetic polymers, which we model as chains of magnetic colloidal nanoparticles characterized by dipole–dipole and Lennard-Jones interactions. As input for the neural network, we use the particle positions and magnetic dipole moments of equilibrium polymer configurations, which we generate via replica-exchange Wang–Landau simulations. We demonstrate that by measuring the classification accuracy of neural networks, we can effectively identify transition points between multiple structural phases without any prior knowledge of their existence or location. We corroborate our findings by investigating relevant conventional order parameters. Our study furthermore examines previously unexplored low-temperature regions of the phase diagram, where we find new structural transitions between highly ordered helicoidal polymer configurations.
36 MATERIALS SCIENCE↗
2-Aminoanthracene Crystallization in Its Compatible Polystyrene Block: RAFT Synthesis and Enhanced Charge Retention in Pentacene Transistor Gate Dielectrics
We synthesized polystyrene-block-polyanthrylaminomethylstyrene (PS-b-PAAS) via RAFT reaction and side chain modification where the PAAS block is 50%. By blending 2-aminoanthracene (2AA) with PS-b-PAAS, the co-aggregation behavior of the PAAS block and 2AA within the thin film was observed by optical microscopy (OM) and x-ray diffraction. At 5 and 10 wt% of 2AA within the thin film, OM results showed a clear morphological difference between PS matrix and PS-b-PAAS matrix. Differences in the 2AA excited state lifetime in these matrices were also established using transient absorption spectroscopy (TAS). Blends were used as gate dielectrics in pentacene transistors. We compared characteristic voltage (Vc, an indicator of threshold voltage) before and after charging of PS-b-PAAS blended with unsubstituted PS and both polymers individually blended with 2AA. For blended PS-b-PAAS and PS, as the concentration of PS-b-PAAS increases, the decreased Vc especially with negative charging of the pentacene indicated a larger concentration of charge carriers induced by the dielectric film. The charging experiments also revealed that the unique structure formed by the 2AA/PS-b-PAAS blend significantly affected the charge storage capability of the organic field-effect transistors (OFET). Furthermore, this work demonstrates the novel co-aggregation structure in the dielectrics, and furthermore its impact on charge storage capability in pentacene OFETs.
36 MATERIALS SCIENCE↗
Rheological behavior of neat and carbon fiber-reinforced poly(ether ketone ketone) for extrusion deposition additive manufacturing
To develop new materials for extrusion additive manufacturing (AM) systems, a fundamental understanding of rheological properties is essential to correlate the effect of processing on material structure and its properties. In this work, the rheological properties of five different grades of neat and carbon fiber (CF)-reinforced poly(ether ketone ketone) are reported. Rheological properties are essential to understand the effect of reinforcing fibers and AM process parameters such as time, temperature, environment, and shear rate on flow behavior during processing. Small-amplitude oscillatory shear tests and steady shear tests indicated neat grades to exhibit less increase in viscosity over time when processed in air than the CF-filled grades. The filled grades showed greater shear thinning and lower sensitivity to temperature. Altogether, this rheological analysis provides a broad framework for determining appropriate processing conditions for extrusion deposition AM of such high-temperature polymer systems.
36 MATERIALS SCIENCE↗
Dynamic heterogeneity and nanophase separation in rubber-toughened amine-cured highly cross-linked polymer networks
Solid state nuclear magnetic resonance (NMR) spectroscopy and small-to wide-angle X-ray scattering (SWAXS) methods were used to characterize the heterogeneous dynamics and polymer domain structure in rubber modified thermoset materials containing the diglycidyl ether of bisphenol A (DGEBA) epoxy resin and a mixture of Jeffamine reactive rubber and 4,4-diaminodicyclohexylmethane (PACM) amine curing agent. The polymer chain dynamics and morphologies as a function of the PACM/Jeffamine ratio were determined. Using dipolar-filtered NMR experiments, the resulting networks are shown to be composed of mobile and rigid regions that are separated on nanometer length scales, along with a dynamically immobilized interface region. Proton NMR spin diffusion experiments measured the dimensions of the mobile phase to range between 9 and 66 nm and varied with the relative PACM concentration. Solid state 13 C magic angle spinning NMR experiments show that the highly mobile phase is composed entirely of the dynamically flexible polyether chains of the Jeffamine rubber, the immobilized interface region is a mixture of DGEBA, PACM, and the Jeffamine rubber, with the PACM cross-linked to DGEBA predominantly residing in the rigid phase. The SWAXS results showed compositional nanophase separation spanning the 11–77 nm range. These measurements of the nanoscale compositional and dynamic heterogeneity provide molecular level insight into the very broad and controllable glass transition temperature distributions observed for these highly cross-linked polymer networks.
36 MATERIALS SCIENCE↗
Thermodynamically leveraged solventless aerobic deconstruction of polyethylene-terephthalate plastics over a single-site molybdenum-dioxo catalyst
Here, we describe the solventless catalytic deconstruction of polyethylene-terephthalate (PET) under an aerobic atmosphere, mediated by an earth-abundant, low-cost activated carbon (AC)-supported single-site molybdenum-dioxo catalyst (AC/MoO 2 ). Catalytic amounts of AC/MoO 2 selectively convert waste PET into its monomer, terephthalic acid (TPA), within 4 h at 265 °C with yields as high as 94% under 1 atm air. Pure crystalline TPA product sublimes from the reaction hot zone, crystallizing on the reactor cold zone, thus avoiding the need for separation and purification steps. This process does not employ any hazardous/toxic reducing agents or solvents, and the catalyst can be recycled multiple times without loss of activity, rendering this process highly atom-efficient. According to computational and experimental mechanistic studies, the AC/MoO 2 catalyst mediates a thermoneutral metal-catalyzed β-scission step, followed by an exothermic step that converts the vinyl benzoate intermediate to TPA and acetaldehyde using trace amounts of moisture in the air. The formation of gaseous acetaldehyde makes the isolation of TPA from the reaction mixture facile and industrially favorable, especially since solvents are unnecessary. The present methodology is also extended to the deconstruction of other frequently used polyester plastics, polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyethylene furanoate (PEF), and operates equally well with post-consumer waste products. Notably, this process is also compatible with plastic mixtures of polyesters with polyolefins, polyamides, and polycarbonates, leading to the selective conversion of each polyester to the corresponding monomer, leaving the residual polymer unchanged and polyester-free.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
HP1-driven phase separation recapitulates the thermodynamics and kinetics of heterochromatin condensate formation
The spatial segregation of pericentromeric heterochromatin (PCH) into distinct, membrane-less nuclear compartments involves the binding of Heterochromatin Protein 1 (HP1) to H3K9me2/3-rich genomic regions. While HP1 exhibits liquid–liquid phase separation properties in vitro, its mechanistic impact on the structure and dynamics of PCH condensate formation in vivo remains largely unresolved. Here, using a minimal theoretical framework, we systematically investigate the mutual coupling between self-interacting HP1-like molecules and the chromatin polymer. We reveal that the specific affinity of HP1 for H3K9me2/3 loci facilitates coacervation in nucleo and promotes the formation of stable PCH condensates at HP1 levels far below the concentration required to observe phase separation in purified protein assays in vitro. These heterotypic HP1–chromatin interactions give rise to a strong dependence of the nucleoplasmic HP1 density on HP1-H3K9me2/3 stoichiometry, consistent with the thermodynamics of multicomponent phase separation. The dynamical cross talk between HP1 and the viscoelastic chromatin scaffold also leads to anomalously slow equilibration kinetics, which strongly depend on the genomic distribution of H3K9me2/3 domains and result in the coexistence of multiple long-lived, microphase-separated PCH compartments. The morphology of these complex coacervates is further found to be governed by the dynamic establishment of the underlying H3K9me2/3 landscape, which may drive their increasingly abnormal, aspherical shapes during cell development. These findings compare favorably to 4D microscopy measurements of HP1 condensate formation in live Drosophila embryos and suggest a general quantitative model of PCH formation based on the interplay between HP1-based phase separation and chromatin polymer mechanics.
3D genomics↗
Biomaniac
Los Alamos National Laboratory researchers are developing a machine-learning based algorithm to revolutionize how biopolymers are designed and optimized. BioManIAC is a software platform that fills the gaps in data to gain insight into new potential polymer properties without making and testing them. Polymer engineers are able to use BioManIAC software to extrapolate and tune new biopolymer properties that allow the user to create small smart libraries, rather than largescale trial and error testing. This targeted design is expected to improve both time to market and R&D expenditure, as well as the resulting mechanical properties of biopolymers, enabling for more direct competition with traditional petroleum-based polymers. Los Alamos is seeking partners to further validate our software platform.
36 MATERIALS SCIENCE↗
Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine
The present invention relates to a polymer comprising a repeating group having the structure of formula (I) wherein R, R1, R2, R3, R4, X, and s are as described herein and salt thereof. Also disclosed is a process of synthesizing such polymers.
36 MATERIALS SCIENCE↗
Structure of Diisobutylene Maleic Acid Copolymer (DIBMA) and Its Lipid Particle as a “Stealth” Membrane-Mimetic for Membrane Protein Research
The study of membrane proteins remains challenging, especially in a native membrane environment. Recently, major progress has been made using maleic acid copolymers, such as styrene maleic acid, to purify membrane proteins and study them directly with native lipids associated with the membrane. Additional maleic acid copolymers, such as diisobutylene maleic acid (DIBMA) membrane-mimetic systems, are being developed and found to have improved spectroscopic properties and pH stability. We studied DIBMA and its lipid particles in solution to better understand its assembly, without and with the lipids, to provide an insight regarding how to use it in solution for better membrane extraction. Using small-angle neutron and X-ray scattering (SANS/SAXS), we show that DIBMA organizes into structures of different size scales at various concentrations and ionic strengths. The polymer performed reasonably well under most solvent conditions except in very low concentrations and high-salt conditions that could result in limited interaction with lipids. To explore DIBMA lipid particles as a suitable membrane-mimetic system for neutron scattering studies of membrane proteins, we measured and determined the contrast-matching point of DIBMA to be ~12% (v/v) D 2 O — similar to that of most protiated lipid molecules but distinct from that of regular protiated proteins — providing a natural contrast for separating their neutron scattering signals. Using SANS contrast variation, we demonstrated that the scattering from the whole lipid particle can be annihilated. Further, we determined that a well-defined lipid nanodisc structure with DIBMA was contrast-matched. These results demonstrate that the DIBMA lipid particle is an outstanding “stealth” membrane-mimetic for membrane proteins. The results provide a structural framework for understanding the organization and assembly process of the polymer itself and the lipid molecules. Such an understanding is imperative for structural techniques such as cryo-electron microscopy, nuclear magnetic resonance, small-angle scattering, and other biophysical techniques.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Surface‐Enforced Alignment of Reprogrammable Liquid Crystalline Elastomers
Abstract Liquid crystalline elastomers (LCEs) are stimuli‐responsive materials capable of undergoing large deformations. The thermomechanical response of LCEs is attributable to the coupling of polymer network properties and disruption of order between liquid crystalline mesogens. Complex deformations have been realized in LCEs by either programming the nematic director via surface‐enforced alignment or localized mechanical deformation in materials incorporating dynamic covalent chemistries. Here, the preparation of LCEs via thiol‐Michael addition reaction is reported that are amenable to surface‐enforced alignment. Afforded by the thiol‐Michael addition reaction, dynamic covalent bonds are uniquely incorporated in chemistries subject to surface‐enforce alignment. Accordingly, LCEs prepared with complex director profiles are able to be programmed and reprogrammed by (re)activating the dynamic covalent chemistry to realize distinctive shape transformations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗