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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Techno-economic Analysis of the Cryogenic Flux Capacitor Compared to Other forms of Hydrogen Production and Storage

The Cryogenic Flux Capacitor (CFC) is a cold, dense energy storage core that is being studied in the cryo-compressed, about 300 bar and 80K, region of gaseous hydrogen (GH2) storage and liquid hydrogen (LH2) region near the normal boiling point. The hydrogens storage is improved by physically bonding the molecules within the nanoscale pores of the aerogel composite blanket material. The process of bonding or debonding is governed by principles of physical adsorption (physisorption) and thermodynamics. The large surface area afforded by the nanoporous aerogel (~1,000 m2/g) allows its storage performance to easily exceed capacities of high-pressure GH2 storage for an equivalent volume. With the integrated aerogel, subscale tests have shown that storage is increased by about 49% over a simple tank filled with GH2 at the same operating temperature and pressure. For LH2 conditions, the CFC is shown to operate at equivalent densities. For the techno-economic analysis (TEA), the source of hydrogen is compared between onsite steam methane reforming (SMR) and onsite solar photovoltaic (PV) panels providing power to electrolyzers to produce GH2. The TEA compares pure hydrogen burning in a combined cycle gas turbine (CCGT) to hydrogen fuel cells with an overall net power output of 650 MW. The SMR system uses natural gas as an input and includes a carbon capture and storage (CCS) system. The levelized cost of electricity is developed based on the capital cost and operating cost of the systems. Sensitivities are discussed around the cost of natural gas, ranging from 1.93 USD per MMBTU to 6.75 USD per MMBTU, and carbon dioxide disposal, ranging from 7 USD per tonne to 10 USD per tonne. For comparison to the conventional CCGT baseline, a baseload scenario is adopted with 85% capacity factor. The results of the study show that onsite hydrogen generation from SMR is about 1 to 3 USD per kg over the life of the plant and the PV hydrogen production produces at 4 to 5 USD per kg. The cost of storage for CFC is compared to other systems, including high-pressure GH2 and atmospheric LH2. The system is shown to provide the lowest costs for all these options at the grid scale, due to its higher capacity than high-pressure GH2 and ability to operate at 80K, receiving refrigeration from liquid nitrogen systems reducing capital and operating costs when compared LH2 storage systems. SMR is competitive with CCGT at the gas prices, both of which have lower LCOE than the PV system. When accounting for variability in gas prices, the PV and electrolyzer system is less sensitive to these changes and provides the lowest LCOE across the whole range.

08 HYDROGEN↗
DOE OSTI2023

Online monitoring the hydrolysis of uranium hexafluoride for intermediates by cryogenic layering and FTIR

Uranium hexafluoride (UF 6 ) is a commonly utilized material feedstock in uranium enrichment processes due to its high vapor pressure and ease of sublimation. When exposed to air, UF 6 undergoes spontaneous hydrolysis to form uranyl fluoride (UO 2 F 2 ) particulates which are utilized for the detection of undeclared nuclear activities by nuclear safeguards organizations. In this study, the kinetics of the hydrolysis reaction and how they relate to particle morphology of the product are still debated in the literature. Here, we report the direct, in situ observation of UF 6 reaction intermediates by cooling the reaction to cryogenic temperatures to significantly reduce the rate of hydrolysis. The reaction is then observable by Fourier transform infrared (FTIR) spectroscopy. The conversion of UF 6 to UOF 4 is observed as well as several other bands associated with possible long lived intermediate complexes. Chemometrics are used to further elucidate the reaction pathway from UF 6 to UO 2 F 2 .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Analysis of Near-Field Magnetic Responses on ZrTe 5 through Cryogenic Magneto-THz Nano-Imaging

One manifestation of light-Weyl fermion interaction is the emergence of chiral magnetic effects under magnetic fields. Probing real space magnetic responses at terahertz (THz) scales is challenging but highly desired, as the local responses are less affected by the topologically trivial inhomogeneity that is ubiquitous in spatially averaged measurements. Here, we implement a cryogenic THz microscopy instrument under a magnetic field environment—a task only recently achieved. We explore the technical approach of this system and characterize the magnetic field’s influence on our AFM operation by statistical noise analysis. We find evidence for local near-field spatial variations in the topological semimetal ZrTe 5 up to a 5-Tesla magnetic field and obtain near-field THz spectra to discuss their implications for future studies on the chiral magnetic effect.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Additively manufactured cryogenic microchannel distillation device for air separation

Abstract The efficiency of air separation is tested using three different small‐scale cryogenic distillation columns. The performance of a random packed column is compared to the performance of two microchannel distillation (MCD) columns that use thin wicking structures and gas flow channels to achieve process intensification. The MCD columns tested include a plate‐type layered column and an additively manufactured porous honeycomb (AMPH) column. For columns with 25.4 cm of active height and run under similar conditions, the packed, plate‐type layering, and AMPH columns achieved approximate height equivalent of a theoretical plate (HETP) values of 5.5, 3.7, and 3.2 cm for nitrogen, and 5.9, 4.9, and 3.3 cm for argon. The AMPH column can produce up to 0.4 SLM of more than 90% purity oxygen with 12 W of cooling lift. These results demonstrate the feasibility of using additive manufacturing to construct MCD devices and pave a way for constructing novel MCD designs.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Cryogenic Carbon Monoxide Oxidation on Cuprous Oxide

Performing oxidation reactions at low temperatures using earth-abundant materials is crucial for advancing solutions for sustainable chemistry. CO oxidation serves as a benchmark reaction to characterize oxidation and to advance fundamental concepts in surface chemistry. While there are several examples of CO oxidation occurring on metal oxides at low temperatures, from 300 K to ∼200 K, reactivity in the cryogenic temperature regime typically requires a metal nanoparticle on a metal oxide. Here, we show oxygen atoms on the (111) facet of Cu 2 O react with CO to form CO 2 at temperatures below 100 K. Combining spectroscopic experimental evidence with calculations, we propose a low barrier path for CO oxidation at reconstructed surface sites on Cu 2 O(111). This finding is a rare example of an earth-abundant metal oxide, in this case copper, that can provide highly reactive multifunctional sites, enabling both adsorption and reaction fundamental steps toward the efficient heterogeneous oxidation of chemicals.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Single-column cryogenic air separation: Enabling efficient oxygen production with rapid startup and low capital costs—application to low-carbon fossil-fuel plants

The rapid integration of intermittent renewable sources into the electricity grid is driving the need for more flexible, low-carbon fossil-fuel plants with lower capital costs. This then drives the need to improve the cryogenic air separation unit (ASU). To address this changing landscape, we explore a Praxair single-column ASU (PSC-ASU) design with the goal of reducing costs and improving flexibility, compared to a conventional double-column ASU. The PSC-ASU incorporates partial air condensation and air pre-separation in the bottom reboiler with a phase separator as well as N 2 -enriched vapor condensation in the upper reboiler to decrease energy consumption, as compared to Linde’s single-column ASU. All three of the above-mentioned ASU designs are simulated in Aspen Plus and analyzed. An economic analysis is applied to evaluate the relative cost savings of the PSC-ASU compared to the double-column ASU. Results suggest that the specific energy consumption of the PSC-ASU is significantly lower than that of Linde’s single-column ASU due to a drastically improved oxygen recovery rate. Although this improved oxygen recovery rate is still lower than that of the double-column ASU, the required pressure ratio of the main air compressor is 21% lower than that of the double-column ASU. As a result, the specific energy consumption of the PSC-ASU is only 1.9% greater than that of the double-column ASU for producing 95.1 mol% O 2 . However, the PSC-ASU reduces the hourly capital cost by 19% due to the elimination of a high-pressure column. This would effectively decrease the total hourly cost of the ASU, and thus the total hourly cost of low-carbon, fossil-fuel power plants that require oxygen.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2023

Data-Driven Modeling of a High Capacity Cryogenic System for Control Optimization

The Cryogenic Moderator System (CMS) is responsible for maintaining a steady flow of cold neutrons for numerous physics experiments at the Spallation Neutron Source (SNS) in Oak Ridge National Laboratory (ORNL). Sudden losses in beam power, known as beam trips, cause a major disturbance to the CMS due to large step changes in cooling demands. Ongoing efforts on upgrading the neutron beam power from 1.4 to 2.0MW are expected to generate larger transients that can further strain the CMS subsystems if they are not properly controlled. To manage such disturbances, four flow valves and one electric heater are adjusted by five decentralized proportional-integral-derivative (PID) controllers. However, the original PID gains were calibrated empirically based only on tracking performance and not based on disturbance rejection. To address this issue without compromising current CMS operations, a control-oriented model was developed to recalibrate the PID controllers offline. The zero-dimensional (0-D) model was based on simple physics-based principles and data-driven system identification techniques. The CMS was broken into several subsystems for analysis, each of which corresponds to a parametric model tied to the thermodynamic states of the working fluid. The model parameters were identified using the nonlinear least squares method where the residuals were calculated from available sensor data. Simulation results show that the proposed model can capture the dynamics of the CMS at steady state and during beam trips.

Maldonado Puente, Bryan↗
DOE OSTI2020

How silicon and boron dopants govern the cryogenic scintillation properties of N -type GaAs

This work is the first report describing how the concentrations of silicon and boron govern the cryogenic scintillation properties of n-type GaAs. It shows that valence band holes are promptly trapped on radiative centers and then combine radiatively with silicon donor band electrons at rates that increase with the density of free carriers. It also presents the range of silicon and boron concentrations needed for efficient light emission under X-ray excitation, which along with its low band gap and apparent absence of afterglow, make scintillating GaAs suitable for the detection of rare, low-energy electronic excitations from interacting dark matter particles. A total of 29 samples from four different suppliers were studied. Luminosities and timing responses were measured for the four principal emission bands centered at 860, 930, 1070, and 1335 nm, and for the total emissions. Excitation pulses of 40 kVp X-rays were provided by a light-excited X-ray tube driven by an ultra-fast laser. Scintillation emissions from 800 to 1350 nm were measured using an InGaAs photomultiplier. Within the concentration ranges of free carriers from 2 x 10 16 /cm 3 to 6 x 10 17 /cm 3 and boron from 1.5 × 10 18 /cm 3 to 6 x 10 18 /cm 3 , nine samples have luminosities > 70 photons/keV and two have luminosities > 110 photons/keV. Other samples in that range have lower luminosities due to higher concentrations of non-radiative centers. The decay times decrease by typically a factor of ten with increasing free carrier concentrations from 10 17 /cm 3 to 2 x 10 18 /cm 3 .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2024

Absolute decay counting of 146 Sm with 4π cryogenic microcalorimetry

We present a methodology for absolute activity counting of long-lived isotopes based on cryogenic Decay Energy Spectroscopy. A 146 Sm source was produced at the TRIUMF Laboratory and then processed and purified at Lawrence Livermore National Laboratory, yielding a pure sample. The source was embedded within a 4π thermal absorber coupled to a magnetic microcalorimeter achieving nearly 100% counting efficiency. Experimental uncertainties were studied and modeled, including thermal coupling of the source to the absorber, pulse pile-up, trigger, and event selection efficiencies. Here, the absolute activity of the pure 146 Sm source was measured to better than 1% uncertainty.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

High-Resolution Photoelectron Imaging and Photodetachment Spectroscopy of Cryogenically Cooled IO –

We report a high-resolution photoelectron imaging and photodetachment spectroscopy study of cryogenically-cooled IO - . The high-resolution photoelectron spectra yield a more accurate electron affinity (EA) of 2.3805(5) eV for IO, as well as a more accurate spin-orbit splitting energy between the 2 Π 3/2 and 2 Π 1/2 states of IO as 2093(5) cm -1 . Photodetachment spectroscopy confirmed several excited states for the IO - anion predicted by theoretical calculations, including two valence-type excited states, the repulsive 3 Π state and a shallow bound 1 Π state. More interestingly, we have observed two vibrational resonances which are proposed to be due to a dipole-induced resonant state, about 230 cm -1 above the detachment threshold of IO - .

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

Cryogenic Vibrationally Resolved Photoelectron Spectroscopy of OH–(H2O): Confirmation of Multidimensional Franck-Condon Simulation Results for the Transition State of the OH + H2O Reaction

We present a transition state spectroscopic study of the OH + H2O reaction using the experimental technique of cryogenic Negative Ion Photoelectron Spectroscopy (NIPES). The recorded NIPE spectrum at 193 nm exhibits multiple vibrational progressions that include excitations to the shared H atom antisymmetric stretching mode with an interval of 0.32 eV as well as other progressions, mainly involving the H bending and O…O symmetric stretching modes. The Vertical Detachment Energy (VDE) was measured at 3.53 eV, whereas an upper limit for the Adiabatic Detachment Energy (ADE) was estimated at 2.90 eV. These values are in excellent agreement with the theoretically computed values of 3.51 eV and 2.83 eV respectively, obtained at the CCSD(T)/aug-cc-pV5Z level of theory. The recorded NIPE spectrum is in very good agreement when compared to the one recently reported from four-dimensional Franck-Condon simulations, in which a similar spectral profile was predicted. Besides observing the ground state, a charge-transfer excited state in the form of [OH–(H2O)+] is identified with a relative energy of 1.39 eV, well matching the previous prediction of 1.36 eV. This work was supported by U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, and performed using EMSL, a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory, which is operated by Battelle Memorial Institute for the DOE. The theoretical calculations were conducted on EMSL’s “Cascade” Supercomputer. This research also used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

Cao, Wenjin↗
DOE OSTI2024

Cryogenic Photoelectron Spectroscopic and Theoretical Study of the Electronic and Geometric Structures of Undercoordinated Osmium Chloride Anions OsCl n – ( n = 3–5)

A series of anionic transition metal halides OsCl n - (n=3–5) have been investigated using a newly developed, home-constructed, cryogenic anion cluster photoelectron spectroscopy. Here, the target anionic species are generated through collision-induced dissociation in a two-stage ion funnel. The measured vertical detachment energies (VDEs) are 3.48 eV, 4.54 eV, and 4.81 eV for n = 3, 4, and 5, respectively. Density functional theory calculations at the B3LYP-D3(BJ)//aug-cc-pVTZ (-pp) level predict the lowest energy structures of OsCl n - (n = 3–5) to be a quintet triangle, quartet square, and quintet square-based pyramid, respectively. The CCSD(T)-calculated VDEs and corresponding adiabatic detachment energies (ADEs) agree well with our experimental measurements. Analysis of the corresponding frontier molecular orbitals (FMOs) and charge density differences suggests that the d-orbitals of the transition metal Os play a primary role in the single-photon detachment processes, and the detached electrons originating from different molecular orbitals are distinguishable.

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

Intramolecular Polarization Contributions to the pKa’s of Carboxylic Acids Through the Chain Length Dependence of Vibrational Tag-Shifts in Cryogenically Cooled Pyridinium-(CH2)n-COOH (n = 1-7) Cations

The pKa’s of acids are known to depend on the ionic strength of an electrolyte solution, an effect that qualitatively results from electrostatic interactions of the acid and conjugate base with proximal ions. Here we explore an intramolecular variation on this theme in which a carboxylic acid group is tethered to a pyridinium cationic charge center with increasingly long alkyl linkages in the series Py+-(CH2)n-COOH, with n = 1-7. The effective acidities of the carboxylic acid group in the isolated cations are determined by recording the red-shifts in the frequencies of the acid OH stretches upon attachment to D2 and N2 molecules, measured by using cryogenic ion spectroscopy. The short chains indeed lead to substantial increases in acidity, with the effect falling off in the range of n = 4-5. The response of the CO stretch on the acid head group is surprisingly strong and, in contrast to the expected red shift of the OH, displays a blue shift as the chain length is reduced. Electronic structure calculations recover these trends and indicate that the proximal cationic charge center acts to draw electron density away from the acid C=O bond. This acts to blue shift the CO stretch while weakening the C-C bond that attaches the head group to the chain.

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

Characterization of Two Positional Isomers of the Cs + Gly Complex Using Two-Color, IR–IR Photobleaching of the Cryogenically Cooled Ions

Metal ion binding to amino acid residues is an important interaction motif that controls the tertiary structures of oligopeptides. Analyses of the vibrational band patterns displayed by the amino acid scaffolds are commonly used to characterize the local docking motifs. Here we carry out two-color, IR-IR photobleaching measurements to obtain isomer-selective vibrational spectra of the Cs + Gly ion-molecule complex isolated in a cryogenically cooled, radiofrequency ion trap. The distinct band patterns of two non-interconverting isomers are observed and traced to different bidentate binding motifs between Cs + and the glycine scaffold. In one isomer, the ion attaches to the oxygen atoms of the carboxyl group whereas in the other it docks to the amino nitrogen and the carbonyl oxygen. Attachment to the acid head group yields a very diffuse absorption associated the OH group engaged in a strong intramolecular H-bond that closes a 5 membered ring. Furthermore, the band assignments, rearrangement pathways and electrostatic distortion of the electron density distributions in the glycine scaffold by the proximal ion are explored with electronic structure calculations and anharmonic theory.

Infrared spectroscopy↗
DOE OSTI2024

Isomer-specific, Cryogenic Ion Vibrational Spectroscopy Investigation of D2-and N2- Tagged, Protonated Formic Acid Complexes Using Two Color, IR-IR Photobleaching

Here we analyze cryogenic ion vibrational spectra of tagged protonated formic acid (PFA) with electronic structure and anharmonic vibrational calculations to establish the isomers generated by electrospray ionization (ESI) followed by buffer gas cooling to ~25 K. Two isomers are identified (the trans form (E,Z) and the cis form (E,E)) and generated in comparable abundance despite the fact that the calculated E,E structure lies 6.40 kJ mol-1 above the E,Z form. A large (~60 kJ mol-1) barrier separates them such that the E,E form can be kinetically trapped upon cooling in the ion trap. The anticooperativity between the H-bonds of the OH groups is explored by measuring the shift in the D2-bound OH fundamental when a second D2 is attached. Both isomers are observed in the N2-tagged counterparts, displaying the expected red-shifted OH bands. These results indicate that ESI generates both isomers and both must be considered when analyzing cluster spectra based on the PFA core ion.

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

Magnetic Phase Diagram of 2D Magnet Fe 5– x GeTe 2 Revealed by Cryogenic Lorentz 4D-STEM

A two-dimensional van der Waals ferromagnet Fe 5–x GeTe 2 (F5GT) exhibits room-temperature magnetic transition and magnetic anisotropy. Studies have identified diverse magnetic states, including stripe domains, skyrmionic type-I and topologically trivial type-II bubbles, depending on the magnetic and thermal history. Yet, the underlying micromagnetic energetics driving these states remains unclear. Here, we establish the magnetic phase diagram of bulk F5GT using cryogenic Lorentz four-dimensional scanning transmission electron microscopy. We reveal that stripe domains spontaneously form upon zero-field cooling, while metastable magnetic bubbles are stabilized by external fields. Transitions from type-I to type-II bubbles are driven by an oblique external field. Micromagnetic simulations confirm that these transitions arise from the interplay of uniaxial anisotropy, dipolar interactions, and external fields, without requiring significant Dzyaloshinskii–Moriya Interaction (DMI). In conclusion, these findings clarify the micromagnetic origin of spin textures of F5GT and establish it as a tunable platform for nanoscale topological magnetism.

2D Magnets↗
DOE OSTI2020

Resolving Nanoscopic and Mesoscopic Heterogeneity of Fluorinated Species in Battery Solid-Electrolyte Interphases by Cryogenic Electron Microscopy

The stability of lithium batteries is tied to the physicochemical properties of the solid-electrolyte interphase (SEI). Owing to the difficulty in characterizing this sensitive interphase, the nanoscale distribution of SEI components is poorly understood. Here, we use cryogenic scanning transmission electron microscopy (cryo-STEM) to map the spatial distribution of SEI components across the metallic Li anode. We reveal that LiF, an SEI component widely believed to play an important role in battery passivation, is absent within the compact SEI film (~15 nm); instead, LiF particles (100–400 nm) precipitate across the electrode surface. We term this larger length scale as the indirect SEI regime. On the basis of these observations, we conclude that LiF cannot be a dominant contribution to anode passivation nor does it influence Li+ transport across the compact SEI film. We refine the traditional SEI structure derived from ensemble-averaged characterizations and nuance the role of SEI components on battery performance.

25 ENERGY STORAGE↗
DOE OSTI2023

Atomic-Scale Corrugations in Crystalline Polypeptoid Nanosheets Revealed by Three-Dimensional Cryogenic Electron Microscopy

Amphiphilic molecules that can crystallize often form molecularly thin nanosheets in aqueous solutions. The possibility of atomic-scale corrugations in these structures has not yet been recognized. We have studied the self-assembly of amphiphilic polypeptoids, a family of bio-inspired polymers that can self-assemble into various crystalline nanostructures. Atomic-scale structure of the crystals in these systems has been inferred using both X-ray diffraction and electron microscopy. We use cryogenic electron microscopy to determine the in-plane and out-of-plane structures of a crystalline nanosheet. Data were collected as a function of tilt angle and analyzed using a hybrid single-particle crystallographic approach. The analysis reveals that adjacent rows of peptoid chains, which are separated by 4.5 Å in the plane of the nanosheet, are offset by 6 Å in the direction perpendicular to the plane of the nanosheet. These atomic-scale corrugations lead to a doubling of the unit cell dimension from 4.5 to 9 Å. Our work provides an alternative interpretation for the observed Å X-ray diffraction peak often reported in polypeptoid crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗