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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Quantifying Value with Effective Complexity

We present a new economic theory of value based on complexity theory. For simplicity, we call this theory ‘complexalism’ (a portmanteau of ‘complexity’ and ‘capitalism’). Complexalism is a framework that establishes valuations by quantifying the present and future complexities of objects and their surroundings. This framework reparameterises questions of economic value into more objectively addressable subcomponents. First, we motivate the importance of developing alternative frameworks for value. Next, we discuss a novel three-dimensional framework to analyse value and the use of effective complexity as a proxy metric of economic value. Finally, we propose explicit methods for quantifying complexity and simulating valuations. The resulting valuations may serve to benchmark prices and can be used in evaluating the market rules of engagement.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Bio-reduction of ferrihydrite-montmorillonite-organic matter complexes: Effect of montmorillonite and fate of organic matter

Organic matter (OM) is often associated with Fe (hydr)oxides such as ferrihydrite (Fh) in soils and sediments, forming binary Fh-OM complexes. Microbial reduction of Fh results in destabilization of the complexes and mineral/OM transformation. However, little is known about the role of clay minerals in such processes, despite their common co-existence with Fh and OM in natural environments. Here Fh-OM complexes were synthesized in the presence of montmorillonite (SWy-2), forming ternary Fh-(SWy-2)-OM complexes. A metal-reducing bacterium Geobacter sulfurreducens was used to reduce Fh in the complexes under circumneutral pH and anoxic conditions with or without H 2 as extra electron donor. Various spectroscopy and mass spectrometry methods were used to monitor the progress of Fh bio-reduction and mineral/OM transformation. Results showed that G. sulfurreducens utilized mineral-bound OM as electron donor and/or carbon source to couple with Fh reduction. Relative to Fh-OM complex, Addition of SWy-2 to Fh-OM complex enhanced the bio-reduction extent of Fh by increasing the proportion of bioavailable OM that was weakly bound to SWy-2. However, its effect on the bio-reduction rate was variable. SWy-2 initially decreased the rate, because it spatially separated OM (electron donor) from Fh (electron acceptor). During later incubation, SWy-2 increased the reduction rate by sorbing biogenic Fe 2+ that would otherwise passivate the Fh and cell surfaces. Bio-reduction transformed mineral-bound OM to microbial products (e.g. necromass, extracellular polymeric substances), but organic compounds with aromatic structures, carboxyl groups and large molecular weight were more resistant to desorption and oxidation. The persistence of these compounds against bio-reduction induced transformation is likely due to their stronger binding with minerals and/or lower nominal oxidation states of carbon relative to other compounds. Our results provide new insights into the role of clay minerals in regulating biogeochemical cycling of solid-phase Fe and transformation of mineral-associated OM in anoxic soil environments.

58 GEOSCIENCES↗
DOE OSTI2026

Regioselective Hydrosilylation Catalysis with Supported Well-Defined Pt(0) Complexes: Effects of Surface Anions and Phosphenium Ligands

Achieving stable, selective single-atom catalysts is challenging because localsurface-site structures are difficult to control. Surface organometallic chemistry and organic−inorganic hybrid materials offer partial solutions, but applications to supporting zero-valent metals are limited. We demonstrate that well-defined, ionically bound N-heterocyclic phosphenium ([NHP] + ) ligands can be generated on silylium-functionalized sulfated zirconia ([ i Pr 3 Si][SZO]). These surface-bound [NHP][SZO] ligands coordinate Pt(0) centers, forming [(NHP)Pt(0)L][SZO] precatalysts that are highly active for alkyne hydrosilylation. Systematic studies reveal that sterically bulky aromatic ligands enhance regioselectivity, achieving performances comparable to molecular Pt catalysts. Further, more-coordinating anions support more-regioselective precatalysts; therefore, SZO supports more-selective species than weaker-coordinating Al(OC(CF 3 ) 3 ) 3 - functionalized silica, a trend confirmed by molecular analogues. These results demonstrate that both the ligand and support control catalytic behavior and enable solid-state structure− activity relationships.

Catalysts↗
DOE OSTI2021

The Effects of Temperature on the Assembly of Gold Nanoparticle by Interpolymer Complexation

Using synchrotron-based small-angle X-ray scattering techniques, we demonstrate that poly(ethylene glycol)-functionalized gold nanoparticles (PEG-AuNPs) are assembled into close-packed structures that include short-range order with face-centered cubic structure, where crystalline qualities are varied by controlling the electrolyte concentration, pH, and temperature of the suspensions. Here, we show that interpolymer complexation with poly(acrylic acid) (PAA) is induced by lowering the pH level of the PEG-AuNPs suspensions, and furthermore, increasing the temperature of the suspension strengthens interparticle attraction, leading to improved supercrystal structures. Our results indicate that this strategy creates robust nanoparticle superlattices with high thermal stability. The effects of PAA and PEG chain lengths on the assemblies are also investigated, and their optimal conditions for creating improved superlattices are discussed.

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

Ultrastructure of Critical-Gel-like Polyzwitterion–Polyoxometalate Complex Coacervates: Effects of Temperature, Salt Concentration, and Shear

The structure of unconventional complex coacervates, such as polymer-nonpolymer complex coacervates, remains less investigated than that of the conventional coacervates formed between oppositely charged polyelectrolytes with symmetric charge species. Yet, their microscopic structural organization is important to further elucidate the mechanism of liquid-liquid-phase separation processes upon complexation. In this work, we characterize the microstructural organization of complex coacervates formed between inorganic polyoxometalate (POM) and polyzwitterion by small-angle X-ray scattering (SAXS) with in situ temperature and shear control. Furthermore, despite the apparent transparent and homogeneous morphology of dense coacervates as observed by optical microscopy, our previous results (Macromolecules 2018, 51, 22, 9405-9411) suggest that dense polyzwitterion-POM coacervates exhibit critical-gel-like networks containing both complex-poor region (mesh pore) and complex-rich region (connective network). SAXS results as reported in this work support that the complex-rich region is actually in the form of loosely packed POM aggregates linked by polyzwitterion, designated as complex particles. The structure of aggregating complex particles is further examined against varied composition and salt concentrations, temperature, and shear, thanks to the high X-ray scattering contrast of POMs from that of other components in the coacervates. The complex particles in the dense coacervates appear to grow with more tightly packed POM aggregates with increasing POM-to-polyzwitterion concentration ratio, in contrast to more loosely packed POM aggregates with decreasing salt concentration. Conversely, increasing temperature could result in smaller complex particles containing more loosely packed POM aggregates, consistent with temperature-dependent viscoelasticity of dense coacervates. Furthermore, such POM-based hybrid dense coacervates exhibit intriguing strain-hardening behavior, resulting from shear-enhanced POM packing inside the complex particles. Distinct from the shear-thinning behavior of most conventional crosslinked polymeric networks, the strain-hardening property combined with thermal- and salt-responsive characteristics of polyzwitterion-POM coacervates could broaden the applications of hybrid organic-inorganic macroion coacervates as smart functional materials working under extreme environmental conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Rigorous computation of short-range order unifies its controversial effects in complex concentrated alloys

Direct experimental observations of chemical short-range order (SRO) in complex concentrated alloys (CCAs) have triggered high interest. However, the reported effects of SRO on yield stresses are controversial, and their atomic-scale mechanisms are elusive, which limits our ability to utilize SRO in alloy design. Here we tackle this challenge using an advanced computational approach that rigorously takes into account the critical lattice distortion in CCAs and further verify our theoretical predictions with experiments. We show that the CoCrNi model alloy has a narrow temperature window around 670 °C for SRO formation. This explains why the mechanical effect of SRO is observed in some experiments but not in others. Here, we propose an effective alloy-doping method to control SRO and reveal atomic-bonding types that dominate SRO formation for different alloys. The strategies and insights generally apply to a broad spectrum of alloys, laying the foundation for designing advanced alloys by manipulating their SRO.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Supercritical water desalination and oxidation (SCWDO): Effectiveness on complex solutions, technoeconomic, and CO 2 impact for produced water treatment

The modern energy-economy is increasingly causing the production of highly saline brines, including from produced water. Supercritical water desalination can concentrate and extract minerals from these brines, but the effects of mixed salt interactions, organic degradation with additives, and the technology's economics are not well understood at supercritical condition. The present study evaluated and experimentally studied an integrated supercritical water desalination and oxidation (SCWDO) process for treating real-produced water samples from oil/natural gas field. The complex interactions between the various anions and cations in produced water were extensively evaluated. Most of the divalent and trivalent ions were extracted below 250 °C while the majority of the monovalent salt were removed between 380 to 410 °C. The treated real produced water was of drinking water quality, with <500 mg/l of total dissolved solid (TDS) and with 100% organics removal. Furthermore, the heat liberated during the organic oxidation could be utilized internally and for electricity generation for enhanced the energy efficiency and lower cost of produced water treatment. With system optimization, the proposed SCWDO process can essentially be made a net zero energy process. A novel process flow diagram for the commercial scale self-powered hybrid SCWDO technology was proposed as a cost-effective produced water treatment to mitigate the environmental crises. Techno-economic analysis showed that produced water treatment cost with SCWDO can be reduced to 2–3 $/m 3 and can be up to 60 % cheaper to traditional deep well reinjection. Additionally, the proposed SCWDO process could achieve net negative CO 2 emission.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2024

Metabolic complexity drives divergence in microbial communities

Microbial communities are shaped by environmental metabolites, but the principles that govern whether different communities will converge or diverge in any given condition remain unknown, posing fundamental questions about the feasibility of microbiome engineering. Here, in this work, we studied the longitudinal assembly dynamics of a set of natural microbial communities grown in laboratory conditions of increasing metabolic complexity. We found that different microbial communities tend to become similar to each other when grown in metabolically simple conditions, but they diverge in composition as the metabolic complexity of the environment increases, a phenomenon we refer to as the divergence-complexity effect. A comparative analysis of these communities revealed that this divergence is driven by community diversity and by the assortment of specialist taxa capable of degrading complex metabolites. An ecological model of community dynamics indicates that the hierarchical structure of metabolism itself, where complex molecules are enzymatically degraded into progressively simpler ones that then participate in cross-feeding between community members, is necessary and sufficient to recapitulate our experimental observations. In addition to helping understand the role of the environment in community assembly, the divergence-complexity effect can provide insight into which environments support multiple community states, enabling the search for desired ecosystem functions towards microbiome engineering applications.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Systemic effects of rising atmospheric vapor pressure deficit on plant physiology and productivity

Abstract Earth is currently undergoing a global increase in atmospheric vapor pressure deficit (VPD), a trend which is expected to continue as climate warms. This phenomenon has been associated with productivity decreases in ecosystems and yield penalties in crops, with these losses attributed to photosynthetic limitations arising from decreased stomatal conductance. Such VPD increases, however, have occurred over decades, which raises the possibility that stomatal acclimation to VPD plays an important role in determining plant productivity under high VPD. Furthermore, evidence points to more far‐ranging and complex effects of elevated VPD on plant physiology, extending to the anatomical, biochemical, and developmental levels, which could vary substantially across species. Because these complex effects are typically not considered in modeling frameworks, we conducted a quantitative literature review documenting temperature‐independent VPD effects on 112 species and 59 traits and physiological variables, in order to develop an integrated and mechanistic physiological framework. We found that VPD increase reduced yield and primary productivity, an effect that was partially mediated by stomatal acclimation, and also linked with changes in leaf anatomy, nutrient, and hormonal status. The productivity decrease was also associated with negative effects on reproductive development, and changes in architecture and growth rates that could decrease the evaporative surface or minimize embolism risk. Cross‐species quantitative relationships were found between levels of VPD increase and trait responses, and we found differences across plant groups, indicating that future VPD impacts will depend on community assembly and crop functional diversity. Our analysis confirms predictions arising from the hydraulic corollary to Darcy's law, outlines a systemic physiological framework of plant responses to rising VPD, and provides recommendations for future research to better understand and mitigate VPD‐mediated climate change effects on ecosystems and agro‐systems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Using machine-learning to understand complex microstructural effects on the mechanical behavior of Ti-6Al-4V alloys

Structural materials properties are highly dependent on their microstructure. Their microstructure is in turn affected by multiple fabrication and thermo-mechanical treatment parameters, all of which conform a highly-dimensional parametric space with often hidden correlations that are difficult to extract by experimentation alone. This is particularly true for alloys of the dual-phase Ti-6Al-4V family, with their greatly complex and rich microstructures, which combine several intrinsic length scales associated with multiple grain and subgrain structures, grains with different crystal lattices (α and β phases), and complex chemistry. In this paper we use a comprehensive set of machine learning techniques to develop predictive tools relating the yield strength and hardening rate of these alloys to a set of input parameters covering extensive ranges. The data generator is a finite-element crystal plasticity model for polycrystal deformation that takes into account slip anisotropy and employs standard dislocation evolution models for the α and β phases of Ti-based alloys. Our dataset includes over two thousand independent simulations and is used to train the machine learning models, which are then used to establish correlations between microstructural parameters and the alloys’ mechanical response. Our results point to the most influential parameters affecting yield strength and hardening rate, information that can then be used to guide experimental synthesis and characterization efforts to save time and resources.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Optimal renormalization of multiscale systems

While model order reduction is a promising approach in dealing with multi-scale time-dependent systems that are too large or too expensive to simulate for long times, the resulting reduced order models can suffer from instabilities. We have recently developed a time-dependent renormalization approach to stabilize such reduced models. In the current work, we extend this framework by introducing a parameter that controls the time-decay of the memory of such models and optimally selecting this parameter based on limited fully resolved simulations. First, we demonstrate our framework on the inviscid Burgers equation whose solution develops a finite-time singularity. Our renormalized reduced order models are stable and accurate for long times while using for their calibration only data from a full order simulation before the occurrence of the singularity. Furthermore, we apply this framework to the 3D Euler equations of incompressible fluid flow, where the problem of finite-time singularity formation is still open and where brute force simulation is only feasible for short times. Our approach allows us to obtain for the first time a perturbatively renormalizable model which is stable for long times and includes all the complex effects present in the 3D Euler dynamics. We find that, in each application, the renormalization coefficients display algebraic decay with increasing resolution, and that the parameter which controls the time-decay of the memory is problem-dependent.

Price, Jacob↗
DOE OSTI2021

Ab initio metadynamics calculations reveal complex interfacial effects in acetic acid deprotonation dynamics

Acid-base reactions play a central role in solution chemistry, with carboxylic acids being particularly important in atmospheric chemical processes. In this work, we harness metadynamics calculations with Born-Oppenheimer molecular dynamics (BOMD) simulations to understand deprotonation dynamics of acetic acid (CH 3 COOH) in both bulk and air-water interfacial environments. Collective variables are carefully chosen in our well-tempered metadynamics simulations to capture the deprotonation process in various aqueous configurations. Herein, our findings show that the free energy barrier for deprotonation of acetic acid at the air-water interface is lower than in the bulk, in accordance with the available experimental data. Furthermore, our well-tempered metadynamics calculations suggest that the variations in free energy are primarily due to intricate solvation shell effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗