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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 1,315 records · Page 73

Amorphous and crystalline TiO 2 nanoparticle negative electrodes for sodium-ion batteries

Titanium dioxide (TiO 2 ) is a promising negative electrode for sodium ion batteries (SIBS). Although TiO 2 materials with amorphous (A-TiO 2 ) and single-phase crystalline structures (C-TiO 2 ) have been separately explored, the study to compare the fundamental electrochemistry of A-TiO 2 and C-TiO 2 is limited. In this work, we investigated A-TiO 2 and C-TiO 2 nanoparticles with identical chemical composition and morphology. C-TiO 2 exhibits enhanced electrochemical performance than A-TiO 2 in terms of rate capability and cycle life. Cyclic voltammetry (CV) analysis suggests reversible Na ion insertion/extraction in C-TiO 2 . However, such process is irreversible in the case of A-TiO 2 . The charge storage mechanisms in both samples were studied to show that diffusion-controlled intercalation process becomes significant in C-TiO 2 sample. The C-TiO 2 sample has a better Na + diffusivity measured through the galvanostatic intermittent titration technique (GITT) compared to A-TiO 2 , which corroborates well with the rate capability study. Furthermore, the evolution of local structure of the TiO 2 samples was analyzed by ex situ pair distribution function (PDF) to understand the variation in electrochemical properties. In conclusion, it reveals that the corner-shared Ti-Ti distance along Na ion diffusion pathway increases with the increase of crystallinity, leading to the expanded diffusion channels and therefore more active sites and faster diffusion.

25 ENERGY STORAGE↗

Exploitation of olive mill wastewater and liquid cow manure for biogas production

Co-digestion of organic waste streams is an innovative technology for the reduction of methane/greenhouse gas emissions. Different organic substrates are combined to generate a homogeneous mixture as input to the anaerobic reactor in order to increase process performance, realize a more efficient use of equipment and cost-sharing by processing multiple waste streams in a single facility. In this study, the potential of anaerobic digestion for the treatment of a mixture containing olive mill wastewater (OMW) and liquid cow manure (LCM) using a two-stage process has been evaluated by using two continuously stirred tank reactors (CSTRs) under mesophilic conditions (35 {sup o}C) in order to separately monitor and control the processes of acidogenesis and methanogenesis. The overall process was studied with a hydraulic retention time (HRT) of 19 days. The digester was continuously fed with an influent composed (v/v) of 20% OMW and 80% LCM. The average removal of dissolved and total COD was 63.2% and 50%, respectively. The volatile solids (VS) removal was 34.2% for the examined mixture of feedstocks operating the system at an overall OLR of 3.63 g CODL{sub reactor}{sup -1}d{sup -1}. Methane production rate at the steady state reached 0.91 L CH{sub 4}L{sub reactor}{sup -1}d{sup -1} or 250.9 L CH{sub 4} at standard temperature and pressure conditions (STP) per kg COD fed to the system.

09 BIOMASS FUELS↗

Kinetically Controlled Formation of Semi-crystalline Conjugated Polymer Nanostructures

Conjugated polymer (CP) materials that are considered as an attractive choice for various electronic and optoelectronic applications possess highly heterogeneous complex structures that can span several orders of magnitude in length scale. This is due to the intricate coupling effects of weak secondary interactions and entropic forces that determine molecular organization in bulk polymer materials. Understanding the influence of molecular interactions on the emergence and evolution of nano- and microscale structures is of paramount importance to the guided design and development of condensed CP materials. Such understanding is even more critical for the rational design of hierarchical systems away from equilibrium, where weak molecular interactions can guide the system along competing kinetic pathways toward local energy minima and metastable architectures. In this work, we studied a promising concept for accessing various kinetically stabilized semi-crystalline CP nanostructures that are formed in the process of controlled chain-growth Kumada catalyst-transfer polymerization initiated by a small-molecule catalytic species which can exist in equilibrium between free and aggregated states. Specifically, we chose a small-molecule perylenedicarboximide (PDCI) polymerization catalytic initiator which has a strong tendency toward reversible supramolecular assembly–disassembly that can be controlled by temperature. Addition of a thiophene monomer to a solution of the PDCI initiator starts the chain-growth polymerization process, which produces distinct nanoscale semi-crystalline polythiophene structures formed under predominant kinetic control. Furthermore, we demonstrated that, depending on the reaction temperature (which affects the fine balance between the position of PDCI assembly–disassembly equilibrium, rate of polymerization, and solvent–solute interactions for the growing polythiophene chains), a range of kinetically trapped hierarchically organized semi-crystalline CP systems with substantially varying optoelectronic properties could be obtained. In addition to spectroscopic and electron microscopic studies, in order to better reveal the structural aspects of the generated polymer nanoscale systems, we carried out a series of X-ray diffraction and neutron scattering experiments which indicated complex hierarchical organization in these kinetically stabilized CP assembled materials. We expect that this in situ polymerization-based approach can lead to a general way to expand access to various semi-crystalline CP nanostructured materials with broadly tunable electronic and optical properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Extensive Soot Compaction by Cloud Processing from Laboratory and Field Observations

Soot particles form during combustion of carbonaceous materials and impact climate and air quality. When freshly emitted, they are typically fractal-like aggregates. After atmospheric aging, they can act as cloud condensation nuclei, and water condensation or evaporation restructure them to more compact aggregates, affecting their optical, aerodynamic, and surface properties. Here we survey the morphology of ambient soot particles from various locations and different environmental and aging conditions. We used electron microscopy and show extensive soot compaction after cloud processing. We further performed laboratory experiments to simulate atmospheric cloud processing under controlled conditions. We find that soot particles sampled after evaporating the cloud droplets, are significantly more compact than freshly emitted and interstitial soot, confirming that cloud processing, not just exposure to high humidity, compacts soot. Our findings have implications for how the radiative, surface, and aerodynamic properties, and the fate of soot particles are represented in numerical models.

54 ENVIRONMENTAL SCIENCES↗

Technetium Removal Using Tc-Goethite Coprecipitation

This report describes the results from laboratory tests performed at Pacific Northwest National Laboratory for the U.S. Department of Energy (DOE) EM-31 Support Program (EMSP) subtask, “Low temperature waste forms coupled with technetium removal using an alternative immobilization process such as Fe(II) treated-goethite precipitation” to increase our understanding of 99Tc long-term stability in goethite mineral form and the process that controls the 99Tc(VII) reduction and removal by the final Fe (oxy)hydroxide forms. The overall objectives of this task were to 1) evaluate the transformation process of Fe (oxy)hydroxide solids to the more crystalline goethite (α-FeOOH) mineral for 99 Tc removal and 2) determine the mechanism that limits 99 Tc(IV) reoxidation in Fe(II)-treated 99 Tc-goethite mineral and 3) evaluate whether there is a long-term 99 Tcoxidation state change for Tc sequestered in the iron solids.

Goethite↗

Flexoelectricity and New Phenomena

It is easy to miss the scientific implications of our recent work on Triboelectricity. Everyone knows that rubbing and contact can produce static electricity; less appreciated is that the thermodynamic driver has been an open question since static electricity was first observed by Thales of Miletus around 585 BC. People think they understand it, for instance one common explanation that can still be found in the current literature is that differences in the work function drives charge transfer, often called the Volta-Helmholtz hypothesis. As summarized in 1967 by Harper, this fails to explain many experimental observations, for instance that charging can occur when two pieces of the same material are rubbed against each other. We are the first to place triboelectricity on a solid foundation rooted in quantum mechanics – the flexoelectric effect. We were able to explain a significant number of previously unexplained phenomena: 1) Bipolar tribocurrents associated with stick-slip, due to the change in sign of the strain gradients. 2) A one-third power scaling of tribocurrents with indentation force. 3) Tribocharging when two identical materials are used, these being due to local variations in the asperities so there are usually local potential differences. 4) Inhomogeneous charging of insulators, related to the statistical nature of asperities. 5) An experimentally observed reversal in the sign of charge transfer for negative and positive curvature, which is related to a change in the sign of the strain gradient. Exploiting our DOE prior funded work on flexoelectricity, we obtained semi-quantitative matching to existing experimental measurements of the surface charge in triboelectric experiments. The work has been well received in the literature. The work has been the focus of a number of popular science press articles, and also formed the basis for a Podcast for children 6-10 “The Rise and Fall of Static Man” posted in December 2019 by NPR as part of their “Wow in the World” series. I was also briefly interviewed by the Chicago PBS station in January 2020. This work are significant for a wide range of energy applications; to quote from an independent source: "Triboelectric power has plenty of potential, says Wenzhuo Wu, an assistant professor of engineering at Purdue. If the basics of static electricity are better understood, we could maximize the efficiency of wind or wave power generators, Wu says. The body's own movement could be used to power internal medical devices. Imagine being able to create a roof shaped to harness the power of a raindrop — the friction of the rain passing over the surface — to generate triboelectricity, powering the building below it." This is the start of new science, some of which we already partially understand such as the role of band bending in charge transfer. We need to understand charge transfer combining elasticity, quantum mechanics, band bending and defect states. These directly involve several of the DOE Grand Challenges: "How do we control material processes at the level of electrons? How do remarkable properties of matter emerge from complex correlations of the atomic or electronic constituents and how can we control these properties? How do we characterize and control matter away—especially very far away— from equilibrium?" I will argue that this work truly falls into the class of disruptive science; it is not just a simple extension, linear science. Not everyone will accept the approach. Since we explain far more about triboelectricity than anyone before, the preponderance of evidence supports the model. The feedback I have received is that many agree with the work, to quote: "The model makes sense, says Michael McAlpine, a professor of engineering at the University of Minnesota. "It's such a simple explanation, I was surprised I didn't put my finger on that," McAlpine says." The proposal received strong reviews. It was also publicized on the Department of Energy Web Site.

16 TIDAL AND WAVE POWER↗

A widespread family of serine/threonine protein phosphatases shares a common regulatory switch with proteasomal proteases

PP2C phosphatases control biological processes including stress responses, development, and cell division in all kingdoms of life. Diverse regulatory domains adapt PP2C phosphatases to specific functions, but how these domains control phosphatase activity was unknown. We present structures representing active and inactive states of the PP2C phosphatase SpoIIE from Bacillus subtilis. Based on structural analyses and genetic and biochemical experiments, we identify an α-helical switch that shifts a carbonyl oxygen into the active site to coordinate a metal cofactor. Our analysis indicates that this switch is widely conserved among PP2C family members, serving as a platform to control phosphatase activity in response to diverse inputs. Remarkably, the switch is shared with proteasomal proteases, which we identify as evolutionary and structural relatives of PP2C phosphatases. Although these proteases use an unrelated catalytic mechanism, rotation of equivalent helices controls protease activity by movement of the equivalent carbonyl oxygen into the active site.

59 BASIC BIOLOGICAL SCIENCES↗

Effects of Controlled Cooling-Induced Ferrite–Pearlite Microstructure on the Cold Forgeability of XC45 Steel

The combination of hot/warm and cold forging with an intermediate controlled cooling process is a promising approach to saving costs in the manufacture of automobile parts. In this work, the effects of the ferrite–pearlite microstructure, which formed after controlled cooling, on the cold forgeability of a medium-carbon steel were investigated. Different specimens for both normal and notched tensile tests were directly heated to high temperature and then cooled down at different cooling rates, producing different ferrite volume fractions, ranging from 6.69 to 40.53%, in the ferrite–pearlite microstructure. The yield strength, ultimate tensile strength, elongation rate, percentage reduction of area, and fracture strain were measured by tensile testing. The yield strength, indicating deformation resistance, and fracture strain, indicating formability, were used to evaluate the cold forgeability. As the ferrite volume fraction increased, the cold forgeability of the dual-phase ferritic–pearlitic steel improved. A quantitatively relationship between the ferrite volume fraction and the evaluation indexes of cold forgeability for XC45 steel was obtained from the test data. To validate the mathematical relationship, different tensile specimens machined from real hot-forged workpieces were tested. There was good agreement between the predicted and measured values. Our predictions from the relationship for cold forgeability had an absolute error less than 5%, which is acceptable for industrial applications and will help to guide the design of combined forging processes.

36 MATERIALS SCIENCE↗

Nitric-glycolic flowsheet reduction/oxidation (redox) model for the defense waste processing facility (DWPF)

Control of the REDuction/OXidation (REDOX) state of glasses containing high concentrations of transition metals, such as High Level Waste (HLW) glasses, is critical in order to eliminate processing difficulties caused by overly reduced or overly oxidized melts. Operation of a HLW melter at Fe +2 /ΣFe ratios of between 0.09 and 0.33, retains radionuclides in the melt and thus the final glass. Specifically, long-lived radioactive 99 Tc species are less volatile in the reduced Tc 4+ state as TcO 2 than as NaTcO 4 or Tc 2 O 7 , and ruthenium radionuclides in the reduced Ru 4+ state are insoluble RuO 2 in the melt which are not as volatile as NaRuO 4 where the Ru is in the +7 oxidation state. Similarly, hazardous volatile Cr 6+ occurs in oxidized melt pools as Na 2 CrO 4 or Na 2 Cr 2 O 7 , while the Cr +3 state is less volatile and remains in the melt as NaCrO 2 or precipitates as chrome rich spinels. The melter REDOX control balances the oxidants and reductants from the feed and from processing additives such as antifoam.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Cyber-Physical System Security With Deceptive Virtual Hosts for Industrial Control Networks

A challenge facing industrial control network administrators is protecting the typically large number of connected assets for which they are responsible. These cyber devices may be tightly coupled with the physical processes they control and human induced failures risk dire real-world consequences. Dynamic virtual honeypots are effective tools for observing and attracting network intruder activity. This paper presents a design and implementation for self-configuring honeypots that passively examine control system network traffic and actively adapt to the observed environment. In contrast to prior work in the field, six tools were analyzed for suitability of network entity information gathering. Ettercap, an established network security tool not commonly used in this capacity, outperformed the other tools and was chosen for implementation. Utilizing Ettercap XML output, a novel four-step algorithm was developed for autonomous creation and update of a Honeyd configuration. This algorithm was tested on an existing small campus grid and sensor network by execution of a collaborative usage scenario. Automatically created virtual hosts were deployed in concert with an anomaly behavior (AB) system in an attack scenario. Virtual hosts were automatically configured with unique emulated network stack behaviors for 92% of the targeted devices. The AB system alerted on 100% of the monitored emulated devices.

97 MATHEMATICS AND COMPUTING↗

LLNL SFA FY11 Program Management and Performance Report: Environmental Transport of Plutonium

The major challenge in predicting the mobility and transport of plutonium (Pu) is determining the dominant geochemical processes that control its behavior in the subsurface. The reaction chemistry of Pu (i.e., aqueous speciation, solubility, sorptivity, redox chemistry, and affinity for colloidal particles, both abiotic and microbially mediated) is particularly complicated. It is generally thought that due to its low solubility and high sorptivity, Pu migration in the environment occurs only when facilitated by transport on particulate matter (i.e., colloidal particles). Despite the recognized importance of colloid-facilitated transport of Pu, very little is known about the geochemical and biochemical mechanisms controlling Pu-colloid formation and association, particularly at femtomolar Pu concentrations observed at DOE sites. This 5-year program is designed to test the important biogeochemical processes governing colloid-facilitated Pu transport in the field.

54 ENVIRONMENTAL SCIENCES↗

Assessing entropy for catalytic processes at complex reactive interfaces

When chemical reactions are accelerated by a catalyst, entropy differences between reactants and their transient intermediates can be the driving force behind the promotion or inhibition of desired and parasitic chemical pathways. Understanding and controlling catalytic processes therefore requires both a fundamental and practicable understanding of entropy in addition to enthalpy. In unstructured media such as the vapor phase equilibrated with sparsely covered surfaces, entropy can be adequately accounted for by well-established approaches based on translational, rotational, and harmonic vibrational partition functions. However, these approximations become inadequate in more complex condensed phase environments, e.g., solid liquid interfaces of confined reaction spaces. In this chapter, we provide an overview of the state-of-art in the computational quantification of entropy and its known ramifications on catalysis. The fundamental roles of thermodynamics and kinetics in catalysis are covered in enough detail to appreciate and contextualize the computational methods employed to compute chemically accurate estimates of entropy. These methods are discussed in appropriate detail and range from the ubiquitous harmonic oscillator approximation where entropy unrelated to high frequency oscillations is typically underestimated, to enhanced free energy sampling with molecular dynamics where the desired accuracy must be weighed against the associated computational cost of obtaining it. The rising importance of machine learning and artificial intelligence in accelerating methodological progress in this field is touched upon, as well. Finally, applications, successes, and pitfalls of using these methods are provided to showcase past and present accomplishments while clarifying where improvements in both understanding and methodology are still needed.

Kollias, Loukas↗

Mechanosensing in cell–matrix adhesions – Converting tension into chemical signals

Cell-matrix adhesions have since long been recognized to be critical for the survival and proliferation of cells. In fact, these adhesive structures do not only physically anchor cells, but they also induce vital intracellular signaling at cell-matrix adhesion sites. Recent progress in the cell adhesion field is now starting to provide data and ideas how this so far enigmatic signaling process is induced and regulated by intracellular acto-myosin tension, or stiffness of the extracellular matrix. Understanding how cells are using this mechanosignaling system will be key to control biological processes such as development, cancer growth, metastasis formation and tissue regeneration. In this review, we illustrate and discuss the mechanosignaling mechanisms important in the regulation of cell-matrix adhesions at the molecular level.

60 APPLIED LIFE SCIENCES↗

What Limits Predictive Certainty of Long-Term Carbon Uptake?

Terrestrial biosphere models can help identify physical processes that control carbon dynamics, including land-atmosphere CO 2 fluxes, and have the potential to project the terrestrial ecosystem response to changing climate. It is important to identify ecosystem processes most responsible for model predictive uncertainty and design improved model representation and observational system studies to reduce that uncertainty. Here we identified model parameters that contribute the most uncertainty to long-term (~100 years) projections of net ecosystem exchange, net primary production, and aboveground biomass within a mechanistic terrestrial biosphere model (Ecosystem Demography, version 2.1) ED2. An uncertainty analysis identified parameters that represent the quantum efficiency of light to photosynthetic conversion, leaf respiration and soil-plant water transfer as the highest contributors to model uncertainty regardless of time frame (annual, decadal, and centennial) and output (e.g., net ecosystem exchange, net primary production, aboveground biomass). Contrary to expectations, the contribution of successional processes related to reproduction, competition, and mortality did not increase as the time scale increased. These findings suggest that uncertainty in the parameters governing short-term ecosystem processes remains the most significant bottleneck to reducing predictive uncertainty. Key actions to reduce parameter uncertainty include more leaf-level trait measurements across multiple sites for quantum efficiency and leaf respiration rate. Further, the empirical representation of soil-plant water transfer should be replaced with a mechanistic, hydraulic representation of water flow, which can be constrained with direct measurements. This analysis focused on aboveground ecosystem processes. The impact of belowground carbon cycling, initial conditions, and meteorological forcing should be addressed in future studies.

54 ENVIRONMENTAL SCIENCES↗

A review on the application of machine learning for combustion in power generation applications

Abstract Although the world is shifting toward using more renewable energy resources, combustion systems will still play an important role in the immediate future of global energy. To follow a sustainable path to the future and reduce global warming impacts, it is important to improve the efficiency and performance of combustion processes and minimize their emissions. Machine learning techniques are a cost-effective solution for improving the sustainability of combustion systems through modeling, prediction, forecasting, optimization, fault detection, and control of processes. The objective of this study is to provide a review and discussion regarding the current state of research on the applications of machine learning techniques in different combustion processes related to power generation. Depending on the type of combustion process, the applications of machine learning techniques are categorized into three main groups: (1) coal and natural gas power plants, (2) biomass combustion, and (3) carbon capture systems. This study discusses the potential benefits and challenges of machine learning in the combustion area and provides some research directions for future studies. Overall, the conducted review demonstrates that machine learning techniques can play a substantial role to shift combustion systems towards lower emission processes with improved operational flexibility and reduced operating cost.

Engineering↗

Controllable Thin‐Film Approaches for Doping and Alloying Transition Metal Dichalcogenides Monolayers

Abstract Two‐dimensional (2D) transition metal dichalcogenides (TMDs) exhibit exciting properties and versatile material chemistry that are promising for device miniaturization, energy, quantum information science, and optoelectronics. Their outstanding structural stability permits the introduction of various foreign dopants that can modulate their optical and electronic properties and induce phase transitions, thereby adding new functionalities such as magnetism, ferroelectricity, and quantum states. To accelerate their technological readiness, it is essential to develop controllable synthesis and processing techniques to precisely engineer the compositions and phases of 2D TMDs. While most reviews emphasize properties and applications of doped TMDs, here, recent progress on thin‐film synthesis and processing techniques that show excellent controllability for substitutional doping of 2D TMDs are reported. These techniques are categorized into bottom–up methods that grow doped samples on substrates directly and top–down methods that use energetic sources to implant dopants into existing 2D crystals. The doped and alloyed variants from Group VI TMDs will be at the center of technical discussions, as they are expected to play essential roles in next‐generation optoelectronic applications. Theoretical backgrounds based on first principles calculations will precede the technical discussions to help the reader understand each element's likelihood of substitutional doping and the expected impact on the material properties.

36 MATERIALS SCIENCE↗

The Importance of Nonequilibrium to Equilibrium Transition Pathways for the Efficiency and Stability of Organic Solar Cells

Controlled morphology of solution-processed thin films have realized impressive achievements for non-fullerene acceptor (NFA)–based organic solar cells (OSCs). Given the large set of donor–acceptor pairs, employing various processing conditions to realize optimal morphology for high efficiency and stable OSCs is a strenuous task. Therefore, comprehensive correlations between processing conditions and morphology evolution pathways have to be developed for efficient performance and stability of devices. Within the framework of the blend system, crystallization transitions of NFA molecules are tracked utilizing the first heating scan of differential scanning calorimeter (DSC) measurement correlating with respective morphology evolution of blend films. Real-time dynamics measurements and morphology characterizations are combined to provide optimal morphology transition pathways as NFA molecules are shown to be released from the mixed phase to form balanced ordered packing with variant processing conditions. Polymer:NFA films are fabricated using blade coating incorporating solvent additive or thermal annealing as processing conditions as a correlation is formulated between performance and stability of solar cells with morphology transition pathways. In conclusion, this work demonstrates the significance of processing condition-controlled transition pathways for the realization of optimal morphology leading to superior OSC devices.

14 SOLAR ENERGY↗

Emerging Techniques for Field Device Security

Critical infrastructure, such as electrical power plants and oil refineries, rely on embedded devices to control essential processes. State of the art security is unable to detect attacks on these devices at the hardware or firmware level. We provide an overview of the hardware used in industrial control system field devices, look at how these devices have been attacked, and discuss techniques and new technologies that may be used to secure them. We follow three themes: (1) Inspectability, the capability for an external arbiter to monitor the internal state of a device. (2) Trustworthiness, the degree to which a system will continue to function correctly despite disruption, error, or attack. (3) Diversity, the use of adaptive systems and complexity to make attacks more difficult by reducing the feasible attack surface.

97 MATHEMATICS AND COMPUTING↗