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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,009 records · Page 56
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Multiscale simulations for multi-continuum Richards equations

In this paper, we study a multiscale method for simulating a dual-continuum unsaturated flow problem within complex heterogeneous fractured porous media. Mathematically, each of the dual continua is modeled by a multiscale Richards equation (for pressure head), and these equations are coupled to one another by transfer terms. On its own, Richards equation is already a nonlinear partial differential equation, and it is exceedingly difficult to solve numerically due to the extra nonlinear dependencies involving the soil water. To deal with multiple scales, our strategy is that starting from a microscopic scale, we upscale the coupled system of dual-continuum Richards equations via homogenization by the two-scale asymptotic expansion, to obtain a homogenized system, at an intermediate scale (level). Based on a hierarchical approach, the homogenization’s effective coefficients are computed through solving the arising cell problems. Furthermore, to tackle the nonlinearity, after time discretization, we use Picard iteration procedure for linearization of the homogenized Richards equations. At each Picard iteration, some degree of multiscale still remains from the intermediate level, so we utilize the generalized multiscale finite element method (GMsFEM) combining with a multi-continuum approach, to upscale the homogenized system to a macroscopic (coarse-grid) level. This scheme involves building uncoupled and coupled multiscale basis functions, which are used not only to construct coarse-grid solution approximation with high accuracy but also (with the coupled multiscale basis) to capture the interactions among continua. These prospects and convergence are demonstrated by several numerical results for the proposed method.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2023

An implicit-in-time DPG formulation of the 1D1V Vlasov-Poisson equations

Efficient solution of the Vlasov equation, which can be up to six-dimensional, is key to the simulation of many difficult problems in plasma physics. The discontinuous Petrov-Galerkin (DPG) finite element methodology provides a framework for the development of stable (in the sense of Ladyzhenskaya–Babuška–Brezzi conditions) finite element formulations, with built-in mechanisms for adaptivity. While DPG has been studied extensively in the context of steady-state problems and to a lesser extent with space-time discretizations of transient problems, relatively little attention has been paid to time-marching approaches. In the present work, we study a first application of time-marching DPG to the Vlasov equation, using backward Euler for a Vlasov-Poisson discretization. We demonstrate adaptive mesh refinement for two problems: the two-stream instability problem, and a cold diode problem. Furthermore, we believe the present work is novel both in its application of unstructured adaptive mesh refinement (as opposed to block-structured adaptivity, which has been studied previously) in the context of Vlasov-Poisson, as well as in its application of DPG to the Vlasov-Poisson system. We also discuss extensive additions to the Camellia library in support of both the present formulation as well as extensions to higher dimensions, Maxwell equations, and space-time formulations.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Dislocation-graphene interactions in Cu/graphene composites and the effect of boundary conditions: a molecular dynamics study

Here, in this paper, systematic molecular dynamics simulations were employed to study dislocation-graphene interactions in Cu/graphene systems using two carefully selected configurations: (i) edge dislocations in the pileup interacting with graphene during nanoindentation and (ii) complex dislocations interacting with graphene in compression of layered nanopillars. The intrinsic and extrinsic size effects were investigated with respect to varying the Cu lamella thickness and pillar sizes, revealing an anomalous extrinsic size effect: the smaller, the weaker. To understand which boundary conditions are physically consistent, both free and periodic graphene were considered. It was seen that edge dislocations in the pileup continuously transmitted across the free graphene through Cu/graphene interfacial sliding and graphene reorientation, whereas transmission was very difficult for periodic graphene as its in-plane deformation was required. In compression of Cu/graphene nanopillars, the strengthening effect of free graphene was found to be less obvious than that of the periodic case, which could be attributed to free graphene edges acting as dislocation sources after the compressed Cu overflowed the graphene sheet from all directions. We therefore conclude that the strengthening effect of periodic graphene inclusions appears to be overestimated, such that free graphene should be more appropriate.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Subtle penetrant size effects on separation of carbon molecular sieve membranes derived from $\mathrm{6FDA:BPDA}$-$\mathrm{DAM}$ polyimide

Economically scalable carbon molecular sieve (CMS) hollow fiber membranes rely upon a tunable bimodal pore morphology to separate gas pairs using angstrom-level size discrimination. Freshly formed CMS membranes experience self-retarding physical aging, reflected by permeance losses and selectivity gains that stabilize over short times compared to the lifetime of the membrane. Self-retarding morphology rearrangements are of special interest here due to tightening of the largest size range of ultramicropores, thereby causing aging for polyimide-derived CMS. We report effects of such aging for two A/B penetrant pairs, C 3 H 6 /C 3 H 8 and CO 2 /CH 4 . These two pairs not only have different average sizes, $\overline{d}_{A/B}$, but also different size differences,Δd A/B , between the members in each pair. We focus primarily on the C 3 H 6 /C 3 H 8 pair, which is the most difficult of the two pairs to separate, and use some CO 2 /CH 4 results as a comparison case. We study CMS derived from 6FDA:BPDA-DAM (1:1) polyimide by pyrolysis at 550 °C, 600 °C and 650 °C. Here we suggest conditions and physical causes that expedite, retard or even suppress the aging process within CMS membranes. Finally, we suggest how analysis of CMS derived from other precursors and other penetrant pairs can be generalized by understanding the results for the 6FDA:BPDA-DAM (1:1) polyimide derived CMS.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Scaling and statistics of bottom-up synthesized armchair graphene nanoribbon transistors

Bottom-up assembled nanomaterials and nanostructures allow for the studies of rich and unprecedented quantum-related and mesoscopic transport phenomena. However, it can be difficult to quantify the correlations between the geometrical or structural parameters obtained from advanced microscopy and measured electrical characteristics when they are made into macroscopic devices. Here, we propose a strategy to connect the nanomaterial morphologies and the device performance through a Monte Carlo device model and apply it to understand the scaling trends of bottom-up synthesized armchair graphene nanoribbon (GNR) transistors. A new nanofabrication process is developed for GNR transistors with channel length down to 7 nm. Further, the impacts of the GNR spatial distributions and the device geometries on the device performance are investigated systematically through comparison of experimental data with the model. Through this study, challenges and opportunities of transistor technologies based on bottom-up synthesized GNRs are pinpointed, paving the way to the further improvement of the GNR device performance for future transistor technology nodes.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Disorder and hydrogenation in graphene nanopowder revealed by complementary X-ray and neutron scattering

Functionalization of graphene's two-dimensional sheets can be used to modify the physical properties of graphene, such as changing its conductivity or inducing ferromagnetism, which is of broad interest for a myriad of applications. However, functionalized graphene can possess significant structural disorder that is often overlooked and is difficult to characterize quantitatively. Here we investigate hydrogenated graphene nanopowder (H-Gr) produced by Birch reduction of graphene oxide. By combining complementary x-ray and neutron diffraction, we show how to quantitatively characterize the H-Gr nanostructure, including the hydrogen content. Further, we show that the majority of the H-Gr consists of highly disordered molecular-scale carbon while a small portion of the sample contains few-layered graphene having an expanded interlayer spacing. Modeling the coherent diffuse scattering for both x-ray and neutron diffraction, and comparing it with the incoherent neutron scattering, the hydrogen to carbon ratio was measured and it was determined that most of the hydrogen resides within the disordered carbon rather than in the graphene. Evidence is presented for hydrogen clustering as well as for hydrogen bonded perpendicular to the plane of molecular-carbon bonds. Our quantitative approach to characterizing carbon nanopowders has broad relevance to understanding disorder and bonding of hydrogen in graphitic carbons and other nanomaterials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

CaMn 0.9 Ti 0.1 O 3 based redox catalysts for chemical looping – Oxidative dehydrogenation of ethane: Effects of Na 2 MoO 4 promoter and degree of reduction on the reaction kinetics

Reduction kinetics and stability of 20 wt% Na 2 MoO 4 -promoted CaMn 0.9 Ti 0.1 O 3 were investigated for its applications in Chemical Looping – Oxidative Dehydrogenation (CL-ODH) of ethane, a potential alternative for ethylene production with higher efficiency and lower emissions. Here, the present work reports a kinetics model and parameters for a Na 2 MoO 4 -promoted, Ti-doped CaMnO 3 (CaMn 0.9 Ti 0.1 O 3 ) redox catalyst under H 2 and C 2 H 4 . A first-order reaction model provides the best fit for the reduction of Na 2 MoO 4 /CaMn 0.9 Ti 0.1 O 3 under H 2 , while the C 2 H 4 reduction is well described by an Avrami–Erofe’ev model. The activation energy for C 2 H 4 oxidation is approximately three times higher than that for H 2 conversion, showing that the activation of C 2 H 4 is significantly more difficult on the surface of the redox catalyst. The reduction rate of Na 2 MoO 4 /CaMn 0.9 Ti 0.1 O 3 under H 2 at 750 °C is more than two orders of magnitude greater than that under C 2 H 4 , while the reduction rate of unpromoted CaMn 0.9 Ti 0.1 O 3 is comparable under H 2 and C 2 H 4 , showing that the addition of Na 2 MoO 4 effectively suppresses C 2 H 4 combustion relative to H 2 oxidation. The kinetics results for Na 2 MoO 4 /CaMn 0.9 Ti 0.1 O 3 confirm its excellent selectivity towards hydrogen combustion, making it a promising candidate under CL-ODH. Additionally, the stability of the CaMn 0.9 Ti 0.1 O 3 @ Na 2 MoO 4 core-shell structure, which was the underlying reason for the excellent selectivity, was examined under both shallow and deep reductions. It was determined that deep reduction of the redox catalyst, e.g. higher than 80% solid conversion, would lead to loss of sodium and hence to decreased selectivity for hydrogen combustion. In contrast, the core-shell structure was well-maintained, exhibiting excellent performance after 50 redox cycles when deep reduction of the redox catalyst was avoided. This study offers a basis for both the CL-ODH reactor design and redox catalyst optimizations.

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

Tailoring microbes to upgrade lignin

Lignin depolymerization generates a mixture of numerous compounds that are difficult to separate cost-effectively. To address this heterogeneity issue, microbes have been employed to “biologically funnel” a broad range of compounds present in depolymerized lignin into common central metabolites that can be converted into a single desirable product. Because the composition of depolymerized lignin varies significantly with the type of biomass and the depolymerization method, microbes should be selected and engineered by considering this compositional variation. An ideal microbe must efficiently metabolize all relevant lignin-derived compounds regardless of the compositional variation of feedstocks, but discovering or developing such a perfect microbe is very challenging. Yet, developing multiple tailored microbes to tolerate a given mixture of lignin-derived compounds and to convert most of these into a target product is more practical. This review discusses recent progress towards the development of such microbes for lignin valorization and offers future directions.

09 BIOMASS FUELS↗
DOE OSTI2021

The coordination properties and ionic radius of actinium: A 120-year-old enigma

Actinium is an elusive element with untamed properties and represents a peculiar case in the periodic table, as its isotopes are all radioactive, the longest-lived one having only a 22-year half-life, and the availability of actinium isotopes remains very low (microgram level, at best), hindering research on its compounds. Despite being a natural element discovered more than 120 years ago, and despite an increasing interest in using one of its isotopes ( 225 Ac) for highly efficient cancer therapies, the chemistry of actinium is still largely unknown relative to other elements. Since Ac is the first element of the actinide series, it is accepted that its ion, Ac 3+ , is the most voluminous trivalent cation of the periodic table. However, the structural data available on Ac 3+ compounds are scarce and have mainly been collected in the 1940-1960's, when actinide chemistry was still in its infancy, and have not been put in perspective with the advances in the chemistry of other elements, making it difficult to accurately evaluate its actual size and coordination chemistry. Here, we review progress made on the chemistry of lanthanides and actinides and reevaluate the structural data published on Ac 3+ since the era of the Manhattan Project. The data are combined across different spectroscopic and characterization methods and presented in the context of periodic trends. When considering crystallographic data, solution chemistry results, and the nuclear properties of actinium isotopes, it appears that some structural parameters ascribed to the Ac 3+ ion may have been overestimated. This review can guide researchers interested in actinide sciences and those who are pursuing the development of actinium-based radiotherapies, from isotope production to clinical trials.

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

Mass transport in nanoarray monolithic catalysts: An experimental-theory study

Reducing the mass transfer resistance globally of a catalyst is a key to enhancing the catalytic reaction kinetics and fully utilizing the catalyst activity. Despite the success in tailoring the external mass transfer in the widely studied washcoat monoliths, the internal mass transfer resistance is difficult to be reduced due to the requirement of increasing macroporosity while maintaining high specific surface area and mechanical stability. Therefore, nanostructured array-based monolithic catalysts (nanoarray catalysts) have been developed in the past decade as a promising class of structured catalysts that may complement or substitute washcoat catalysts. This work fundamentally elucidates the enhanced mass transport properties of the nanoarray monolithic catalysts by a combination of experimental measurements and theoretical modeling. Using a low-dimensional model, the relative contributions of resistances were quantified in terms of chemical kinetics, internal and external mass transfers based on a probe model of C2H4 oxidation over the TiO2 supported Pt-based monolithic catalysts. The nanoarray catalysts displayed a lower internal mass transfer resistance than the washcoat counterparts as a result of the high macroporosity and small thickness of nanoarray layers. Finally, the nanoarray configuration provides a new pathway towards designing high-performance monolithic reactors and catalysts with low internal diffusion limitations for various gas phase reactions.

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

Investigating biomass composition and size effects on fast pyrolysis using global sensitivity analysis and CFD simulations

It is notoriously difficult to build an accurate universal model for biomass pyrolysis due to its sensitivity to a wide number of critical material attributes such as chemical species and physical sizes. In this work, a biomass pyrolysis kinetics with 32 heterogeneous reactions and 59 species was implemented in an open-source multiphase computational fluid dynamics (CFD) software MFiX and validated against two different experimental pyrolysis data sets that provided detailed data describing chemical component yields. The reaction scheme was then used to build a surrogate model and assess the sensitivity of pyrolysis yields to feedstock compositions. The sensitivity analysis determined that the yield of bio-char showed a strong positive sensitivity to the carbon-rich lignin and tannin pseudo-species in the reaction scheme while the bio-oil and bio-gas were correlated to oxygen-rich lignin pseudo-species. The reaction scheme was then integrated into a coarse-grained discrete element model to simulate fast pyrolysis in a bubbling fluidized bed over a range of feedstock particle sizes. The reactor simulations showed further sensitivity to particle size and hydrodynamics. Notably, particles under 0.5 mm have small heat transfer limitations but left the reactor before completely converting and thus reduced the bio-oil yield. Results from this study can be used to guide future development of highly accurate models for fast pyrolysis reactors with a variety of feedstock properties and operating conditions.

09 BIOMASS FUELS↗
DOE OSTI2021

Flame aerosol synthesis of hollow alumina nanoshells for application in thermal insulation

Commercial implementation of hollow nanoshell materials is often limited by difficult scale-up and high cost. Here we present a scalable, continuous, and potentially low-cost route to hollow nanostructured materials using a High Temperature Reducing Jet flame aerosol reactor. The key advantage of this process over traditional flame aerosol synthesis methods is separation of flame chemistry and particle formation, which allows production of hollow nanoshells from an aqueous salt solution without any template or surfactant. We produced amorphous hollow alumina with an average diameter of 181 nm and shell thickness below 10 nm, and demonstrated the generality of the method by also producing hollow SiO 2 , ZrO 2 , Ga 2 O 3 , and Co 2 O 3 . We characterized the morphology, phase transition, thermal stability, and thermal conductivity of the flame-made hollow alumina by electron microscopy, x-ray diffraction, and thermal analysis methods. As a prototypical application, we incorporated hollow alumina into thermal insulation, combining it with common fiberglass insulation to reduce the thermal conductivity by 30% relative to pure fiberglass, to 0.028 W m -1 K -1 while maintaining robust fire-resistance and elasticity.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Accuracy of predictions made by machine learned models for biocrude yields obtained from hydrothermal liquefaction of organic wastes

Hydrothermal liquefaction (HTL) has potential for converting abundant wet organic wastes into renewable fuels. Because HTL consists of a complex reaction network, deterministic, physics-based prediction of its biocrude yield is prohibitively difficult. Data-driven methods provide an alternative to the physics-based approach; however, rigorous testing must be performed to ensure the accuracy of predictions made by data-driven methods. To this end, a data set was assembled consisting of 570 data points appearing in the open literature. The data set was divided into training, validation, and test sub-sets and used for evaluating different machine learning regression approaches to predict biocrude yield. Among the tested algorithms, Random Forest and eXtreme Gradient Boosting (XGBoost) predicted biocrude yields in a test set that had not been used for training with the greatest accuracy, with root mean square errors (RMSE) of 8.34 and 8.57, respectively. Further refinement of the Random Forest model reduced its RMSE to 8.07. In comparison, predictions of a series of literature models resulted in RMSE ranging from 9.16 in the most accurate case to 27.6 in the least accurate; most literature models yielded RMSE values > 10. Using biocrude yield predictions from the most accurate Random Forest model and a probabilistic economic analysis found that the model accuracy is sufficient to prioritize allocation of resources based on projected minimum fuel selling price. In our report the models and analysis represent a major advance in the ability to use readily available data to predict biocrude yields on new feedstocks that have not previously been studied.

42 ENGINEERING↗
DOE OSTI2022

Importance of residence-time control of industrial screw-conveying reactors: Application to dilute-acid hydrolysis of biomass

Horizontal screw reactors are utilized in biorefineries for acid-catalyzed hydrolysis of xylan, which is a multi-step chemical reaction requiring accurate residence-time control. However, it is difficult to obtain online analytical measurement of reactant species. In this work, a residence-time distribution (RTD) is exhibited whose characteristics influence species yields. Sensitivity of product yield to RTD was investigated to understand the relative importance of operating control vs. inherent reactor dispersion. We find that reactor operation using a commonly used theoretical residence-time relationship can result in substantial yield losses. Instead, a model that accounts for the actual reactor RTD provides much improved results. The dispersion caused by reactor conditions only slightly hinders achieving theoretical optimal xylose yield (less than 3% yield loss for coefficient of variation less than 0.35), provided a validated RTD model is used to target the desired mean residence-time. In contrast, neglecting to account for the RTD by using the simplistic theoretical calculation results in xylose yields that are as much as 16% lower than the theoretical maximum.

09 BIOMASS FUELS↗
DOE OSTI2022

Towards fast-charging high-energy lithium-ion batteries: From nano- to micro-structuring perspectives

Electric vehicles (EVs) have been playing an indispensable role in reducing greenhouse gas emissions for our modern society. However, current EVs are difficult to meet people’s diverse travel needs, especially in long endurance and fast-charging capacities. At the heart of this issue is the physicochemical limit of current lithium-ion batteries (LIBs), which are the core parts for powering the vehicles. Hence, LIBs with simultaneous high energy and power are critically required to further promote the development of EVs. Here, in this review, we first summarize the key electrochemical processes in electrochemical reactions which lead to the corresponding overpotentials in or between multiple battery components. Furthermore, numerical simulations are employed to quantitatively analyze the effects of versatile electrode parameters on electrochemical properties in high-energy NMC811//graphite systems. On the basis of the in-depth understandings from simulation, recent experimental efforts on designing electroactive materials and electrode architectures across multiple length scales are discussed. Among them, nano-structuring can promote local mass transport and stabilize the interfaces at the particle level, while micro-structuring can establish efficient pathways for charge carriers at the electrode level. Finally, we conclude that a tight feedback loop among structure engineering, characterization and simulation should be followed to speed up the understanding of the deficiencies existing in current electrode designs as well as point out the possible electrode optimization routes for next-generation fast-charging LIBs.

25 ENERGY STORAGE↗
DOE OSTI2023

Bona fide upcycling strategy of anhydride cured epoxy and reutilization of decomposed dual monomers into multipurpose applications

Waste epoxy materials become an enormous problem to society and the environment. The advantages of epoxy resins derive from their rigid and chemically stable networks, but these qualities also make them difficult to dispose of or recycle. In this work, we demonstrated an efficient degradation of anhydride cured epoxy resin by aminolysis in aminoethanol without using any catalysts. The epoxy resin was fully decomposed at 160 °C in 4 h, resulting in two distinct high purity monomers (HHPA-OH and BPA-OH). To fully realize this upcycling approach, The BPA-OH was used to synthesize a polyurethane coating with an excellent glass transition temperature (88.9 °C), scratch hardness (8H), gouge hardness (6H), adhesive strength (5B), and strong solvent resistance. The HHPA-OH with two hydroxyl groups was reacted with methacrylic anhydride to form a dimethacrylate monomer which was then used as a viable crosslinker for photo-curable 3D printing thermosetting polymer with tensile strength as high as 64 MPa and impact strength of 4.86 kJ/m 2 . This work demonstrates a feasible pathway to convert anhydride cured epoxy waste to new monomeric recyclates for superior polymer products.

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

Elucidating the role of $\mathrm{Fe}$-$\mathrm{Mo}$ interactions in the metal oxide precursors for Fe promoted $\mathrm{Mo/ZSM}$-5 catalysts in non-oxidative methane dehydroaromatization

Literature shows that adding Fe as a separate phase to MoO 3 /ZSM-5 catalysts can improve benzene selectivity in methane dehydroaromatization (MDA), but only when added in small quantities, making it difficult to characterize the state of Fe in the catalyst and understand the role of Fe-Mo interactions on the catalytic properties. We explore how the nature of the Mo-Fe interactions in the catalyst precursor can influence the stability and product selectivity in MDA, by employing for the first time Fe 2 (MoO 4 ) 3 /ZSM-5 as a catalyst precursor in MDA. We have compared the activity of Fe 2 (MoO 4 ) 3 /ZSM-5 with monometallic MoO 3 /ZSM-5 and mixed MoO 3 + Fe 2 O 3 /ZSM-5 containing equivalent Mo and Fe loadings and found that Fe 2 (MoO 4 ) 3 /ZSM-5 shows higher benzene selectivity than the mixed MoO 3 + Fe 2 O 3 /ZSM-5 catalyst and exhibits higher stability in reaction compared to the monometallic MoO3/ZSM-5 catalyst. Structural characterization suggests that Fe 2 (MoO 4 ) 3 partially segregates to Fe 2 O 3 and amorphous MoO x during thermal pretreatment. The MoO x species migrate into the zeolite channels during pretreatment, while Fe oxides remain on the external surface of the zeolite. Gas adsorption/desorption techniques and density functional theory calculations demonstrate that the preexisting Fe 2 O 3 phases on the external surface of the zeolite in the mixed MoO 3 + Fe 2 O 3 /ZSM-5 precursor trap (MoO 3 ) 3 clusters preventing them from migrating into the zeolite channels during pretreatment, whereas gradual formation of amorphous MoOx together with the segregation of the Fe 2 O 3 phase when using the Fe 2 (MoO 4 ) 3 precursor diminishes trapping of (MoO 3 ) 3 and consequently enhances migration and anchoring of the MoO x species in the zeolite channels, boosting selectivity to benzene. Characterization of used catalysts suggests that the presence of Fe promotes formation of structured carbon nanofibers which reduce the rate of catalyst deactivation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗