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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 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Tricyclononenes and tricyclononadienes as efficient monomers for controlled ROMP: understanding structure–propagation rate relationships and enabling facile post-polymerization modification

Grubbs 3rd-generation (G3) pre-catalyst-initiated ring-opening metathesis polymerization (ROMP) remains an indispensable tool in the polymer chemist's toolbox. Tricyclononenes (TCN) and tricyclononadienes (TCND) represent under-explored classes of monomers for ROMP that have the potential to both advance fundamental knowledge (e.g., structure-polymerization kinetics relationships) and serve as practical tools for the polymer chemist (e.g., post-polymerization functionalization). In this work, a library of TCN and TCND imides, monoesters, and diesters, along with their exo-norbornene counterparts, were synthesized to compare their behaviors in G3-initiated ROMP. Real-time 1 H NMR was used to study their polymerization kinetics; propagation rates ( k p ) were extracted for each monomer. To understand the relationships between monomer structure and ROMP propagation rates, density functional theory methods were used to calculate a variety of electronic and steric parameters for each monomer. While electronic parameters (e.g., HOMO energy levels) correlated positively with the measured k p values, steric parameters generally gave improved correlations, which indicates that monomer size and shape are better predictors for k p than electronic parameters for this data set. Furthermore, the TCND diester—which contains an electron-deficient cyclobutene that is resistant to ROMP—and its polymer p(TCND) are shown to be highly reactive toward DBU-catalyzed conjugate addition reactions with thiols, providing a protecting- and activating-group free strategy for post-polymerization modification.

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

Towards a theoretical understanding of excitonic properties of phthalocyanine thin films. I. Low-temperature exciton absorption spectra

Phthalocyanine (Pc)-based molecular thin films have emerged in recent years as a promising class of organic semiconductor materials for optoelectronic applications owing to their long exciton coherence length and fast exciton diffusion. However, the dependence of their exciton properties on the dimensionality and thermodynamic conditions, presence of metal ions, and effects of chemical modifications to the PC systems is not yet fully understood. As a first step towards a more comprehensive theoretical understanding of the excitonic properties of Pc thin films, we model their low-temperature exciton absorption spectra by employing the Frenkel Hamiltonian. The latter is derived from quantum-chemical estimates of site energies and exciton–exciton couplings. The predicted exciton absorption spectra of octabutoxy phthalocyanine (H 2 OBPc) is found to be strongly dependent on the dimensionality of the model as well as the distance cutoff for including the monomer–monomer exciton coupling. We also caution that the widely used dipole–dipole approximation could substantially overestimate the excitonic coupling between different monomers compared to a more accurate evaluation using the respective transition densities.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Understanding the Mn dissolution mechanism in rock salt-type Li 4 Mn 2 O 5 cathodes

For the first time, a detailed exploration of Mn dissolution in disordered rock salt (DRX) Li 4 Mn 2 O 5 is presented. Herein, we apply a suite of synchrotron and lab scale X-ray techniques to both the cathode and the separator harvested from pristine, charged, or cycled lithium half-cells containing the disordered rock salt (DRX) material Li 4 Mn 2 O 5 , in order to understand Mn dissolution processes throughout charging and discharging. Previous research has hypothesized two concurrent effects that may drive Mn dissolution in cells during cycling: acid-induced disproportionation of Jahn–Teller active Mn 3+ and structural rearrangement of the cathode lattice. Through depth probing of the Mn oxidation state in both the cathode and separator via soft X-ray absorption spectroscopy (XAS), hard XAS, and X-ray photoelectron spectroscopy (XPS) in progressive states-of-charge, as well as extended X-ray absorption fine structure (EXAFS) analysis of the local Mn environment, the primary driving force of Mn dissolution is determined to be high-voltage structural rearrangement above 4.2 V. Mn dissolution is, additionally, a main source of capacity fade in Li 4 Mn 2 O 5 DRX cells, which retain only 59% capacity after 20 cycles.

Theibault, Monica↗
DOE OSTI2018

Fundamental understanding of chemical processes in extreme ultraviolet resist materials

New photoresists are needed to advance extreme ultraviolet (EUV) lithography. The tailored design of efficient photoresists is enabled by a fundamental understanding of EUV induced chemistry. Processes that occur in the resist film after absorption of an EUV photon are discussed, and a new approach to study these processes on a fundamental level is described. The processes of photoabsorption, electron emission, and molecular fragmentation were studied experimentally in the gas-phase on analogs of the monomer units employed in chemically amplified EUV resists. To demonstrate the dependence of the EUV absorption cross section on selective light harvesting substituents, halogenated methylphenols were characterized employing the following techniques. Photoelectron spectroscopy was utilized to investigate kinetic energies and yield of electrons emitted by a molecule. The emission of Auger electrons was detected following photoionization in the case of iodo-methylphenol. Mass-spectrometry was used to deduce the molecular fragmentation pathways following electron emission and atomic relaxation. To gain insight on the interaction of emitted electrons with neutral molecules in a condensed film, the fragmentation pattern of neutral gas-phase molecules, interacting with an electron beam, was studied and observed to be similar to EUV photon fragmentation. Below the ionization threshold, electrons were confirmed to dissociate iodo-methylphenol by resonant electron attachment.

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

Understanding the mechanism of hardness enhancement in tantalum-substituted tungsten monoboride solid solutions

The differential strain behavior of Ta x W 1-x B solid solutions has been studied as a function of composition using high-pressure radial X-ray diffraction in a diamond-anvil cell under non-hydrostatic pressure (up to ~65 GPa) to understand the hardening mechanisms in this family of materials. The hardness of tungsten monoboride (WB) can be increased by adding tantalum and reaches a maximum at a doping level of 50 at. % with a value of 42.8 ± 2.6 GPa under an applied load of 0.49 N. Plateaus were observed in the differential strain data for both the (020) and (002) directions, suggesting that this is the primary slip system in this material. These plateaus were modified by the addition of Ta, indicating that strengthening of the (002) and (020) planes by solid solution hardening was primarily responsible for the hardness enhancements in Ta x W 1-x B solid solutions. In contrast, the differential strain supported by the (200) plane linearly increases with pressure up to the highest pressures reached in this work (>60 GPa) and shows almost no change with metal composition. Because of the very different compression behavior in the (200) and (020) planes, change in the b/a ratio with pressure provides a unique way to visualize the onset of plastic behavior. This onset varies from ~15 GPa for samples with 5% Ta to more than 30 GPa for the sample with 50% Ta. Finally, the ambient bulk modulus of each solid-solution sample was determined using the second-order Birch-Murnaghan equation-of-state and found to be ~340 GPa for all phases.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Understanding the anharmonic vibrational structure of the carbon dioxide dimer

Understanding the vibrational structure of the CO 2 system is important to confirm the potential energy surface and interactions in such van der Waals complexes. In this work, we use our previously developed mbCO2 potential function to explore the vibrational structure of the CO 2 monomer and dimer. The potential function has been trained to reproduce the potential energies at the CCSD(T)-F12b/aug-cc-pVTZ level of electronic structure theory. The harmonic approximation, as well as anharmonic corrections using vibrational structure theories such as vibrational self-consistent field, vibrational second-order Moller-Plesset perturbation, and vibrational configuration interaction (VCI), is applied to address the vibrational motions. We compare the vibrational results using the mbCO2 potential function with traditional electronic structure theory results and to experimental frequencies. The anharmonic results for the monomer most closely match the experimental data to within 3 cm -1 , including the Fermi dyad frequencies. The intermolecular and intramolecular dimer frequencies were treated separately and show good agreement with the most recent theoretical and experimental results from the literature. The VCI treatment of the dimer vibrational motions accounts for vibrational mixing and delocalization, such that we observe the dimer Fermi resonance phenomena, both in the intramolecular and intermolecular regions.

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

Understanding turbulence in compressing plasma as a quasi-EOS

Inspired by experimental Z-pinch results, we investigate plasma turbulence undergoing compression. In addition to Z-pinches, plasma turbulence can be compressed in a range of natural and laboratory settings, including inertial fusion experiments and astrophysical molecular clouds. The plasma viscosity, when modeled as described by Braginskii, depends strongly on both temperature and ionization state, giving it the possibility to have a large range of behavior. Here, we highlight the importance of viscous variation in these settings, as well as various insights that can be gained by considering this variation. Included are a “sudden viscous dissipation” effect that leads to a new concept for inertial fusion or X-ray bursts and a bound on turbulent energy behavior under compression. This bound, which was previously applied in inviscid molecular cloud turbulence, is here shown in an application to turbulence that transitions from inviscid to viscous regimes. In conclusion, the task of understanding turbulence under compression can be cast as the process of seeking a “quasi equation of state” for turbulent energy under compression.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Second harmonic microscopy of poled x-cut thin film lithium niobate: Understanding the contrast mechanism

Thin film lithium niobate has been of great interest recently, and an understanding of periodically poled thin films is crucial for both fundamental physics and device developments. Second-harmonic (SH) microscopy allows for the noninvasive visualization and analysis of ferroelectric domain structures and walls. While the technique is well understood in bulk lithium niobate, SH microscopy in thin films is largely influenced by interfacial reflections and resonant enhancements, which depend on film thicknesses and substrate materials. We present a comprehensive analysis of SH microscopy in x-cut lithium niobate thin films, based on a full three-dimensional focus calculation and accounting for interface reflections. We show that the dominant signal in backreflection originates from a copropagating phase-matched process observed through reflections, rather than direct detection of the counterpropagating signal as in bulk samples. We simulate the SH signatures of domain structures by a simple model of the domain wall as an extensionless transition from a −χ(2) to a +χ(2) region. This allows us to explain the main observation of domain structures in the thin-film geometry, and, in particular, we show that the SH signal from thin poled films allows to unambiguously distinguish areas, which are completely or only partly inverted in depth.

Rüsing, M. (ORCID:0000000346824577)↗
DOE OSTI2019

Understanding the effects of dipolar interactions on the thermodynamics of diblock copolymer melts

We present results highlighting the roles of dipolar interactions in affecting thermodynamics of diblock copolymer melts. Field theoretic methods and coarse-grained molecular dynamics (MD) simulations are used to understand the effects of dipolar interactions among copolymer segments. In particular, the effects of dipolar interactions on disorder-lamellar transition and domain spacing of the lamellar morphology are studied. It is shown that dipolar interactions stabilize the lamellar morphology over the disordered phase. Furthermore, the domain spacing for the lamellar morphology is predicted to increase with an increase in disparity between dipole moments of two kinds of monomers in the diblock or equivalently a mismatch in the dielectric constant of homopolymers forming the diblock. MD simulations reveal that additional orientational effects resulting from the anisotropic nature of the dipolar interaction potential are significant for highly polar monomers. In contrast, the field theoretic models based on orientationally averaged dipolar interaction potentials, such as those used in this work, fail to capture the effects of orientational correlations.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Understanding thermal annealing of artificial spin ice

Here, we have performed a detailed study on thermal annealing of the moment configuration in artificial spin ice. Permalloy (Ni 80 Fe 20 ) artificial spin ice samples were examined in the prototypical square ice geometry, studying annealing as a function of island thickness, island shape, and annealing temperature and duration. We also measured the Curie temperature as a function of film thickness, finding that thickness has a strong effect on the Curie temperature in regimes of relevance to many studies of the dynamics of artificial spin ice systems. Increasing the interaction energy between island moments and reducing the energy barrier to flipping the island moments allow the system to more closely approach the collective low energy state of the moments upon annealing, suggesting new channels for understanding the thermalization processes in these important model systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Understanding ICF hohlraums using NIF gated laser-entrance-hole images

The newly available ns-gated laser-entrance-hole (LEH) imager on the National Ignition Facility provides routine, non-perturbative measurements of the x-ray emission from laser-heated plasmas inside the hohlraum as viewed at 19° to the hohlraum axis through one of its LEHs. Multiple images are acquired for a series of times and filter-selected x-ray energy bands within a single shot. The images provide time dependent data on phenomena including the effective radius of the LEH, the length of the gold-plasma “bubble” evolving off the interior wall surface heated by the outer beams, the evolving radius of the x-ray heated hohlraum wall, and the radius of the ablation front of the fusion capsule. Here, these measurements are explained and illustrated with sample data. These techniques are then applied to understand hohlraum behavior as a function of gas fill. For hohlraums with helium gas fill densities of 0.15 to 0.30 mg/cm 3 , synthetic images computed from simulations agree well with experimental gated LEH images when an inhibited heat transport model [Jones et al., Phys. Plasmas 24, 056312 (2017)] is used. This model can be adjusted to reproduce the expansion rate of the laser-heated plasma bubble in such a way as to improve agreement with the images. At the higher 0.6 mg/cc gas fill, the experimental images show more pronounced 3D features, resulting in slightly less good agreement with the 2D simulations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Progress towards a phenomenological picture and theoretical understanding of glassy dynamics and vitrification near interfaces and under nanoconfinement

The nature of alterations to dynamics and vitrification in the nanoscale vicinity of interfaces-commonly referred to as "nanoconfinement" effects on the glass transition-has been an open question for a quarter century. We first analyze experimental and simulation results over the last decade to construct an overall phenomenological picture. Key features include the following: after a metrology- and chemistry-dependent onset, near-interface relaxation times obey a fractional power law decoupling relation with bulk relaxation; relaxation times vary in a double-exponential manner with distance from the interface, with an intrinsic dynamical length scale appearing to saturate at low temperatures; the activation barrier and vitrification temperature T-g approach bulk behavior in a spatially exponential manner; and all these behaviors depend quantitatively on the nature of the interface. We demonstrate that the thickness dependence of film-averaged T-g for individual systems provides a poor basis for discrimination between different theories, and thus we assess their merits based on the above dynamical gradient properties. Entropy-based theories appear to exhibit significant inconsistencies with the phenomenology. Diverse free-volume-motivated theories vary in their agreement with observations, with approaches invoking cooperative motion exhibiting the most promise. The elastically cooperative nonlinear Langevin equation theory appears to capture the largest portion of the phenomenology, although important aspects remain to be addressed. A full theoretical understanding requires improved confrontation with simulations and experiments that probe spatially heterogeneous dynamics within the accessible 1-ps to 1-year time window, minimal use of adjustable parameters, and recognition of the rich quantitative dependence on chemistry and interface. Published under license by AIP Publishing.

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

Understanding the effects of radiative preheat and self-emission from shock heating on equation of state measurement at 100s of Mbar using spherically converging shock waves in a NIF hohlraum

Over the last six years many experiments have been done at the National Ignition Facility to measure the Hugoniot of materials, such as CH plastic at extreme pressures, up to 800 Mbar. The “Gbar” design employs a strong spherically converging shock launched through a solid ball of material using a hohlraum radiation drive. Here, the shock front conditions are characterized using x-ray radiography. In this paper we examine the role of radiation in heating the unshocked material in front of the shock to understand the impact it has on equation of state measurements and how it drives the measured data off the theoretical Hugoniot curve. In particular, the two main sources of radiation heating are the preheating of the unshocked material by the high-energy kilo-electron-volt x-rays in the hohlraum and the heating of the material in front of the shock, as the shocked material becomes hot enough to radiate significantly. Using our model, we estimate that preheating can reach 4 eV in unshocked material, and that radiation heating can begin to drive data off the Hugoniot significantly, as pressures reach above 400 Mb.

Equations of state↗
DOE OSTI2020

Understanding chemical and physical mechanisms in atomic layer deposition

Atomic layer deposition (ALD) is a powerful tool for achieving atomic level control in the deposition of thin films. However, several physical and chemical phenomena can occur which cause deviation from “ideal” film growth during ALD. Understanding the underlying mechanisms that cause these deviations is important to achieving even better control over the growth of the deposited material. Herein, we review several precursor chemisorption mechanisms and the effect of chemisorption on ALD growth. We then follow with a discussion on diffusion and its impact on film growth during ALD. Together, these two fundamental processes of chemisorption and diffusion underlie the majority of mechanisms which contribute to material growth during a given ALD process, and the recognition of their role allows for more rational design of ALD parameters.

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

Advances in physics understanding of high poloidal beta regime toward steady-state operation of CFETR

Experimental and modeling investigations of the high βp scenarios on the DIII-D and EAST tokamaks show advantages in high energy confinement, avoidance of n = 1 MHD, and core-edge integration with reduced heat flux, making this scenario an attractive option for CFETR steady-state operation. Experiments show that plasmas with high confinement and high density can be achieved with neutral beam injection on DIII-D (β p ~ 2.2, β N ~ 3.5, f BS ~ 50%, f Gw ~ 1.0, H 98y2 ~ 1.5) and pure RF power on EAST (β P ~ 2.0, β N ~ 1.6, f BS ~ 50%, f Gw ~ 0.8, H 98y2 > 1.3). By tailoring the current density profile, a q-profile with local (off-axis) negative shear is achieved that yields improved confinement and MHD stability. Transport analysis and simulation suggest that the combination of high density gradient and high Shafranov shift allows turbulence stabilization and higher confinement. Using on-axis ECH injection, tungsten accumulation is avoided on EAST, and this is reproduced in modeling. Reduced heat flux (by >40%) and maintenance of high core confinement is achieved with active feedback control of the radiated divertor, an important result for long pulse operation in tokamaks. In conclusion, the improved physics understanding and validated modeling tools are used to design a 1GW steady-state scenario for CFETR.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

A first-principles understanding of point defects and impurities in GaN

Attaining control over the electrical conductivity of gallium nitride through impurity doping is one of the foremost achievements in semiconductor science. Yet, unwanted contaminants and point defects continue to limit device performance, and experimental techniques alone are insufficient for elucidating the behavior of these unintentionally incorporated species. Methodological advancements have made first-principles calculations more powerful than ever and capable of quantitative predictions, though care must still be taken in comparing results from theory and experiment. In this Tutorial, we explain the basic concepts that define the behavior of dopants, unintentional impurities, and point defects in GaN. We also describe how to interpret experimental results in the context of theoretical calculations and also discuss how the properties of defects and impurities vary in III-nitride alloys. Lastly, we examine how the physics of defects and impurities in GaN is relevant for understanding other wide-bandgap semiconductor materials, such as the II–IV-nitrides, boron nitride, and the transition metal nitrides.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Using statistical modeling to predict and understand fusion experiments

Over 300 cryogenic layered direct-drive inertial confinement fusion implosions have been successfully executed on the OMEGA Laser System in the last decade. However, extracting sufficient understanding from these experiments to develop new designs or to identify or mitigate degradation sources remains challenging. Recently, a statistical modeling approach was developed to successfully design and predict improved implosion experiments on OMEGA. Here, we show that one-dimensional simulations can be used to predict the outcomes of systematically perturbed three-dimensional simulations and that this statistical modeling approach can be used to identify or rule out physical mechanisms for some of the degradation sources observed on the OMEGA Laser System for direct-drive cryogenic inertial confinement fusion. In this instance, we investigate the fusion yield dependencies on the ion temperature asymmetries and laser beam size observed in experiments by comparing with trends in three-dimensional synthetic simulation databases. Using the statistical model on these systematically perturbed simulations, we find that the statistically inferred dependency on the measured ion temperature asymmetries is well explained by imposed ℓ =1 modes. However, we find that the dependency on the laser beam size is only dominated by the illumination non-uniformity for some extreme cases.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗