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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Error field measurements and correction on MUSE permanent magnet stellarator

The magnetic field topology and error fields are measured in the MUSE permanent magnet stellarator with an electron beam and fluorescent rod. The effective magnetization of the magnets is determined by measuring rational flux surface locations. Electron magnetic drift effects must be considered self-consistently due to the small magnetic shear on MUSE. Error fields are characterized by flux surface shape deviation and magnetic island chain width and phase. Error fields are then corrected by adjusting the permanent magnet (PM) holders as rigid bodies. Resonant error fields are on the order of or smaller than 3 x 10 -6 of the toroidal field after correction and surface shape matches well with the design. Resonant components of the quasi-symmetry deviation are estimated, using a novel magnetic drift measurement, to be in the 10 −4 range. The PM approach is validated as a low-cost and precise way to build optimized stellarators.

electron beam mapping↗
DOE OSTI2018

Thermally Rearranged Polymer Membranes Containing Tröger's Base Units Have Exceptional Performance for Air Separations

Abstract The influence of segmental chain motion on the gas separation performance of thermally rearranged (TR) polymer membranes is established for TR polybenzoxazoles featuring Tröger's base (TB) monomer subunits as exceptionally rigid sites of contortion along the polymer backbone. These polymers are accessed from solution‐processable ortho‐acetate functionalized polyimides, which are readily synthesized as high‐molecular‐weight polymers for membrane casting. We find that thermal rearrangement leads to a small increase in d‐spacing between polymer chains and a dramatic pore‐network reconfiguration that increases both membrane permeability and O 2 /N 2 selectivity, putting its performance above the 2015 upper bound.

Meckler, Stephen M.↗
DOE OSTI2018

Thermally Rearranged Polymer Membranes Containing Tröger's Base Units Have Exceptional Performance for Air Separations

The influence of segmental chain motion on the gas separation performance of thermally rearranged (TR) polymer membranes is established for TR polybenzoxazoles featuring Tröger's base (TB) monomer subunits as exceptionally rigid sites of contortion along the polymer backbone. These polymers are accessed from solution-processable ortho-acetate functionalized polyimides, which are readily synthesized as high-molecular-weight polymers for membrane casting. We discover that thermal rearrangement leads to a small increase in d-spacing between polymer chains and a dramatic pore-network reconfiguration that increases both membrane permeability and O 2 /N 2 selectivity, enabling its performance above the 2015 upper bound.

36 MATERIALS SCIENCE↗
DOE OSTI2022

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↗
DOE OSTI2016

Self-assembly and glass-formation in a lattice model of telechelic polymer melts: Influence of stiffness of the sticky bonds

Telechelic polymers are chain macromolecules that may self-assemble through the association of their two mono-functional end groups (called “stickers”). A deep understanding of the relation between microscopic molecular details and the macroscopic physical properties of telechelic polymers is important in guiding the rational design of telechelic polymer materials with desired properties. The lattice cluster theory (LCT) for strongly interacting, self-assembling telechelic polymers provides a theoretical tool that enables establishing the connections between important microscopic molecular details of self-assembling polymers and their bulk thermodynamics. The original LCT for self-assembly of telechelic polymers considers a model of fully flexible linear chains [J. Dudowicz and K. F. Freed, J. Chem. Phys. 136, 064902 (2012)], while our recent work introduces a significant improvement to the LCT by including a description of chain semiflexibility for the bonds within each individual telechelic chain [W.-S. Xu and K. F. Freed, J. Chem. Phys. 143, 024901 (2015)], but the physically associative (or called “sticky”) bonds between the ends of the telechelics are left as fully flexible. Motivated by the ubiquitous presence of steric constraints on the association of real telechelic polymers that impart an additional degree of bond stiffness (or rigidity), the present paper further extends the LCT to permit the sticky bonds to be semiflexible but to have a stiffness differing from that within each telechelic chain. An analytical expression for the Helmholtz free energy is provided for this model of linear telechelic polymer melts, and illustrative calculations demonstrate the significant influence of the stiffness of the sticky bonds on the self-assembly and thermodynamics of telechelic polymers. A brief discussion is also provided for the impact of self-assembly on glass-formation by combining the LCT description for this extended model of telechelic polymers with the Adam-Gibbs relation between the structural relaxation time and the configurational entropy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Nuclear Spin Relaxation and Molecular Interactions of a Novel Triazolium-Based Ionic Liquid

Nuclear spin relaxation, small-angle X-ray scattering (SAXS), and electrospray ionization mass spectrometry (ESI-MS) techniques are used to determine supramolecular arrangement of 3-methyl-1-octyl-4-phenyl-1H-triazol-1,2,3-ium bis(trifluoromethanesulfonyl)imide [OMPhTz][Tf{sub 2}N], an example of a triazolium-based ionic liquid. The results obtained showed first-order thermodynamic dependence for nuclear spin relaxation of the anion. First-order relaxation dependence is interpreted as through-bond dipolar relaxation. Greater than first-order dependence was found in the aliphatic protons, aromatic carbons (including nearest neighbors), and carbons at the end of the aliphatic tail. Greater than first order thermodynamic dependence of spin relaxation rates is interpreted as relaxation resulting from at least one mechanism additional to through-bond dipolar relaxation. In rigid portions of the cation, an additional spin relaxation mechanism is attributed to anisotropic effects, while greater than first order thermodynamic dependence of the octyl side chain’s spin relaxation rates is attributed to cation–cation interactions. Little interaction between the anion and the cation was observed by spin relaxation studies or by ESI-MS. No extended supramolecular structure was observed in this study, which was further supported by MS and SAXS. nuclear Overhauser enhancement (NOE) factors are used in conjunction with spin–lattice relaxation time (T{sub 1}) measurements to calculate rotational correlation times for C–H bonds (the time it takes for the vector represented by the bond between the two atoms to rotate by one radian). The rotational correlation times are used to represent segmental reorientation dynamics of the cation. A combination of techniques is used to determine the segmental interactions and dynamics of this example of a triazolium-based ionic liquid.

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

Chain entanglements enable regeneration of high-performance thermosets

Thermoset plastics underpin structural materials, electronics and transportation, yet the permanent covalent networks that prevent flow and provide dimensional stability also make them difficult to recycle without sacrificing performance. In this work we show that high-performance thermosets can be built around dense chain entanglements, the physical interlacing of long polymer strands, rather than dense permanent crosslinks, with only a small number of selectively cleavable junctions preserving connectivity. Long, rigid, entangled polyolefin backbones generated by frontal polymerization form glassy polymers with high stiffness, high toughness and excellent creep suppression yet can be fully deconstructed into soluble, linear oligomers. Varying oligomer length and end-group chemistry enables their reuse as re-entangling building blocks that regenerate thermosets with thermal and mechanical properties that remain unchanged across generations. The strategy further extends to high-temperature fibre-reinforced composite matrices and additively manufactured structures, establishing chain entanglement as a design principle for durable, regenerable thermosets.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Role of tunable polymer flexibility in controlling wetting behavior and thermal properties of poly(1,3-cyclohexadiene)-silica nanocomposites

We present how altering the chain flexibility affects the nanoscale organization of polymer-grafted nanoparticles (PGNPs) and its ultimate impact on macroscale thermal properties. To isolate the role of chain flexibility on wetting behavior in athermal polymer nanocomposites (PNC), the graft and matrix chemistry is kept identical by utilizing 1,3-cyclohexadiene-based polymer materials. Increasing the rigidity and molecular weight of both the graft and matrix is found to favor mixing of poly(1,3-cyclohexadiene) PCHD-grafted silica NPs with the matrix, supported by a concomitant increase in glass transition temperatures of the PNCs. Further, the associated entropic factors that drive wetting behavior and dispersion of PGNPs are discussed, emphasizing the dominant role-played by chain flexibility. Alterations in graft flexibility had the strongest impact on dispersion and Tg values of the PNC, while molecular weight (MW) plays a secondary role. This investigation is a unique demonstration of how chain flexibility alteration in athermal semiflexible systems can be used to alter NP organization by altering filler-matrix wettability which also impacts thermal properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Interaction of a magnetic island chain in a tokamak plasma with a resonant magnetic perturbation of rapidly oscillating phase

An investigation is made here into the interaction of a magnetic island chain, embedded in a tokamak plasma, with an externally generated magnetic perturbation of the same helicity whose helical phase is rapidly oscillating. The analysis is similar in form to the classic analysis used by Kapitza [Sov. Phys. JETP 21, 588 (1951)] to examine the angular motion of a rigid pendulum whose pivot point undergoes rapid vertical oscillations. The phase oscillations are found to modify the existing terms, and also to give rise to new terms, in the equations governing the secular evolution of the island chain's radial width and helical phase. An examination of the properties of the new secular evolution equation reveals that it is possible to phase-lock an island chain to an external magnetic perturbation with an oscillating helical phase in a stabilizing phase relation provided that the amplitude, ϵ, of the phase oscillations (in radians) is such that | J 0 ( ϵ ) | << 1 , and the mean angular frequency of the perturbation closely matches the natural angular frequency of the island chain.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2015

Different singularities in the functions of extended kinetic theory at the origin of the yield stress in granular flows

We use previous results from discrete element simulations of simple shear flows of rigid, identical spheres in the collisional regime to show that the volume fraction-dependence of the stresses is singular at the shear rigidity. Here, we identify the shear rigidity, which is a decreasing function of the interparticle friction, as the maximum volume fraction beyond which a random collisional assembly of grains cannot be sheared without developing force chains that span the entire domain. In the framework of extended kinetic theory, i.e., kinetic theory that accounts for the decreasing in the collisional dissipation due to the breaking of molecular chaos at volume fractions larger than 0.49, we also show that the volume fraction-dependence of the correlation length (measure of the velocity correlation) is singular at random close packing, independent of the interparticle friction. The difference in the singularities ensures that the ratio of the shear stress to the pressure at shear rigidity is different from zero even in the case of frictionless spheres: we identify that with the yield stress ratio of granular materials, and we show that the theoretical predictions, once the different singularities are inserted into the functions of extended kinetic theory, are in excellent agreement with the results of numerical simulations.

42 ENGINEERING↗
DOE OSTI2022

Tuning the Mechanical and Electric Properties of Conjugated Polymer Semiconductors: Side–Chain Design Based on Asymmetric Benzodithiophene Building Blocks

Understanding molecular design rules for stretchable polymer semiconductors is important for enabling next generation stretchable electronic circuits. To simultaneously improve both electrical properties and mechanical stretchability, a design strategy is reported in introducing conjugated rigid fused-rings with bulky side groups in semiconducting polymers. In this work, the understanding of this design concept is improved by systematically investigating the effect of different types of bulky side groups asymmetrically substituted on conjugated polymer semiconductor backbones. Specifically, four types of side groups are investigated, including naphthalene (NaPh), biphenyl (PhPh), thienylphenyl (ThPh), and alkylphenyl (C4Ph), asymmetrically substituted on benzodithiophene units, namely asy-BDT. With the four types of side groups installed on BDT-containing conjugated polymers in an asymmetrical fashion, it is observed that they reduced the polymer chain aggregation and film crystallinity, hence improving the film stretchability. Furthermore, the fully conjugated polymer back-bone allows maintenance of good charge carrier mobilities. Specifically, polymer PDPP-C4Ph (with C4Ph side groups) shows the highest mobility in the fully stretchable transistor and maintained its mobility even after being subjected to hundreds of stretching-releasing cycles at 25% strain. Altogether, the results provide anunderstanding of the use of asymmetrically substituted fused-ring conjugated polymer structures to tune mechanical and charge transport properties.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Bonding Hierarchy Gives Rise to High Thermoelectric Performance in Layered Zintl Compound BaAu 2 P 4

The search for new thermoelectric materials has gained rapid progress in recent years as thermoelectric technology offers the potential for environmentally friendly and sustainable energy conversion methods from waste heat to electricity. In this work, we use first-principles calculations based on density functional theory to predict high thermoelectric performance in BaAu 2 P 4 , a layered Zintl compound with a small band gap. BaAu 2 P 4 exhibits crystallographic heterogeneity in which rigid [Au 2 P 4 ] 2– units are separated by layers of Ba 2+ cations, which are bonded relatively weakly to the lattice through electrostatic interactions. The phosphorus atoms are covalently bonded to each other and form infinite chains within the crystal. While the phosphorus chains facilitate large electrical conductivity, the presence of multiple bands near the Fermi level gives rise to an enhanced Seebeck coefficient. On the other hand, the loosely bound Ba along with Au strongly scatter the heat carrying acoustic phonons, significantly reducing the lattice thermal conduction along the stacking direction. As a consequence of this bonding hierarchy (i.e., coexisting rigid and fluctuating sublattices), BaAu 2 P 4 exhibits a large power factor and low lattice thermal conductivity, which results in a high thermoelectric figure of merit ($zT$). Thus, our findings should encourage the exploration of new thermoelectric materials in the family of layered compounds with small band gaps and crystallographic heterogeneity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Intrinsically Hierarchical Nanoporous Polymers via Polymerization-Induced Microphase Separation

The synthesis of microporous polymers generally requires postpolymerization modification via hyper-cross-linking to trap the polymeric network in a state with high void volume. An alternative approach utilizes rigid, sterically demanding monomers to inhibit efficient packing, thus leading to a high degree of free volume between polymer side groups and main chains. In this work we combine polymers of intrinsic microporosity with polymerization-induced microphase separation (PIMS), a versatile methodology for the synthesis of nanostructured materials that can be rendered mesoporous. Copolymerization of various styrenic monomers with divinylbenzene in the presence of a poly(lactide) terminated with a chain-transfer agent (PLA-CTA) results in kinetic trapping of a microphase-separated state. Subsequent etching of PLA provides a bicontinuous mesoporous network. Using equilibrium and kinetic nitrogen sorption experiments as well as positron annihilation lifetime spectroscopy (PALS), we demonstrate that variations in the steric characteristics of the styrenic monomer impart the network with microporosity, resulting in hierarchically (meso and micro) porous materials. Additionally, structure–property relationships of the styrenic monomer with total surface area and pore volume indicate that the glass transition temperature (T g ) of the corresponding styrenic homopolymers provides a reasonable measure of the steric interactions and resultant microporosity in these systems. Finally, PALS provides insight into micro- and mesoscopic void volume differences between porous monoliths containing either tert-butyl or TMS-modified styrenic monomers compared to the parent, unmodified styrene.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Intramolecular structure and dynamics in computationally designed peptide-based polymers displaying tunable chain stiffness

Here, polymers assembled using computationally designed coiled coil bundlemers display tunable stiffness via control of interbundlemer covalent connectivity as confirmed using small-angle neutron scattering. Neutron spin echo spectroscopy reveals that rigid rod polymers show a decay rate Γ~Q 2 (Q is the scattering vector) expected of straight cylinders. Semirigid polymers assembled using bundlemers linked via 4-armed organic linker show flexible segmental dynamics at mid-Q and Γ~Q 2 behavior at high Q. The results give insight into linker flexibility-dependent interbundlemer dynamics in the hybrid polymers.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Artificial Transmembrane Channel Constructed from Shape-Persistent Covalent Organic Molecular Cages Capable of Ion and Small Molecule Transport

Shape-persistent arylene ethynylene molecular cages have been investigated as transmembrane channels for ions and small molecules. The molecular cages were obtained starting from tetrayne monomers through alkyne metathesis cyclooligomerization. We found these porphyrin-based rigid molecular cages can insert into the lipid bilayer and efficiently transport ions and small molecules (e.g., calcein). Our study reveals longer hydrophobic alkyl chains on the cage molecule promote the channeling efficiency, while shorter and/or more polar side chains impair such activity. Kinetic analysis shows linear correlation between the rate of proton transport and the concentration of the cage, suggesting the active species is likely a monomeric cage. We found that C70-encapsulated cages are nearly inactive for transmembrane ion transportation, indicating that ions are likely transported through the internal cavity of the cage. Discrete shape-persistent organic cages represent highly stable synthetic ion channels or pores, which could have interesting applications in biomimetic signaling and drug delivery.

alkyne metathesis↗
DOE OSTI2026

Microstructure of amide-functionalized polyethylenes determined by NMR relaxometry

Amidation of polyethylenes creates a range of amide-containing materials with enhanced properties, but the effect of these functional groups on the microstructure of these new materials is not known. Here we employ solid-state nuclear magnetic resonance (NMR) techniques to analyze the microstructure of amide-modified polyethylenes. While a decrease in crystallinity was observed with increasing amounts of functionalization, we found by measuring the chain mobility of the crystalline, amorphous, and interphasial regions of the polyethylenes with NMR relaxation techniques that the grafted amidyl groups partition into the rigid amorphous fraction (RAF) between the crystalline and amorphous regions. The chemical specificity of these NMR experiments creates precise assessments of the location of functional groups within the materials. Together, these insights into the microstructure and morphology of amide-containing polyethylenes lay a foundation for a deeper understanding of the structure and properties of functional polyolefins.

Haber, Shira [Lawrence Berkeley National Laborator↗