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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 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Reconfigurable structural color by reversible switching of colloidal discoid liquid crystal alignment

Combining the effects of alternating-current (AC) electric fields and sedimentation reconfigures colloidal discoids between planar and homeotropic orientational alignments, thereby controlling the material’s structural color. Here, we self-assemble micrometer-size polystyrene discoids in an isopropanol-water mixture. After sedimentation, the discoids adopt a homeotropic alignment, with the minor axis perpendicular to the substrate. Adding an AC electric field (1 kHz) of ≥0.50 V switches the discoids to planar alignment—with the minor axis parallel to the substrate—within ∼100 s. Removing the field switches them back to homeotropic alignment within ∼300 s. Kinetic modeling of the field-induced torques yields good agreement with these measurements. The peak wavelength and intensity of the crystal’s diffraction response shift significantly upon reconfiguration; scattering simulation predicts these shifts. The reconfiguration is maintained for at least 10 cycles. This method is a simple, scalable avenue to reconfigure the optical properties of colloidal crystals produced from simple dielectric spheroids.

colloidal crystals↗
DOE OSTI2019

Genome engineering of E. coli for improved styrene production and polymerization

Microbial production of exogenous organic compounds is challenging as biosynthetic pathways are often complex and produce metabolites that are toxic to the hosts. Biogenic styrene is an example of this problem, which if addressed could result in a more sustainable supply of this important component of the plastics industry. In this study, we engineered Escherichia coli for the production of styrene. We systematically optimized the production capability by first screening different pathway expression levels in E. coli strains. We then further designed and constructed a transcription regulator library targeting 54 genes with 85,420 mutations, and tested this library for increased styrene resistance and production. A series of tolerant mutants not only exhibited improved styrene tolerance but also produced higher styrene concentrations compared to the parent strain. The best producing mutant, ST05 LexA_E45I, produced a 3.45-fold increase in styrene compared to the parent strain. The produced styrene was extracted via gas stripping into dodecane and used in a direct free radical synthesis of polystyrene.

09 BIOMASS FUELS↗
DOE OSTI2023

Phase imaging of irradiated foils at the OMEGA EP facility using phase-stepping X-ray Talbot–Lau deflectometry

Abstract Diagnosing the evolution of laser-generated high energy density (HED) systems is fundamental to develop a correct understanding of the behavior of matter under extreme conditions. Talbot–Lau interferometry constitutes a promising tool, since it permits simultaneous single-shot X-ray radiography and phase-contrast imaging of dense plasmas. We present the results of an experiment at OMEGA EP that aims to probe the ablation front of a laser-irradiated foil using a Talbot–Lau X-ray interferometer. A polystyrene (CH) foil was irradiated by a laser of 133 J, 1 ns and probed with 8 keV laser-produced backlighter radiation from Cu foils driven by a short-pulse laser (153 J, 11 ps). The ablation front interferograms were processed in combination with a set of reference images obtained ex situ using phase-stepping. We managed to obtain attenuation and phase-shift images of a laser-irradiated foil for electron densities above ${10}^{22}\;{\mathrm{cm}}^{-3}$ . These results showcase the capabilities of Talbot–Lau X-ray diagnostic methods to diagnose HED laser-generated plasmas through high-resolution imaging.

47 OTHER INSTRUMENTATION↗
DOE OSTI2017

Conceptual design of initial opacity experiments on the national ignition facility

Accurate models of X-ray absorption and re-emission in partly stripped ions are necessary to calculate the structure of stars, the performance of hohlraums for inertial confinement fusion and many other systems in high-energy-density plasma physics. Despite theoretical progress, a persistent discrepancy exists with recent experiments at the Sandia Z facility studying iron in conditions characteristic of the solar radiative–convective transition region. The increased iron opacity measured at Z could help resolve a longstanding issue with the standard solar model, but requires a radical departure for opacity theory. To replicate the Z measurements, an opacity experiment has been designed for the National Facility (NIF). The design uses established techniques scaled to NIF. A laser-heated hohlraum will produce X-ray-heated uniform iron plasmas in local thermodynamic equilibrium (LTE) at temperatures ${\geqslant}150$ eV and electron densities ${\geqslant}7\times 10^{21}~\text{cm}^{-3}$ . The iron will be probed using continuum X-rays emitted in a ${\sim}200$ ps, ${\sim}200~\unicode[STIX]{x03BC}\text{m}$ diameter source from a 2 mm diameter polystyrene (CH) capsule implosion. In this design, $2/3$ of the NIF beams deliver 500 kJ to the ${\sim}6$ mm diameter hohlraum, and the remaining $1/3$ directly drive the CH capsule with 200 kJ. Calculations indicate this capsule backlighter should outshine the iron sample, delivering a point-projection transmission opacity measurement to a time-integrated X-ray spectrometer viewing down the hohlraum axis. Preliminary experiments to develop the backlighter and hohlraum are underway, informing simulated measurements to guide the final design.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Fourier Transform-Plasmon Waveguide Spectroscopy: A Nondestructive Multifrequency Method for Simultaneously Determining Polymer Thickness and Apparent Index of Refraction

Fourier transform (FT)-plasmon waveguide resonance (PWR) spectroscopy measures light reflectivity at a waveguide interface as the incident frequency and angle are scanned. Under conditions of total internal reflection, the reflected light intensity is attenuated when the incident frequency and angle satisfy conditions for exciting surface plasmon modes in the metal as well as guided modes within the waveguide. Expanding upon the concept of two-frequency surface plasmon resonance developed by Peterlinz and Georgiadis [ Opt. Commun. 1996, 130, 260], the apparent index of refraction and the thickness of a waveguide can be measured precisely and simultaneously by FT-PWR with an average percent relative error of 0.4%. Measuring reflectivity for a range of frequencies extends the analysis to a wide variety of sample compositions and thicknesses since frequencies with the maximum attenuation can be selected to optimize the analysis. Additionally, the ability to measure reflectivity curves with both p- and s-polarized light provides anisotropic indices of refraction. FT-PWR is demonstrated using polystyrene waveguides of varying thickness, and the validity of FT-PWR measurements are verified by comparing the results to data from profilometry and atomic force microscopy (AFM).

36 MATERIALS SCIENCE↗
DOE OSTI2020

Functionalized Polymer Thin Films for Plutonium Capture and Isotopic Screening from Aqueous Sources

The rapid screening of plutonium from aqueous sources remains a critical challenge for nuclear nonproliferation efforts. The determination of trace-level Pu isotopes in water requires offsite sample preparation and analysis; therefore, new methods that combine plutonium purification, concentration, and isotopic screening in a fieldable detection system will provide an invaluable tool for nuclear safeguards. This contribution describes the development and characterization of thin polymer-ligand films for the isolation and concentration of waterborne Pu for direct spectroscopic analyses. Submicron thin films were prepared through spin coating onto Si wafers and consisted of combinations of polystyrene (PS) with dibenzoylmethane, thenoyltrifluoroacetone, and di(2-ethylhexyl)phosphoric acid (HDEHP). Pu uptake studies from solutions at pH from 2.3 to 6.3 indicated that only films containing HDEHP exhibited significant recovery of Pu. High alpha spectroscopy peak energy resolutions were achieved for PS-HDEHP films over a range of film thicknesses from 30 to 250 nm. Furthermore, a separate study was performed to evaluate uptake from a primarily Pu(V) solution where it was observed that doubling the HDEHP loading in the film increased uptake of Pu by an order of magnitude. X-ray photoelectron spectroscopy (XPS) analysis revealed that HDEHP was highly concentrated within the first few nanometers of the film at the higher loading. XPS analysis also revealed that, in the presence of water, HDEHP was stripped from the surface layer of the film at circumneutral pH. While significant losses of ligand were seen in all samples, higher loadings of HDEHP resulted in measurable amounts of ligand retained after a 12-h soak in water. Findings of this study are being used to guide the development of thin-film composite membrane-based detection methods for the rapid, fieldable analysis of Pu in water.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Improving Thermal Stability of Perovskite Solar Cells by Suppressing Ion Migration Using Copolymer Grain Encapsulation

Thermal stability of organic–inorganic hybrid perovskites (OIHPs) remains as one of the critical challenges against the stable operation of perovskite solar cells (PSCs) in direct sunlight with elevated temperatures. Here, we show that the addition of a polystyrene-co-polyacrylonitrile (SAN) copolymer can significantly enhance thermal stability of OIHPs and improve the stability of the corresponding PSCs by suppressing the migration of organic cations in OHIP. The methylammonium lead iodide (MAPI) with SAN incorporated within the perovskite layer featured a superior thermal stability compared to pure MAPI without SAN, only displaying an average of 5–15% decrease in PCE even after continuous thermal aging for 24 h at 100 °C. The secondary ion mass spectrometry revealed that the thermal degradation of the pure MAPI was largely associated with MA+ out-migration. Conducting atomic force microscopy analysis further indicated that the incorporated SAN led to a suppression of ionic currents present at the grain boundaries of the perovskite film, which was understood by high immiscibility between SAN and MA+ components as confirmed by the experimentally estimated Flory–Huggins parameter between them. This study newly identifies a potential of using polymer grain encapsulation for enhancing thermal stability of OIHPs and their solar cell performance by suppressing the out-diffusion of cationic organic components.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Catalytic Upcycling of Polyolefins

The large production volumes of commodity polyolefins (specifically, polyethylene, polypropylene, polystyrene, and poly(vinyl chloride)), in conjunction with their low unit values and multitude of short-term uses, have resulted in a significant and pressing waste management challenge. Only a small fraction of these polyolefins is currently mechanically recycled, with the rest being incinerated, accumulating in landfills, or leaking into the natural environment. Since polyolefins are energy-rich materials, there is considerable interest in recouping some of their chemical value while simultaneously motivating more responsible end-of-life management. An emerging strategy is catalytic depolymerization, in which a portion of the C–C bonds in the polyolefin backbone is broken with the assistance of a catalyst and, in some cases, additional small molecule reagents. When the products are small molecules or materials with higher value in their own right, or as chemical feedstocks, the process is called upcycling. This review summarizes recent progress for four major catalytic upcycling strategies: hydrogenolysis, (hydro)cracking, tandem processes involving metathesis, and selective oxidation. Key considerations include macromolecular reaction mechanisms relative to small molecule mechanisms, catalyst design for macromolecular transformations, and the effect of process conditions on product selectivity. Metrics for describing polyolefin upcycling are critically evaluated, and an outlook for future advances is described.

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

Analysis of Tar and Oil Derived from Pyrolysis and Copyrolysis of Waste Plastics and Biomass

Pyrolysis has been proposed as a potential technology for managing the growing volume of plastic waste generated worldwide. Co-pyrolysis of plastic waste with biomass is a promising technology for generating fuel and chemical products. However, this process generates tar as a waste product. The chemical properties of this tar have yet to be thoroughly analyzed. Further, this study presents the results of gas chromatography–mass spectrometry (GC–MS), Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA) of oil and tar obtained from the pyrolysis of pure plastics including high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyethylene (PE), polystyrene (PS), and plastic-biomass mixtures. GC–MS analysis revealed the presence of C 7 –C 37 carbon-containing hydrocarbons, which include alkanes and alkenes as the dominant products. FTIR data revealed the presence of various functional groups, including alcohols, aldehydes, ketones, and carboxylic acids, indicating the complexity of the pyrolysis and copyrolysis oil obtained from waste plastics and biomass. TGA data show that tar from all four plastics has a higher decomposition rate, suggesting the presence of heavier hydrocarbons compared with their corresponding oils. This research will be of interest to researchers looking to advance the study of plastic and biomass waste management.

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

Formation of Stable Radicals by Mechanochemistry and Their Application for Magic Angle Spinning Dynamic Nuclear Polarization Solid-State NMR Spectroscopy

High-field magic angle spinning (MAS) dynamic nuclear polarization (DNP) solid-state nuclear magnetic resonance (SSNMR) is becoming a common technique for improving the sensitivity in NMR by the hyperpolarization of nuclear spins. Recently, we have shown that gamma irradiation is capable of creating long-lived free radicals that are amenable to MAS DNP in quartz and a variety of organic solids. Here, we demonstrate that mechanochemical ball milling is able to generate millimolar concentrations of stable radical species in diverse materials, such as polystyrene, cellulose, borosilicate glass, and fused quartz. High-field electron paramagnetic resonance (EPR) was used to obtain further insight into the nature of the radicals formed in ball milled quartz and borosilicate glass. Finally, we further show that radicals generated in quartz by ball milling can be used for solid-effect DNP. We obtained 29 Si DNP enhancements of approximately 114 and 33 at 110 K and room temperature, respectively, from a sample of ball milled quartz.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Mesoscale Polymer Dissolution Probed by Raman Spectroscopy and Molecular Simulations

The diffusion of various solvents into a polystyrene (PS) matrix was probed experimentally by monitoring the temporal profiles of the Raman spectra and theoretically from molecular dynamics (MD) simulations of the binary system. The simulation results assist in providing a fundamental, molecular level connection between the mixing/dissolution processes and the difference = solvent – PS in the values of the Hildebrand parameter () between the two components of the binary systems: solvents having similar values of with PS (small ) exhibit fast diffusion into the polymer matrix, whereas the diffusion slows down considerably when the ’s are different (large ). To this end, the Hildebrand parameter was identified as a useful descriptor that governs the process of mixing in polymer – solvent binary systems. The experiments also provide insight into further refinements of the models specific to non-Fickian diffusion phenomena that need to be used in the simulations.

Chang, Tsun-Mei↗
DOE OSTI2018

Anisotropic Ion Diffusion and Electrochemically Driven Transport in Nanostructured Block Copolymer Electrolytes

Nanostructured block copolymer electrolytes have the potential to enable solid-state batteries with lithium metal anodes. We present complete continuum characterization of ion transport in a lamellar polystyrene-b-poly(ethylene oxide) copolymer/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolyte as a function of salt concentration. Electrochemical measurements are used to determine the Stefan–Maxwell salt diffusion coefficients $^D_{+, 0}$, $^D_{-, 0}$, and $^D_{+, -}$. Individual self-diffusion coefficients of the lithium- and TFSI-containing species were measured by pulsed-field gradient NMR (PFG-NMR). The NMR data indicate that salt diffusion is locally anisotropic, and this enables determination of a diffusion coefficient parallel to the lamellae, D ∥ , and a diffusion coefficient through defects in the lamellae, D ⊥ . We quantify anisotropic diffusion by defining an NMR morphology factor and demonstrate that it is correlated to defect density seen by transmission electron microscopy. We find agreement between the electrochemically determined Stefan–Maxwell diffusion coefficients and the diffusion coefficient D⊥ determined by PFG-NMR. Our work indicates that the performance of nanostructured block copolymer electrolytes in batteries is strongly influenced by ion transport through defects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Polymer Chain Diffusion in All-Polymer Nanocomposites: Confinement vs Chain Acceleration

All-polymer nanocomposites, in which soft, polymer-based nanoparticles are dispersed in the polymer matrix, have received great interest lately due to their potential use in a range of applications, including drug delivery and self-healing materials. However, the impact of this new class of nanoparticles on the dynamics of a linear polymer matrix in an all-polymer nanocomposite is still largely unknown. In this work, we report that the addition of polystyrene soft nanoparticles accelerates the diffusion of high molecular weight linear PS chains over a range of nanoparticle loadings. Our results show that at nanoparticle loadings below 1%, the diffusion of the linear matrix increases, presumably via a constraint release mechanism. At loadings above 1%, the increase in diffusion is mitigated by confinement effects of the nanoparticles. Thus, the response of these all-polymer nanocomposites is dominated by the balance of entropic confinement of the chain, which slows diffusion and a constraint release mechanism that speeds up the diffusion. However, the diffusion of the linear chain in the all-polymer nanocomposite is faster than that of the same chain in the melt at all loadings, diverging from the behavior of most nanocomposites with hard, impenetrable nanoparticles. Thus, the mechanism that accelerates the chain diffusion dominates in these systems. This behavior is unusual and fundamentally different than what has been reported for nanocomposites with hard inorganic nanoparticles, indicating that new perspectives are needed for these materials where the control of loading can either accelerate or decelerate the dynamics of the matrix in a distinctive manner.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Effect of Surface Alignment on Connectivity in Phosphonium-Containing Diblock Copolymer Anion-Exchange Membranes

The performance of ion-exchange membranes in fuel cells is critically linked to their ion-conducting morphology. In this report, we analyzed the connectivity of anion-exchange membranes (AEMs) by electrostatic force microscopy (EFM). As a tapping-mode AFM-based technique, EFM probes height, phase, and electrostatic force gradient through two-pass interleave scans, which reveals the direct relationship between membrane surface morphology and connectivity of the ionic domain. The AEMs are diblock copolymers of a polyisoprene (PIp) block and a polystyrenic block containing the phosphonium ion (P(R3P+)MS). Different alignments of cylinders were observed in the bulk and on the surface for AEMs with different ionexchange capacities (IECs) and preparation methods. The impacts of the cylinder alignment on the connectivity of the ionic domain were then investigated by EFM. For AEM 13 with IEC = 0.44 mmol/g and a hexagonal morphology, cylinders aligned parallel to the surface, which led to many disconnected regions observed throughout the membrane. In contrast, the perpendicularly aligned channels of AEM 16 with IEC = 0.87 mmol/g consisted only of a well-connected ionic phase throughout the membrane.

25 ENERGY STORAGE↗
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 OSTI2017

Ultralow stress, thermally stable cross-linked polymer films of polydivinylbenzene (PDVB)

Although closely related to polystyrene, poly(divinylbenzene) (PDVB) has found limited utility due to the difficulties associated with its synthesis. As a highly cross-linked polymer, PDVB is infusible and insoluble and thus nearly impossible to shape into films by either melt or solvent-based processes. Here, we report the initiated chemical vapor deposition (iCVD) of nearly stress-free, highly transparent, free-standing films of PDVB up to 25 μm thick. Films initially grow under tensile intrinsic stress but become more compressive with thickness and eventually converge to zero-stress values once they reach ≥10 μm in thickness. Upon initial heating, the evaporative loss of unreacted monomer left in the polymer matrix induces between 35 and 45 MPa of tensile stress in the films. Afterward, subsequent heating cycles induce reversible stress and film expansion behaviors. We estimate the degree of cross-linking to be 44%, resulting in high thermal stability (up to 300 °C) and mechanical stiffness (Young’s modulus of 5.2 GPa). As a result, the low stress combined with high cross-linking makes iCVD PDVB an excellent candidate for protective coatings in harsh environments.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Structured Ionomer Thin Films at Water Interface: Molecular Dynamics Simulation Insight

Controlling the structure and dynamics of thin films of ionizable polymers at water interfaces is critical to their many applications. As the chemical diversity within one polymer is increased, controlling the structure and dynamics of the polymer, which is a key to their use, becomes a challenge. Here molecular dynamics simulations (MD) are used to obtain molecular insight into the structure and dynamics of thin films of one such macromolecule at the interface with water. The polymer consists of an ABCBA topology with randomly sulfonated polystyrene (C), tethered symmetrically to flexible poly(ethylene- r -propylene) blocks (B), and end-capped by a poly( t -butylstyrene) block (A). The compositions of the interfacial and bulk regions of thin films of the ABCBA polymers are followed as a function of exposure time to water. We find that interfacial rearrangements take place where buried ionic segments migrate toward the water interface. The hydrophobic blocks collapse and rearrange to minimize their exposure to water. In conclusion, the water that initially drives interfacial reengagements breaks the ionic clusters within the film, forming a dynamic hydrophilic internal network within the hydrophobic segments.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Effect of the Micelle Opening in Self-assembled Amphiphilic Block Co-polymer Films on the Infiltration of Inorganic Precursors

Infiltration of the polymer templates with inorganic precursors using the selective vapor-phase infiltration approach, or sequential infiltration synthesis (SIS), allows the design of materials with advanced properties. Swelling of the block co-polymer (BCP) templates enables the additional control of the structure, porosity, and thickness of the composite or inorganic materials. Here, we use the highly precise quartz crystal microbalance (QCM) technique to investigate quantitatively the effect of the micelle opening by swelling and inorganic precursor infiltrating on the evolution of porosity in amphiphilic BCPs. We show that swelling of the polystyrene-block-poly-4-vinyl pyridine (PS-b-P4VP) BCP in ethanol at 75 °C occurs rapidly and results in a stable polymer structure in 30 min. By using an alumina model system, we found that swelling enables access to all available polar domains of the PS-b-P4VP film leading to an increase in the SIS-infiltrated alumina mass as compared to the nonswelled BCP layer. Our results demonstrate that swelling of the 110 nm thick BCP template results in the formation of 192 nm thick alumina films with 2 times larger alumina mass and 4 times larger effective pore volume than in case of the nonswelled sample. In the case of the thicker polymer template, the difference due to swelling becomes even more substantial because the fraction of accessible polymer is increased much more than in thin films. Our findings provide important insights into the mechanism of the infiltration of the inorganic precursors into swelled and nonswelled, spin-coated BCP templates enabling the design of highly porous thick ceramic films by SIS.

She, Yunlong↗