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At least 883 records · Page 49

Differential Power Processing for Increased Energy Production and Reliability of Photovoltaic Systems

Conventional energy conversion architectures in photovoltaic (PV) systems are often forced to tradeoff conversion efficiency and power production. This paper introduces an energy conversion approach that enables each PV element to operate at its maximum power point (MPP) while processing only a small fraction of the total power produced. This is accomplished by providing only the mismatch in the MPP current of a set of series-connected PV elements. Differential power processing increases overall conversion efficiency and overcomes the challenges associated with unmatched MPPs (due to partial shading, damage, manufacturing tolerances, etc.). Several differential power processing architectures are analyzed and compared with Monte Carlo simulations. Local control of the differential converters enables distributed protection and monitoring. Reliability analysis shows significantly increased overall system reliability. Simulation and experimental results are included to demonstrate the benefits of this approach at both the panel and subpanel level.

Shenoy, PS↗

Fukushima Daiichi—A Case Study for BWR Instrumentation and Control Systems Performance During a Severe Accident, Rev 1

This report provides an assessment of the performance of various instrumentation and control (I&C) and monitoring systems, with a focus on the first few days of the Fukushima Daiichi accident starting on March 11, 2011. Similar to what occurred at the Three Mile Island Unit 2 (TMI-2) accident in 1979, operator responses were challenged when information on key parameters was lost, erroneous, or misleading. While numerous improvements in instrumentation capabilities have been made since the TMI-2 event, the accident at Fukushima Daiichi suggests the potential for further improvement. The objective of this research is to review the performance of the Fukushima Daiichi Units 1–3 instrumentation systems that could have helped ensure that plant operators and emergency responders had relevant, accurate, and timely knowledge of plant conditions as they managed the accident response. As was the case with TMI-2, forensic analyses of plant instrumentation failures will be a long-term effort. As an introduction to this long-term research, this report focuses on the information available in the control room during the accident and illustrates the challenges to operators in their understanding of plant conditions during the progression of the accident. I&C systems monitor the success or failure of achievement of light water reactor safety principles in which the protection of the reactor fuel, reactor coolant system, and reactor containment is accomplished. This report (1) provides an overview of the safety principles; (2) notes parameters associated with the boiling water reactor (BWR)/3 and BWR/4 protection, actuation, and monitoring systems as they relate to the achievement of these principles; (3) presents data from past research on predicted instrumentation performance during severe accidents, and (4) assesses performance of the key I&C and monitoring systems associated with BWR/3 and BWR/4 reactors like those at Fukushima Daiichi. Lessons learned or potential improvements associated with the performance of these systems in the context of severe accidents are delineated. As background information, an overview of key BWR/3- and BWR/4-Mark I reactor designs (BWR/3 and BWR/4 with a Mark I containment) reactor protection, engineered safety features actuation, and accident monitoring systems is provided. A brief description of plant safety systems used to prevent or mitigate reactor accidents is also provided. This background information provides context for the brief discussion of previous research that has been conducted on BWR severe accidents and for the discussion of the accident sequences, which led to core damage at Fukushima Daiichi Units 1–3. The progression of the accident sequences at Fukushima Daiichi Units 1–3 occurred very much as predicted in prior severe accident research conducted in the United States and internationally, given the complete station blackout that occurred when the tsunami generated by one of the most powerful earthquakes ever recorded rolled onshore.

Accident Tolerant Equipment↗

Connecting Minds: AI Use Cases to Bridge Power Systems and Large Language Models for Practical Applications

Recent advances in artificial intelligence (AI) and development of large language models (LLMs) present the opportunity to develop a new generation of power systems applications. In contrast with early power system AI applications based on structured numerical data, LLMs offer unique capabilities to perform logical reasoning using text documents, unstructured data, and application programming interface (API) calls to computational software. This paper seeks to bridge the knowledge gap between power systems engineers and LLM developers through a crosscutting explanation of use cases, characteristics, requirements, practical considerations from the perspectives of both LLM capabilities and industry needs. Specific focus is given to applications that can be realistically deployed by electric utilities. After introducing the architecture of LLMs and unique challenges of the power systems domain, this paper proposes twenty representative LLM applications grouped into categories of 1) power system operations, 2) asset management, 3) system planning and analytics, and 4) energy management and protection systems. Five use cases are presented within each category with descriptions of the motivation, objectives, approaches, example inputs / outputs, and benefits of each use case.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Managing Records for the Long Term - 12363

The U.S. Department of Energy (DOE) is responsible for managing vast amounts of information documenting historical and current operations. This information is critical to the operations of the DOE Office of Legacy Management. Managing legacy records and information is challenging in terms of accessibility and changing technology. The Office of Legacy Management is meeting these challenges by making records and information management an organizational priority. The Office of Legacy Management mission is to manage DOE post-closure responsibilities at former Cold War weapons sites to ensure the future protection of human health and the environment. These responsibilities include environmental stewardship and long-term preservation and management of operational and environmental cleanup records associated with each site. A primary organizational goal for the Office of Legacy Management is to 'Preserve, Protect, and Share Records and Information'. Managing records for long-term preservation is an important responsibility. Adequate and dedicated resources and management support are required to perform this responsibility successfully. Records tell the story of an organization and may be required to defend an organization in court, provide historical information, identify lessons learned, or provide valuable information for researchers. Loss of records or the inability to retrieve records because of poor records management processes can have serious consequences and even lead to an organisation's downfall. Organizations must invest time and resources to establish a good records management program because of its significance to the organization as a whole. The Office of Legacy Management will continue to research and apply innovative ways of doing business to ensure that the organization stays at the forefront of effective records and information management. DOE is committed to preserving records that document our nation's Cold War legacy, and the Office of Legacy Management will keep records management as a high priority. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Remote In-bore Laser Cutting and Welding Tools for use in Future Nuclear Fusion Reactors - 18348

The maintenance, replacement and decommissioning of future nuclear fusion reactors will require quick and reliable cutting and joining of in-vessel pipework. Initial design studies for nuclear fusion reactors for power generation have estimated cutting and welding could account for up to 60% of the maintenance duration using conventional in-situ processing techniques (dry-mechanical cutting and arc welding) and that new methods are required to expedite the process. Additionally, the expected radioactivity and limited access at the cutting and welding sites mean that these processes cannot be done manually and robotic tools are required. To this end, remote in-bore laser cutting and welding tools have been developed for use in 90 mm internal diameter steel pipes. Here, we will present the designs of the remote in-bore laser cutting and welding tools, and how the tools fit within the overall remote maintenance strategy of a nuclear fusion reactor. Initial high-power laser trials were performed with prototype tools which successfully demonstrated their laser processing, thermal management and dust protection functionality. Although the tools described herein have been developed specifically for use within the fusion reactor environment, however the tool design and technology demonstrated here is readily transferable to many remote applications in challenging environments such as fission reactor maintenance, nuclear decommissioning and other in-accessible pipework. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Stakeholder-Engaged Structured Decision Making for the Los Alamos Legacy Cleanup Mission - 20501

The Los Alamos National Laboratory (LANL) environmental legacy cleanup program requires decisions to be made for environmental remediation, decommissioning and disposal or management of radioactive waste. This legacy cleanup program was established to address groundwater contamination, material disposal areas (MDAs) that have been used to dispose of radioactive and other waste material, and 'aggregate areas' that might produce radioactive or other chemical waste as a result of remediation activities. The LANL site is regulated for environmental concerns under the Resource Conservation and Recovery Act (RCRA). However, some parts of LANL, such as material disposal area G (MDA G), have disposed of radioactive waste under DOE Order 435.1, and are subject to other regulations. For example, decommissioning the remote-handled TRU material stored in 33 shafts at MDA G falls under EPA's 40 CFR 191. Collectively, the regulations are all aimed in the same direction of finding the best solution, either through constructs such as 'as low as reasonably achievable' (ALARA), considering balancing factors as opposed to only cost and human health risk, and, under EPA regulations such as RCRA and NEPA, evaluating impact from all chemicals and both human health and ecological endpoints. Despite the basic goals and objectives of the regulations or their guidance, the main challenge is in their implementation. Arguably perhaps, but really in principle, all of these (and similar) regulations are asking for a decision analysis to be performed. Implementation challenges encountered have included lack of understanding of decision analysis in the industry, lack of effective stakeholder engagement in the decision analysis process, and lack of appreciation of the need to separate value judgments from science, the latter leading to developing conservative, or protective, science-based models. Conservative models lead to poor solutions, lack of effective stakeholder engagement leads to long drawn out protracted approaches to finding a solution (which also might never be found with this approach), and lack of understanding of decision analysis and Bayesian statistics causes poor models to be built, which creates unfortunate situations of 'garbage in, garbage out' becoming the basis for decision making. Stakeholder-engaged structured decision making (SDM) is an approach to solving problems that relies on the theory of decision science to involve stakeholders in the decision-making process. This approach incorporates stakeholder values using a scientifically rigorous methodology that separates value judgments from science in a way that helps avoid the pitfalls of biased, protective, or conservative modeling. This approach has its foundation in Keeney's 1992 treatise on value-focused thinking [1]. Keeney advocated a paradigm shift in decision making based on the idea that the standard way of thinking about decisions is backwards. The standard approach of focusing first on identifying alternatives rather than on articulating values results in a reactive approach with the emphasis on mechanics and fixed choices instead of the core values that have meaning to stakeholders. This paradigm shift effectively engages all stakeholders in the decision-making process while using a values focused thinking approach that can lead to the identification of decision opportunities and the creation of better alternatives. The intent is to be proactive and generate solutions that are related directly to values and objectives as identified by stakeholders. There are, perhaps, two overarching reasons why SDM can be used to benefit LANL's environmental legacy cleanup. Some of LANL's remaining waste management and environmental management problems are challenging and complex (for example, the Cr and RDX plumes, and MDAs) and while the traditional approach has, arguably, worked well for relatively simple risk-based problems, it cannot, or should not, be applied to more complex problems if the most effective and efficient solutions are desired. The second reason is cost. This has perhaps become more critical since publication of the Government Accountability Office (GAO) reports that DoE's environmental liability is considered a high-risk concern for the nation [2]. The focus of SDM is on structuring solutions to decision risk problems by first addressing stakeholder and decision maker values and subsequently developing decision objectives and ways to measure those objectives, preference weighting across objectives, identifying decision alternatives that best achieve those values, and characterizing uncertainty in predictions of the measures. Because a complete decision model is created using SDM, it can be evaluated to find the main elements of the model that drive, or predict, the best solution. This approach creates complete decision models that are transparent, traceable, reproducible and technically defensible. The science behind SDM, or decision analysis, is well founded, yet it is not unusual to see ad hoc approaches to decision making implemented under various environmental regulations that are pertinent to the LANL site, including NEPA, RCRA and DOE Order 435.1. Such ad hoc approaches are often not transparent or traceable, and lack reproducibility and technical defensibility. The LANL legacy cleanup program has embarked on using SDM to address the complex problems that remain. Stakeholder meetings have been held, and a prototype version of the stakeholder value system has been developed. Further meetings are expected in the future to address specific project needs. This is a long-term endeavor considering the complex environmental problems faced by DOE EM in Los Alamos (EM-LA), and careful planning, consideration of stakeholder value systems, and engagement with stakeholders throughout the SDM process is expected to lead to a successful endpoint. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

ARPA-E Program: Advanced Management Protection of Energy Storage Devices (AMPED) - Monthly Report - November 2013

Technology has been developed that enables monitoring of individual cells in high - capacity lithium-ion battery packs, with a distributed array of wireless Bluetooth 4.0 tags and sensors, and without proliferation of extensive wiring harnesses. Given the safety challenges facing lithium-ion batteries in electric vehicle, civilian aviation and defense applications, these wireless sensors may be particularly important to these emerging markets. These wireless sensors will enhance the performance, reliability and safety of such energy storage systems. Specific accomplishments to date include, but are not limited to: (1) the development of wireless tags using Bluetooth 4.0 standard to monitor a large array of sensors in battery pack; (2) sensor suites enabling the simultaneous monitoring of cell voltage, cell current, cell temperature, and package strain, indicative of swelling and increased internal pressure, (3) small receivers compatible with USB ports on portable computers; (4) software drivers and logging software; (5) a 7S2P battery simulator, enabling the safe development of wireless BMS hardware in the laboratory; (6) demonstrated data transmission out of metal enclosures, including battery box, with small variable aperture opening; (7) test data demonstrating the accurate and reliable operation of sensors, with transmission of terminal voltage, cell temperature and package strain at distances up to 110 feet; (8) quantification of the data transmission error as a function of distance, in both indoor and outdoor operation; (9) electromagnetic interference testing during operation with live, high -capacity battery management system at Yardney Technical Products; (10) demonstrat ed operation with live high-capacity lithium-ion battery pack during charge-discharge cycling; (11) development of special polymer-gel lithium-ion batteries with embedded temperature sensors, capable of measuring the core temperature of individual of the cells during charge-discharge cycling at various temperatures, thereby enabling earlier warning of thermal runaway than possible with external sensors. Ultimately, the team plans to extend this work to include: (12) flexible wireless controllers, also using Bluetooth 4.0 standard, essential for balancing large-scale battery packs. LLNL received $925K for this project, and has $191K remaining after accomplishing these objectives.

25 ENERGY STORAGE↗

The Promise of Emergent Nanobiotechnologies for In Vivo Applications and Implications for Safety and Security

Nanotechnology, the multi-disciplinary field based on the exploitation of the unique physicochemical properties of nanoparticles (NPs) and nanoscale materials, has opened a new realm of possibilities for biological research and biomedical applications. The development and deployment of mRNA-NP vaccines for COVID-19, for example, may revolutionize vaccines and therapeutics. However, regulatory and ethical frameworks that protect the health and safety of the global community and environment are lagging, particularly for nanotechnology geared towards biological applications (i.e., bio-nanotechnology). Considering this, the following review, while not comprehensive, attempts to illustrate the breadth and promise of bionanotechnology developments, and how they may present future safety and security challenges. Specifically, we address current advancements to streamline the development of engineered NPs for in vivo applications and provide discussion on nano-bio interactions, NP in vivo delivery, nano-enhancement of human performance, nanomedicine, and the impacts of NPs on human health and the environment.

59 BASIC BIOLOGICAL SCIENCES↗

MO-D-BRB-01: Pediatric Treatment Planning I: Overview of Planning Strategies and Challenges

Most Medical Physicists working in radiotherapy departments see few pediatric patients. This is because, fortunately, children get cancer at a rate nearly 100 times lower than adults. Children have not smoked, abused alcohol, or been exposed to environmental carcinogens for decades, and of course, have not fallen victim to the aging process. Children get very different cancers than adults. Breast or prostate cancers, typical in adults, are rarely seen in children but instead a variety of tumors occur in children that are rarely seen in adults; examples are germinomas, ependymomas and primitive neuroectodermal tumors, which require treatment of the child’s brain or neuroblastoma, requiring treatment in the abdomen. The treatment of children with cancer using radiation therapy is one of the most challenging planning and delivery problems facing the physicist. This is because bones, brain, breast tissue, and other organs are more sensitive to radiation in children than in adults. Because most therapy departments treat mostly adults, when the rare 8 year-old patient comes to the department for treatment, the physicist may not understand the clinical issues of his disease which drive the planning and delivery decisions. Additionally, children are more prone than adults to developing secondary cancers after radiation. For bilateral retinoblastoma for example, an irradiated child has a 40% chance of developing a second cancer by age 50. The dosimetric tradeoffs made during the planning process are complex and require careful consideration for children treated with radiotherapy. In the first presentation, an overview of childhood cancers and their corresponding treatment techniques will be given. These can be some of the most complex treatments that are delivered in the radiation therapy department. These cancers include leukemia treated with total body irradiation, medulloblastoma, treated with craniospinal irradiation plus a conformal boost to the posterior fossa, neuroblastoma, requiring focal abdominal irradiation to avoid kidney, liver, and vertebral body damage, retinoblastoma, requiring treatment to an eye while minimizing dose to surrounding tissues, and a variety of other tumors which occur anywhere in the body. Case studies will be presented showing the treatment technique and resulting dosimetry, highlighting the objectives for tumor coverage and organ-at-risk sparing. Practical issues that have to be faced when treating children will also be discussed such as daily sedation and immobilization. Late effects based on the current understanding of dose-volume response in normal tissues will be discussed. In the second presentation, specific focus will be on pediatric proton therapy. We will review literature publications on dosimetric comparison of proton versus photon plans, common pediatric tumors treated with protons, and available clinical outcomes. We will describe simulation technique, treatment planning, image guidance for setup verification, and proton beam delivery unique to pediatric and adolescent patients. Finally, we will discuss desired improvements, outlook, and opportunities for medical physicists in pediatric proton therapy. Learning Objectives: Improve understanding about childhood cancer and treatment with radiation Understand treatment planning and delivery issues and associated late effects specific to children Become aware of specific treatment methods for the most challenging pediatric cancers Know the current status, techniques, and desired improvements for pediatric proton therapy.

60 APPLIED LIFE SCIENCES↗

MO-D-BRB-02: Pediatric Treatment Planning II: Applications of Proton Beams for Pediatric Treatment

Most Medical Physicists working in radiotherapy departments see few pediatric patients. This is because, fortunately, children get cancer at a rate nearly 100 times lower than adults. Children have not smoked, abused alcohol, or been exposed to environmental carcinogens for decades, and of course, have not fallen victim to the aging process. Children get very different cancers than adults. Breast or prostate cancers, typical in adults, are rarely seen in children but instead a variety of tumors occur in children that are rarely seen in adults; examples are germinomas, ependymomas and primitive neuroectodermal tumors, which require treatment of the child’s brain or neuroblastoma, requiring treatment in the abdomen. The treatment of children with cancer using radiation therapy is one of the most challenging planning and delivery problems facing the physicist. This is because bones, brain, breast tissue, and other organs are more sensitive to radiation in children than in adults. Because most therapy departments treat mostly adults, when the rare 8 year-old patient comes to the department for treatment, the physicist may not understand the clinical issues of his disease which drive the planning and delivery decisions. Additionally, children are more prone than adults to developing secondary cancers after radiation. For bilateral retinoblastoma for example, an irradiated child has a 40% chance of developing a second cancer by age 50. The dosimetric tradeoffs made during the planning process are complex and require careful consideration for children treated with radiotherapy. In the first presentation, an overview of childhood cancers and their corresponding treatment techniques will be given. These can be some of the most complex treatments that are delivered in the radiation therapy department. These cancers include leukemia treated with total body irradiation, medulloblastoma, treated with craniospinal irradiation plus a conformal boost to the posterior fossa, neuroblastoma, requiring focal abdominal irradiation to avoid kidney, liver, and vertebral body damage, retinoblastoma, requiring treatment to an eye while minimizing dose to surrounding tissues, and a variety of other tumors which occur anywhere in the body. Case studies will be presented showing the treatment technique and resulting dosimetry, highlighting the objectives for tumor coverage and organ-at-risk sparing. Practical issues that have to be faced when treating children will also be discussed such as daily sedation and immobilization. Late effects based on the current understanding of dose-volume response in normal tissues will be discussed. In the second presentation, specific focus will be on pediatric proton therapy. We will review literature publications on dosimetric comparison of proton versus photon plans, common pediatric tumors treated with protons, and available clinical outcomes. We will describe simulation technique, treatment planning, image guidance for setup verification, and proton beam delivery unique to pediatric and adolescent patients. Finally, we will discuss desired improvements, outlook, and opportunities for medical physicists in pediatric proton therapy. Learning Objectives: Improve understanding about childhood cancer and treatment with radiation Understand treatment planning and delivery issues and associated late effects specific to children Become aware of specific treatment methods for the most challenging pediatric cancers Know the current status, techniques, and desired improvements for pediatric proton therapy.

60 APPLIED LIFE SCIENCES↗

TH-EF-204-00: AAPM-AMPR (Russia)-SEFM (Spain) Joint Course On Challenges and Advantages of Small Field Radiation Treatment Techniques

Joanna E. Cygler, Jan Seuntjens, J. Daniel Bourland, M. Saiful Huq, Josep Puxeu Vaque, Daniel Zucca Aparicio, Tatiana Krylova, Yuri Kirpichev, Eric Ford, Caridad Borras Stereotactic Radiation Therapy (SRT) utilizes small static and dynamic (IMRT) fields, to successfully treat malignant and benign diseases using techniques such as Stereotactic Radiosurgery (SRS) and Stereotactic Body Radiation Therapy (SBRT). SRT is characterized by sharp dose gradients for individual fields and their resultant dose distributions. For appropriate targets, small field radiotherapy offers improved treatment quality by allowing better sparing of organs at risk while delivering the prescribed target dose. Specialized small field treatment delivery systems, such as robotic-controlled linear accelerators, gamma radiosurgery units, and dynamic arc linear accelerators may utilize rigid fixation, image guidance, and tumor tracking, to insure precise dose delivery to static or moving targets. However, in addition to great advantages, small field delivery techniques present special technical challenges for dose calibration due to unique geometries and small field sizes not covered by existing reference dosimetry protocols such as AAPM TG-51 or IAEA TRS 398. In recent years extensive research has been performed to understand small field dosimetry and measurement instrumentation. AAPM, IAEA and ICRU task groups are expected to provide soon recommendations on the dosimetry of small radiation fields. In this symposium we will: 1] discuss the physics, instrumentation, methodologies and challenges for small field radiation dose measurements; 2] review IAEA and ICRU recommendations on prescribing, recording and reporting of small field radiation therapy; 3] discuss selected clinical applications and technical aspects for specialized image-guided, small field, linear accelerator based treatment techniques such as IMRT and SBRT. Learning Objectives: To learn the physics of small fields in contrast to dosimetry of conventional fields To learn about detectors suitable for small fields To learn about the role of Monte Carlo simulations in determination of small field output factors To provide an overview of the IAEA small field dosimetry recommendations To provide an overview of the content of the ICRU report on Prescribing, Reporting and Recording of Small Field Radiation Therapy. To learn about special technical considerations in delivering IMRT and SBRT treatments To appreciate specific challenges of IMRT implementation J. Seuntjens, Natural Sciences and Engineering Research Council; Canadian Institutes of Health Research.

60 APPLIED LIFE SCIENCES↗

Thinking Globally about U.S. Extended Deterrence

In contrast to the Cold War bilateral global competition between the United States and the Soviet Union, the modern nuclear age features a more complex, multiplayer arena on the regional scale. With the exception of the U.S. and Russia, most major powers retain relatively small nuclear arsenals or technical hedge capabilities. The U.S., with strong interests and security partnerships in Europe, Northeast Asia, and the Middle East, must navigate through long-standing rivalries and active conflicts while attempting to divine the intentions of less experienced nuclear decision makers in charge of weak domestic institutions. As a result, analysts and policymakers must think globally about U.S. extended deterrence. How have the requirements of extended deterrence and assurance changed? Are there important threads that connect each region? What should the U.S. do differently? To explore these questions, Lawrence Livermore National Laboratory’s Center for Global Security Research, in partnership with the Carnegie Endowment for International Peace and the Pacific Forum CSIS, held a workshop on “Thinking Globally about U.S. Extended Deterrence” in Washington, DC on November 2, 2015. The workshop brought together approximately 40 U.S. and foreign deterrence specialists and government officials, all attending in their private capacities. The participants joined a day of not-for-attribution discussions on the changing deterrence and assurance requirements, the threads that connect the regions, and U.S. strategy to deal with emerging challenges. The following is a summary of key takeaways.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Environmental hormesis and its fundamental biological basis: Rewriting the history of toxicology

Highlights: • Autophagy is activated in the framework of hormesis. • Low doses of stressors promote health and extend lifespan. • Health can be maximized via calorie restriction and intermittent fasting. • Hormesis can protect against aging diseases and exogenous environmental stresses. • Hormesis provides a perspective for enhancing community health and patient success. It has long been debated whether a little stress may be “good” for you. Extensive evidence has now sufficiently accumulated demonstrating that low doses of a vast range of chemical and physical agents induce protective/beneficial effects while the opposite occurs at higher doses, a phenomenon known as hormesis. Low doses of environmental agents have recently induced autophagy, a critical adaptive response that protects essentially all cell types, as well as being transgenerational via epigenetic mechanisms. These collective findings highlight a generalized and substantial ongoing dose-response transformation with significant implications for disease biology and clinical applications, challenging the history and practice of toxicology and pharmacology along with an appeal to stake holders to reexamine the process of risk assessment, with the goal of optimizing public health rather than simply avoiding harm.

54 ENVIRONMENTAL SCIENCES↗

Chemical “Pickling” of Phosphite Additives Mitigates Impedance Rise in Li Ion Batteries

The use of high-voltage, high-capacity positive electrodes in lithium-ion batteries presents a challenge, given their tendency to degrade organic electrolytes. To prevent this damage, electrolyte additives modifying the cathode surface are required. Tris(trimethylsilyl) phosphite (TMSPi) is one of such electrolyte additives. However, the mechanism for its protective action (similarly to other phosphite, borate, and boroxane compounds) remains not completely understood. In LiPF6 containing carbonate electrolytes, TMSPi undergoes reactions yielding numerous products. Here we demonstrate that one of these products, PF2OSiMe3, is responsible for mitigation of impedance rise that occurs in aged cells during charge/discharge cycling. This same agent can also be responsible for reducing parasitic oxidation currents and transition metal loss during prolonged cell cycling. Mechanistic underpinnings of this protective action are examined using computational methods. Our study suggests that this beneficial action originates mainly through inhibition of catalytic centers for electrolyte oxidation that are present on the cathode surface, by forming capping ligands on the transition metal ions that block solvent access to such centers.

capacity fade↗

Selective Chloride-Mediated Neat Ethanol Oxidation to 1,1-Diethoxyethane via an Electrochemically Generated Ethyl Hypochlorite Intermediate

Selective primary alcohol oxidation to form aldehydes products without overoxidation to carboxylic acids remains a key chemistry challenge. Using simple alkylammonium chloride as the electrolyte with a glassy carbon working electrode in neat ethanol solvent, 1,1-diethoxyethane (DEE) was prepared with >95% faradaic efficiency (FE). DEE serves as a storage platform protecting acetaldehyde from overoxidation and volatilization. UV–vis spectroscopy shows that the reaction proceeds through an ethyl hypochlorite intermediate as the sole chloride oxidation product, and that this intermediate decomposes unimolecularly (rate constant k = (6.896 ± 0.516) × 10 –4 s –1 ) to form HCl catalyst and acetaldehyde, which undergoes rapid nucleophilic attack by ethanol solvent to form the DEE product. As a result, this indirect oxidation mechanism enables ethanol oxidation at much less positive potentials due to the fast kinetics for chloride anion oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of solar fuels photoanodes through combinatorial integration of Ni–La–Co–Ce oxide catalysts on BiVO 4

The development of an efficient photoanode remains the primary materials challenge in the establishment of a scalable technology for solar water splitting. The typical photoanode architecture consists of a semiconductor light absorber coated with a metal oxide that serves a combination of functions, including corrosion protection, electrocatalysis, light trapping, hole transport, and elimination of deleterious recombination sites. To date, such coatings have been mostly limited to simple materials such as TiO 2 and Co-Pi, with extensive experimental and theoretical effort required to provide an understanding of the physics and chemistry of the semiconductor-coating interface. In order to provide a more efficient exploration of metal oxide coatings for a given light absorber, we introduce a high throughput methodology wherein a uniform BiVO 4 thin film is coated with 858 unique metal oxides covering a range of metal oxide loadings and the full Ni–La–Co–Ce oxide quaternary composition space. Photoelectrochemical characterization of each photoanode reveals that approximately one third of the coatings lower the photoanode performance while select combinations of metal oxide composition and loading provide up to a 14-fold increase in the maximum photoelectrochemical power generation for oxygen evolution in pH 13 electrolyte. Particular Ce-rich coatings also exhibit an anti-reflection effect that further amplifies the performance, yielding a 20-fold enhancement in power conversion efficiency compared to bare BiVO 4 . By use of in situ optical spectroscopy and comparisons between the metal oxide coatings and their extrinsic optical and electrocatalytic properties, we present a suite of data-driven discoveries, including composition regions which form optimal interfaces with BiVO 4 and photoanodes that are suitable for integration with a photocathode due to their excellent power conversion and solar transmission efficiencies. The high throughput experimentation and informatics provides a powerful platform for both identifying the pertinent interfaces for further study and discovering high performance photoanodes for incorporation into efficient water splitting devices.

10 SYNTHETIC FUELS↗

BEOL compatible high tunnel magneto resistance perpendicular magnetic tunnel junctions using a sacrificial Mg layer as CoFeB free layer cap

Perpendicularly magnetized MgO-based tunnel junctions are envisaged for future generation spin-torque transfer magnetoresistive random access memory devices. Achieving a high tunnel magneto resistance and preserving it together with the perpendicular magnetic anisotropy during BEOL CMOS processing are key challenges to overcome. The industry standard technique to deposit the CoFeB/MgO/CoFeB tunnel junctions is physical vapor deposition. In this letter, we report on the use of an ultrathin Mg layer as free layer cap to protect the CoFeB free layer from sputtering induced damage during the Ta electrode deposition. When Ta is deposited directly on CoFeB, a fraction of the surface of the CoFeB is sputtered even when Ta is deposited with very low deposition rates. When depositing a thin Mg layer prior to Ta deposition, the sputtering of CoFeB is prevented. The ultra-thin Mg layer is sputtered completely after Ta deposition. Therefore, the Mg acts as a sacrificial layer that protects the CoFeB from sputter-induced damage during the Ta deposition. The Ta-capped CoFeB free layer using the sacrificial Mg interlayer has significantly better electrical and magnetic properties than the equivalent stack without protective layer. We demonstrate a tunnel magneto resistance increase up to 30% in bottom pinned magnetic tunnel junctions and tunnel magneto resistance values of 160% at resistance area product of 5 Ω.μm{sup 2}. Moreover, the free layer maintains perpendicular magnetic anisotropy after 400 °C annealing.

36 MATERIALS SCIENCE↗

Phasor-Based Adaptive Control of a Test-Feeder Distribution Network

Control in the power distribution system is needed to match the generation of electricity (that is, supply) with the demand for power (that is, load) at all times while maintaining a high level of power quality [1] (see "Summary"). The complexity of controlling the electric distribution system increases when distributed intermittent energy sources, such as solar photovoltaics (PVs), displace large-scale dispatchable generation [2]-[10]. Furthermore, if the supply from distributed resources exceeds the time-varying demand across a feeder, then the feeder-level voltage will increase. In extreme cases, large voltage increases will trigger the disconnection of distributed generation to protect electrical equipment and ensure customer safety. Consequently, coordinating renewable energy sources that are distributed throughout the distribution system-to match real-time demand across an entire power network-brings the additional challenge of maintaining a high level of supply reliability.

24 POWER TRANSMISSION AND DISTRIBUTION↗