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At least 199 records · Page 11

A Multi-Region SEIR Model Incorporating Inter-County Mobility and Time-Dependent Transmission Dynamics: Application to COVID-19 Disease Outbreak Data in North Carolina.

Classical infectious disease compartmental models typically do not incorporate spatial heterogeneity or mobility. We develop a multi-region susceptible-exposed-infected-recovered (SEIR) model in which disease dynamics are coupled via inter-region mobility and the transmission rate is both region and time dependent. We calibrate the model using rolling averages of daily COVID-19 data in all 100 North Carolina counties. Mobility parameters are prescribed using daily inter-county commuter data. The number of transmission rate parameters is substantially reduced by hypothesizing that the dynamics correlate with county-level population density. Parameter estimation is carried out using several objective functions with error terms at different scales. An additive combination of least squares error at the county-level and the state-level, along with a quadratic transmission rate polynomial, yields the lowest overall error at both spatial scales. The calibrated model is used to simulate regional effects of perturbing disease transmission rates in adjacent counties and to illustrate effects of the state’s mobility infrastructure on disease dynamics and spread for a new disease outbreak.

COVID-19 modeling↗

Incorporate day-ahead robustness and real-time incentives for electricity market design

In this paper, we propose a two-stage electricity market framework to explore the participation of distributed energy resources (DERs) in a day-ahead (DA) market and a real-time (RT) market. The objective is to determine the optimal bidding strategies of the aggregated DERs in the DA market and generate online incentive signals for DER-owners to optimize the social-welfare taking into account network operational constraints. Distributionally robust optimization is used to explicitly incorporate data-based statistical information of renewable forecasts into the supply/demand decisions in the DA market. We evaluate the conservativeness of bidding strategies distinguished by different risk aversion settings. In the RT market, a bi-level time-varying optimization problem is proposed to design the online incentive signals to tradeoff the RT imbalance penalty for distribution system operators (DSOs) and the costs of individual DER-owners. This enables tracking their optimal dispatch to provide fast balancing services, in the presence of time-varying network states while satisfying the voltage regulation requirement. Simulation results on both DA wholesale market and RT balancing market demonstrate the necessity of this two-stage design, and its robustness to uncertainties, the performance of convergence, the tracking ability and the feasibility of the resulting network operations.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Incorporation of market signals for the optimal design of post combustion carbon capture systems

Recent studies have shown that fossil generators equipped with post-combustion carbon capture (PCC) systems are needed to reduce the cost of deep decarbonization. Such generators need to be flexible and responsive to grid conditions, particularly in a high variable renewable energy (VRE) environment. In this work, we evaluate the net present value (NPV) of retrofitting an existing natural gas combined cycle (NGCC) unit with a flexible PCC system while incorporating market signals from a high VRE grid. We use our industrial partner’s NGCC configuration as representative of existing NGCC units and Svante’s rapid-temperature swing adsorption (TSA) for PCC. Because of its ability to rapidly startup/shutdown and ramp-up/ramp-down, the chosen capture technology is very attractive for load-following operations. For a given set of market signals, we formulate a two-stage stochastic multi-period optimization problem, under the price-taker assumption, to simultaneously optimize the design of the capture system and operation of the entire plant. Rigorous models for the NGCC unit, PCC system, and compression system are developed using commercial process simulators and validated with either plant or vendor data. For computational tractability, we develop surrogate/reduced-order models for use in the optimization problem. The surrogate model for the NGCC plant is constructed by linearizing the rigorous dynamic model at 75% load, while data-driven nonlinear surrogate models for the capture and compression systems are constructed using simulation data from the rigorous models. The optimization problem, formulated as a mixed integer bilinear program, is implemented in the IDAES® integrated platform and solved to global optimality using Gurobi 9.5. Using this formulation, we determine the profitability of retrofitting an existing NGCC unit with the chosen capture system for multiple regions in the U.S. under two scenarios with different carbon prices. Importantly, the results show that the optimal decision strongly depends on the region and on the carbon price, thereby demonstrating the importance of the inclusion of market signals in the design process.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Synthesis and characterization of UiO-66-NH 2 incorporated graphene aerogel composites and their utilization for absorption of organic liquids

This work details the synthesis, materials characterization and absorption capacity of graphene aerogel (GA) loaded with UiO-66-NH 2 metal organic framework (MOF). Throughout the study, a series of density-tunable MOF/GA composites were synthesized by adjusting the MOF/graphene oxide (GO) mass ratio of the precursors before hydrothermal reduction and subsequent critical point drying to achieve MOF-x%/GA composites, with x, ranging from 0 to 100, denoting the weight percent ratio of MOF to GO in the starting solution. Scanning electron microscopy (SEM) images and Barrett-Joyner-Halenda (BJH) pore size calculations supported that MOF loading enlarged the macroporous (>50 nm) structure of the GA framework but had no influence on the mesoporous (2–50 nm) structure of GA. The degree of MOF loading first decreased and then increased the density of resulting composites, exhibiting a minimum for the 10–30% samples. Such behavior with respect to MOF loading has not been reported previously. MOF-x%/GA samples were further investigated for absorption capacity using various organic liquids. MOF-30%/GA proved to be the best absorbent sample for all solvents tested, achieving the highest capacity for chloroform at 147.0 ± 10.0 mg/mg. The behavior is attributed to the structural changes induced by the MOF incorporation as well as the interactions between the organic molecules and the MOF.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optimized molecular aggregation via incorporating fluorinated unit in the polymer donor for 17.3% efficiency organic solar cells

Regulating molecular aggregation state via chemical modification of photovoltaic materials to optimize the blend morphology is an effective and challenging strategy to improve the photovoltaic performance of organic solar cells (OSCs). Here, in this work, we demonstrate a random terpolymerization strategy by incorporating 1,3-bis(5-bromo-4-fluorothiophen-2-yl)-5,7-bis(2-ethylhexyl)-4H,8H-benzo[1,2-c:4,5-c']bisthiophene-4,8-dione (BFT, 30 mol%) unit with fluorinated π-bridges into the molecular backbone of PM6 and develop a terpolymer PF1. Benefiting from the strong electronegativity of fluorine atom and noncovalent interaction of F---S, the energy levels, molecular ordering, and aggregation properties of the polymer donors are precisely regulated. Notably, in the active layer film based on PF1: Y6, the π-π stacking distance can reduce to 3.51 Å, which is significantly smaller than that of PM6:Y6 (3.65 Å) and boosts the effective exciton dissociation and charge transport, thereby effectively optimize the photovoltaic properties of the related devices. As a result, the PF1:Y6-based OSCs achieved a power conversion efficiency (PCE) of up to 17.3%, which is much higher than that of the controlled OSCs based on PM6:Y6 (PCE = 16.2%). These results demonstrate high-efficiency OSCs enabled by regulating molecular aggregation via terpolymerization strategy.

14 SOLAR ENERGY↗

Incorporating PCM-enabled thermal energy storage into 3D printable cementitious composites

This paper delineates the feasibility of incorporating microencapsulated phase change materials (mPCM) into 3D printable cementitious composite materials. A comprehensive experimental program was carried out to evaluate the impacts of mPCM on the printability, microstructures, mechanical and thermal properties of cementitious 3D printing ‘inks’. Results showed that the mPCM affected the printability of the cementitious ink material based on its physical properties (e.g., particle size) and volume loading – at lower volume loadings, mPCM increased the flowability of the cementitious ink material while leading to increased compressive strength and thermal conductivity for the hardened printed material. However, further increase in mPCM dosage led to a decrease in printability and, therefore, decrease in compressive strength and thermal conductivity as compared to the reference mixture. Here the results also showed that the inclusion of mPCM influence the printing parameters. In general, the inclusion of higher volume contents of mPCM necessitates a higher extrusion rate to achieve a desirable extrudability. Lastly, a thermal network model was formulated for 3D printed mPCM charged building components (e.g., wall). The study shows that microencapsulated PCM materials have good potential to be used in 3D printable cementitious mixtures for improving the thermal and energy performance of 3D printed buildings.

36 MATERIALS SCIENCE↗

Iron incorporation in synthetic precipitated calcium silicate hydrates

Effect of Fe{sup 3+} on the precipitation of synthetic calcium silicate hydrates (C-S-H) under controlled conditions has been evaluated. Using extremely basic either initial calcium nitrate or sodium silicate solutions (pH > 11), incipient formation of ferrihydrite in both solutions was observed. In this case both C-S-H and iron-containing siliceous hydrogarnet are formed. For pH < 11, ferrihydrite was absent. Only C-S-H is formed. The presence of magnetically dilute Fe{sup 3+} in the C-S-H was shown by EPR and the atomic Fe/Si ratio of the C-S-H phase was shown to be between 0.01% and 0.1% by measuring and modelling the {sup 29}Si spin-lattice relaxation in NMR experiments. A uniform distribution of Fe{sup 3+} when C-S-H precipitates in the absence of initial ferrihydrite is obtained. When initial ferrihydrite is present, a non-uniform distribution of Fe{sup 3+} is found and the concentration of Fe{sup 3+} in the C-S-H is merely 3% of the overall iron concentration, suggesting the initial formation of ferrihydrite restricts the incorporation of iron into C-S-H.

36 MATERIALS SCIENCE↗

Electromagnetic wave absorption of multifunctional cementitious composites incorporating polyvinyl alcohol (PVA) fibers and fly ash: Effects of microstructure and hydration

Highlights: • The cementitious composite shows excellent wide-band electromagnetic wave absorption in a frequency range of 2–18 GHz. • The PVA fibers and the fly ash change the dielectric properties of the cementitious composite by Debye polarization. • The iron oxide of the cementitious binders contributes to the magnetic properties of the composites. • The impacts of the microstructure and the hydration of the cementitious composite on its microwave absorption are analyzed. This paper devises a novel method for the adjustment of the pore structure and the hydration of cement to improve the electromagnetic wave absorption of the cementitious composites incorporating polyvinyl alcohol (PVA) fibers and fly ash in a frequency range of 2–18 GHz. The underlying mechanism of the absorption is investigated to explore the possibility of the structural and functional integration of these composites. The electromagnetic parameters of the prepared cementitious composites and those of the raw materials are analyzed in a frequency range of 0.5–18 GHz. Moreover, the pore structure and the chemical environment of the cementitious composites are examined by mercury intrusion porosimetry (MIP), back-scattered electron detector (BSE), and X-ray photoelectron spectroscopy (XPS). The results indicate that the PVA fibers and the high-volume fly ash have a positive effect on electromagnetic wave absorption of the cementitious composites through the adjustment of their pore structure and hydration.

36 MATERIALS SCIENCE↗

Crosslinked polymeric ionic liquid stationary phases incorporating a combination of silver(I) and copper(II) ions for olefin separations by gas chromatography

The development of efficient and selective olefin separation technologies is a critical challenge within the chemical industry given the high energy demands of conventional cryogenic distillation methods. To address this, the study explores the effectiveness of polymeric ionic liquid (PIL) stationary phases in gas chromatography (GC) that incorporate both silver(I) ([Ag + ]) and copper(II) ([Cu 2+ ]) ions for enhanced olefin separation via π-complexation interactions. Further, the effects of both non-crosslinked and crosslinked PIL stationary phases containing varying ratios of [Ag⁺] and [Cu²⁺] ions were systematically investigated to evaluate their impact on the separation of olefins from paraffins and structurally similar olefins. Retention measurements using a broad range of olefinic probes revealed that [Ag⁺] ions provided stronger and more consistent π-complexation in PIL-based stationary phases, while [Cu²⁺] ions preferentially enhance olefin retention in crosslinked systems. Furthermore, thermal stability studies showed that [Ag + ]-containing PIL stationary phases maintain stable olefin separation efficiency over prolonged exposure under elevated temperatures, while crosslinked PIL stationary phases containing [Cu 2+ ] ions exhibited stronger retention due to increased surface adsorption. These findings provide insight into the tunability of metal–olefin interactions using PIL-based stationary phases and suggest design strategies for achieving thermally stable and highly selective chromatographic separations of unsaturated hydrocarbons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Incorporating space and time into random forest models for analyzing geospatial patterns of drug-related crime incidents in a major U.S. metropolitan area

The opioid crisis has hit American cities hard, and research on spatial and temporal patterns of drug-related activities including detecting and predicting clusters of crime incidents involving particular types of drugs is useful for distinguishing hot zones where drugs are present that in turn can further provide a basis for assessing and providing related treatment services. In this study, we investigated spatiotemporal patterns of more than 52,000 reported incidents of drug-related crime at block group granularity in Chicago, IL between 2016 and 2019. We applied a space-time analysis framework and machine learning approaches to build a model using training data that identified whether certain locations and built environment and sociodemographic factors were correlated with drug-related crime incident patterns, and establish the top contributing factors that underlaid the trends. Space and time, together with multiple driving factors, were incorporated into a random forest model to analyze these changing patterns. We accommodated both spatial and temporal autocorrelation in the model learning process to assist with capturing the changes over time and tested the capabilities of the space-time random forest model by predicting drug-related activity hot zones. Overall, we focused particularly on crime incidents that involved heroin and synthetic drugs as these have been key drug types that have highly impacted cities during the opioid crisis in the U.S.

97 MATHEMATICS AND COMPUTING↗

Incorporating corrosion design constraints in desalination process optimization: A case study in mechanical vapor compression

Corrosion is an expensive and complex challenge for desalination, yet current design approaches do not explicitly account for corrosion mechanisms in process modeling and technoeconomic analysis. Here, to address this gap, we present a workflow for incorporating corrosion design constraints directly into desalination process optimization models. We develop surrogate models for general and localized corrosion metrics as functions of temperature, pH, salinity, dissolved oxygen, and material using data from OLI Systems’ Corrosion Analyzer. We then integrate these surrogates as corrosion design constraints in a cost-optimization MVC model that minimizes the levelized cost of water (LCOW). For a case study of mechanical vapor compression (MVC) treating seawater across a range of recoveries, we find dissolved oxygen (DO) is the dominant driver of localized corrosion, and thus of cost-optimal material choice and operating conditions. Reducing the DO from 8 mg/L to 0.5 mg/L reduces the LCOW by 15-35%, informing the breakeven costs for implementing DO removal or selecting highly corrosion-resistant alloys. This framework is broadly applicable across corrosion types, materials, and components and enables desalination process design that minimizes capital costs.

36 MATERIALS SCIENCE↗

Structure and dynamics of ILs-based gel polymer electrolytes and its enhanced conductive properties with the incorporation of Al 2 O 3 nanofibers

Here, this work reports the enhanced mobility of ions in ionic liquid (IL)-based gel polymer electrolytes (GPEs) with the incorporation of Al 2 O 3 nanofibers. A combination of PVDF-HFP, EMIMTFSI and LiTFSI with 3 wt% Al 2 O 3 nanofibers has been prepared through solution casting technique. The room temperature ionic conductivity of PVDF-HFP: ILs electrolyte (45:55, weight ratio of 0.82) (GPE) is found to be 2.7 × 10 –5 S cm –1 , which increases up to 7.8 × 10 –5 S cm –1 in Al 2 O 3 containing GPE (Al-GPE). Pulsed field gradient (PFG) NMR results validate the increased ionic conductivity observed in Al-GPE. We found that the diffusivity of Li + , TFSI – and EMIM + increases when Al 2 O 3 nanofibers are well-distributed in the GPE matrix. The surface morphology and the amorphicity of GPEs are examined through SEM and XRD analyses. Lastly, the local structure of Al 2 O 3 fibers and the molecular-level interactions of ions with polymer, and their effect on the diffusivity of ions are established through solid-state NMR detecting 27 Al, 1 H, 13 C, 19 F nuclei including 2D 13 C{ 1 H} HETCOR NMR experiments. The 13 C DPMAS and CPMAS experiments highlight the dynamic heterogeneity associated with the ions that are embedded in the rigid and the mobile phase of GPEs. While some of the ionic species strongly interact with polymer chains in the rigid environment, the majority of them reside in the mobile phase and contribute to the overall increased conductivity. Most importantly, Al 2 O 3 nanofibers significantly affect the dynamics of ionic species that are present in the mobile phase between the polymer chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Landslide monitoring using seismic refraction tomography – The importance of incorporating topographic variations

Seismic refraction tomography provides images of the elastic properties of subsurface materials in landslide settings. Seismic velocities are sensitive to changes in moisture content, which is a triggering factor in the initiation of many landslides. However, the application of the method to long-term monitoring of landslides is rarely used, given the challenges in undertaking repeat surveys and in handling and minimizing the errors arising from processing time-lapse surveys. This work presents a simple method and workflow for producing a reliable time-series of inverted seismic velocity models. This method is tested using data acquired during a recent, novel, long-term seismic refraction monitoring campaign at an active landslide in the UK. Potential sources of error include those arising from inaccurate and inconsistent determination of first-arrival times, inaccurate receiver positioning, and selection of inappropriate inversion starting models. At our site, a comparative analysis of variations in seismic velocity to real-world variations in topography over time shows that topographic error alone can account for changes in seismic velocity of greater than ±10% in a significant proportion (23%) of the data acquired. The seismic velocity variations arising from real material property changes at the near-surface of the landslide, linked to other sources of environmental data, are demonstrated to be of a similar magnitude. Over the monitoring period we observe subtle variations in the bulk seismic velocity of the sliding layer that are demonstrably related to variations in moisture content. This highlights the need to incorporate accurate topographic information for each time-step in the monitoring time-series. The goal of the proposed workflow is to minimize the sources of potential errors, and to preserve the changes observed by real variations in the subsurface. Following the workflow produces spatially comparable, time-lapse velocity cross-sections formulated from disparate, discretely-acquired datasets. These practical steps aim to aid the use of the seismic refraction tomography method for the long-term monitoring of landslides prone to hydrological destabilization.

Whiteley, J. S.↗

Influence of physical and chemical hydrology on bioremediation of a U-contaminated aquifer informed by reactive transport modeling incorporating 238 U/ 235 U ratios

Microbially-catalyzed reductive immobilization of aqueous uranium (U) as a solid phase has been proposed as a U remediation technique. Both laboratory and field experiments have demonstrated that this reduction reaction alters the 238 U/ 235 U ratio, producing a 238 U-enriched U(IV) solid. In contrast, other major U reactive transport processes fractionate these isotopes much less. This suggests the potential to quantify the extent of bioreduction occurring in groundwater containing U using the 238 U/ 235 U ratio, which would substantially improve upon current practices largely relying on U concentration measurements alone. Current reactive transport models for uranium dynamics include only concentration measurements, which are strongly influenced by highly coupled reactive transformation and aqueous transport processes. The complex physical and chemical behavior of U potentially compromises such quantitative analysis of U storage and release. Here we report the first numerical reactive transport model which explicitly incorporates variations in the 238 U/ 235 U ratio of U and demonstrates improved interpretation of the principal chemical reactions and groundwater transport processes affecting the subsurface mobility and distribution of this widespread contaminant. Recent U bioreduction studies performed in a contaminated aquifer in Rifle, Colorado, USA applied Rayleigh distillation models to interpret U stable isotope fractionation observed as a result of acetate amendment. These simplified models were unable to resolve the spatiotemporal pattern of U isotope fractionation recorded in the aqueous solutes. Here, we employ the multi-component, isotope-enabled CrunchTope reactive transport software to interpret these measured U isotope ratios, and demonstrate accurate reproduction of observed trends in both geochemistry and 238 U/ 235 U ratios for two consecutive years of field experiments. Overall, our results indicate that accurately modeling both the U concentration and isotope ratio distributions greatly constrains the parameter space of the model. We find that the transport properties of U in the Rifle aquifer are governed by the presence of low-permeability regions, which the isotopes are uniquely sensitive to. When U reduction is spatially constrained by these low-permeability regions, the shift in the 238 U/ 235 U ratio becomes more muted. Accurate modeling of observed U isotope ratios thus provides a powerful means to better understand bioremediation, and the current study serves to advance the application of this novel method.

238U/235U↗

Effect of metal-free mesoporous silica incorporated ZSM-5 composite on thermo-catalytic pyrolysis of polypropylene

Although different zeolites impregnated with transition metals have been used in catalytic deconstruction of waste plastics to other products, the influence of hierarchical structures on conversion and product selectivity in plastic upcycling has not been thoroughly investigated. This research explores a transition metal free zeolite-based hierarchical composite, synthesized by incorporating SBA-15 in ZSM-5 framework, for efficient thermos-catalytic upcycling of polypropylene (PP). Thermogravimetric analysis reveals that ZSM-5@SBA-15 can break down PP at a significantly lower temperature, 240 °C, compared to that of pristine PP using ZSM-5 or SBA-15. In addition, pyrolysis of PP at 400 °C using ZSM-5@SBA-15 composite outperforms ZSM-5 or SBA-15 used separately and yields 90 % conversion with 70 % selectivity to propene. The presence of mesopores in the catalyst appears to reduce the diffusion resistance of intermediate products for successive scission, thereby reducing the activation energy of reaction and improving catalytic activity. In conclusion, the hierarchical composite ZSM-5@SBA-15 has significant potential for upcycling of PP into valuable monomers and lighter olefins, with lower energy demands, enhancing the economic feasibility of the process.

ZSM-5@SBA-15↗

Chemical durability and corrosion-induced microstructure evolution of compositionally complex titanate pyrochlore waste forms with uranium incorporation

Chemical durability of compositionally-complex rare-earth titanate pyrochlore solid solutions with or without uranium incorporation was investigated by semi-dynamic leaching testing. A Ti-enriched amorphous passivation film formed on the surface due to the surface alteration-reorganization mechanism with preferential release of the weakly oxygen-bonded rare earth elements. Elemental release was found to be strongly correlated with chemical disorder, with a negligible correlation with entropy. The release rate of the uranium gradually decreased with increasing numbers of components, implying a possibility of designing and optimizing waste form performance with enhanced chemical durability by controlling composition complexity and chemical disorder for effective nuclear waste management.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A constitutive model incorporating grain refinement strengthening on metallic alloys

Surface nano-crystallization techniques have been recently developed as one of the most efficient ways to optimize materials’ structure, and therefore develop the local and global mechanical behavior as to increase strength without compromising ductility. Here, in this work, we present a constitutive model incorporating grain refinement hardening to simulate the nano-crystallization technique, specifically, surface mechanical attrition treatment. The computation is implemented using user-defined VUMAT subroutines. As an example of its application, a geometry model with full coverage of random impacts are employed. The results show that the model has rather precise predictability of grain size evolution during plastic deformation. The readily embedded with a computational code of material dynamics enables this novel model to be a promising tool to study the dynamic evolution of microstructures under plastic deformation.

36 MATERIALS SCIENCE↗

Synthesis and thermodynamics of uranium-incorporated α-Fe 2 O 3 nanoparticles

Hematite nanoparticles were synthesized with U(VI) in circumneutral water through a coprecipitation and hydrothermal treatment process. XRD, TEM, and EXAFS analyses reveal that uranium may aggregate along grain boundaries and occupy Fe sites within hematite. The described synthesis method produces crystalline, single-phase iron oxide nanoparticles absent of surface-bound uranyl complexes. EXAFS data were comparable to spectra from existing studies whose syntheses were more representative of naturally occurring, extended aging processes. Herein this work provides and validates an accelerated method of synthesizing uranium-immobilized iron oxide nanoparticles for further mechanistic studies. High temperature oxide melt solution calorimetry measurements were performed to calculate the thermodynamic stability of uranium-incorporated iron oxide nanoparticles. Increasing uranium content within hematite resulted in more positive formation enthalpies. Standard formation enthalpies of U x Fe 2–2x O 3 were as high as 76.88 ± 2.83 kJ/mol relative to their binary oxides, or -764.04 ± 3.74 kJ/mol relative to their constituent elements, at x = 0.037. Data on the thermodynamic stability of uranium retention pathways may assist in predicting waste uranyl remobilization, as well as in developing more effective methods to retain uranium captured from aqueous environments.

36 MATERIALS SCIENCE↗