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At least 865 records · Page 48

Direct Subsurface Measurements through Precise Micro Drilling

Wellbore integrity is a significant problem in the U.S. and worldwide, which has serious adverse environmental and energy security consequences. Wells are constructed with a cement barrier designed to last about 50 years. Indirect measurements and models are commonly used to identify wellbore damage and leakage, often producing subjective and even erroneous results. The research presented herein focuses on new technologies to improve monitoring and detection of wellbore failures (leaks) by developing a multi-step machine learning approach to localize two types of thermal defects within a wellbore model, a prototype mechatronic system for automatically drilling small diameter holes of arbitrary depth to monitor the integrity of oil and gas wells in situ, and benchtop testing and analyses to support the development of an autonomous real-time diagnostic tool to enable sensor emplacement for monitoring wellbore integrity. Each technology was supported by experimental results. This research has provided tools to aid in the detection of wellbore leaks and significantly enhanced our understanding of the interaction between small-hole drilling and wellbore materials.

42 ENGINEERING↗

Development of a Reconstruction Methodology Based on X-Ray Computed Tomography to Generate Realistic 3D Concrete Microstructures in MOSAIC

Despite being passive components, concrete structures represent a major capital investment in nuclear power plants. However, some concrete components are critical for the safety and long-term operation of the reactors: the concrete containment building protects the reactors from external aggression. The concrete biological shield (CBS) contains the radiation exiting the reactor to protect equipment and personnel. Depending on the design, the CBS also has a function for supporting the reactor’s systems. This function needs to be ensured in-service and during accident scenarios. After several decades of use, the CBS is exposed to high-energy irradiation over an extended operation time, exceeding the fluence level currently considered detrimental for the concrete’s structural properties. Such conditions occur at different times depending on the reactor’s operation and design. Nevertheless, from the perspective of subsequent license application, it is mandatory to assess the potential effects of prolonged irradiation on concrete. Unlike steel components, concrete structures are built with local constituents (cement, sand, and coarse aggregates) to avoid prohibitive transportation costs. Thus, concrete performance is determined by the tolerance or the susceptibility of its constituents against any aging mechanism. The tolerance against irradiation of the CBSs may vary greatly among the 56 nuclear power plants and 93 nuclear power reactors that form the current US light-water reactor fleet. Irradiation-induced degradation is mainly a result of amorphization-induced expansions of the silicated minerals present in the aggregates. The neutron irradiation–induced expansion varies from one rock-forming mineral to another: well framework–structured silicates (e.g., quartz and feldspars) exhibit higher swelling than chained (e.g., pyroxene) or isolated silicates (e.g., garnet). Silicates make up nearly 90% of the Earth’s crust. Other common minerals present in construction aggregates are carbonates found, for example, in limestone. Irradiated carbonates exhibit only very minor expansions.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Summary of Expansions and Updates in GREET ® 2021

The GREET® (Greenhouse gases, Regulated Emissions, and Energy use in Technologies) model has been developed by Argonne National Laboratory (Argonne) with the support of the U.S. Department of Energy (DOE). GREET is a life-cycle analysis (LCA) tool, structured to systematically examine the energy and environmental effects of a wide variety of transportation fuels and vehicle technologies in major transportation sectors (i.e., road, air, marine, and rail) and other end-use sectors, and energy systems. Within the transportation sector, GREET covers road, air, water, and rail transportation sub-sectors. Recently, GREET was expanded to cover the building sector. Historically, GREET includes LCA of various materials such as steel, aluminum, cement, and different plastic types. Argonne has expanded and updated the model in various sectors in GREET 2021, and this report provides a summary of the release.

09 BIOMASS FUELS↗

Flowsheet for Conversion of Anion Resin from Nitrate to Sulfate Form for Disposal

Nitrate form anion exchange resins are specifically prohibited for disposal in TRU waste. At some DOE sites, spent resin was mixed with cement to immobilize the resin in a monolith with varying success. At SRS starting in the 1980s, spent anion resin has generally been converted to a more chemically stable form or it was digested with permanganate and transferred as a slurry to the HLW tank farm. In the early years of the site it is reported that over 20 metric tons of organic resin were transferred directly to the tank farm without any attempt to digest it. It appears that in the future conversion to a stable sulfate form could well be the favored disposal path for spent nitrate-form anion resin. This report will document the site history of converting between ionic forms (nitrate to sulfate) and will document process flowsheet conditions for performing that conversion.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Corrosion Detection LDRD Seedling (Final Report)

Automation techniques for recognizing material defects are very common in fields like infrastructure survey and civil engineering; however, the defects are usually easily distinguishable from their background, on a larger scale (e.g. cement bridges), and very specific. Extracting information about a defect that is near or equal to the background of the data can be extremely difficult. Images with heavy background corrosion, pitting, cracking, and man-made defects (such as welding) makes extracting information on a specific defect near-impossible. This is especially true when the defect is on the micron level and the dynamic range of your image taking instrument is low. So, a simplified, Java-based Fiji™ (ImageJ) defect detection program, dependent on a ‘flag’ system, was proposed for data that has a micron level hairline crack that is near or equal to the background. The utilization of the built-in functions, plugins, and macro scripting capability of the Java-based software sends a series of flags to the user that help to identify if the surface contains a defect of interest and to characterize that defect.

42 ENGINEERING↗

Secure & Sustainable Disposition of Security Sensitive Materials

Dual-stage Disintegrator with in-line briquettor Disintegrated paper transitioned from a waste to a commodity Briquettes reused to make an industrial cellulose fiber additive for construction products such as asphalt sealants, roofing cement, driveway coatings, etc. Briquettes are now also being blended with mixed paper and recycled

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Energy efficiency for the growing South Carolina manufacturing industries. Final Report

The overall goals of the proposed project were to establish a DOE Industrial Assessment Center with Clemson University as the main center and to cement the Clemson IAC as the "go to" resource for energy efficiency expertise and assistance to manufacturing businesses in the state of South Carolina. The Clemson IAC included a satellite support center through partnership with the SCE&G Energy Innovation Center at the Clemson University Restoration Institute (CURI) in North Charleston, SC. The Clemson IAC was the first IAC based in the state with the goal to serve the entire state. The Clemson IAC provided SMEs with no-cost energy assessments, trained the next generation of energy-savvy engineers, and provided outreach to non-participating SMEs. Project objectives were structured into five 12-month Budget Periods. In the first Budget Period, the primary objective was to establish methods and materials for Clemson IAC assessments, training, and outreach. In the remaining Budget Periods, the primary objectives were to perform assessments, train students, and pursue outreach to hard-to-reach SMEs that did not participate in energy assessments. Expected outcomes in the first Budget Period included the development of standard procedures for performing energy assessments, including data acquisition, processing, and communication both within the team and in assessment reports prepared for SMEs. Outcomes related to student training in the first Budget Period included detailed curriculum and internship plans for students pursuing the DOE IAC Certificate and energy-related Clemson University certificates. Outcomes in the first Budget Period also included the development of outreach materials and plans for outreach events. In Budget Periods 2 through 5, major expected outcomes are trained students and completed energy assessments and reports for SMEs. Decision points and Go-No Go criteria for the end of each Budget Period, presented in more detail below, are based on the number of students in training and the number of energy assessments performed.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Foam Fracturing Study for Stimulation Development of Enhanced Geothermal Systems

The large thermal gradients and high subsurface temperatures of the western region of the U.S. hold great potential for the implementation of enhanced geothermal systems (EGS). The development of these potential EGS resources requires stimulation of the reservoir to enhance permeability and it has been widely reported that a substantial amount of water will be required should conventional hydraulic stimulation be used. This presents a huge challenge and a high risk to the geothermal development because the water stress1 in these areas is already high or extremely high. The use of foam, a gas/liquid mixture predominantly composed of gas, in fracturing is considered and explored in this project as a potential approach to address water concerns with hydraulic stimulation in the development of EGS. This project, led by Oak Ridge National Laboratory (ORNL) in collaboration with Temple University, was awarded in an open lab call in 2018, and was part of the DOE GTO waterless stimulation initiative. The goal of the project was to demonstrate the feasibility of foam fracturing for EGS development through two primary tasks: Task 1: Laboratory study of the effectiveness of foam fracturing for representative geological materials, including cyclic pressurization using foam (led by ORNL) and Task 2: High temperature foam material selection and characterization (led by Temple University). In FY19, ORNL finished the critical review on serval issues associated with foam fracturing and the implementation of the proposed tasks in a lab study (Wang, et al., 2019), and completed the foam fracturing testing using cement as a model material (Wang, et al, 2020a). The work at ORNL was geared up to develop a brand-new foam testing system in FY20. The purchase of main components for the new system was finished in the first half of the FY20. The assembly of the foam testing system and foam fracturing testing were completed in the second half of the FY20 (Wang, et al., 2021a). Task 1 required the development of a test system which can be used to perform hydraulic fracturing of geological specimens with both water and foamed liquids at pressure up to 6,000 psi (41.4 MPa). The system possesses several capabilities that conventional injection systems lack for hydraulic fracturing. In addition to its ability to generate foam with controlled quality, it is capable of cycling pressure levels between specified values up to frequencies of 50 Hz. The latter capability was developed to evaluate the hypothesis that cyclic loading of samples would produce enhanced fracturing. The system consists of two sections: one for foam generation and another for foam injection. The foam is generated through separate control and pressurization of liquid and gas phases with controlled flow rates. The injection section is equipped with a low-flow Coriolis flow that monitors the density of foam to ensure the injection is in the range of target foam quality2. Experimental results of foam fracturing are reported for cylindrical granite specimens using water and aqueous N2 foam as the fracturing fluids. All experiments were performed for unconfined conditions. The effects of injection mode (i.e., monotonic vs cyclic pressurization) on breakdown pressure and failure response sample were investigated using water alone as a fracturing fluid and foams with a range of compositions. It was found that in the case of monotonic injection, the breakdown pressure of granite specimens tended to be slightly higher when fracturing with foam. Additionally, with a foam quality of 90%, the water use can be reduced by 50 to 84%, depending on hole size. On the other hand, it was observed that the breakdown pressure can be brought down to 70% of the monotonic breakdown pressure by using low cycle fatigue. Finally, discussions are presented regarding injectivity and water use reduction.

15 GEOTHERMAL ENERGY↗

High Yield, Economical and Environmentally Benign Production of Rare Earth Elements from Coal Ash (Phase II Final Summary Report)

Fly ash stored in landfills and ponds across the United States is an attractive, abundant domestic resource for the cost-effective recovery of rare earth elements (REE) and other critical minerals (CM). Physical Sciences Inc. (PSI) and its team members, Winner Water Services (WWS) and University of Kentucky/Center for Applied Energy Research (UK/CAER) successfully executed a multiphase program that developed technologies and their implementation in a pilot plant. We demonstrated plant operations for cost-effective and environmentally-friendly production of rare earth element oxide (REO) concentrates, and the critical minerals scandium and aluminum (in the forms of salts or oxide products), from coal ash. We also constructed and demonstrated a research-scale (0.5 kg/day) micropilot facility to validate the key physical and chemical processing operations, predict yields, and troubleshoot process bottlenecks. The project team then designed, constructed and operated two decoupled pilot plants: (1) an operational pilot plant for physical separation processes with capacity of 0.4 metric tons per day (tpd), where we optimized processes to produce selected ash fractions as the feedstock for chemical processing and as valuable byproducts such as cenospheres, magnetic ash, and secondary fuel carbon, and (2) an operational pilot plant for chemical ash processing with a capacity of 0.5 tpd that developed optimized processes for the production of: (a) REO concentrates, (b) critical minerals (Sc, Al), and (c) beneficiated ash as a valuable byproduct suitable for cement applications. In Phase I, the project team (with Equinox Chemicals in place of WWS) developed and demonstrated the feasibility of the physical and chemical separation processes, developed the design of a pilot plant, and began the development of a preliminary techno-economic model. In the baseline (initial) Phase II program, the project team developed and demonstrated the above pilot scale plant, producing salable REE concentrates, including Y and Sc (REYSc), plus commercially viable byproducts, using environmentally safe and high-yield physical and chemical enrichment processes. The team successfully demonstrated chemical pilot design, construction, shakedown, and operations of the plant. We produced the Phase II deliverable REYSc concentrate ((50 g of >60 wt.% purity REYSc salts on elemental basis), generated the feed for the Phase II follow-on program, identified processing challenges for future optimizations, and refined the techno-economic model. In the Phase II follow-on program, the project team: (1) developed and demonstrated processes to increase the REE amount by 3X (content basis) and convert the Phase II REE salt mixture to an oxide mixture, (2) produced/delivered >38 g of REO mixture with >85 wt.% purity (elemental basis); (3) developed processes to recover critical minerals scandium and aluminum from intermediate streams; (4) produced/delivered > 1 g of scandium salt mixture with >85 wt. % purity (elemental basis); (5) produced/delivered > 100 g of aluminum oxide type material with >70% wt. purity (elemental basis); and (6) updated the techno-economic model from the baseline Phase II program to assess CAPEX and OPEX of a commercial operation. This program has developed extensive databases on process chemistry, unit operations, plant engineering, and techno-economics that will enable further scale-up toward commercial plant design. Specific future developments will be focused on achieving dramatic savings in energy, reagent usage, and operating costs. The combined results will contribute significantly for maturing the technologies of REE recovery from coal byproducts and promote the establishment of domestic REE and CM supply chains.

01 COAL, LIGNITE, AND PEAT↗

Newly acquired core enhances geologic understanding of the northern Paradox Basin Cane Creek play, southeastern Utah

The Cane Creek interval is an emerging unconventional heterolithic play within the Pennsylvanian Paradox Formation of the northern Paradox Basin, southeastern Utah. Structural controls (basement uplifts, salt movement, faults, fractures) likely control production from the Cane Creek, where total oil production of ~10 MMBO is just a fraction of current estimates of the undiscovered resource (up to 1.2 BBOE). Oil production has been most successful from unstimulated horizontal wells in the Cane Creek Unit in the central play area, whereas areas to the north (Greentown and Gunnison Valley) have to date proven to be largely unproductive from vertical and horizontal wells drilled without the benefit of 3D seismic or the deployment of modern hydraulic fracturing techniques. However, the limited historical drilling has shown significant promise (e.g., significant shows). The lack of core data in the northern part of the play has impeded thorough assessment of reservoir quality, character, and lithological facies heterogeneity. The Cane Creek is informally divided into three distinct zones. The upper A and basal C zones are composed of fabric destructive and wavy bedded anhydrite, dolomitic mudstone, and organic-rich algal laminated mudstones (source rock). The middle B zone is generally wave rippled and burrowed, low-permeability sandstone-siltstone (reservoir) with subordinate displacive anhydrite. Recent potash cores collected from the Salt Valley anticline near Crescent Junction, Utah (but east of the main play area), show thicker reservoir sandstone/siltstone packages (~40 ft) in the B zone, and parts of the C zone, in the northern part of the Paradox Basin in comparison to the central (~35 ft) and southern (~30 ft) areas. Source rock analyses from northern core/cuttings also indicate that it is well positioned within the oil window (VRo ~0.8), with thin organic-rich mudstone beds containing up to 20 wt% TOC. Because the siliciclastic reservoir rocks have low permeabilities (0.009–0.202 mD) and variable porosities (6–17%) due to dolomite-anhydrite cement, naturally occurring and possibly stimulated fractures may be essential for hydrocarbon recovery. To better understand the northern part of the Cane Creek play, a new core was obtained from the research stratigraphic well State 16-2 (January 2021). Details from this new core will help characterize reservoir quality via core analyses, petrography, fracture orientations, geomechanics, and correlation of facies and depositional trends. Additionally, an evaluation of matrix porosity/permeability will be conducted to determine its contribution to productivity.

02 PETROLEUM↗

SULI Research Report Paper

The Intelligence and Space Research Group 4 (ISR-4) at the Los Alamos National Laboratory focuses on signal processing and developing space electronics for various national security missions. The Space and Atmospheric Burst Reporting System (SABRS) is a sensing payload designed for nuclear detonation detection. As the sensors from previous payloads become obsolete, the requirement for a novel payload design increases. SABRS Prime is the successor to the previous SABRS payloads and is scheduled for delivery in 2028. As part of the SABRS Prompt Gamma Instrument Interface Board, high frequency signals from silicon photomultiplier tubes need to be split and subsequently transmitted to the Analog to Digital Converter. Prior to developing the Space Grade Instrument Interface Board, evaluation modules with Commercial off-the-shelf (COTS) components are evaluated and tested under rigorous conditions. Verification of power levels and gain specifications are some of the important steps taken during the evaluation stage. Working on the Signal Splitting Board has enabled me to work with various schematic software applications and learn more about the processes behind designing space grade electronic components. In addition, I conducted research on efficiency improvements for space-based power systems. Changes in design approaches were found to be the most significant sources of improvement. Being able to interact with researchers and peers across various scientific disciplines has given me a better insight into my future pursuits. Working in a R&D environment has cemented my decision to work on space applications for Quantum Sensing and pursue a PhD in Electrical Engineering. The SULI internship program at the Los Alamos National Laboratory has helped me develop the skillset of a researcher, understand the rigorous processes behind developing space grade hardware, and improve my critical thinking abilities to support the development of reliable instrumentation for deep space missions.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Biopolymer Modified Cementitious Systems with Radically Superior Strength and Durability

This project was a pioneering study of the effect of nanochitin additives on setting time, rheological, and mechanical properties of cementitious materials. Chitin is the second most abundant biopolymer in nature after cellulose and is readily available from byproducts of the growing seafood industry. In this study, chitin powder from shrimp shells was processed into chitin nanocrystals (ChNCs) and chitin nanofibers (ChNFs). Ch-Cs delayed initial and final set times with their high ionic surface charges likely by electrostatic repulsion. The viscosity of fresh cement paste increased with Ch-NFs, while Ch-NCs did not significantly affect rheological properties. The distinct effects of the two nanochitin forms are attributed to the mobility of the different morphologies of the rod-like ChNCs vs. the entangled and restrained network of the ChNFs. Nanochitin forms showed encouraging results by significantly increasing flexural strength by ~40% at the optimum concentration of 0.05 wt% and significant increases in fracture energy. These bio-additives were found promising and future studies should continue to evaluate their use in concrete.

36 MATERIALS SCIENCE↗

Cost of Capturing CO 2 from Industrial Sources

This systems analysis by the National Energy Technology Laboratory's Strategic Systems Analysis and Engineering directorate) evaluates the cost and performance impacts of capturing CO 2 emissions from nine industrial sources (ammonia, ethylene oxide, and ethanol production, natural gas process, coal- and gas-to-liquids, refinery hydrogen production, iron and steel, and cement manufacturing). The industrial sectors examined are segregated according to the CO 2 purity level of the flue gas stream, prior to treatment. Certain sectors naturally produce a gas stream that is inherently high in CO 2 purity, and these sectors can achieve 99-100% removal. Other sectors produce a lower purity CO 2 flue gas stream and achieving 90-99% removal requires deeper levels of treatment, adding cost. In addition to the report that documents the analysis, a Carbon Capture Retrofit Database tool was also created that allows users to apply CO 2 capture to selected industries, to evaluate the cost of capture and compare across multiple plants, as well as across different industries. Users have the ability to change select input parameters (such as fuel price, capture rate, and financing assumptions) to evaluate the impact on industrial CO 2 capture economics.

20 FOSSIL-FUELED POWER PLANTS↗

Remining and Restoring Abandoned US Mining Sites: The Case for Materials Needed for Zero-Carbon Transition

The electricity generation sector is responsible for 25% of the world’s greenhouse gas (GHG) emissions and thus has been the focus of efforts to transition to clean energy and sustainable development in many nations. In the past 20 years, renewable energy sources have been the fastest-growing energy source in the world, comprising almost 29% of the world’s electricity generation in 2020. Renewable energy sources are expected to comprise nearly 95% of the world’s power capacity growth through 2026, with a share of planned capacity expansion of up to 46% in 2026. The rapid development of renewable energy sources and technologies will require an enormous amount of raw materials to replace coal and gas plants and increase in the capacity to handle growing electricity demand because renewable energy sources have a low-power density and intermittent behavior. Accounting for the expected scale of rapidly deploying renewable energy sources that require rare earth elements (REEs), cement, and steel, the mining industry may face a supply problem for the materials critical for clean energy. And, as the exploration and development of new mining sites can be expensive and risky, the mining industry may require economic stimuli to grow supply. The increasing demand for renewable energy resources makes mining a threat to the environment unless proper regulations are established and calls for remining, cleanup, and circular economic development are made. Mining also contributes to environmental injustices related to the exploitation and pollution of lands near communities that are dependent on biodiversity in the area, while not always benefiting from technological advancements provided by the use of renewable energy and technologies. This study explored the opportunity of remining abandoned mining waste to extract metals and minerals essential for the production of renewable energy sources. The authors analyzed materials used in the production of these technologies, materials readily available in the United States, and which materials can be extracted locally in the United States from abandoned mine waste. The authors also studied environmental injustices that populations near mining sites experience and ways to mitigate these injustices, such as providing more control over extraction and cleanup activities, providing more job opportunities in those areas, and offsetting costs associated with cleanup and land restoration projects.

42 ENGINEERING↗

Development of an Extremely Durable Concrete (EDC) - A Novel approach coupling Chemistry and Autogenous Crack Width Control (Final Report)

Concrete cracking is a challenging issue and a constant threat to the durability of modern physical infrastructure. It is most commonly produced by mechanical loading and environmental deformations endured under field conditions, and structural deterioration accelerates at large crack widths. There is an urgent need for dramatic reductions in O&M cost, energy use, and emissions for infrastructure. The goal of this project is to fundamentally design an Extremely Durable Concrete (EDC) with a life expectancy at least five times that of current concrete by deploying a coupled micromechanical and chemical approach in material design. EDC is expected to embody an autogenously tight crack width (<50μm), high ductility (>3%), and stable chemistry using a green binder based on Limestone Calcined Clay Cement (LC3), which together will produce a resilient formulation with self-healing capability.

36 MATERIALS SCIENCE↗

Methane Pyrolysis for CO2-free H2 and Carbon Nanomaterials (Abstract)

We propose to continue to develop a new process for producing CO2-free hydrogen (H2) from inexpensive and domestically-abundant natural gas (NG), while simultaneously reducing H2’s net production cost to $1.0/kg through the sale of valuable crystalline solid carbon co-product. Producing clean hydrogen at this price is a DOE Hydrogen Energy Earthshot goal. Cost effective production of clean H2 is also of commercial relevance to project partners Southern California Gas Company (SoCalGas) and startup company C4-MCP, who aim to further develop, demonstrate at scale, and ultimately deploy the new process technology developed on this project in order to meet regulatory demands in the State of California. In the current project we have focused on i) understanding the catalyst science for thermocatalytic decomposition of methane (TCD), which resulted in the development of a patent pending bimetallic catalyst offering favorable activity, stability, and selectivity under industrially relevant process conditions, ii) developing a novel, patent pending process to enable the separation of produced carbon and catalyst, and re-synthesis of the catalyst using recycled materials, iii) performing limited characterization of the produced carbon materials, and iv) performing detailed process modeling in order to perform techno economic assessment. The additional scope proposed here will accelerate the commercial deployment of TCD for CO2-free H2 and valuable solid carbon nanotubes (CNT) co-product, by i) scaling up the production of CNT co-product using a scalable, fluidized bed reactor (25 g catalyst scale versus the 1 g catalyst scale demonstrated to-date), ii) producing at least 40 g of CNT product, produced via multiple cycles of TCD, carbon-catalyst separation, and catalyst re-synthesis, to enable the production of sufficient quantities of solid carbon so as to explore its market potential, iii) understanding the quality of the co-product CNTs, produced at larger scale, through advanced characterization, and iv) beginning to explore multiple promising high volume carbon product applications (thermoplastics, automotive composites, battery, and cement reinforcement applications).

08 HYDROGEN↗

Storing Co 2 in Built Infrastructure: Co 2 Carbonation of Precast Concrete Products

The overall objective of the proposed study was to advance the technical understanding of CO 2 incorporation into novel cementitious materials for the development of high value products that provide a net reduction in carbon emissions. This project combined two primary phases of research that addressed technical barriers related to (i) optimizing CO 2 storage capability of cementitious materials, (ii) evaluating and enhancing physical properties of novel carbonated materials, and (iii) assessing the reductions in life cycle CO 2 emissions attributed to CO 2 carbonation of precast cementitious materials. Engineered cementitious composites (ECC) are a class of highly ductile concrete composites that have been shown to be very durable when used in the built environment. CO 2 carbonation of ECC was examined in this study and it was found that precast ECC specimens could sequester up to 35% CO 2 by cement mass after 24 hours of curing at a CO 2 pressure of 0.5 MPa and 23°C and had a strain capacity of 3%. Carbonation conditions were optimized at the bench-scale and then utilized to create full-scale CO 2 -cured ECC railroad ties that were field tested on a train track. Rail ties were selected for this initial assessment of CO 2 storage in precast concrete materials due to the large market for concrete ties in the railroad industry. Although the full-scale rail ties passed all of the required American Railway Engineering and Maintenance-of-Way Association qualifying mechanical tests, on-track testing of the CO 2 -cured ECC rail ties was unsuccessful due to fiber alignment in the ECC the during the rail tie casting process which prevented the material from achieving the expected level of strain capacity. This result highlights the challenge in scaling up bench-scale processes to full-scale product manufacturing and requires additional investigation into the casting process of large-scale infrastructure elements using ECC combined with carbonation curing. Life cycle assessment of a CO 2 -cured ECC rail tie versus a traditional concrete rail tie indicates that the ECC tie can have lifecycle carbon savings of between 11% and 51% depending on how much longer its useful lifetime is compared to traditional concrete rail ties. Both carbon and cost savings are driven by a reduction in the need to replace broken rail ties, so the key factor is the extent to which a CO 2 -cured ECC rail tie will have increased lifetime durability compared to alternative rail ties.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Theory and Simulation of Ultrafast Multidimensional Nonlinear X-ray Spectroscopy of Molecules (Final Report)

Emerging X-ray free electron laser (XFEL) beam sources offer new types of probes of matter with unprecedented spatial and temporal resolutions. These experimental advances must be met by robust theoretical and computational tools that provide predictive modeling capacity of the underlining electronic and structural dynamics. The latter will be essential for the design of sophisticated multi-pulse experiments and for their interpretation. The proposed research effort will focus on developing cutting- edge simulation tools for nonlinear multidimensional X-ray/optical spectroscopies and aims to address key questions in Priority Research Opportunities 1 (Probing and controlling electron motion within a molecule) and 3 (Capturing rare events and intermediate states in the transformation of matter) as mentioned in the BES Roundtable Report “Opportunities for Basic Research at the Frontiers of XFEL Ultrafast Science”. XFEL multidimensional nonlinear techniques, which combine sequences of X-ray and possibly optical pulses, provide a unique experimental toolbox for probing the dynamics of core and valence electronic excitations, as well as material structure. Predictive modeling of these dynamical processes requires the combination of analytical theory for nonlinear interactions of light and matter, robust quantum-chemical methodologies for the accurate description of electronic structure of various materials, and multiscale ab initio electron and nuclear dynamics techniques operating beyond Born-Oppenheimer approximation. These challenges will be addressed with three research thrusts (i) Develop and implement theoretical apparatus for modeling a broad range of multidimensional spectroscopic techniques enabled by present and upcoming XFEL facilities. This thrust also includes the incorporation of a computational module in the DOE supported open-source NWChem computational chemistry package as well as the development of other open-source codes ready for dissemination across a broad user base; (ii) Propose and design new multi-pulse experiments that make use of the capabilities of the incoming LCLS-II facility; (iii) Perform selected applications to specific molecular systems that can be carried out at LCLS-II and demonstrate how these X-ray sources may be used to study nonadiabatic dynamics through conical interactions, electronic correlations in multi-core excitons, and charge transfer/energy transfer processes. The proposed research will be carried out by a multi-disciplinary four-institution research team which combines academia and national laboratories and spans the broad and necessary expertise in theoretical spectroscopy, nonlinear optics, quantum chemistry, molecular non-adiabatic dynamics and code development. The work will be performed in a highly interactive team environment with junior researchers shared between institutions thus cementing cross- disciplinary interactions. The developed simulation tools will be immediately deployed for XFEL facility users, both experimentalists and theorists, via freely distributed codes and databases. Altogether, this project will facilitate establishing XFEL-based multidimensional spectroscopies as a novel diagnostic tool for monitoring electronic and structural dynamics in molecular materials.

74 ATOMIC AND MOLECULAR PHYSICS↗