Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “solid phase processing”

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 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Multiphase Model of Semisolid Slurry Generation and Isothermal Holding During Cooling Slope Rheoprocessing of A356 Al Alloy

In the present paper, we present an experimentally validated 3D multiphase and multiscale solidification model to understand the transport processes involved during slurry generation with a cooling slope. In this process, superheated liquid alloy is poured at the top of the cooling slope and allowed to flow along the slope under the influence of gravity. As the melt flows down the slope, it progressively loses its superheat, starts solidifying at the melt/slope interface with formation of solid crystals, and eventually exits the slope as semisolid slurry. In the present simulation, the three phases considered are the parent melt as the primary phase, and the solid grains and air as secondary phases. The air phase forms a definable air/liquid melt interface as the free surface. After exiting the slope, the slurry fills an isothermal holding bath maintained at the slope exit temperature, which promotes further globularization of microstructure. The outcomes of the present model include prediction of volume fractions of the three different phases considered, grain evolution, grain growth, size, sphericity and distribution of solid grains, temperature field, velocity field, macrosegregation and microsegregation. In addition, the model is found to be capable of making predictions of morphological evolution of primary grains at the onset of isothermal coarsening. The results obtained from the present simulations are validated by performing quantitative image analysis of micrographs of the rapidly oil-quenched semisolid slurry samples, collected from strategic locations along the slope and from the isothermal slurry holding bath.

36 MATERIALS SCIENCE↗
DOE OSTI2026

All-organic self-separating three-dimensionally nanoarchitected electrochemical energy storage devices

This work realizes a three-dimensionally (3D) nanoarchitected, all organic, "self-separating" lithium-ion electrochemical energy storage (EES) device that is cycled as a solid-state full cell. The device is enabled by a monolithic carbon anode with a co-continuous pore network, derived from the structure direction of resols by an ultra-large molar mass block copolymer (BCP), poly(styrene-block-2-dimethylaminoethyl methacrylate) (SA). Electropolymerization of a single-phase conductive and redox-active material, poly((2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methyl 9,10-dioxo-9,10-dihydroanthracene-2-carboxylate) (PAQEDOT), into the pore space provides the cathode of the cell. The device is electronically contacted to the relevant electrode network enabled by the co-continuous nature of each electrode. Electrochemical processing via cycling against external lithium in an electrolyte generates a solid electrolyte interphase (SEI) as a separator and lithiates the cell electrodes, after which the EES device is cycled in the solid state. While the full cell does not demonstrate high cyclability, the best full cell demonstrates a discharge capacity of 267 milliamp hours per gram (mAh/g). This work marks, to the best of knowledge of the authors, the first example of an all-organic materials derived 3D nanoarchitected EES device, as well as the first design of "self-separating" cell fabrication. Furthermore, generalization of the design to another co-continuous carbon form factor is demonstrated.

FOS: Physical sciences↗
DOE OSTI2023

The Riddle of Dark LLZO: Cobalt Diffusion in Garnet Separators of Solid‐State Lithium Batteries

Abstract Solid‐state batteries (SSBs) with a Li 7 La 3 Zr 2 O 12 (LLZO) garnet electrolyte are attracting much attention as robust and safe alternative to conventional lithium‐ion batteries. Technical challenges in the practical implementation of garnet SSBs are related to the need for high‐temperature sintering, which often leads to undesirable chemical reactions with the cathode material. While these reactions are well understood for composite cathodes, very little is known about similar processes between cathode and separator during battery fabrication. This work focuses on understanding the processes between the composite LiCoO 2 ‐LLZO cathode and the LLZO separator and how they affect the battery performance. The extensive diffusion of Co‐ions within LLZO, which leads to the often‐observed LLZO darkening, is shown to have a significant impact on ionic conductivity, electronic conductivity, and dendrite stability of the separator. Experimental data coupled with large‐scale molecular dynamics simulations uncover the diffusion mechanism for Co‐ions and identify secondary phases that form during these interactions. In addition to extensive Co‐ion diffusion within the grains, a non‐uniform segregation of Co‐ions at grain boundaries is found leading to the formation of three distinct Co‐containing phases. This work offers a general approach to studying the fundamental ion diffusion processes that occur during the fabrication of oxide SSBs.

electrochemical properties↗
DOE OSTI2016

Passivation of Nickel Vacancy Defects in Nickel Oxide Solar Cells by Targeted Atomic Deposition of Boron

Localized trap states, which are deleterious to the performance of many solar-energy materials, often originate from the under-coordinated bonding associated with defects. Recently, the concept of targeted atomic deposition (TAD) was introduced as a process that permits the passivation of trap states using a vapor-phase precursor that selectively reacts with only the surface defect sites. In this work, we demonstrate the passivation of nickel oxide (NiO) with the TAD process using diborane gas for selective, low-temperature deposition of boron (B) under continuous flow in a chemical vapor deposition (CVD) system. NiO is a ubiquitous cathode material used in dye-sensitized solar cells (DSSCs), organic photovoltaic devices, and organo-lead halide perovskite solar cells. The deposition of B at 100 °C is shown to follow first-order kinetics, exhibiting saturation at a B to Ni atomic ratio of ~10%. Electrochemical measurements, combined with first-principles calculations, indicate that B passivates Ni vacancy defects by partially saturating the bonding of the oxygen atoms adjacent to the vacancy. p-Type DSSCs were fabricated using TAD-treated NiO and show a modest improvement in photovoltaic performance metrics. The results highlight the potential ubiquity of TAD passivation with a range of atomic precursors and vapor-phase processes.

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

Decision-tree structures utilizing a phase-transition material

The rich internal physics due to competing electronic phases present in phase-transition materials such as VO2 offer the potential for compact building block design for emerging non-von Neumann computing technologies. Here, based on the relaxation dynamics of an insulator-metal phase transition, we demonstrate experimentally a decision-tree classifier embedded within a single volatile resistive switching device. The tree is constructed by the combination of the voltage pulse and relaxation time and can adapt to different tasks. We use machine learning to analyze the relaxation process, enabling a predictive voltage-relaxation time phase diagram for the electrical resistance state. Classification of the etiology of the chronic cough is presented as a proof-of-principle use case. Further, our approach can be generalized to broader classes of solid-state and solid-liquid interfacial systems that demonstrate a variety of phase relaxations.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Probing the state of hydrogen in δ − AlOOH at mantle conditions with machine learning potential

Hydrous and nominally anhydrous minerals are a fundamental class of solids of enormous significance to geophysics. They are the water carriers in the deep geological water cycle and impact structural, elastic, plastic, and thermodynamic properties and phase relations in Earth's forming aggregates (rocks). They play a critical role in the geochemical and geophysical processes that shape the planet. Their complexity has prevented predictive calculations of their properties, but progress in materials simulations ushered by machine-learning potentials is transforming this state of affairs. Here, we adopt a hybrid approach that combines deep learning potentials (DPs) with the strongly constrained and appropriately normed meta-generalized gradient approximation functional to simulate a prototypical hydrous system. We illustrate the success of this approach to simulate δ − AlOOH ( δ ) , a phase capable of transporting water down to near the core-mantle boundary of the Earth ( ∼ 2900 km depth and ∼ 135 GPa ) in subducting slabs. A high-throughput sampling of phase space using molecular dynamics simulations with DPs sheds light on the hydrogen-bond behavior and proton diffusion at geophysical conditions. These simulations provide a pathway for a deeper understanding of these crucial components that shape Earth's internal state. Published by the American Physical Society 2024

Luo, Chenxing (ORCID:0000000341166851)↗
DOE OSTI2018

Thermal Expansion of EuF{sub 2+x} Single Crystals and Their Thermal Stability

Thermal expansion of an EuF{sub 2.136} nonstoichiometric crystal with the fluorite structure type (Eu{sub 0.864}{sup 2+}Eu{sub 0.136}{sup 3+}F{sub 2.136}, lattice parameter 5.82171(5) Å) has been experimentally investigated in the temperature range of 9–500 K. The coefficient of thermal expansion is α = 15.8 × 10{sup –6} K{sup –1} at T = 300 K. The observed anomalies in the behavior of the coefficient of thermal expansion at T > 400 K are related to the oxidation processes with partition of Eu{sup 2+} ions. It is established by differential scanning calorimetry that the onset temperature of EuF{sub 2+x} oxidation in air is 430 K and that this process occurs in three stages. X-ray diffraction analysis shows that the oxidation is accompanied by the formation of a phase mixture based on two modifications of the Eu{sub 1–y}{sup 3+}Eu{sub y}{sup 2+}F{sub 3–y} solid solution with the structure types of tysonite (LaF{sub 3}), orthorhombic β-YF{sub 3} phase, and europium oxyfluorides of variable composition EuO{sub 1–x}F{sub 1+2x}, with dominance of the latter.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Ti{sub 2}AlN thin films synthesized by annealing of (Ti+Al)/AlN multilayers

Highlights: • Epitaxial thin films of the MAX phase Ti{sub 2}AlN are obtained by thermal annealing. • A new metastable (Ti,Al,N) solid solution with the structure of α-T is evidenced. • The formation of the MAX phase occurs at low temperature (600 °C). - Abstract: Single-phase Ti{sub 2}AlN thin films were obtained by annealing in vacuum of (Ti + Al)/AlN multilayers deposited at room temperature by magnetron sputtering onto single-crystalline (0001) 4H-SiC and (0001) Al{sub 2}O{sub 3} substrates. In-situ X-ray diffraction experiments combined with ex-situ cross-sectional transmission electron microscopy observations reveal that interdiffusion processes occur in the multilayer at a temperature of ∼400 °C leading to the formation of a (Ti, Al, N) solid solution, having the hexagonal structure of α-Ti, whereas the formation of Ti{sub 2}AlN occurs at 550–600 °C. Highly oriented (0002) Ti{sub 2}AlN thin films can be obtained after an annealing at 750 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Bench-Scale Evaluation of the Genifuel Hydrothermal Processing Technology for Wastewater Solids

Hydrothermal Liquefaction (HTL) and Catalytic Hydrothermal Gasification (CHG) proof-of-concept bench-scale tests were performed to assess the potential of the Genifuel hydrothermal process technology for handling municipal wastewater sludge. HTL tests were conducted at 300-350°C and 20 MPa on three different feeds: primary sludge (11.9 wt% solids), secondary sludge (9.7 wt% solids), and post-digester sludge (also referred to as digested solids) (16.0 wt% solids). Corresponding CHG tests were conducted at 350°C and 20 MPa on the HTL aqueous phase output using a ruthenium based catalyst. A comprehensive analysis of all feed and effluent phases was also performed. Total mass and carbon balances closed to within ± 15% in all but one case. Biocrude yields from HTL tests were 37%, 25%, and 34% for primary sludge, secondary sludge, and digested solids feeds, respectively. The biocrude yields accounted for 59%, 39%, and 49% of the carbon in the feed for primary sludge, secondary sludge, and digested solids feeds, respectively. Biocrude composition and quality were comparable to that seen with biocrudes generated from algae feeds. Subsequent hydrotreating (i.e., upgrading) of the biocrude produced from primary sludge and digested solids resulted in a product with comparable physical and chemical properties to petroleum crude oil. CHG product gas consisted primarily of methane, with methane yields (relative to CHG input) on a carbon basis of 47%, 61%, and 64% for aqueous feeds that were the output of HTL tests with primary sludge, secondary sludge, and digested solids, respectively. Siloxane concentrations in the CHG product gas were below the detection limit and well below fuel input composition limits set by several engine manufacturers. Relative to that of the sludge feeds, the HTL-CHG process resulted in a reduction in chemical oxygen demand (COD) of greater than 99.9% and a reduction in residual solids for disposal of 94-99%. The test results, as a whole, support further long term testing in a larger scale integrated system that is representative of what would be installed at a water resource recovery facility (WRRF) in order to fully assess the technical and economic viability of this technology for wastewater sludge treatment.

biocrude↗
DOE OSTI2019

Development of a Trace Detection Method for Mercury Speciation in Hanford Tank Waste - 19014

The U.S. Department of Energy's (DOE) Hanford Site in southeast Washington State stores 56 million gallons of chemical and radioactive waste stored in underground tanks. Mercury species in liquid and solid fractions of Hanford tank waste pose a risk to the implementation and execution of DoE's River Protection Project mission due to mercury concentration limits imposed under waste acceptance criteria, toxicity characteristic leaching procedure restrictions for secondary waste disposal, and air emission permits. Although there is currently no processing of tank waste at Hanford, waste processing is imminent, and representative mercury inventory tracking will be important to anticipate and mitigate stack emissions and secondary liquid waste disposal issues. A methodology to accurately determine total mercury and mercury speciation in Hanford tank waste, while maintaining low mercury detection limits, currently does not exist at Hanford. Moreover, the mercury species in the waste solids are unknown and may be waste type-specific. The development of an analytical method to separate and speciate mercury in tank waste was undertaken by the Pacific Northwest National Laboratory (PNNL) while leveraging an existing non-radiological, ultra-trace mercury detection technique frequently performed at PNNL's Marine Sciences Laboratory in Sequim, Washington. The ultimate goal of this work is to develop an analytical method to obtain detailed mercury speciation information and update flowsheet modeling assumptions related to mercury partitioning at Hanford. The first phase of testing was completed in the development of an analytical methodology for the low-level determination of total mercury, elemental mercury, methylmercury, and dimethylmercury in Hanford tank waste. This paper presents Phase I testing which focused on determining whether mercury species can be preconcentrated from aqueous Hanford tank waste solution onto a solid substrate, while simultaneously eliminating or very significantly reducing the parent radionuclide activity. This was demonstrated by developing protocols for the separation and preconcentration of total mercury and methylmercury onto solid substrates, then measuring the substrates for radiological content at PNNL's Radiochemical Processing Laboratory on the Hanford Site. The mercury content was successfully separated onto stable substrates and the radionuclide activity reduction was significant enough that the preconcentrated samples could be subjected to quantification using far less restrictive handling and radiological controls than would be required for the parent sample (i.e., contamination area fume hood vs. hot cell). This mercury separation method required no sample dilution, which enables maximum mercury detectability, while still allowing mercury speciation. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Interface morphogenesis with a deformable secondary phase in solid-state lithium batteries

Here, the complex morphological evolution of lithium metal at the solid-state electrolyte interface limits performance of solid-state batteries, leading to inhomogeneous reactions and contact loss. Inspired by biological morphogenesis, we developed an interfacial self-regulation concept in which a deformable secondary phase dynamically aggregates at the interface in response to local electro-chemo-mechanical stimuli, enhancing contact. The stripping of a lithium electrode that contains 5 to 20 mole % electrochemically inactive sodium domains causes spontaneous sodium accumulation across the interface, with the sodium deforming to attain intimate electrical contact without blocking lithium transport. This process, characterized with operando x-ray tomography and electron microscopy, mitigates voiding and improves cycling at low stack pressures. The counterintuitive strategy of adding electrochemically inactive alkali metal to improve performance demonstrates the utility of interfacial self-regulation for solid-state batteries.

Yoon, Sun Geun [Georgia Institute of Technology, A↗
DOE OSTI2020

Multiscale and Multimodal Characterization of 2D Titanium Carbonitride MXene

Here, a comprehensive study on the prototype solid solution phase carbonitride MXene Ti 3 CN is conducted using nuclear magnetic resonance, electron spin resonance, total and quasi-elastic neutron scattering, combined with density functional theory-based electronic structure and molecular dynamic calculations. The combination of experiment and theory lead toward rational atomic structural models of Ti 3 CN. The remnant Al ions from the etching process significantly tune the interlayer spacing, distinct from the more typical MXene, Ti 3 C 2 , prepared similarly. Neutron scattering indicates the surface terminations of Ti 3 CN display high oxygen and fluorine concentrations and rather low hydroxyl and hydrogen concentrations. Calculations show that the structure including both the residual Al ions and mixed surface terminations give the best agreement with the measurements. The water molecules in Ti 3 CN are highly immobile, in strong contrast to those in Ti 3 C 2 . The analysis of the electronic structure suggests that the nitride MXene displays higher conductivity than the carbides. Finally, the absence of hydroxyl groups in terminations, the solid-solution in the anion sites, the remnants within layers, and immobile water altogether make the carbonitrides a unique series in the MXene family, implying a further exploration of their exotic properties and applications in energy storage.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Advanced techniques for characterization of ion beam modified materials

Understanding the mechanisms of damage formation in materials irradiated with energetic ions is essential for the field of ion-beam materials modification and engineering. Utilizing incident ions, electrons, photons, and positrons, various analysis techniques, including Rutherford backscattering spectrometry (RBS), electron RBS, Raman spectroscopy, high-resolution X-ray diffraction, small-angle X-ray scattering, and positron annihilation spectroscopy, are routinely used or gaining increasing attention in characterizing ion beam modified materials. The distinctive information, recent developments, and some perspectives in these techniques are reviewed in this paper. Applications of these techniques are discussed to demonstrate their unique ability for studying ion-solid interactions and the corresponding radiation effects in modified depths ranging from a few nm to a few tens of μm, and to provide information on electronic and atomic structure of the materials, defect configuration and concentration, as well as phase stability, amorphization and recrystallization processes. Finally, such knowledge contributes to our fundamental understanding over a wide range of extreme conditions essential for enhancing material performance and also for design and synthesis of new materials to address a broad variety of future energy applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Phase evolution and structural modulation during in situ lithiation of MoS 2 , WS 2 and graphite in TEM

Li-ion batteries function by Li intercalating into and through the layered electrode materials. Intercalation is a solid-state interaction resulting in the formation of new phases. The new observations presented here reveal that at the nanoscale the intercalation mechanism is fundamentally different from the existing models and is actually driven by nonuniform phase distributions rather than the localized Li concentration: the lithiation process is a ‘distribution-dependent’ phenomena. Direct structure imaging of 2H and 1T dual-phase microstructures in lithiated MoS 2 and WS 2 along with the localized chemical segregation has been demonstrated in the current study. Li, a perennial challenge for the TEM, is detected and imaged using a low-dose, direct-electron detection camera on an aberration-corrected TEM and confirmed by image simulation. This study shows the presence of fully lithiated nanoscale domains of 2D host matrix in the vicinity of Li-lean regions. This confirms the nanoscale phase formation followed by Oswald ripening, where the less-stable smaller domains dissolves at the expense of the larger and more stable phases.

25 ENERGY STORAGE↗
DOE OSTI2017

Quantification of in-contact probe-sample electrostatic forces with dynamic atomic force microscopy

Here, atomic force microscopy (AFM) methods utilizing resonant mechanical vibrations of cantilevers in contact with a sample surface have shown sensitivities as high as few picometers for detecting surface displacements. Such a high sensitivity is harnessed in several AFM imaging modes. Here, we demonstrate a cantilever-resonance-based method to quantify electrostatic forces on a probe in the probe-sample junction in the presence of a surface potential or when a bias voltage is applied to the AFM probe. We find that the electrostatic forces acting on the probe tip apex can produce signals equivalent to a few pm of surface displacement. In combination with modeling, the measurements of the force were used to access the strength of the electrical field at the probe tip apex in contact with a sample. We find an evidence that the electric field strength in the junction can reach ca. 1 V nm –1 at a bias voltage of a few volts and is limited by non-ideality of the tip-sample contact. This field is sufficiently strong to significantly influence material states and kinetic processes through charge injection, Maxwell stress, shifts of phase equilibria, and reduction of energy barriers for activated processes. Besides, the results provide a baseline for accounting for the effects of local electrostatic forces in electromechanical AFM measurements as well as offer additional means to probe ionic mobility and field-induced phenomena in solids.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Processing of transparent polycrystalline AlON:Ce 3+ scintillators

A new polycrystalline ceramic scintillator is reported for potential use in radiation detection and medical imaging applications. The goal was to develop cerium-activated aluminum oxynitride (AlON:Ce 3+ ) ceramics, which can be produced using ceramic processes in comparison to the high-cost, low-yield single-crystal growth technique. A phase pure AlON:Ce 3+ powder with cubic symmetry was successfully synthesized at high temperature under a reducing atmosphere to convert Ce 4+ to Ce 3+ in the solid solution. We explored two different activator concentrations (0.5 and 1.0 mol%). Fully dense and transparent AlON:Ce 3+ ceramics were produced by a liquid-phase-assisted pressureless sintering. The crystal field splitting around the Ce 3+ activator in the AlON was comparable to the splitting induced by Br₋ and the Cl₋ ligands, which produced an emission spectrum perfectly matching the maximum quantum efficiency range of the photomultiplier tube for radiation detection. Both optical excitation and radiation ionizations in AlON:Ce 3+ were demonstrated. Lastly, challenges and mechanisms related to the radioluminescence efficiency are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Pretreatment of Algae for the Production of Fuels and Chemical Coproducts

Algal biomass is a promising resource for producing renewable fuels and chemicals, but despite decades of research, algal biorefining remains in a pre-commercial state. Recent economic analyses have indicated that high-value co-products are necessary to offset the cost of fuel production, implying the need for algae fractionation technology. One promising fractionation approach is Combined Algal Processing (CAP), which pretreats and extracts algal biomass to produce a fermentable aqueous hydrolysate, an organic lipid fraction, and a residual solids fraction. The CAP approach has historically employed a dilute acid pretreatment to lyse cells and solubilize algal carbohydrates for fermentation of the hydrolysate phase, but we recently identified alternative pretreatments with the potential to decrease costs and environmental impacts, including different implementations of dilute acid pretreatment, dilute alkali pretreatment, enzymatic pretreatment, and flash hydrolysis. We conducted a screening of six different pretreatment approaches across nine algae strains of varying composition, and measured pretreatment effectiveness as a combination of carbon and nitrogen solubilization, lipid extraction yield, and lipid speciation. In this screening, we found traditional dilute acid pretreatment to provide the most robust pretreatment performance, though other pretreatments were competitive, and some performed better for certain strains of algae. These results highlight the interplay between algae composition and pretreatment effectiveness.

algae↗
DOE OSTI2020

Three-colour digital holographic microscopy based on a Mach – Zender interferometer and a solid-state RGB laser

We have developed a facility for recording colour digital holograms involving a Mach – Zender interferometer and a pulsed solid-state RGB laser, which radiates simultaneously at three wavelengths: 451, 532, and 634 nm. These wavelengths are obtained in the conversion of the radiation of a pulsed Nd{sup 3+} : YAG laser (1064 nm), which operates in the regime of intracavity parametric oscillation at a wavelength of 1570 nm, with the subsequent conversion of its frequencies to the red, green, and blue spectral regions in nonlinear KTP-crystal elements. The combination of this three-wavelength pulsed light source with the Mach – Zender interferometer provides the simultaneous recording of three spectral digital holograms with one matrix RGB radiation detector. Pulsed three-colour digital holography shows promise for the analysis of fast processes and rapidly varying colour phase objects. (paper)

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗