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Creep in multi-principal element materials –– A review

The ongoing push towards enhanced energy efficiency and reduced emissions has necessitated the creation of materials with superior performance, especially under extreme conditions. Modern industries, such as aerospace, energy production, and nuclear power, rely heavily on materials that can withstand elevated temperatures without compromising structural integrity. At these heightened temperatures, materials, even when subjected to mechanical stresses well below their yield strength, may experience slow deformation leading to eventual rupture — a phenomenon known as creep. With the expansive design space that comes with the high entropy concept and their reported excellent high temperature strength, multi-principal element materials (MPEMs) have attracted interest in the scientific community for high-temperature applications. Here, this review offers a comprehensive examination of existing studies on creep in MPEMs, which includes multi-principal element−alloys, −bulk metallic glasses, −ceramics, and −superalloys, comparing published findings on MPEMs with pure elements, traditional alloys, bulk metallic glasses, and superalloys. The sub-topics covered include a comparison among different creep-testing methods, creep mechanisms, creep exponents, creep strain rates, activation volume, and creep-activation energy. Modeling efforts for predicting creep behavior of MPEMs are also reviewed. Methods for improving creep resistance by performing heat treatments and/or modifying microstructures are discussed. Overall, the current state of MPEMs has not yet surpassed the creep performance of commercial alloys. Finally, directions for future efforts are suggested, such as experimenting in various controlled environments, expanding the number of compositions tested, exploring advanced manufacturing techniques, and using machine-learning to predict creep properties based on compositions and microstructures.

36 MATERIALS SCIENCE↗

Analysis of Bis(trifluoromethylsulfonyl)imide Interactions with Metal Cations Through a Chemical Informatics Approach

Nominally weakly coordinating anions are useful for modulating the solubility and chemical properties of metal complexes, but identification and analysis of the systematics of the interactions of anions with cationic metal complexes has not received the attention it deserves. Here, a chemical informatics approach is demonstrated for identifying and quantitatively analyzing the ways that the bis(trifluoromethylsulfonyl)imide anion (TFSI) can interact with metal-containing species. An open access computer program (PyCIFTer) was developed to facilitate large-scale structural analysis of TFSI-containing species by utilization of experimental atomic coordinate data from single-crystal X-ray diffraction (XRD) studies obtained from the Cambridge Structural Database (CSD). PyCIFTer establishes a three-dimensional vector space from the raw atomic coordinates, generating acyclic, undirected graphs that are used to rapidly analyze the structural properties (bond lengths and angles) of TFSI in individual structures in sequential/batch fashion. The structures are sorted by PyCIFTer into groups based on pre-set and chemically sensible criteria, affording a comprehensive and systematic view of TFSI structural chemistry. This approach avoids tedious one-at-a-time interrogation of structures, a prospect unreasonable in this case, and many others of contemporary chemical relevance; there were over 1500 structures in the CSD containing TFSI as of November 2024. The results demonstrate that TFSI only rarely binds to cations in the solid state, favoring the formation of species in which TFSI is found in cations’ outer coordination spheres. The prospect of applying PyCIFTer to other moieties is also discussed. PyCIFTer is also schematically compared to the commercial CSD Python application programming interface (API). Taken together, this work demonstrates the usefulness of modular workflows for sequential/batch analysis of structural data from XRD, an approach that appears poised to accelerate the translation of legacy structural results into new chemical insights and hypotheses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intrinsic Kinetics of Polyethylene Terephthalate Pyrolysis via Micropyrolysis and Multivariate Chromatographic Analysis

This study provides an in-depth investigation of the primary decomposition of polyethylene terephthalate (PET) via pyrolysis, employing an experimental-analytic workflow that integrates design of experiments (DoE), micropyrolysis coupled with comprehensive two-dimensional gas chromatography (GC×GC), and multivariate data analysis to verify intrinsic kinetic conditions and elucidate evolving product distributions for mapping key reaction pathways. Peaks that could not be identified using commercial spectral libraries were assigned using Mass Frontier simulations, enabling the identification of divinyl terephthalate, ethyl vinyl terephthalate, and 2-(benzoyloxy)ethyl vinyl terephthalate. A polar×polar (non-orthogonal) column set tailored for the detection of carboxylic acids enhanced the quantification of benzoic acid, 4-vinylbenzoic acid, 4-ethylbenzoic acid, and methylbenzoic acid by up to 6-fold relative to an orthogonal column combination (non-polar×mid-polar). Moreover, pyrolysis variables were systematically evaluated using a Box- Behnken design (BBD), encompassing pyrolysis temperature (500−600 °C), sample weight (50−150 μg), and carrier gas flow rate (100−300 mL min −1 ). Among these, pyrolysis temperature was the only statistically significant factor influencing product yields, ranging from 58.78 to 84.26 wt %. In contrast, neither the sample weight nor the carrier gas flow rate had a significant effect on product yields within the evaluated experimental space. At 600 °C, the major pyrolysis products were benzoic acid (up to 20.20 ± 1.46 wt %) and CO 2 (up to 21.28 ± 1.46 wt %), which can be produced through decarboxylation reactions. These findings underscore the critical importance of selecting appropriate analytical columns for the accurate quantification of heteroatomcontaining products such as carboxylic acids, which may otherwise be underestimated or undetected due to their reactivity with the stationary phase of non-polar and mid-polar columns, as well as other GC components. They also highlight the importance of selecting pyrolysis conditions for investigating the primary decomposition of PET under an isothermal kinetically limited regime.

aromatic compounds↗

Findings on subtask 3.3 – applicability of automated brine chemistry determinations for treatment and recovery processes through facility automation/modularization: engineering design study

Under the Energy & Environmental Research Center’s (EERC’s) ~$\$$22 million Phase II Brine Extraction and Storage Test (BEST) Program, a multimillion-dollar brine treatment technology test bed facility was established in western North Dakota to provide a platform for evaluating developing technologies and approaches for brine treatment and volume reduction. The initial facility, and associated research effort, was funded by the U.S. Department of Energy (DOE), with in-kind contributions provided by several industry participants and the state of North Dakota. Since its opening, the Brine Technology Test Facility (BTTF) has supported performance evaluations of desalination technologies capable of treating high-salinity produced water (PW) and enabled data collection for multiple approaches of PW management and critical material recovery. As part of the decommissioning process for the original project, facility ownership and liability were transferred to Select Water, which is providing the EERC with a continuing site access option for state or federal research and/or commercial technology development. This report documents the findings from a design study conducted by the EERC and the engineering firm that was originally contracted to design and construct the facility (Advanced Engineering and Environmental Services, LLC [AE2S]) that evaluated the current status of BTTF and its systems and developed a retrofit design to increase the facility’s capabilities through automation and modularization of its PW treatment infrastructure. The proposed retrofit will provide DOE and industry with an expanded range of conditioned PW that can be produced at the facility for evaluating fit-for-purpose water treatment technologies, online instrumentation for brine chemistry determination, and systems that recover critical materials like lithium and magnesium. The current facility consists of an 9600-square-foot facility that includes a 40-foot by 65-foot Class 1, Division 2-rated demonstration area and associated control rooms and lab-ready space capable of sourcing oil and gas PW and wastewater from industrial sources or tailoring brine compositions up to 300,000 mg/L total dissolved solids (TDS) and supplying them at rates up to 25 gpm for extended-duration technology demonstrations. The colocation of the facility with Select Water’s water management facilities allows for access and unloading of more than 10,000 bbl/day of trucked water delivered to site and associated access to on-site Class I and Class II brine disposal wells and nearby hazardous waste landfills operated and/or contracted by Select Water to dispose of concentrate and/or effluents associated with the testing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Li 2.9 Fe 0.9 Zr 0.1 Cl 6 as Redox-Active Catholyte for Solid-State Li-Ion Batteries

Solid electrolytes are one of the key challenges that hinder the commercialization of all-solid-state batteries. Most efforts have been made to advance the development of solid electrolytes as separators, while the development of catholytes, particularly redox-active catholytes, has been less extensively studied. The high loading of catholytes in composite cathodes, while facilitating ionic conduction, drastically decreases the energy density of the battery. Here, we report an alternative strategy to improve the energy density by using Li 2.9 Fe 0.9 Zr 0.1 Cl 6 as a redox-active catholyte. With a composite cathode containing uncoated LiCoO2 and Li 2.9 Fe 0.9 Zr 0.1 Cl 6 , the solid-state cell not only shows excellent rate capability and stable long-term cycling, benefiting from the high ionic conductivity of Li 2.9 Fe 0.9 Zr 0.1 Cl 6 , but also shows a high cathode specific capacity of ~153 mAh·g –1 . This study broadens the chemical space of the materials design for lithium-ion conductors with redox-active elements (e.g., Fe, Ti, V, and Cr), offering new opportunities to reduce the cost and improve the energy density for all-solid-state batteries.

36 MATERIALS SCIENCE↗

Generalizability of heat-related health risk associations observed in a large healthcare claims database of patients with commercial health insurance

Extreme ambient heat is unambiguously associated with higher risk of illness and death. The Optum Labs Data Warehouse (OLDW), a database of medical claims from US-based patients with commercial or Medicare Advantage health insurance, has been used to quantify heat-related health impacts. Whether results for the insured sub-population are generalizable to the broader population has to our knowledge not been documented. We sought to address this question, for the US population in California from 2012 to 2019. We examined changes in daily rates of emergency department (ED) encounters and in-patient hospitalization encounters for all-causes, heat-related outcomes, renal disease, mental/behavioral disorders, cardiovascular disease, and respiratory disease. OLDW was the source for health data for insured individuals in California, and health data for the broader population were gathered from the California Department of Health Care Access and Information (HCAI). We defined extreme heat exposure as any day in a group of 2 or more days with maximum temperatures exceeding the county-specific 97.5 th percentile and used a space-time-stratified case–crossover design to assess and compare the impacts of heat on health. Average incidence rates of medical encounters differed by dataset. However, rate ratios for ED encounters were similar across datasets for all causes (ratio of incidence rate ratios (rIRR) = 0.989; 95% confidence interval (CI) = 0.973, 1.011), heat-related causes (rIRR = 1.080; 95% CI = 0.999, 1.168), renal disease (rIRR = 0.963; 95% CI = 0.718, 1.292), and mental health disorders (rIRR = 1.098; 95% CI = 1.004, 1.201). Rate ratios for inpatient encounters were also similar. This work presents evidence that OLDW can continue to be a resource for estimating the health impacts of extreme heat.

54 ENVIRONMENTAL SCIENCES↗

Design and Development of a Fixtureless, Pass-through Machine Tool for Extrusion Machining

The aerospace, construction/architecture, and transportation manufacturing industries rely heavily on the mass production of near-net shape metallic and composite extrusions. While the production of raw extrusions is a relatively fast process, adding functional features such as holes and slots require additional time, cost, and energy to produce. To compensate for the inherent flexibility of extrusions, conventional machining requires rigid purpose-built fixtures for operations such as trimming, drilling and thinning. This approach requires that the machine tools be as large or larger than the parts themselves. This results in the need for excess shop floor space, energy for auxiliary equipment and motion systems, and significant capital expenditure. Considerable engineering expense and time involved in the designing, building, and proving out of part-specific fixtures for holding the components in specific configurations while machining add to the overall manufacturing cost. The primary objective of the technical collaboration between Oak Ridge National Laboratory and Fairmount Technologies (FT) is to improve the XM-3, a fixtureless CNC milling machine designed by FT. The machine was developed to trim, drill, and thin extrusions without part specific fixturing to make the manufacturing process more efficient and flexible. Dynamic measurements of the existing structure were collected, and modeling efforts were made to evaluate optimal machining parameters for the current system. Areas of improvement to increase the system stiffness, manufacturability, and machining efficiency were evaluated and highlighted for the next generation design. The impact of this effort may enable agile manufacturing across the commercial and defense aerospace industries, and other industries where extrusions are utilized like in the construction, architecture, and transportation industries.

42 ENGINEERING↗

Design and Development of a Fixtureless, Pass-through Machine Tool for Extrusion Machining

The aerospace, construction/architecture, and transportation manufacturing industries rely heavily on the mass production of near-net shape metallic and composite extrusions. While the production of raw extrusions is a relatively fast process, adding functional features such as holes and slots require additional time, cost, and energy to produce. To compensate for the inherent flexibility of extrusions, conventional machining requires rigid purpose-built fixtures for operations such as trimming, drilling and thinning. This approach requires that the machine tools be as large or larger than the parts themselves. This results in the need for excess shop floor space, energy for auxiliary equipment and motion systems, and significant capital expenditure. Considerable engineering expense and time involved in the designing, building, and proving out of part-specific fixtures for holding the components in specific configurations while machining add to the overall manufacturing cost. The primary objective of the technical collaboration between Oak Ridge National Laboratory and Fairmount Technologies (FT) is to improve the XM-3, a fixtureless CNC milling machine designed by FT. The machine was developed to trim, drill, and thin extrusions without part specific fixturing to make the manufacturing process more efficient and flexible. Dynamic measurements of the existing structure were collected, and modeling efforts were made to evaluate optimal machining parameters for the current system. Areas of improvement to increase the system stiffness, manufacturability, and machining efficiency were evaluated and highlighted for the next generation design. The impact of this effort may enable agile manufacturing across the commercial and defense aerospace industries, and other industries where extrusions are utilized like in the construction, architecture, and transportation industries.

42 ENGINEERING↗

Fast neutron irradiation capability in existing thermal test reactors

In today’s nuclear industry, momentum towards the design, licensing, and construction of advanced nuclear demonstration plants, including fast reactors, is at a remarkably high level. However, there are currently no dedicated fast spectrum irradiation test facilities in the United States to support the development of fast spectrum technologies. As a result, a unique situation is developing where most of these plants will likely be designed by leveraging historic nuclear material technologies, but where the further optimization and advancement is impeded by the lack of fast neutron irradiation test facilities. While these circumstances present a challenge, there are some near-term opportunities that, if seized, can still help develop advanced fast reactor materials to a meaningful level of readiness to support future commercial fast reactors. Here, in this paper, we assess the feasibility of using thermal neutron filtering materials in existing experiment positions in the Advanced Test Reactor (ATR) at Idaho National Laboratory and the High Flux Isotope Reactor (HFIR) at Oak Ridge National Laboratory to simulate fast reactor test environments for nonfuel test specimens. Items investigated include the incident neutron flux (both fast and thermal), the total neutron fluence and cumulative atom displacements, helium production rate due to thermal neutron capture in nickel, and the potential impact that the thermal neutron filter material has on the cycle length of a given reactor. It is concluded that while HFIR provides the highest fast flux of all the options investigated, it is limited in the amount of thermal neutron filtering material that can be introduced into an experiment position without significantly affecting the operation of the reactor. Irradiation in Outboard-A positions in the ATR was found to be the most realistic near-term experiment avenue due to having ample space for several capsules in a moderately fast flux.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Equilipy: a python package for calculating phase equilibria

The CALPHAD (CALculation of PHAse Diagram) approach (Nigel Saunders & Miodownik, 1998) provides predictions for thermodynamically stable phases in multicomponent-multiphase materials across a wide range of temperatures. Consequently, the CALPHAD calculations became an essential tool in materials and process design (Luo, 2015). Such design tasks frequently require navigating a high-dimensional space due to multiple components involved in the system. This increasing complexity demands high-throughput CALPHAD calculations, especially in the rapidly evolving field of alloy design. In response to the need, we developed Equilipy an open-source Python package designed for calculating phase equilibria of multicomponent-multiphase systems. Equilipy is specifically tailored for high-throughput CALPHAD calculations, offering parallel computations across multiple processors and nodes with the given NPT input conditions namely elemental compositions (N), pressure (P), and temperature (T). Equilipy utilizes the program structure and Gibbs energy functions from the Fortran-based program, Thermochimica (Piro et al., 2013), with incorporating a new Gibbs energy minimization algorithm. This algorithm, originally developed by Capitani and Brown in 1987 (Capitani & Brown, 1987), has been revised and implemented to enhance the stability and performance of calculations. The Fortran codes are precompiled and interfaced with Python via F2PY, ensuring high computation speed. Benchmark tests shown in Figure 1 demonstrate that Equilipy’s computation speed is comparable to those of established commercial software, TC-Python and PanPython. This result highlights its efficiency and potential applications in various scientific and industrial fields.

97 MATHEMATICS AND COMPUTING↗

Core Design Optimization of the Westinghouse Lead Fast Reactor

Westinghouse is pursuing an advanced Nuclear Power Plant design based on Lead Fast Reactor (LFR) technology for global commercialization. To achieve an optimal combination of key attributes, such as safety, sustainability, and economic competitiveness, Westinghouse and ANL partnered in developing and applying a formalized core design optimization strategy. An LFR analysis workflow was developed to automate a suite of reactor physics, fuels performance, safety, and economics simulations on a selected LFR concept. The workflow streamlines analysis of a wide range of LFR designs with different dimensions and fuel types to assess their viability and economic performance, significantly reducing human processing time and risks of processing errors. The LFR optimization exercise was defined, resulting in selection of the design constraints (geometric, neutronics, thermo-mechanical, safety, thermal-hydraulics, and economics) and performance metrics researched (minimization of both the fuels LCOE and the first core inventory cost). A total of 14 varied design parameters were considered, including assembly dimensions, coolant temperature, and enrichment distribution throughout the core. The LFR analysis workflow was connected to DAKOTA for sensitivity and optimization analyses. Due to the extremely large size of the potential LFR optimization solution space relative to the computing time required to characterize one LFR solution, a multi-stage optimization approach was proposed to breakdown the problem into several stages with more reasonable sizes. This optimization approach enabled finding various viable core solutions with different cost tradeoffs that were considered by Westinghouse and justify selection of a smaller core with multi-batch 2-year cycle length.

Stauff, Nicolas E.↗

Illinois Storage Corridor - CarbonSAFE Phase III: Policy, Regulatory, Legal and Permitting Characteristics; Subtask 5.5

The Illinois Storage Corridor (ISC) project aims to advance the commercial development and implementation of carbon capture and storage (CCS) technologies within a region in Illinois of suitable geology for carbon dioxide (CO 2 ) storage in deep saline aquifers. The project partners have annual emissions greater than 6.5 million tonnes per year; storage hubs are being explored at two sites—one near the One Earth Energy facility in east-central Illinois, and one near the Prairie State Generating Company campus in southwest Illinois. To implement the technology, legal, policy, and economic considerations must be explored. The United States Environmental Protection Agency (US EPA) administers the Underground Injection Control (UIC) program and is responsible for issuing Class VI permits to construct and operate CO 2 injection wells, i.e., a UIC Class VI well permit is required to inject CO 2 into the subsurface for geologic sequestration. The largest consideration of the Class VI well requirements is to protect underground sources of drinking water (USDWs). Additionally discussed are considerations for Class VI permits relating to public engagement. Besides permitting, property rights to storage sites, subsurface pore spaces, and areas for pipeline transportation must be secured. Pore space rights is still a novel concept being explored and not yet addressed by the Illinois legislature. It is believed that surface property rights are required for the subsurface pore space below, so long as there is not a separated mineral estate in the subsurface. Illinois legislature has addressed securing rights-of-way for CO 2 transportation, allowing for easements and the exercise of eminent domain to secure such rights. Economically, the incentives for CCS are ever-expanding. Recently, the federal government broadened the availability and increased the dollar-amounts for the § 45Q tax credits for geological storage of carbon oxides. Congress has also authorized the Advanced Industrial Facilities Development Program which allocates billions of dollars in funds to installing technology at industrial facilities to reduce greenhouse gas emissions. On the state level, Illinois has had its own incentives for CCS projects since 2009 and expanded its emission-related goals again in 2021. The law enacted in 2021 specifically creates a commission to explore implementing CCS at Prairie State Generating Company, a partner on the Illinois Storage Corridor project.

54 ENVIRONMENTAL SCIENCES↗

Statistical generic design of glass and optimization: Selective review on oxide glasses

Designing a single glass composition for a multidimensional property space is challenging, and the difficulty increases with the number of design criteria. Traditionally, the task is accomplished using multiple statistical models that describe the relationships between composition (C) and property (P) values, i.e., C-P models. Recently, the structure (S)-property (P) statistical modeling has emerged as a complementary approach. The S-P modeling approach has also been shown to be a preferred method for modeling glass properties, particularly when a small data set is available, such as in single-component studies, or when strong nonlinearities exist between composition and properties. The combined model package, C-S-P, implements the concept of generic glass design, i.e., designing glass for performance by first selecting a specific or optimized set of glass network structural groups using S-P models and then transferring the designed structures (genes) to a particular composition using C-S models. This article reviews a set of supporting cases from the previous C-S-P modeling studies of phosphate, silicate, and borosilicate glasses, which are relevant for many critical commercial applications. The methodology for developing the statistical C-S-P database is presented, enabling the application of P?S?C to achieve a generic glass design and optimization, targeting multiple design criteria for both performance and processing properties simultaneously.

Network structure↗

Multi-system analysis of offshore geologic carbon storage: a review of open-source data science solutions

Geologic carbon storage projects are maturing worldwide and the footprint of deployment in the offshore is expanding. At present, there are ten projects in operation or that have been completed, more than 50 in construction and development, and dozens of characterization studies completed or underway. Offshore geologic carbon storage offers potential benefits over onshore geologic carbon storage. These offshore projects are generally remote in location, distant from population centers, and avoid complicated pore space rights while having abundant prospective storage potential. Some offshore fields targeted for carbon storage have comparatively fewer prior borehole penetrations except for areas that have been explored for petroleum production, minimizing potential issues such as pressure interference and infrastructure impacts. Yet offshore geologic carbon storage projects face distinctive technical and economic challenges, such as seafloor geohazards (e.g., seabed instability), expensive maritime transport, and meteorological-oceanographic conditions that can damage infrastructure and impact operations. Analytical capabilities and improved computational speeds have advanced engineering, earth and energy sciences in the wake of the arrival of modern data science over the last decade. These advancements have created an opportunity for integrated, multi-systems modeling approaches utilizing artificial intelligence and machine learning that are no longer limited by computational issues. Analytical tools developed alongside this advancement in data science can be leveraged to calibrate the potential advantages and challenges of carbon storage operations in the offshore. New methods and approaches that incorporate data science to analyze multiple aspects of engineered and natural systems can provide insights that complement the characterization and onsite engineering that traditional commercial and operational software addresses. These new methods and approaches can potentially improve the outcome of energy operations and carbon storage. Providing multi-system, science-driven data analytics enhances the knowledge base that offshore developers, operators, and regulatory bodies may draw from to improve offshore site selection and operational efficiency. Here, we provide a brief synopsis of geologic carbon storage efforts to date, an overview of the engineered and natural systems involved in offshore geologic carbon storage, and a review of publicly available, open-source, offshore and/or carbon storage related data- and science-driven tools developed by 2010 or later that are suitable for screening and assessing regions for offshore geologic carbon storage.

artificial intelligence↗

Electrolyte and Cutoff Potential Effects on Cycle Life of Li4Ti5O12/LiNi0.9Mn0.1O2 Batteries for Behind-the-Meter Storage Applications

Behind-the-Meter Storage (BTMS) is a stationary battery energy storage system that is connected to the electrical distribution system on the customer's side of the utility's service meter. BTMS systems are used to store electrical energy from the grid as well as inconstant, renewable energy, such as local solar and wind generation. A successful BTMS system will allow the customer to pair their energy generation and storage to optimize electrical consumption from the grid, improving reliability and minimizing cost. For BTMS applications, batteries must be designed and optimized with different set of criteria from other leading segments of the Li-ion battery market, like transportation, due the system being stationary and proximal to the residential or commercial building it's benefitting. BTMS applications prioritize safety, cost (low/no-critical materials), reliability (20-year calendar life), and durability (10,000 cycle life), while having the ability to (minimally) compromise energy density and rate capability. Lithium titanate (Li4Ti5O12-, LTO) is a promising anode candidate for BTMS applications due to its high safety and capacity retention, while maintaining a reasonable 160 mAhg-1 reversable capacity and composition of relatively abundant materials. (1) Specifically, LTO has a high working voltage which helps to prevent Li dendrite formation, improving safety. Furthermore, LTO also has negligible lithiation-based volume change, leading to less mechanical pulverization, or loss of active material, upon cycling. For the cathode, materials with little or no Co are of high interest due to the high cost and low abundance of Co. LiMn2O4 (LMO) has been paired with LTO for BTMS applications in the past due to its safety, low cost (abundancy), and reasonably high operating voltage. (2-4) However, the low capacity of LMO limits energy density and specific energy. While not the highest priority for BTMS applications, increasing energy density will enable deployment in space constrained BTMS applications and decrease total cost. LiNi0.9Mn0.1O2 (LN-MO) is a recently developed material with promise due to its high operating voltage and relatively low price. (5) However, Ni-rich layered oxides, including LNMO, tend to struggle with capacity retention during high-voltage cycling due to mechanical pulverization, irreversible phase transitions, and unstable solid-electrolyte interphase. The study presented here focuses on building an understanding of how electrolyte solvent and varied cutoff potentials will impact the cycle life of LTO/LN-MO cells. Specifically, a comparison is provided between ethylene carbonate (EC), ethyl methyl carbonate (EMC), fluoroethylene carbonate (FEC), and Gen2 electrolyte solvents with 1M Lithium hexafluorophosphate (LiPF6) salt, cycling to two upper termination potentials, 2.6V and 2.7V. Electrochemical testing and diagnostics (e.g., differential capacity analysis, area specific impedance, constant voltage hold, and rate capability) and post-mortem characterization will be used to understand the aging behavior and failure mechanisms of the 8 cell combinations (four electrolytes and two voltage cutoffs). Cells with FEC electrolyte showed a lower initial capacity compared to cells with Gen2, EMC, and EC cycling at both voltages; however, the cells with FEC showed consistent trends in capacity retention with 2.6V and 2.7V termination potentials, while the cells with the other electrolytes showed much higher rates of capacity loss when cycling to the higher voltage. These results indicate that FEC may play a role in improving durability of high-voltage, Ni-rich electrode systems for use in high-cycle applications, such as BTMS.

electrolyte↗

Investigating the interactions between wakes and floating wind turbines using FAST.Farm

As floating offshore wind progresses to commercial maturity, wake and array effects across a farm of floating offshore wind turbines (FOWTs) will become increasingly important. While wakes of land-based and bottom-fixed offshore wind turbines have been extensively studied, only recently has this topic become relevant for floating turbines. This work presents an investigation of the mutual interaction between the motions of floating wind turbines and wakes using FAST.Farm. While FAST.Farm has been extensively validated across a wide range of conditions, it has never been validated for FOWT applications. Hence, in the first part of this work, we validate FAST.Farm by comparing simulations of a single FOWT against high-fidelity results from large-eddy simulations available in the literature. The validation is based on wake meandering, mean wake deflection, and velocity deficit at different downstream locations. This validation showed that the original axisymmetric (polar) wake model of FAST.Farm overpredicts the vertical wake deflection induced by shaft tilt and floater pitch, while the new curled wake model is capable of properly capturing the vertical wake deflection. In the second part, we use FAST.Farm to analyze a small three-unit array of FOWTs with a spacing of 7 diameters across a wide range of environmental conditions. The same National Renewable Energy Laboratory 5 MW reference wind turbine atop the OC4-DeepCwind semisubmersible is adopted for the three FOWTs and for the validation against high-fidelity simulations. To assess the effect of the floating substructure, we compare the power production, tower-base moments, and blade-root moments obtained for the floating turbines with the results obtained in a fixed-bottom configuration. The main differences introduced by the floating substructure are the motions induced by the waves, the change in the natural frequencies of the tower caused by differences in the boundary condition at its base, and the larger vertical deflection of the wake deficit due to the mean pitch of the platform. The impact of these differences, as well as other minor effects, are analyzed in detail.

16 TIDAL AND WAVE POWER↗

Elucidating the mechanical and thermal response of nanotwinned Ni alloys

Transformative advances in nanoscale materials synthesis, characterization and modeling are enabling the synthesis of materials with unprecedent properties and greater understanding of the nanoscale mechanisms that underpin these properties. Nanotwinned Cu alloys have received considerable attention due to their impressive balance of strength and ductility, but they have limited microstructural stability. Recent instantiation of nanotwins in sputter deposited Ni-Mo-W, and several commercial Ni-based superalloys, point to the potential development of a new class of high temperature materials with a very beneficial suite of mechanical and physical properties. The experimental study described in this report was undertaken to elucidate the nanoscale origins of the thermal and mechanical behavior of nanotwinned Ni alloys. Micropillar compression experiments have shown nanotwinned Ni 85 Mo 15-x W x alloys to possess unusually high strengths above 3.5GPa and enhanced microstructural stability. The strength of these nanotwinned alloys is determined by the abrupt formation of shear bands. This study focused on identifying the nanoscale trigger, or triggers, for shear banding in nanotwinned materials using in situ experiments and atomic-scale postmortem analysis. Contrasting and comparing the mechanical response and postmortem nanostructures of “Mo-rich” and “W-rich” nanotwinned specimens elucidated the importance of the lateral motion of easy glide defects that results in erasure of twins and local coarsening of the nanotwinned microstructure. This twin coarsening was then associated with very localized plasticity, strain softening, and shear band formation. The difference between alloys was further studied by considering the role of various material factors: stacking fault energy, coherent twin boundary spacing and flatness, grain size, and the interactions of solute atoms with twin and grain boundaries. The effect of alloy composition and sputtering power and temperature were also investigated and used to control twin spacing and geometry. Combined with atomic-scale simulations, these experiments insights should allow us to identify strategies for achieving concomitant ultrahigh strength and ductility in nanotwinned Ni alloys. In parallel but synergistic studies, our work was buoyed by collaborative state-of-the-art nanoscale orientation and strain mapping at the DOE National Center for Electron Microscopy (NCEM). For example, novel 4D-STEM techniques were used to acquire nanoscale strain maps. The extremely fine twin spacing limited our measurements of atomic-scale thermal expansion within twins, but recent results from NCEM suggest that it will soon be possible to conduct such measurements and to unravel the origins of the novel thermal expansion characteristics of nanotwinned Ni alloys.

36 MATERIALS SCIENCE↗

Field Validation of MVA Technology for Offshore CCS: Novel Ultra-High-Resolution 3D Marine Seismic Technology (P-Cable) (Final Report)

The objectives of the proposed study were to deploy and validate a specific monitoring technology, high-resolution 3D marine seismic (HR3D), appropriate for large-demonstration and commercial-scale offshore CCS sites. The project accomplished successful acquisition two HR3D seismic surveys. The first HR3D dataset was over the offshore injection site of the Tomakomai, Japan integrated pilot CCS project, which at the time of survey acquisition was actively injecting CO 2 . The first survey also represented a successful international collaboration between the DOE NETL program and Japan’s national CCS program and was the first successful acquisition and use of HR3D over an active CO 2 injection site (Meckel, Feng et al. 2019). The Tomakomai HR3D survey successfully tested a novel 4-streamer HR3D system array in which, for the first time, no cross-cable (aka “P-Cable”) was utilized and only four GeoEel streamers were used instead of the standard 12-streamer configuration. Consequently, this was not, strictly speaking, a deployment of the “P-Cable” system of (Planke and Berndt 2004) but rather a modified version, thereof, and it is the first known demonstration of the modified system configuration. One very positive outcome from the Japanese collaboration earlier in the project was the ability to learn from the Japanese how they used tail buoys with GPS to determine the position of the seismic source and receivers in time and space. Based on that experience, GCCC designed and built six GPS receivers that could be used to position the streamer receivers and the seismic source via tail buoys. A fundamental advance that was made on the original design, was the ability to directly power the tail buoy GPS units and transfer data through the streamers (i.e., vs. the batteries used at Tomakomai). The bulkiness of the GPS batteries caused drag and episodic surging of the buoys, which affected data quality by lifting up the tail end of the streamers so the receivers were not at the same depth. The units were tested onshore for accuracy and functionality, and the design was subsequently and successfully tested in marine acquisition mode during the SLP survey acquisition. The marine acquisition test and survey satisfied Subtasks 2.2.2, Novel Positioning Technology Selection and Subtask 2.2.3, Novel Positioning Technology Deployment. Results of the novel positioning technology selection (Subtask 2.2.2) were considered successful and will be incorporated in future HR3D seismic acquisition projects to reduce costs, improve deployment safety at sea, and integrate both seismic and data recording via a single data transfer through the streamers to the recording system. The project also established a permitting process through NETL NEPA compliance, which included an Environmental Assessment in a marine setting and is required for conducting these types of surveys using Federal funding. The permitting process charted a “boilerplate,” which can allow future surveys related to other funded projects to move forward more expeditiously. Future improvements that could be considered are more robust seals on the GPS module and stronger materials (especially joints) on tail buoy fabrication. These would increase fixed costs, but would be advisable and probably more economic long-term if multiple HR3D surveys are planned. Project Accomplishments include: • Pre-survey Sensitivity Study • Marine geochemistry methods and data analysis • Successful HR3D seismic dataset acquired @ Tomakomai active CO 2 injection marine site • Developed advanced seismic processing techniques • No NRMS anomalies detected in overburden; Demonstration of containment • Repeatability study • Second survey collected @ San Luis Pass, TX • 4D application using positioning techniques developed in the project for monitoring were successful

3D seismic GPS positioning↗