Search NASA⌕ Search

SEARCH · Search NASA

Results for “Isolation and Confinement”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Environmental damping and vibrational coupling of confined fluids within isolated carbon nanotubes

Abstract Because of their large surface areas, nanotubes and nanowires demonstrate exquisite mechanical coupling to their surroundings, promising advanced sensors and nanomechanical devices. However, this environmental sensitivity has resulted in several ambiguous observations of vibrational coupling across various experiments. Herein, we demonstrate a temperature-dependent Radial Breathing Mode (RBM) frequency in free-standing, electron-diffraction-assigned Double-Walled Carbon Nanotubes (DWNTs) that shows an unexpected and thermally reversible frequency downshift of 10 to 15%, for systems isolated in vacuum. An analysis based on a harmonic oscillator model assigns the distinctive frequency cusp, produced over 93 scans of 3 distinct DWNTs, along with the hyperbolic trajectory, to a reversible increase in damping from graphitic ribbons on the exterior surface. Strain-dependent coupling from self-tensioned, suspended DWNTs maintains the ratio of spring-to-damping frequencies, producing a stable saturation of RBM in the low-tension limit. In contrast, when the interior of DWNTs is subjected to a water-filling process, the RBM thermal trajectory is altered to that of a Langmuir isobar and elliptical trajectories, allowing measurement of the enthalpy of confined fluid phase change. These mechanisms and quantitative theory provide new insights into the environmental coupling of nanomechanical systems and the implications for devices and nanofluidic conduits.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Long-lived electronic spin qubits in single-walled carbon nanotubes

Abstract Electron spins in solid-state systems offer the promise of spin-based information processing devices. Single-walled carbon nanotubes (SWCNTs), an all-carbon one-dimensional material whose spin-free environment and weak spin-orbit coupling promise long spin coherence times, offer a diverse degree of freedom for extended range of functionality not available to bulk systems. A key requirement limiting spin qubit implementation in SWCNTs is disciplined confinement of isolated spins. Here, we report the creation of highly confined electron spins in SWCNTs via a bottom-up approach. The record long coherence time of 8.2 µs and spin-lattice relaxation time of 13 ms of these electronic spin qubits allow demonstration of quantum control operation manifested as Rabi oscillation. Investigation of the decoherence mechanism reveals an intrinsic coherence time of tens of milliseconds. These findings evident that combining molecular approaches with inorganic crystalline systems provides a powerful route for reproducible and scalable quantum materials suitable for qubit applications.

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

Control of zeolite pore interior for chemoselective alkyne/olefin separations

The efficient removal of alkyne impurities for the production of polymer-grade lower olefins remains an important and challenging goal for many industries. We report a strategy to control the pore interior of faujasite (FAU) zeolites by the confinement of isolated open nickel(II) sites in their six-membered rings. Under ambient conditions, Ni@FAU showed remarkable adsorption of alkynes and efficient separations of acetylene/ethylene, propyne/propylene, and butyne/1,3-butadiene mixtures, with unprecedented dynamic separation selectivities of 100, 92, and 83, respectively. Additionally, in situ neutron diffraction and inelastic neutron scattering revealed that confined nickel(II) sites enabled chemoselective and reversible binding to acetylene through the formation of metastable [Ni(II)(C 2 H 2 ) 3 ] complexes. Control of the chemistry of pore interiors of easily scalable zeolites has unlocked their potential in challenging industrial separations.

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

String-Breaking Dynamics in Quantum Adiabatic and Diabatic Processes

Confinement prohibits isolation of color charges, e.g., quarks, in nature via a process called string breaking : the separation of two charges results in an increase in the energy of a color flux, visualized as a string, connecting those charges. Eventually, creating additional charges is energetically favored, hence breaking the string. Such a phenomenon can be probed in simpler models, including quantum spin chains, enabling enhanced understanding of string-breaking dynamics. A challenging task is to understand how string breaking occurs as time elapses, in an out-of-equilibrium setting. This work establishes the phenomenology of dynamical string breaking induced by a gradual increase of string tension over time. It, thus, goes beyond instantaneous quench processes and enables tracking the real-time evolution of strings in a more controlled setting. We focus on domain-wall confinement in a family of quantum Ising chains. Our results indicate that, for sufficiently short strings and slow evolution, string breaking can be described by the transition dynamics of a two-state quantum system akin to a Landau-Zener process. For longer strings, a more intricate spatiotemporal pattern emerges: the string breaks by forming a superposition of bubbles (domains of flipped spins of varying sizes), which involve highly excited states. We finally demonstrate that string breaking driven only by quantum fluctuations can be realized in the presence of sufficiently long-ranged interactions. This work holds immediate relevance for studying string breaking in quantum-simulation experiments.

Ising model↗
DOE OSTI2021

Isolating the Electrocatalytic Activity of a Confined NiFe Motif within Zirconium Phosphate

Unique classes of active-site motifs are needed for improved electrocatalysis. Herein, the activity of a new catalyst motif is engineered and isolated for the oxygen evolution reaction (OER) created by nickel–iron transition metal electrocatalysts confined within a layered zirconium phosphate matrix. It is found that with optimal intercalation, confined NiFe catalysts have an order of magnitude improved mass activity compared to more conventional surface-adsorbed systems in 0.1 m KOH. Interestingly, the confined environments within the layered structure also stabilize Fe-rich compositions (90%) with exceptional mass activity compared to known Fe-rich OER catalysts. Through controls and by grafting inert molecules to the outer surface, it is evidenced that the intercalated Ni/Fe species stay within the interlayer during catalysis and serve as the active site. After determining a possible structure (wycherproofite), density functional theory is shown to correlate with the observed experimental compositional trends. It is further demonstrated that the improved activity of this motif is correlated to the Fe and water content/composition within the confined space. This work highlights the catalytic enhancement possibilities available through zirconium phosphate and isolates the activity from the intercalated species versus surface/edge ones, thus opening new avenues to develop and understand catalysts within unique nanoscale chemical environments.

36 MATERIALS SCIENCE↗
DOE OSTI2022

MOF-enabled confinement and related effects for chemical catalyst presentation and utilization

A defining characteristic of nearly all catalytically functional MOFs is uniform, molecular-scale porosity. MOF pores, linkers and nodes that define them, help regulate reactant and product transport, catalyst siting, catalyst accessibility, catalyst stability, catalyst activity, co-catalyst proximity, composition of the chemical environment at and beyond the catalytic active site, chemical intermediate and transition-state conformations, thermodynamic affinity of molecular guests for MOF interior sites, framework charge and density of charge-compensating ions, pore hydrophobicity/hydrophilicity, pore and channel rigidity vs. flexibility, and other features and properties. Collectively and individually, these properties help define overall catalyst functional behaviour. Here, this review focuses on how porous, catalyst-containing MOFs capitalize on molecular-scale confinement, containment, isolation, environment modulation, energy delivery, and mobility to accomplish desired chemical transformations with potentially superior selectivity or other efficacy, especially in comparison to catalysts in homogeneous solution environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Radiation Hardened Foam Cold Test Plan – Phase-I: Foam Adhesion, Contamination Fixation, Moisture Stresses, Pipe Cutting, and Thermal Profile Testing

This document outlines the Phase-I test objectives and implementation plan for a down-selective foam fixative technology intended to facilitate activities in support of the Savannah River Site (SRS) F/H labs deactivation and decommissioning (D&D) efforts. It is a collaborative effort between Savannah River National Laboratory (SRNL), Florida International University (FIU), and the SRS F/H labs team intended to test and evaluate the potential of an intumescent, fire-retardant foam in mitigating the release of contamination during dismantling operations on radioactively contaminated piping in legacy facilities. The cold test plan addresses specific requirements highlighted by site and safety personnel and will be executed in FIU’s Outdoor Test and Evaluation Facility using a mock-up that replicates the operational conditions at the proposed hot test location at F/H labs. Results from the cold test plan will inform the hot test at F/H labs, which will use the foam fixative to confine and/or isolate residual contamination within a 3-dimensional void space of Hastelloy C-22 piping designated for removal from the site and transported to a proper disposal facility. Phase-I testing will address eight test objectives: (1) evaluation of the adhesion and bonding properties of foam fixative in piping, (2) evaluation of the adhesion of the foam fixative in piping under varying moisture conditions, (3) determination of the heat profile of the foam fixative during curing, (4) determination of the relationship between pipe diameter and foam fixative quantity, (5) determination of the internal pipe pressure after foam deployment and curing, (6) development of a leak test standard operating procedure to test for the effectiveness of the foam plug, (7) initiation of a literature review to determine if using a hot tap is a viable method to deliver foam into piping, and (8) initiation of a 10-foot mock up test that will be used in Phase-II cold testing. The cold test will be conducted at FIU and all testing activities will comply with SRNL Conduct of R&D Protocols (SRNL-IM-2020-00019).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Radiation Hardened Foam Cold Test Plan - Phase II: Foam Characterization Testing and Environmental Chamber Testing of FoamBag Fixative Foam

This document outlines the Phase II test objectives and implementation plan for a down-select foam fixative technology intended to facilitate activities in support of the Savannah River Site (SRS) F/H labs deactivation and decommissioning (D&D) efforts. It is a collaborative effort between Savannah River National Laboratory (SRNL), Florida International University (FIU), and the SRS F/H labs team intended to test and evaluate the potential of a polyurethane resin foam in mitigating the release of contamination during dismantling operations on radioactively contaminated piping in legacy facilities. The cold test plan addresses specific requirements highlighted by site and safety personnel and will be executed at FIU and SRNL test and lab facilities. Results from the cold tests will inform the hot test at F/H labs, which will use the foam fixative to confine and/or isolate residual contamination within a 3-dimensional void space of Hastelloy C-22 piping designated for removal from the area and transported to a designated disposal facility. Phase I testing was previously conducted using Hilti CP620 fixative foam. Results from Phase I testing indicate Hilti CP-620 fixative foam is incompatible with SRS site hot taps as an effective foam delivery method into Hastelloy C-22 piping. Phase II testing will be conducted using FoamBag TM fixative foam as an alternative fixative foam option. Phase II testing will address eight test objectives: (1) evaluation of the adhesion and bonding properties of FoamBag TM in Hastelloy C-22 piping, (2) evaluation of the adhesion of FoamBag TM in piping under various moisture conditions, (3) determination of the heat profile of FoamBag TM during curing, (4) determination of the internal pipe pressure after FoamBag TM deployment and curing, (5) conduct a leak test to determine if FoamBag TM is effective at creating a full seal within piping, (6) headspace testing of FoamBag TM to determine if there are any associated off-gas hazards during FoamBag TM curing, (7) conduct environmental chamber testing of FoamBag TM to understand how environmental parameters impacts FoamBag TM curing, and (8) conduct fire testing to evaluate FoamBag TM fire retardant characteristics.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Resource loading system and method for use in atmosphere containment scenarios

The invention provides a system for preventing fluid exchange between the interior and exterior of containment enclosures such as process-, hazard-, and research-enclosure systems generally, gloveboxes, containment systems, isolation systems, confinement systems, cleanrooms, negative air systems, and positive air system areas while simultaneously providing material transfer into and out of the enclosures. The invention also provides a method for transporting material into or out of a containment structure.

Dilday, Jr., Daniel R.↗
DOE OSTI2022

Presentation of gas-phase-reactant-accessible single-rhodium-atom catalysts for CO oxidation, via MOF confinement of an Anderson polyoxometalate

Geometric or electronic confinement of guests within nanoporous hosts holds promise for imparting catalytic functionality, including single-metal-atom catalytic functionality, to existing materials. When the nanoporous host is a metal–organic framework (MOF), single-metal-ion catalysts have typically been installed by grafting to an open site on an inorganic node, with the node effectively becoming the support for the catalyst. This approach, however, imposes compositional constraints, as the node not only needs to be receptive to grafting, but also must be capable of stabilizing the framework against solvent evacuation, chemical exposure, and heating. Here, we show that disk-like, Anderson polyoxometalate clusters (RhMo 6 O 24 n- and Mo 7 O 24 m- ; POMs) can be confined in pore-specific and orientation-specific fashion within the hierarchically porous, Zr(IV)-based MOF, NU1K. Self-limiting loading of one cluster per pore, and associated nano-confinement, serve to isolate each POM and prevent consolidation caused by sintering. Additionally, the oriented confinement serves to expose individual rhodium atoms to candidate gas-phase reactants, while enabling the rhodium atom to employ a well-defined oxy-molybdenum cluster, rather than a MOF node, as a support. Synchrotron-based difference-electron-density maps and differential pair-distribution-function analyses of scattered X-rays establish cluster siting and orientation and confirm isolation. Nanoconfined (i.e., MOF- and POM-confined) single-rhodium(III)-atoms are catalytically competent for an illustrative gas-phase reaction, CO oxidation by O 2 , with the MOF-isolated POM enormously outperforming nonporous, MOF-free, solid (NH 4 ) 3 [H 6 RhMo 6 O 24 ]·6H 2 O. This paper highlights the value of MOF-based nano-confinement and oriented isolation of planar POMs as a means of uniformly presenting and stabilizing potent single-metal-atom catalysts, in reactant-accessible form, on well-defined supports.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

On the mechanism of intermolecular nitrogen-atom transfer from a lattice-isolated diruthenium nitride intermediate

Catalyst confinement within microporous media provides the opportunity to site isolate reactive intermediates, enforce intermolecular functionalization chemistry by co-localizing reactive intermediates and substrates in molecular-scale interstices, and harness non-covalent host–guest interactions to achieve selectivities that are complementary to those accessible in solution. As part of an ongoing program to develop synthetically useful nitrogen-atom transfer (NAT) catalysts, we have demonstrated intermolecular benzylic amination of toluene at a Ru 2 nitride intermediate confined within the interstices of a Ru2-based metal–organic framework (MOF), Ru 3 (btc) 2 X 3 (btc = 1,3,5-benzenetricarboxylate, i.e., Ru-HKUST-1 for X = Cl). Nitride confinement within the extended MOF lattice enabled intermolecular C–H functionalization of benzylic C–H bonds in preference to nitride dimerization, which was encountered with soluble molecular analogues. Detailed study of the kinetic isotope effects (KIEs, i.e., k H /k D ) of C–H amination, assayed both as intramolecular effects using partially labeled toluene and as intermolecular effects using a mixture of per-labeled and unlabeled toluene, provided evidence for restricted substrate mobility on the time scale of interstitial NAT. Analysis of these KIEs as a function of material mesoporosity provided approximate experimental values for functionalization in the absence of mass transport barriers. Here, we disclose a combined experimental and computational investigation of the mechanism of NAT from a Ru 2 nitride to the C–H bond of toluene. Computed kinetic isotope effects for a H-atom abstraction (HAA)/radical rebound (RR) mechanism are in good agreement with experimental data obtained for C–H amination at the rapid diffusion limit. These results provide the first detailed analysis of the mechanism of intermolecular NAT to a C–H bond, bolster the use of KIEs as a probe of confinement effects on NAT within MOF lattices, and provide mechanistic insights unavailable by experiment because rate-determining mass transport obscured the underlying chemical kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Size-Controlled Nanoparticles Embedded in a Mesoporous Architecture Leading to Efficient and Selective Hydrogenolysis of Polyolefins

A catalytic architecture, comprising a mesoporous silica shell surrounding platinum nanoparticles (NPs) supported on a solid silica sphere (mSiO2/Pt-X/SiO2; X is the mean NP diameter), catalyzes hydrogenolysis of melt-phase polyethylene (PE) into a narrow C23-centered distribution of hydrocarbons in high yield using very low Pt loadings (~10 -5 g Pt/g PE). During catalysis, a polymer chain enters a pore and contacts a Pt NP where the C–C bond cleavage occurs and then the smaller fragment exits the pore. mSiO 2 /Pt/SiO 2 resists sintering or leaching of Pt and provides high yields of liquids; however, many structural and chemical effects on catalysis are not yet resolved. Here, we report the effects of Pt NP size on activity and selectivity in PE hydrogenolysis. Time-dependent conversion and yields and a lumped kinetics model based on the competitive adsorption of long vs short chains reveal that the activity of catalytic material is highest with the smallest NPs, consistent with a structure-sensitive reaction. Remarkably, the three mSiO 2 /Pt-X/SiO 2 catalysts give equivalent selectivity. We propose that mesoscale pores in the catalytic architecture template the C 23 -centered distribution, whereas the active Pt sites influence the carbon–carbon bond cleavage rate. This conclusion provides a framework for catalyst design by separating the C–C bond cleavage activity at catalytic sites from selectivity for chain lengths of the products influenced by the structure of the catalytic architecture. The increased activity, selectivity, efficiency, and lifetime obtained using this architecture highlight the benefits of localized and confined environments for isolated catalytic particles under condensed-phase reaction conditions.

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

Atomically Precise Single-Site Catalysts via Exsolution in a Polyoxometalate–Metal–Organic-Framework Architecture

Single-site catalysts (SSCs) achieve a high catalytic performance through atomically dispersed active sites. A challenge facing the development of SSCs is aggregation of active catalytic species. Reducing the loading of these sites to very low levels is a common strategy to mitigate aggregation and sintering; however, this limits the tools that can be used to characterize the SSCs. Here we report a sintering-resistant SSC with high loading that is achieved by incorporating Anderson–Evans polyoxometalate clusters (POMs, MMo 6 O 24 , M = Rh/Pt) within NU-1000, a Zr-based metal–organic framework (MOF). The dual confinement provided by isolating the active site within the POM, then isolating the POMs within the MOF, facilitates the formation of isolated noble metal sites with low coordination numbers via exsolution from the POM during activation. The high loading (up to 3.2 wt %) that can be achieved without sintering allowed the local structure transformation in the POM cluster and the surrounding MOF to be evaluated using in situ X-ray scattering with pair distribution function (PDF) analysis. Notably, the Rh/Pt···Mo distance in the active catalyst is shorter than the M···M bond lengths in the respective bulk metals. Furthermore, models of the active cluster structure were identified based on the PDF data with complementary computation and X-ray absorption spectroscopy analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Triaxial Shear Tests on Simulated Sierra White Fault Gouge & Borehole Simulation in Sierra White Gouge

Laboratory shear tests were conducted on pulverized Sierra White granite (SWG) to investigate slip mechanisms in naturally occurring faults. Synthetic fault geometries were constructed by sandwiching fine grained SWG powder in between steel forcing blocks. For dry experiments, ~3.5 g of SWG powder was poured onto the face of the lower steel forcing block and leveled. For saturated experiments, enough fluid was added to the ~3.5 g of Sierra White granite powder to form a slurry. This slurry was applied to the lower forcing block and leveled. Inclined forcing blocks with 25.4 mm diameter and 35° faces, which were machined from ground steel rods with fine teeth on the faces, help to hold the gouge in place and prevent delamination at the interface. The top forcing block had a 2.03 mm centered hole to allow pore fluid access to the gouge. A fine steel mesh prevented back flow of the gouge into pore fluid lines. Samples were isolated from the confining medium using three layers of heat shrink polyolefin, as shown in Figure 1. The outer layer was shrunk over the o-rings on the end caps to form an impermeable seal, which was reinforced with steel tie wires on both sides of the o-rings. Hardened steel spacers and copper shim stock was placed between the steel forcing blocks and the end caps to preserve the parallelism of the Hastelloy wetted parts. For dry samples, the end caps were plugged, while the end caps for the saturated samples were connected to pore lines.

58 GEOSCIENCES↗
DOE OSTI2024

Structural transformation of dusty plasma crystal in dc discharge plasma by changing confinement ring bias

We report an experimental study of the structural transition of a stable complex plasma crystal to a solid-liquid phase coexistence by the controlled adjustment of the confinement potential, while keeping all other parameters constant. The experiments are carried out on a tabletop linear dusty plasma experimental device, which consists of a circular powered electrode and an extended grounded cathode plate. A stationary crystal of melamine formaldehyde particles is formed in a background of argon plasma inside a confining ring that is isolated from the cathode by a ceramic cover. The stable crystal structure breaks in the core region and transitions to a coexistent state by carefully changing the confining potential, thereby modifying the sheath structure. The transition is confirmed by evaluating the variation in different characteristic parameters such as the pair correlation function, local bond order parameter, and dust kinetic temperature as a function of confining bias potential. It is found that melting in the core is due to the onset of dust fluctuations in the layers beneath the topmost layer, which grow in amplitude as the confining bias potential is reduced below a threshold value. The present technique of changing confinement provides a unique feature to study structural transitions of plasma crystals without affecting the overall plasma parameters.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Structural transformation of dusty plasma crystal in dc discharge plasma by changing confinement ring bias

We report an experimental study of the structural transition of a stable complex plasma crystal to a solid-liquid phase coexistence by the controlled adjustment of the confinement potential, while keeping all other parameters constant. The experiments are carried out on a tabletop linear dusty plasma experimental device, which consists of a circular powered electrode and an extended grounded cathode plate. A stationary crystal of melamine formaldehyde particles is formed in a background of argon plasma inside a confining ring that is isolated from the cathode by a ceramic cover. The stable crystal structure breaks in the core region and transitions to a coexistent state by carefully changing the confining potential, thereby modifying the sheath structure. The transition is confirmed by evaluating the variation in different characteristic parameters such as the pair correlation function, local bond order parameter, and dust kinetic temperature as a function of confining bias potential. It is found that melting in the core is due to the onset of dust fluctuations in the layers beneath the topmost layer, which grow in amplitude as the confining bias potential is reduced below a threshold value. The present technique of changing confinement provides a unique feature to study structural transitions of plasma crystals without affecting the overall plasma parameters.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Deterministic Localization of Strain-Induced Single-Photon Emitters in Multilayer GaSe

The nanoscale strain has emerged as a powerful tool for controlling single-photon emitters (SPEs) in atomically thin transition metal dichalcogenides (TMDCs). However, quantum emitters in monolayer TMDCs are typically unstable in ambient conditions. Multilayer TMDCs could be a solution, but they suffer from low quantum efficiency, resulting in low brightness of the SPEs. Here, we report the deterministic spatial localization of strain-induced SPEs in multilayer GaSe by nanopillar arrays. The strain-controlled quantum confinement effect introduces well-isolated sub-bandgap photoluminescence and corresponding suppression of the broad band edge photoluminescence. Clear photon-antibunching behavior is observed from the quantum dot-like GaSe sub-bandgap exciton emission at 3.5 K. The strain-dependent confinement potential and the brightness are found to be strongly correlated, suggesting a promising route for tuning and controlling SPEs. The comprehensive investigations of strain-engineered GaSe SPEs provide a solid foundation for the development of 2D devices for quantum photonic technologies.

2D materials↗