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At least 55 records · Page 3

Extraction of Terpenoids from Pine Needle Biomass Using Dimethyl Ether

Pine needles are an industrial feedstock for extracts used in a variety of applications, but conventional extraction methods often result in a degradation of the terpenoid compounds that naturally occur in loblolly pine ( Pinus taeda ). Separation of these compounds from pine biomass is an energy-intensive operation, typically requiring a significant input of thermal energy. An alternative separation approach with potential energy savings is extraction with a condensable gas, namely, dimethyl ether. Biomass materials are exposed to liquid dimethyl ether under pressure, which mobilizes the organics. The extract is then separated from the insoluble pine matter, and dimethyl ether is volatilized away from the separated organic species. A variety of terpene derivatives were extracted from pine needle biomass using this approach, including monoterpenes, sesquiterpenes, and related oxygenates, which were identified using two-dimensional gas chromatography/mass spectrometry. Additionally, the dimethyl ether-treated needles resemble needles subjected to low-temperature drying, whereas needles treated with a high-temperature drying method appear to have shrunken structures. The results suggest that dimethyl ether extraction has significant potential for separating valuable organics from complex matrices without the application of thermal energy during treatment.

dimethyl ether (DME) extraction↗

Nuclear Structural Component Relevant Properties of Nickel-Based Alloys Produced via Additive Manufacturing

Idaho National Laboratory initiated examination of nickel-based alloys manufactured via three different additive manufacturing methods for potential applications in nuclear, high temperature structural components. The three methods analyzed included laser powder bed fusion, blown powder laser directed energy deposition, and wire-fed gas metal arc directed energy deposition. With the rapid push towards additive manufacturing, codes do not exist that definitively define what is or is not tolerable for each process and application, such as with conventional, wrought products. This report contains the initial work to understand possible manufacturing methods for high temperature alloys, and specifically, void formation, microstructure evolution, corrosion, and mechanical properties. To generate mechanical test data, specimens were tested irrespective of voids and microstructures were analyzed to better understand how to negate/improve these issues. The preliminary results showed major decreases in mechanical performance for material tested. Test specimens will continue to be produced to further improve each additive manufacturing processes, quantify void acceptance, and better understand the most suitable high temperature alloys receptive to additive manufacturing and high temperature nuclear applications.

36 MATERIALS SCIENCE↗

HTGR Simulation Methods & International Collaborations

ART-GCR “Methods” activity is split between Experimental Validation data from the ANL NSTF and OSU HTTF (next three presentations). HTGR core simulation (this presentation). International collaboration within OECD Generation-IV (Gen-IV) and USA/Japan bi-lateral agreements (this presentation) HTGR Simulation Methods No new NE-52 funding for HTGR Methods support in FY20; ~$200K FY19 carry-over funds only. Consists of international code-to-code benchmarks (IAEA CRP on HTGR UAM and OECD/NEA MHTGR-350) and refinement of a few-group Pebble Bed Reactor (PBR) cross section (XS) generation methodology. Funding will be requested in FY21 to produce the final reports for the two benchmarks and continue the development of the PBR XS generation methodology. Additional (non-ART) HTGR-related support work at INL NEAMS: HTR-Application work package at INL Create a benchmark for the pebble shuffling and depletion algorithms being developed for NEAMS Griffin code. iFOA award with X-Energy: Develop independent Monte Carlo model of Xe-100 design. Independent design confirmatory analysis of Xe-100 design using NEAMS tools Griffin and Pronghorn. Support X-Energy design team to use their own legacy design tools (VSOP99 and MGT). Support NEAMS Griffin and Pronghorn development team for the iFOA needs (received $50K additional funding for required development).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Underpotential Deposition of 3D Transition Metals: Versatile Electrosynthesis of Single-Atom Catalysts on Oxidized Carbon Supports

Use of single-atom catalysts (SACs) has become a popular strategy for tuning activity and selectivity toward specific pathways. However, conventional SAC synthesis methods require high temperatures and pressures, complicated procedures, and expensive equipment. Recently, underpotential deposition (UPD) has been investigated as a promising alternative, yielding high-loading SAC electrodes under ambient conditions and within minutes. Yet only few studies have employed UPD to synthesize SACs, and all have been limited to UPD of Cu. In this work, a flexible UPD approach for synthesis of mono- and bi-metallic Cu, Fe, Co, and Ni SACs directly on oxidized, commercially available carbon electrodes is reported. The UPD mechanism is investigated using in situ X-ray absorption spectroscopy and, finally, the catalytic performance of a UPD-synthesized Co SAC is assessed for electrochemical nitrate reduction to ammonia. In conclusion, the findings expand upon the usefulness and versatility of UPD for SAC synthesis, with hopes of enabling future research toward realization of fast, reliable, and fully electrified SAC synthesis processes.

36 MATERIALS SCIENCE↗

Effects of Ball Milling on the Electrochemical Capacity and Interfacial Stability of Li 2 MnO 3 Cathode Materials

The cycling mechanism of Li 2 MnO 3 cathode materials synthesized by conventional solid-state methods at high temperatures (800-900 °C) has been intensively investigated. Previous studies showed that CO 2 and O 2 gas evolution accounts for most of the charge capacity, followed by some Mn reduction during discharge. In this work, we analyze the effects of ball milling on the structure, surface contaminant, and electrochemical capacity of Li 2 MnO 3 cathode material, with or without a graphitic fluoride (C-F) additive. At the same time, C-F is added to form a protective coating layer that reduces unwanted reactions with the electrolyte during later electrochemical cycling. We find that the C-F ball-milled material shows Li 2 MnO 3 /LiMnO 2 composite phases, while the purely ball-milled material shows a single Li 2 MnO 3 phase. Furthermore, we characterize surface species and gas evolution during the first cycle, which reveals the decomposition of Li 2 CO 3 and the carbonate electrolyte during the first charge, especially during the high potential region (>4.4 V), and the electrochemical reduction of only a small fraction of the evolved gas on the first discharge (<2.75 V). The appearance further demonstrates the repetitive nature of this process during charge and disappearance during discharge of Mn 2p 3/2 X-ray photoelectron spectroscopy (XPS) spectra signals during the first two cycles. These processes result in first discharge specific capacities of only 155 and 170 mAh/g after first charge specific capacities of 210 and 320 mAh/g for the pure ball-milled and ball-milled with C-F materials, respectively. These studies demonstrate the interfacial instability introduced by ball milling. However, the electrochemical capacity is significantly increased, necessitating further investigation to determine whether ball milling can activate Mn-containing cathode materials.

25 ENERGY STORAGE↗

A Minimum Creep Rate for 2-1/4Cr-1Mo Steel Consistent With the ASME Section III, Division 5 Rules

This technical note describes a minimum creep rate model for 2-1/4Cr-1Mo steel that is consistent with the current creep strain equation embedded in the ASME Boiler & Pressure Vessel Code Section III, Division 5, Subsection HB, Subpart B isochronous stress–strain curves. Minimum creep rate models for all the Section III, Division 5 Class A materials are required for the development of improved high temperature design methods. Of all the Class A materials, only 2-1/4Cr-1Mo does not have a readily identifying minimum creep rate term in the current isochronous stress–strain curve model.

36 MATERIALS SCIENCE↗

Fundamental R&D for high-Q0 650 MHz SRF cavities for hadron linacs

Upcoming projects requiring high-Q0 ~650 MHz elliptical cavities, such as MSU’s Facility for Rare Isotope Beams’ energy upgrade and Fermilab’s PIP-II, drive a need to better understand RF losses due to magnetic flux. With sample sets from two different Niobium vendors, we explore the efficacy of the fast-cooldown method, and high- temperature annealing in promoting flux expulsion. Additionally, we report the results of vertical tests comparing the effect of electropolishing and furnace baking treatments on the cavity flux sensitivity. We also directly measure the flux pinning force in niobium samples, and correlate it with different heat treatments, and flux expulsion performance.

K.McGee, K.McGee↗

Estimates of Quantum Tunneling Effects for Hydrogen Diffusion in PuO 2

We detail the estimation of activation energies and quantum nuclear vibrational tunneling effects for hydrogen diffusion in PuO 2 based on Density Functional Theory calculations and a quantum double well approximation. We find that results are relatively insensitive to choice of exchange correlation functional. In addition, the representation of spin in the system and use of an extended Hubbard U correction has only a small effect on hydrogen point defect formation energies when the PuO 2 lattice is held fixed at the experimental density. We then compute approximate activation energies for transitions between hydrogen interstitial sites seeded by a semi-empirical quantum model and determine the quantum tunneling enhancement relative to classical kinetic rates. Our model indicates that diffusion rates in H/PuO 2 systems could be enhanced by more than one order of magnitude at ambient conditions and that these effects persist at high temperature. The method we propose here can be used as a fast screening tool for assessing possible quantum nuclear vibrational effects in any number of condensed phase materials and surfaces, where hydrogen hopping tends to follow well defined minimum energy pathways.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Method and device for a high temperature vacuum-safe solder resist utilizing laser ablation of solderable surfaces for an electronic module assembly

A process for manufacturing an electronic component having attaches includes providing a first component having a first attach, forming trenches on a portion of the first attach with a laser to form a solder stop, and providing a second component comprising a second attach. The process further includes providing solder between the first attach and the second attach to form a connection between the first component and the second component, where the trenches contain the solder to a usable area. A device produced by the process is disclosed as well.

Stabach, Jennifer↗

Optical systems fabricated by printing-based assembly

Provided are optical devices and systems fabricated, at least in part, via printing-based assembly and integration of device components. In specific embodiments the present invention provides light emitting systems, light collecting systems, light sensing systems and photovoltaic systems comprising printable semiconductor elements, including large area, high performance macroelectronic devices. Optical systems of the present invention comprise semiconductor elements assembled, organized and/or integrated with other device components via printing techniques that exhibit performance characteristics and functionality comparable to single crystalline semiconductor based devices fabricated using conventional high temperature processing methods. Optical systems of the present invention have device geometries and configurations, such as form factors, component densities, and component positions, accessed by printing that provide a range of useful device functionalities. Optical systems of the present invention include devices and device arrays exhibiting a range of useful physical and mechanical properties including flexibility, shapeability, conformability and stretchablity.

Rogers, John↗

Application of the van der Pauw method for electrical conductivity measurements at high temperatures using an insulating compressing ring

High quality data on the high temperature electrical properties of ceramics, particularly oxides, is of great value for material selection, design, and modeling for a broad range of emerging applications. Utilizing the mismatch in the coefficient of thermal expansion between two materials, a purely mechanical method for establishing electrical contact in the van der Pauw geometry to measure the bulk resistivity of ceramic disks at high temperatures is presented. Measurements of a reference material, 20 mol. % Gd-doped cerium oxide, are presented up to 1000 °C. The viability of electrical measurements up to a maximum temperature of 1600 °C is also considered. Measurements are performed using multiple techniques and compared to literature values finding excellent agreement. Finally, the approach described in this work enables the van der Pauw method to be applied to many ceramic materials over a wide range of temperatures and environments.

47 OTHER INSTRUMENTATION↗

Carbon–Mineral Slurry Electrodes for Energy-Efficient Lithium Leaching from Low-Grade Clay Feedstocks

Lithium extraction from clay deposits is typically hampered by low lithium grades and the high capital and energy demands of conventional processing. We report an ambient temperature electrochemical leaching method that bypasses high-temperature roasting and concentrated-acid leaching, directly liberating 93% of lithium from low-grade hectorite in 24 h at 1 V, with 77% Faradaic efficiency, an energy intensity of 3.91 MWh/t lithium carbonate equivalent (LCE). Utilizing a carbon-mineral composite slurry electrode strategy we achieve electron-driven lattice deconstruction through iron oxidation coupled with proton uptake to drive lithium deintercalation, offering a new strategy for low-temperature critical-metal recovery. A preliminary cost analysis highlights pathways to achieving cost intensities below $3000/t LCE. Challenges remain in improving current density, extraction kinetics, and demonstrating process scalability, however, this work establishes a foundation for effective electrochemical lithium extraction from abundant but previously uneconomical clay deposits.

Haddad, Andrew Z↗

Investigation of Best-Practices and Computationally Inexpensive Radiative Exchange Models for Discrete Element Method Modeling of Aluminosilicate Particles in Concentrating Solar Power Environments

Chemically inert, aluminosilicate based particles have been investigated as both a thermal transport and sensible energy storage medium for concentrating solar power facilities. These particles will experience a wide range of operating temperatures (300-1000 K) and handling conditions (dense to dilute falling particle curtains, dense granular flows, or dense structures), requiring specially-designed and optimized infrastructures. The relative influence of collisional and frictional interactions between particles varies based on temperature-dependent particulate properties and greatly impacts the bulk, granular flow behavior. These underlying physics are captured using discrete element method modeling tools. However, this modeling method is computationally expensive as each particle position and interaction is tracked during the simulation. These modeling methods are further complicated by introducing temperature-dependent particle properties, high-temperature radiative exchange, and directional irradiation sources experienced by granular flows in concentrating solar power environments. In this study, coupled experimental and numerical slump testing of aluminosilicate particles was performed and computationally efficient radiative exchange models were evaluated to establish best-practices for discrete element method models for concentrating solar power environments. The three particle types investigated included Carbobead HSP 30 /60, Carbobead CP 30/60, and Granusil 4030. Existing modeling limitations and computationally-efficient multi-modal heat transfer models were evaluated using Aspherix®, a commercial discrete element method software. High-temperature (< 1073 K) slump testing of aluminosilicate particles was performed to investigate the deviation between experimentally-observed and numerically-predicted angles of repose introduced by computation-time reduction practices including the relaxation of the particle elastic modulus and coarse-graining. Coarse-graining is used to use a single modeled particle that is representative of a collection of smaller particles, decreasing the computational cost at the expense of geometric accuracy. Additionally, relaxation of the elastic modulus is used to reduce computational time at the expense of an increased, modeled particle overlap. Prior studies have determined that aluminosilicate particles retain a high elastic modulus at high temperatures (< 1073 K), requiring small simulation timesteps to ensure resolved contact forces resemble appropriate solid mechanics. A parametric study was performed to evaluate the influence of computation time improvements on the deviation between experimental and modeled angle of repose across high temperatures < 1073 K. Additionally, numerical case studies were performed on candidate particle systems at varying porosities and temperatures. These studies were performed to investigate the influence of computationally-efficient radiative-exchange modeling methods coupled to Aspherix® on modeled accuracy and computation time. The recently-developed distance-based approximation was evaluated in estimating radiative exchange between particles and participating surfaces located in close proximity. The distance based approximation was developed to use tabulated estimates of the radiative distribution factor between individual particles and surfaces in close proximity (< 40 particle radii). These methods were expanded to the aluminosilicate particles of interest, including the influence of particle size distributions. To capture radiative exchange between particles and surfaces not in close proximity (> 40 particle radii) and to capture the absorption of directional irradiation from concentrating solar resources, a volumetrically-averaged radiative distribution factor was calculated between the modeled granular flow and surfaces using Monte Carlo ray-tracing for participating media. Volume-averaged absorption and scattering coefficients were predicted using a volumetric discretization of the modeled domain with monodisperse approximations based on geometric optics and experimentally-determined scattering phase functions for aluminosilicate particles.

14 SOLAR ENERGY↗

Designing Cladded Components for High Temperature Nuclear Service: Part I—Analysis Methods

Use of corrosion-resistant cladding can greatly extend the design life of structural components in many advanced reactor systems. However, there are currently no ASME design rules for cladded components to guard against creep-fatigue failure and ratcheting strain accumulation in elevated temperature nuclear service. This paper, presented in two parts, addresses this gap by proposing a design strategy for cladded components that do not require long-term testing of clad materials. The proposed approach relies on approximate design analysis methods for two types of clad materials—a soft clad that creeps much faster than and has lower yield stress than the class A base material and a hard clad that creeps much slower than and has higher yield stress than the class A base material. Part I discusses the approximate analysis strategies for the clad materials—treat a soft clad as perfectly compliant and a hard clad as linear elastic—and Part II develops a complete set of design rules for each of the two types of cladded components. In conclusion, finite element analyses of representative high temperature reactor components show that the proposed design analysis methods can bound the design quantities in soft cladded components and approximate the design quantities in hard cladded components.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Modification of a Silicon Photomultiplier for Reduced High Temperature Dark Count Rate

In this work we present a novel method for improving the high-temperature performance of silicon photomultipliers (SiPMs) via focused ion beam (FIB) modification of individual microcells. The literature suggests that most of the dark count rate (DCR) in a SiPM is contributed by a small percentage (<5%) of microcells. By using a FIB to electrically deactivate this relatively small number of microcells, we believe we can greatly reduce the overall DCR of the SiPM at the expense of a small reduction in overall photodetection efficiency, thereby improving its high temperature performance. In this report we describe our methods for characterizing the SiPM to determine which individual microcells contribute the most to the DCR, preparing the SiPM for FIB, and modifying the SiPM using the FIB to deactivate the identified microcells.

42 ENGINEERING↗

Simulation studies of polypeptoids using replica exchange with dynamical scaling and dihedral biasing

Polypeptoids differ from polypeptides in that the amide bond can more frequently adopt both cis and trans conformations. The transition between the two conformations requires overcoming a large energy barrier, making it difficult for conventional molecular simulations to adequately visit the cis and trans structures. A replica-exchange method is presented that allows for easy rotations of the amide bond and also an efficient linking to a high temperature replica. The method allows for just three replicas (one at the temperature and Hamiltonian of interest, a second high temperature replica with a biased dihedral potential, and a third connecting them) to overcome the amide bond sampling problem and also enhance sampling for other coordinates. Here our results indicate that for short peptoid oligomers, the conformations can range from all cis to all trans with an average cis/trans ratio that depends on side chain and potential model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis method comparison of compositionally complex rare earth-based Ruddlesden–Popper n = 1 T'-type cuprates

The multicomponent approach has been successfully expanded to the Ruddlesden–Popper structure with the synthesis of two different high-entropy cuprate compositions: (La 0.2 Nd 0.2 Gd 0.2 Tb 0.2 Dy 0.2 ) 2 CuO 4 and (La 0.2 Pr 0.2 Nd 0.2 Sm 0.2 Eu 0.2 ) 2 CuO 4 . Additionally, the effect of synthesis method is explored using both solid-state reaction and polymeric steric entrapment (PSE) methods. It is found that PSE leads to more randomly distributed cation species, providing an advantageous method of synthesis for the growing field of high entropy oxides. In situ high-temperature x-ray diffraction tracks the amorphous to crystalline phase transformation in (La 0.2 Nd 0.2 Gd 0.2 Tb 0.2 Dy 0.2 ) 2 CuO 4 powder, synthesized using the PSE method. Using the High-Temperature XRD data, a method for gaining information on the kinetic behavior is also applied. Magnetometry of both compositions indicates ferrimagnetic behavior at low temperatures.

36 MATERIALS SCIENCE↗