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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 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Frictional behavior and adhesion of Ag and Au films applied to aluminum oxide by oxygen-ion assisted Screen Cage Ion Plating (SCIP)

A modified dc-diode ion plating system, by utilizing a metallic screen cage as a cathode, is introduced for coating nonconductors such as ceramics. Screen cage ion plating (SCIP) is used to apply Ag and Au lubricating films on aluminum oxide surfaces. This process has excellent ability to coat around corners to produce three-dimensional coverage of the substrate. A dramatic increase in adhesion is achieved when plating is performed in a reactive 50 percent O2 - 50 percent Ar glow discharge compared to the adhesion when plating is performed in 100 percent Ar. The presence of oxygen ion assistance contributes to the excellent adhesion as measured in a pull-type adhesion tester. The Ag and Au film adhesion is significantly increased (less than 70MPa) and generally exceeds the cohesion of the substrate such that portions of the alumina are pulled out.

Spalvins, Talivaldis↗
DOE OSTI2019

Dynamical properties of a room temperature ionic liquid: Using molecular dynamics simulations to implement a dynamic ion cage model [plus supplemental information]

The transport behavior of ionic liquids (ILs) is pivotal for a variety of applications, especially when ILs are used as electrolytes. Many aspects of the transport dynamics of ILs remain to be understood. Here, a common ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimNTf 2 ), was studied with molecular dynamics simulations. The results show that BmimNTf 2 displays typical structural relaxation, subdiffusive behavior, and a breakdown of the Stokes-Einstein diffusion relation as in glass-forming liquids. In addition, the simulations show that the translational dynamics, reorientation dynamics, and structural relaxation dynamics are well described by the Vogel-Fulcher-Tammann equation like fragile glass forming liquids. Building on previous work that employed ion cage models, it was found that the diffusion dynamics of the cations and anions were well described by a hopping process random walk where the step time is the ion cage lifetime obtained from the cage correlation function. Detailed analysis of the ion cage structures indicated that the electrostatic potential energy of the ion cage dominates the diffusion dynamics of the caged ion. The ion orientational relaxation dynamics showed that ion reorientation is a necessary step for ion cage restructuring. The dynamic ion cage model description of ion diffusion presented here may have implications for designing ILs to control their transport behavior.

36 MATERIALS SCIENCE↗
NASA NTRS1995

Screen-Cage Ion Plating Of Silver On Polycrystalline Alumina

Screen-cage ion plating (SCIP) cost-effective technique offering high throwing power for deposition of adherent metal films on ceramic substrates. Applies silver films to complexly shaped substrates of polycrystalline alumina. Silver adheres tenaciously and reduces friction. SCIP holds promise for applying lubricating soft metallic films to high-temperature ceramic components of advanced combustion engines. Other potential uses include coating substrates with metal for protection against corrosion, depositing electrical conductors on dielectric substrates, making optically reflective or electrically or thermally conductive surface layers, and applying decorative metal coats to ceramic trophies or sculptures.

Spalvins, Talivaldis↗
NASA NTRS1992

Screen Cage Ion Plating (SCIP) and scratch testing of polycrystalline aluminum oxide

A screen cage ion plating (SCIP) technique was developed to apply silver films on electrically nonconducting aluminum oxide. It is shown that SCIP has remarkable throwing power; surfaces to be coated need not be in direct line of sight with the evaporation source. Scratch tests, employing a diamond stylus with a 200 micro m radius tip, were performed on uncoated and on silver coated alumina. Subsequent surface analysis show that a significant amount of silver remains on the scratched surfaces, even in areas where high stylus load produced severe crack patterns in the ceramic. Friction coefficients were lowered during the scratch tests on the coated alumina indicating that this modification of the ion planting process should be useful for applying lubricating films of soft metals to electrical insulating materials. The very good throwing power of SCIP also strongly suggests general applicability of this process in other areas of technology, e.g., electronics, in addition to tribology.

Spalvins, Talivaldis↗
DOE OSTI2019

Effect of an external electric field on the dynamics and intramolecular structures of ions in an ionic liquid

Simulations of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide in an external electric field have been performed using a Drude particle polarizable force field. The structure of the ions has been analyzed, with close attention paid to the configurations of the ions. The “charge arm” concept is used to explain certain changes of these configurations that would be difficult to rationalize otherwise, e.g., trans → cis isomerization of the bis(trifluoromethylsulfonyl)imide anion and extension of the alkyl chain of the cation. It has also been shown that the ions orient themselves so that their charge arms align with and stretch out along the field, and these effects occur at lower external electric field strengths than cause a change in the inherent diffusion of the ions. Here, the dynamics of the system parallel and perpendicular to the field were analyzed, and it was found that the applied field affected the diffusion normal to the field. This is explained as a secondary effect of a change in the ion cage formed by the surrounding counterions of a given ion in the ionic liquid. The breakdown of the ion cages was rationalized by correlating changes to the inherent diffusion of the ions with other changes to the diffusion and bulk structure of the liquid, as well as considering the average forces on the ions compared to the force the ions would be expected to experience in an electric field. Parallel to the field, a drift was observed at every electric field studied. In electric fields with no changes to the ion cage structure, the relationship between the drift and electric field was found to be linear, becoming nonlinear as the ion cage structure breaks down.

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

Diversity-oriented synthesis of polymer membranes with ion solvation cages

Microporous polymers feature shape-persistent free volume elements (FVEs), which are permeated by small molecules and ions when used as membranes for chemical separations, water purification, fuel cells, and batteries. It remains a significant challenge to identify FVEs with analyte specificity, due to difficulties in generating microporous polymer libraries with sufficient diversity for screening their properties. Here, we describe a diversity-oriented synthetic (DOS) strategy for microporous polymer membranes from which we identified those whose FVEs serve as solid solvation cages for lithium ions (Li + ). Furthermore, key elements of our strategy included diversification of bis(catechol)-type monomers via multi-component Mannich reactions to introduce Li+-coordinating functionality within individual FVEs, topology-enforcing polymerizations for generating macromolecular skeletal diversity for networking FVEs into different pore architectures, and several classes of on-polymer reactions for diversifying pore geometries and dielectric properties. Lead candidate polymer membranes featuring explicit ion solvation cages exhibited both higher ionic conductivity and higher cation transference number than control membranes where FVEs were aspecific, which indicates conventional bounds for membrane permeability and selectivity for ion transport can be overcome.4 These advantages are tied to enhanced Li + partitioning from the electrolyte when the cages are present, higher diffusion barriers for anions within the pores, and network-enforced restrictions on the number of solvent molecules bound to Li+ by comparison to the bulk electrolyte, which reduces the effective mass of the working ion. Such membranes show promise as anode-stabilizing interlayers in high-voltage lithium-metal batteries for electric mobility.

42 ENGINEERING↗
DOE OSTI2020

Ultrafast vibrational dynamics of a trigonal planar anionic probe in ionic liquids (ILs): A two-dimensional infrared (2DIR) spectroscopic investigation

A major impediment limiting the widespread application of ionic liquids (ILs) is their high shear viscosity. Incorporation of a tricyanomethanide (TCM - ) anion in ILs leads to low shear viscosity and improvement of several characteristics suitable for large scale applications. However, properties including interactions of TCM - with the local environment and dynamics of TCM - have not been thoroughly investigated. Herein, we have studied the ultrafast dynamics of TCM - in several imidazolium ILs using linear IR and two-dimensional infrared spectroscopy techniques. The spectral diffusion dynamics of the CN stretching modes of TCM - in all ILs exhibit a nonexponential behavior with a short time component of ~2 ps and a long time component spanning ~9 ps to 14 ps. The TCM - vibrational probe reports a significantly faster relaxation of ILs compared to those observed previously using linear vibrational probes, such as thiocyanate and selenocyanate. Our results indicate a rapid relaxation of the local ion-cage structure embedding the vibrational probe in the ILs. The faster relaxation suggests that the lifetime of the local ion-cage structure decreases in the presence of TCM - in the ILs. Linear IR spectroscopic results show that the hydrogen-bonding interaction between TCM - and imidazolium cations in ILs is much weaker. Shorter ion-cage lifetimes together with weaker hydrogen-bonding interactions account for the low shear viscosity of TCM - based ILs compared to commonly used ILs. In addition, this work demonstrates that TCM - can be used as a potential vibrational reporter to study the structure and dynamics of ILs and other molecular systems.

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

Assessing the Effect of Explicit Polarizability on Models of Carbon Dioxide Solvation in Ionic Liquids

Ionic liquids are an important possible carbon capture material because of their anomalously high sorption selectivity for carbon dioxide over other gases common in air. Many research groups have investigated the molecular origins of this property and provided important insights, including using 1D and 2D-IR spectroscopy. Molecular dynamics simulations have been indispensable to the interpretation of these experiments. In prior molecular dynamics simulation work, charge-scaled force fields have typically been used to provide a mean-field treatment of effects vital to ionic liquid systems such as charge transfer and polarization. Here, we compare models of carbon dioxide solvated in ionic liquids with explicit polarization to models of the same with implicit polarizability through charge-scaling. We calculate structural, dynamical, and spectroscopic properties, and make comparisons to the same items measured in experiment. In this study, we focus on two ionic liquids: 1-butyl-3- methylimidazolium (BMIM + ) paired with bis(trifluoromethane sulfonyl imide) (Tf 2 N − ) and 1-butyl-3-methylimidazolium (BMIM+) paired with hexafluorophosphate (PF 6 − ). We find that many structural, dynamical, and spectroscopic properties are changed when polarization is modeled explicitly. We also find that explicit polarizability softens local ion cages around the carbon dioxide and that the long-time diffusion of the carbon dioxide is gated by the reorganization of the ionic liquid molecules. Comparisons to experiment show modest improvement of many observables compared with experiment for the explicitly polarizable model over the charge-scaled model. Overall, our results show that charge-scaled force fields are likely sufficient to compute spectroscopic properties of carbon dioxide in ionic liquids and suggest some interpretive rules for understanding their structural and dynamical properties. Those using charge-scaled force fields should generally assume that the ion cages around solutes such as carbon dioxide are too stiff and cation-rich in their models and adjust their interpretations and predictions accordingly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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↗
NASA NTRS1998

The Improvement of Ion Plated Ag and Au Film Adherence to Si3N4 and SiC Surfaces for Increased Tribological Performance

A modified dc-diode plating system, utilizing a metallic screen cage as a cathode and referred as SCREEN CAGE ION PLATING (SCIP), is used to deposit Ag and Au lubricating films on Si3N4 and SiC surfaces. When deposition is performed in Ar or N2, glow discharge, the surface displays poor adhesive strength (less than 5 MPa). A dramatic increase in adhesive strength (less than 80 MPa) is achieved when plating is performed in a reactive 50% 02 + 50% Ar glow discharge. The excited/ionized oxygen species (O2(+)/O(+) in the glow discharge contribute to the oxidation of the Si3N4 or SiC surfaces as determined by X-ray Photoelectron Spectroscopy (XTS) depth profiling. The reactively sputter-oxidized S3N4 or SiC surfaces and the activated-oxidized-metastable Ag or Au species formed in the plasma cooperatively contribute to the increased adherence. As a result, the linear thermal expansion coefficient mismatch at the interface is reduced. These lubricating Ag and Au films under sliding conditions reduce the friction coefficient by a factor of 2-1/2 to 4.

Spalvins, Talivaldis↗
DOE OSTI2019

Fluid Structure of Molten LiCl–Li Solutions

Molten mixtures of lithium chloride and metallic lithium (LiCl-Li) play an essential role in the electrolytic reduction of various metal oxides. These mixtures possess unique high temperature physical and chemical properties that have been investigated for decades. However, due to their extreme chemical reactivity, no study to date has been capable of definitively proving the basic physical nature of Li dissolution in molten LiCl. In this study, the evolution of the structure of molten LiCl-Li is probed as metallic Li is electrochemically introduced into the melt in situ, using synchrotron radiation experiments based on high energy wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS). The time-resolved scattering results indicate the formation of transient Cl- ion cages surrounding low-density voids with a periodicity of similar to 8.3 angstrom, which suggests the formation of metastable Li nanocluster. The structure of the LiCl-Li nanoclusters in the solution is modeled using ab initio molecular dynamics (AIMD) simulations. We report the simulation results are in agreement with the X-ray diffraction measurement and suggest the nanoclusters are predominantly Li-8, along with smaller clusters.

25 ENERGY STORAGE↗
DOE OSTI2020

Structural dynamics in proteins induced by and probed with X-ray free-electron laser pulses

X-ray free-electron lasers (XFELs) enable crystallographic structure determination beyond the limitations imposed upon synchrotron measurements by radiation damage. The need for very short XFEL pulses is relieved through gating of Bragg diffraction by loss of crystalline order as damage progresses, but not if ionization events are spatially non-uniform due to underlying elemental distributions, as in biological samples. Indeed, correlated movements of iron and sulfur ions were observed in XFEL-irradiated ferredoxin microcrystals using unusually long pulses of 80 fs. Here, we report a femtosecond time-resolved X-ray pump/X-ray probe experiment on protein nanocrystals. We observe changes in the protein backbone and aromatic residues as well as disulfide bridges. Simulations show that the latter’s correlated structural dynamics are much slower than expected for the predicted high atomic charge states due to significant impact of ion caging and plasma electron screening. This indicates that dense-environment effects can strongly affect local radiation damage-induced structural dynamics.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗
DOE OSTI2024

Time-resolved X-ray Spectroscopy from the Atomic Orbital Ground State Up

X-ray spectroscopy has been a key method to determine ground and excited state properties of quantum materials with atomic specificity. Now, new x-ray facilities are opening the door to the study of pump-probe x-ray spectroscopy - specifically time-resolved x-ray absorption (trXAS) and time-resolved resonant inelastic x-ray scattering (trRIXS). In this paper we will present simulations of each of these spectroscopies using a time-domain full atomic multiplet, charge transfer Hamiltonian, adapted to study the properties of a generalized cluster model including a central transition metal ion caged by ligand atoms in a planar geometry. The numerically evaluated trXAS and trRIXS cross-sections for representative electron configurations 3d9 and 3d8 demonstrate the insights that can be obtained from charge transfer pumping, and how this nonequilibrium process affects ground and excited state properties. The straightforward characterization of the excitations in these systems, based on our analysis of the simulations, can serve as a benchmark for future experiments, as access to these time-resolved spectroscopic techniques becomes more widely available.

Jost, Daniel↗
NASA NTRS1987

Air ion exposure system for plants

A system was developed for subjecting plants to elevated air ion levels. This system consisted of a rectangular Plexiglas chamber lined with a Faraday cage. Air ions were generated by corona discharge from frayed stainless steel fibers placed at one end of the chamber. This source was capable of producing varying levels of either positive or negative air ions. During plant exposures, environmental conditions were controlled by operating the unit in a growth chamber.

NASA Discipline Number 61-10↗
DOE OSTI2019

Comparing Empty and Filled Fullerene Cages with High-Resolution Trapped Ion Mobility Spectrometry

We have used trapped ion mobility spectrometry (TIMS) to obtain highly accurate experimental collision cross sections (CCS) for the fullerene C{sub 80}{sup −} and the endohedral metallofullerenes La{sub 2}@C{sub 80}{sup −}, Sc{sub 3}N@C{sub 80}{sup −}, and Er{sub 3}N@C{sub 80}{sup −} in molecular nitrogen. The CCS values of the endohedral fullerenes are 0.2% larger than that of the empty cage. Using a combination of density functional theory and trajectory calculations, we were able to reproduce these experimental findings theoretically. Two effects are discussed that contribute to the CCS differences: (i) a small increase in fullerene cage size upon endohedral doping and (ii) charge transfer from the encapsulated moieties to the cage thus increasing the attractive charge-induced dipole interaction between the (endohedral) fullerene ion and the nitrogen bath gas molecules. .

77 NANOSCIENCE AND NANOTECHNOLOGY↗