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DOE OSTI2020

Combustion Performance and Emissions Optimization Through Integration of a Miniaturized High-Temperature Multi Process Monitoring System

The main objective of this research program is to design, manufacture, and demonstrate a miniaturized, multi-process, monitoring system (mMPMS) for boiler condition management and easy system deployment to obtain a higher spatial resolution. This system will facilitate a Condition-Based Maintenance (CBM) philosophy that actively monitors the health of assets to predict and prevent failures and maximize availability and generating capacity at a reduced cost. CBM systems can provide boiler data that the advanced process control (APC) system can utilize for plant performance optimization, which is increasingly relevant as coal power plants shift from predominantly base-load operation to predominantly transient operation involving large load swings. The mMPMS is based on an electrochemical sensor that provides a real-time indication of the risk of damage to key locations in the radiant or convective section of a coal-fired boiler such as metal loss rates, heat flux, metal surface temperature, and deposit thickness. These indications can be utilized to optimize boiler performance as well as improve boiler availability in conjunction with corresponding operating conditions. This monitoring system was developed and tested in the high-temperature regions of coal-fired utility boilers in this project but can be applied to many other industries and applications as well. This project leveraged the existing electrochemical noise-based monitoring system and the new sensor design is small enough to be installed through the webbing of the waterwalls without the need for long shut-downs to bend tubes and to make it feasible to obtain high spatial resolution in the boiler. Data is transferred to the plant distributed control system (DCS) and any other control system. The sensor body that houses the sensor assembly was designed to ensure good conductive contact with boiler tubes to ensure the sensor is held at an identical temperature to the tube surface temperature. The data acquisition and signal conditioning modules were redesigned into a small footprint with optimized cooling of the module. System software was developed specifically for the new signal conditioning module and is compatible with plant PLCs. After the preliminary testing at a pilot-scale facility, five mMPMS were installed at a full-scale pulverized coal-fired plant, Basin Electric Power Cooperative’s Leland Olds Unit 1. The systems were demonstrated over a 6-week period during typical operation. Sensor measurements of deposit thickness were validated during the demonstration and subsequently leveraged to determine sensor-based boiler cleaning strategies. These strategies have the benefit of reduced thermal stresses on boiler tubes from over-cleaning and improved boiler water management. At the end of the project, continued development of the sensor technology was carried out at PacifiCorp’s Hunter Station. REI leveraged the permanent installation of the mMPMS in Unit 3 made possible by DOE funding on a separate program. The work at Hunter Plant focused on application of machine learning and artificial intelligence-based models for integration of sensor signals into control and optimization of Hunter Unit 3 processes.

Advanced Sensors, Corrosion, Ash Deposition, Optim↗

DOE OSTI2025

Single Primary Heat Extraction and Removal Emulator (SPHERE) Long Duration Testing

For the development of heat-pipe cooled microreactors, it is crucial to thoroughly understand the characteristics and functioning of heat pipes across a wide spectrum of operating conditions. Passive heat removal and its long-term performance stability are critical factors in this context. Enhanced experimental data is vital for evaluating the operational lifespan of alkali metal heat pipes. Idaho National Laboratory (INL) has successfully conducted an extended duration test on a high-performance sodium-filled heat pipe, closely monitoring the axial temperature profile, power supplied by the heaters, and heat removed by a gas-gap calorimeter. The results from this testing provide valuable data that are instrumental in supporting heat pipe validation efforts. Specifically, this data aids in the development and validation of Sockeye, the Multiphysics Object-Oriented Simulation Environment (MOOSE) tool under the US-DOE NEAMS program designed for heat pipe modeling. By comparing experimental results with Sockeye’s predictions, the tool's accuracy and reliability can be assessed and improved, thereby enhancing its capability to simulate heat pipe operations under various conditions.

22 - GENERAL STUDIES OF NUCLEAR REACTORS↗

NASA NTRS2022

The Future: Nasa’s Surface Biology and Geology Mission and the Dark (Aquatic) Side

With the release of NASA’s Earth System Observatory (ESO) measurement targets that includes studying the Earth’s Surface Biology and Geology (SBG), a global visible to shortwave infrared imaging spectrometer and a multispectral thermal infrared imager have been planned to launch in the late 2020s. This mission will enable unprecedented interdisciplinary science and applications relevant to studying the biology and geology of the Earth's surface. Measurement targets are directly aligned for studying coastal and inland waters ecosystems and water quality, including coralreef ecosystems, snow and ice, mineralogy, volcanology, biology, ecology, biodiversity, and components of radiative forcing from the surface such as greenhouse gas emissions. The observations not only have scientific value in studying feedbacks and interactions of surface processes (e.g., harmful algal blooms, domoic acid, oil spills, and other hazardous events), but also societal benefit – with the capacity to support real-world decision-making such as response to theseevents and inland water conservation, protection of drinking water quality for public and environmental health, and habitat conservation. The work presented here outlines the conducted mission and architecture study and the initiation of science performance trades (signal sensitivity; spectral, spatial, and temporal resolution; and atmospheric effects) informing the design of the SBG segment of the ESO providing the most value to myriad science and applications as possible. Science and applications synergies and algorithms with the Plankton, Aerosol, Cloud, and ocean Ecosystem (PACE) and the Geostationary Littoral Imaging and Monitoring Radiometer (GLIMR) is opportunistic for advancing aquatics research and applications.

THE FUTURE↗

DOE OSTI2023

Validating a Tethered Balloon System and Optical Technologies for Marine Wildlife Detection and Tracking

The interactions between marine wildlife and marine energy devices are not well understood, leading to regulatory delays for device deployments and testing. Technologies that enable marine wildlife observations can help to fill data gaps and reduce uncertainties about animal–device interactions. A validation test conducted in Galveston Bay near La Porte, Texas, in December 2022 used a technology package consisting of a tethered balloon system and three independent sensor systems, including three-band visible, eight-band multispectral, and single-band thermal to detect three marine-mammal-shaped surrogates. The field campaign aimed to provide an initial step to evaluating the use of the TBS and the effectiveness of the sensor suite for marine wildlife observations and detection. From 2 December to 7 December 2022, 6 flights were conducted under varying altitudes and environmental conditions resulting in the collection of 5454 images. A subset of the images was classified and analyzed with two collection criteria including Beaufort wind force scale and TBS altitude to assess a range of observations of a surrogate from near-shore to offshore based on pixel count. The results of this validation test demonstrate the potential for using TBSs and imaging sensors for marine wildlife observations and offer valuable information for further development and application of this technology for marine energy and other blue economy sectors.

47 OTHER INSTRUMENTATION↗

DOE OSTI2021

Diagnosing nuclear power plant pipe wall thinning due to flow accelerated corrosion using a passive, thermal non-destructive evaluation method: Feasibility assessment via numerical experiments

Flow accelerated corrosion (FAC) in nuclear power plant pipes is one of the leading causes of accidents, fatalities, damage and outages. Current FAC identification methods employ expensive sensing technology and are “active” methods, where the response of the piping system to an externally-generated thermal, mechanical or optical excitation must be measured. As a result, these techniques require a disruptive and time-consuming setup. Here we propose a method that utilizes pipe surface temperature measurements to passively monitor for FAC-induced pipe wall thinning without the need for expensive equipment or post-installation setup time. This diagnostic method utilizes a simulation data-driven diagnostic model to estimate the amount of thickness reduction in a pipe based on changes in measured steady-state pipe temperatures. In order to reduce the computational burden of generating large, simulation-based datasets, the behavior of the insulation of the pipe was modeled using a suitably calibrated heat transfer boundary parameter. Additionally, global sensitivity analysis was performed to determine system parameter(s), such as the temperature of water flowing inside the pipe, which significantly affect the steady state pipe wall temperature and could cause errors in diagnosis. Two diagnostic models, one using only the change in steady-state temperature as an indicator for FAC-induced pipe wall thinning and the other using water temperature as an additional diagnostic model input were evaluated for their ability to estimate thickness reductions in a pipe using simulated pipe wall temperature data. For the numerical experiments conducted in this work, both models estimated wall thickness with errors within 0.5 mm, indicating that the proposed technique can potentially be used as a low-cost, first-pass method for FAC monitoring.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

NASA NTRSDate not supplied

Utilization of Machine Learning Techniques for Managing the Tracking and Data Relay Satellite Constellation

National Aeronautics and Space Administration’s (NASA) Goddard Space Flight Center (GSFC) operates a constellation of ten geosynchronous Tracking and Data Relay Satellites (TDRS). The TDRS constellation consists of multiple geosynchronous communication relay satellites located around the equator so they can provide continual coverage of any mission in low earth orbit. The TDRS are located primarily in three oceanic regions around the earth. NASA’s White Sands Complex provides the ground communication support for TDRS located over the Atlantic and Pacific Oceans. Another TDRS ground station in Guam supports the TDRS over the Indian Ocean. With these satellites the TDRS network can provide continuous coverage of satellites in low-earth orbit. The NASA Space Network (SN) project office at GSFC manages the constellation of spacecraft. Major customers of the TDRS constellation include, but are not limited to, the International Space Station and the Hubble Space Telescope. The TDRS constellation has three generations of satellites and has been active for over 30 years providing reliable communication links between customer satellites and corresponding ground stations. However, one of the major concerns for TDRS, and in any space mission, is to ensure the health and safety of the spacecraft. Generally, engineers use telemetry data to monitor and analyze the performance and state of health of the spacecraft. Telemetry data contains hundreds of parameters that monitor each important component in the spacecraft, which can be utilized to recognize and characterize the behavior of the spacecraft. Each parameter contains considerable information to represent time-dependent properties of each spacecraft subsystem and component. During the entire life of a TDRS spacecraft, thousands of gigabytes of telemetry data are transmitted in real-time from the spacecraft to the ground station at the White Sands Complex in Las Cruces, New Mexico, and recorded as historical data sets for engineers to process and analyze the events that occurred on-orbit. These parameters contain the function of multiple spacecraft subsystems, such as the attitude control system (ACS), Thermal, Electrical Power Subsystem (EPS), etc. . The first and second generations have exceeded their required lifetime and NASA is keen to manage these spacecrafts carefully in order to maximize the remaining life using the spacecraft telemetry. The challenge is to know when the risk of losing a spacecraft in geosynchronous orbit exceeds the benefit of continued operations for customer support. In the TDRS fleet, the EPS is the most critical subsystem related to spacecraft operations. Failure of the EPS would strand a spacecraft in geosynchronous orbit. Since EPS provides power to the spacecraft, component failures ultimately lead to the inability to support the spacecraft loads and the communications payload. For instance, TDRS-8 has several anomalies in EPS including the Bus Voltage Limiter (BVL) shunt current, solar array loss of circuits, and failed battery cells. Any of these anomalies can cause critical issues to the spacecraft. Therefore, developing a system to analyze and perform early detection of a potential anomaly is an important issue in telemetry data analysis. In recent years, Telemetry Mining (TM) has been proposed to process telemetry data by using Data Mining (DM) techniques such as classification, clustering, regression and anomaly detection. Anomaly detection, also known as outlier detection, has been widely used in many data mining areas such as remote sensing, medical data processing and digital image processing. The goal of anomaly detection is to detect abnormal data, which contains a relatively low probability of occurrence among the entire data set. Early detection of anomalies is one of the most significant issues in managing the spacecraft configuration. If anomalies can be detected early enough, then the redundant resources can be used to extend the life of the operational spacecraft. We present an unsupervised anomaly detection method to process the EPS data extracted from TDRS-8. This is different from traditional analytical methods, which use telemetry data to illustrate behavior and physical meaning of each spacecraft component. TM connects multiple parameters as a vector and then conducts data analysis on this high dimension telemetry vector. This method is looking at the properties of a high dimensional vector that is able to consider the relationship between different parameters in the anomaly detection problem. This kind of method performs much better than the traditional limit checking method. In addition, we propose a new approach of real-time anomaly detection to process telemetry data in real-time, which can then be applied to spacecraft monitoring with high reliability, low cost and high accuracy.

Machine Learning (ML)↗

NASA NTRS2019

Design of an Automated Ultrasonic Scanning System for In-Situ Composite Cure Monitoring and Defect Detection

The preliminary design and development of an automated ultrasonic scanning system for in-situ composite cure monitoring and defect detection in the high temperature environment of an oven was completed. This preliminary design is a stepping stone to deployment in the high temperature and high pressure environment of an autoclave, the primary cure method of aerospace grade thermoset composites. Cure monitoring with real-time defect detection during the process could determine when defects form and how they move. In addition, real-time defect detection during cure could assist validating physics-based process models for predicting defects at all stages of the cure cycle. A physics-based process model for predicting porosity and fiber waviness originating during cure is currently under development by the NASA Advanced Composites Project (ACP). For the design, an ultrasonic contact scanner is enclosed in an insulating box that is placed inside an oven during cure. Throughout the cure cycle, the box is nitrogen-cooled to approximately room temperature to maintain a standard operating environment for the scanner. The composite part is mounted on the outside of the box in a vacuum bag on the build/tool plate. The build plate is attached to the bottom surface of the box. The scanner inspects the composite panel through the build plate, tracking the movement of defects introduced during layup and searching for new defects that may form during cure. The focus of this paper is the evaluation and selection of the build plate material and thickness. The selection was based on the required operating temperature of the scanner, the cure temperature of the composite material, thermal conductivity models of the candidate build plates, and a series of ultrasonic attenuation tests. This analysis led to the determination that a 63.5 mm thick build plate of borosilicate glass would be utilized for the system. The borosilicate glass plate was selected as the build plate material due to the low ultrasonic attenuation it demonstrated, its ability to efficiently insulate the scanner while supporting an elevated temperature on the part side of the plate, and the availability of a 63.5 mm thick plate without the need for lamination.

Hudson, Tyler B.↗

DOE OSTI2024

Photonic curing for innovative fabrication of flexible metal oxide optoelectronics

Abstract Flexible optoelectronics, based on non-planar substrates, hold promise for diverse applications such as wearables, health monitors, and displays due to their cost-effective manufacturing methods. Despite the superior properties of metal oxides, the challenge of processing them at high temperatures incompatible with plastic substrates necessitates innovative annealing approaches. Photonic curing, which delivers microsecond to millisecond broadband (200–1500 nm) light pulses on a sample, emerges as a viable solution. Depending on the optical properties, the targeted film absorbs the radiant energy resulting in rapid heating while the transparent substrate absorbs a minimal amount of light and remains at ambient temperature. The light intensity can be high, but since the light pulse is short, the total energy absorbed by the sample remains low and will not damage the plastic substrate. This perspective explores the innovative application of photonic curing to fabricate flexible metal oxide optoelectronics, including thin-film transistors, metal–insulator–metal devices, solar cells, transparent conductors, and Li batteries, emphasizing the conversion of sol–gel precursors to metal oxides. However, this technique was initially developed for sintering metal nanoparticles to conductive patterns and poses intriguing challenges in explaining its mechanism for metal oxide conversion, especially considering the limited absorption of visible light by most sol–gel precursors. The review delves into UV-induced photochemistry, common flexible metal-oxide optoelectronic components, and non-intuitive distinctions between photonic curing and thermal annealing. By elucidating the distinctive role of photonic curing in overcoming temperature-related challenges and advancing the fabrication of flexible metal oxide optoelectronics, this perspective offers valuable insights that could shape the future of flexible optoelectronics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

NASA NTRS2015

AMO EXPRESS: A Command and Control Experiment for Crew Autonomy

NASA is investigating a range of future human spaceflight missions, including both Mars-distance and Near Earth Object (NEO) targets. Of significant importance for these missions is the balance between crew autonomy and vehicle automation. As distance from Earth results in increasing communication delays, future crews need both the capability and authority to independently make decisions. However, small crews cannot take on all functions performed by ground today, and so vehicles must be more automated to reduce the crew workload for such missions. NASA's Advanced Exploration Systems Program funded Autonomous Mission Operations (AMO) project conducted an autonomous command and control demonstration of intelligent procedures to automatically initialize a rack onboard the International Space Station (ISS) with power and thermal interfaces, and involving core and payload command and telemetry processing, without support from ground controllers. This autonomous operations capability is enabling in scenarios such as a crew medical emergency, and representative of other spacecraft autonomy challenges. The experiment was conducted using the Expedite the Processing of Experiments for Space Station (EXPRESS) rack 7, which was located in the Port 2 location within the U.S Laboratory onboard the International Space Station (ISS). Activation and deactivation of this facility is time consuming and operationally intensive, requiring coordination of three flight control positions, 47 nominal steps, 57 commands, 276 telemetry checks, and coordination of multiple ISS systems (both core and payload). The autonomous operations concept includes a reduction of the amount of data a crew operator is required to verify during activation or de-activation, as well as integration of procedure execution status and relevant data in a single integrated display. During execution, the auto-procedures provide a step-by-step messaging paradigm and a high level status upon termination. This messaging and high level status is the only data generated for operator display. To enhance situational awareness of the operator, the Web-based Procedure Display (WebPD) provides a novel approach to the issues of procedure display and execution tracking. For this demonstration, the procedure was initiated and monitored from the ground. As the Timeliner sequences executed, their high level execution status was transmitted to ground, for WebPD consumption.

Stetson, Howard K.↗

NASA NTRS2011

Optimization of Indium Bump Morphology for Improved Flip Chip Devices

Flip-chip hybridization, also known as bump bonding, is a packaging technique for microelectronic devices that directly connects an active element or detector to a substrate readout face-to-face, eliminating the need for wire bonding. In order to make conductive links between the two parts, a solder material is used between the bond pads on each side. Solder bumps, composed of indium metal, are typically deposited by thermal evaporation onto the active regions of the device and substrate. While indium bump technology has been a part of the electronic interconnect process field for many years and has been extensively employed in the infrared imager industry, obtaining a reliable, high-yield process for high-density patterns of bumps can be quite difficult. Under the right conditions, a moderate hydrogen plasma exposure can raise the temperature of the indium bump to the point where it can flow. This flow can result in a desirable shape where indium will efficiently wet the metal contact pad to provide good electrical contact to the underlying readout or imager circuit. However, it is extremely important to carefully control this process as the intensity of the hydrogen plasma treatment dramatically affects the indium bump morphology. To ensure the fine-tuning of this reflow process, it is necessary to have realtime feedback on the status of the bumps. With an appropriately placed viewport in a plasma chamber, one can image a small field (a square of approximately 5 millimeters on each side) of the bumps (10-20 microns in size) during the hydrogen plasma reflow process. By monitoring the shape of the bumps in real time using a video camera mounted to a telescoping 12 magnifying zoom lens and associated optical elements, an engineer can precisely determine when the reflow of the bumps has occurred, and can shut off the plasma before evaporation or de-wetting takes place.

Jones, Todd J.↗

DOE OSTI2024

Long-Term field testing of the accuracy and HVAC energy savings potential of occupancy presence sensors in A Single-Family home

The energy-saving potential of occupancy-centric smart thermostats has been extensively explored in simulations but lacked field testing for energy savings quantification and sensor performance assessment in real buildings. This paper presents a long-term field study conducted in a single-family home in Texas, U.S. to evaluate the performance of occupancy-centric controls (OCC) of HVAC (heating, ventilation, and air-conditioning) system in terms of energy savings, sensor accuracy, and impact on electric peak demand. The test site was equipped with a commercial off-the-shelf (COTS) smart thermostat and multiple occupancy presence sensors for OCC implementation. Additionally, a sub-metering system was installed to monitor electricity consumption of various end-use equipment, including the HVAC system. A supplementary device was installed to track the ground-truth occupancy for the accuracy evaluation of the occupancy presence sensor. Scenarios of baseline and OCC controls were alternated weekly over the 20-month testing period. The results indicated an effective OCC execution, as evidenced by indoor temperature profiles. During the 2023 cooling season, OCC achieved total energy savings of 1,958 kWh, corresponding to a 17.6% energy savings ratio. Under certain conditions, daily HVAC energy savings reached as high as 17 kWh, with a savings ratio of 35%. Sensor performance showed an overall accuracy of 83.8%, a False Positive Rate (FPR) of 12.8%, and a False Negative Rate (FNR) of 47.4%. A key limitation was the sensor’s inability to detect stationary occupants during sleep, leading to a midnight FNR of nearly 100% and significantly compromising thermal comfort. Additionally, the implementation of OCC resulted in extended periods of high electricity demand on summer afternoons, affecting occupant’s thermal comfort and posing potential challenges to community-level grid operations if OCC were widely adopted. Furthermore, this study addresses a critical research gap by empirically investigating energy-saving potential and occupancy sensor performance in residential buildings. Through a comprehensive field-testing study, the research examines the interrelationship between sensor accuracy, energy savings, and thermal comfort, an area that has received limited attention in the current literature.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

NASA NTRS2019

The International Space Station (ISS) Port 1 (P1) External Active Thermal Control System (EATCS) Ammonia Leak

From 2011 to 2017, the crew onboard the International Space Station (ISS) was at risk of dire consequences due to an external ammonia leak. Ammonia is used in the External Active Thermal Control System (EATCS) to cool the pressurized modules and external electrical systems. Engineers at NASA's Johnson Space Center (JSC) initially detected the leak in one of two cooling loops by monitoring the system ammonia inventory decay over time. White flakes seen on High Definition (HD) cameras were also thought to be associated with the leakage but not confirmed. Initially, the leak was small enough that the ammonia inventory and system operations were not in jeopardy. However, the leak began to accelerate to the point where troubleshooting and corrective action were vital to the sustainability of the ISS. Therefore, it became imperative that the leak be located and repaired for ISS operations to continue. No tools were readily available on the ISS to locate such a leak when it was initially detected, however NASA engineers were already in the process of developing a new device for this purpose called the Robotic External Leak Locator (RELL). The RELL is a robotic instrument package with a mass spectrometer and an ion pressure gauge. Initial checkout operations with RELL happened to coincide with the increasing leak, and ammonia vapors were measured around the P1 EATCS Radiator #3 flexible jumper hoses. The leak stopped after the radiator and its flexible hoses were remotely isolated from the loop and the ammonia from the isolated segment was vented to space. Astronauts conducted a spacewalk that successfully removed the hoses, which were returned to ground for further investigation. The purpose of this paper is to review the leak detection and isolation efforts, investigation results, lessons learned and the recovery plan.

Cowan, Darnell T.↗

NASA NTRS2019

The International Space Station (ISS) Port 1 (P1) External Active Thermal Control System (EATCS) Ammonia Leak

Cowan, Darnell T.↗

NASA NTRS2013

Common Practice Lightning Strike Protection Characterization Technique to Quantify Damage Mechanisms on Composite Substrates

To support FAA certification airworthiness standards, composite substrates are subjected to lightning direct-effect electrical waveforms to determine performance characteristics of the lightning strike protection (LSP) conductive layers used to protect composite substrates. Test results collected from independent LSP studies are often incomparable due to variability in test procedures & applied practices at different organizations, which impairs performance correlations between different LSP data sets. Under a NASA supported contract, The Boeing Company developed technical procedures and documentation as guidance in order to facilitate a test method for conducting universal common practice lightning strike protection test procedures. The procedures obtain conformity in future lightning strike protection evaluations to allow meaningful performance correlations across data sets. This universal common practice guidance provides the manufacturing specifications to fabricate carbon fiber reinforced plastic (CFRP) test panels, including finish, grounding configuration, and acceptable methods for pretest nondestructive inspection (NDI) and posttest destructive inspection. The test operations guidance elaborates on the provisions contained in SAE ARP5416 to address inconsistencies in the generation of damage protection performance data, so as to provide for maximum achievable correlation across capable lab facilities. In addition, the guidance details a direct effects test bed design to aid in quantification of the multi-physical phenomena surrounding a lightning direct attachment supporting validation data requirements for the development of predictive computational modeling. The lightning test bed is designed to accommodate a repeatable installation procedure to secure the test panel and eliminate test installation uncertainty. It also facilitates a means to capture the electrical waveform parameters in 2 dimensions, along with the mechanical displacement and thermal heating parameters which occur during lightning attachment. Following guidance defined in the universal common practice LSP test documents, protected and unprotected CFRP panels were evaluated at 20, 40 and 100KAmps. This report presents analyzed data demonstrating the scientific usefulness of the common practice approach. Descriptions of the common practice CFRP test articles, LSP test bed fixture, and monitoring techniques to capture the electrical, mechanical and thermal parameters during lightning attachment are presented here. Two methods of measuring the electrical currents were evaluated, inductive current probes and a newly developed fiberoptic sensor. Two mechanical displacement methods were also examined, optical laser measurement sensors and a digital imaging correlation camera system. Recommendations are provided to help users implement the common practice test approach and obtain LSP test characterizations comparable across data sets.

Szatkowski, George N.↗

DOE OSTI2023

Constraining the Reaction Rate of Criegee Intermediates with Carboxylic Acids during the Multiphase Ozonolysis of Aerosolized Alkenes

Criegee intermediates (CIs) are central to the ozonolysis of unsaturated organic compounds, controlling the formation of small fragmentation reaction products and higher molecular weight oligomeric compounds through competing unimolecular and bimolecular pathways. In particular, the reaction of thermalized CI with carboxylic acids (RCOOH) to produce oligomeric α-acyloxyalkyl hydroperoxides (AAHPs) is of interest to the chemical transformation of organic compounds in the atmosphere. In the gas phase, the CI + RCOOH reaction proceeds at supercollisional rates, consistent with a barrierless reaction mechanism. However, the rate of this reaction in condensed phases remains uncertain. Here, we report the results of aerosol flow tube studies of the ozonolysis of submicron organic aerosol containing mixtures of an internal n-alkene (Z-9-tricosene, tri) and a saturated acid (2-hexyldecanoic acid, HDA). The decay of the reactants and formation of reaction products are monitored using atmospheric pressure chemical ionization mass spectrometry (APCI–MS). A 6-fold decrease in the reactive uptake of ozone is observed with increasing acid concentration, consistent with a previous study using alcohol additives. The decay of HDA with ozone exposure shows that HDA scavenges CIs at rates comparable to competing unimolecular pathways involving CIs. The decay kinetics of HDA are analyzed using a simple kinetic model in order to constrain the ratio of the CI + RCOOH and unimolecular CI rate constants. Empirical fitting to this model, combined with theoretical estimates of the unimolecular loss rate, yields a CI + RCOOH rate constant of 1.85 ± 0.27 × 10 –19 cm 3 molec –1 s –1 , which is six orders of magnitude slower than the expected diffusion limit in a liquid organic matrix. Stochastic kinetic simulations are conducted with different values of the CI + RCOOH rate constant to validate this result and show that the diffusion-limited rate is indeed much too rapid to reproduce the experimental results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

West Valley Demonstration Project (WVDP) Annual Site Environmental Report (ASER) for Calendar Year 2025

The report, prepared for the U.S. Department of Energy West Valley Demonstration Project office (DOE-WVDP), summarizes the environmental protection program at the WVDP for calendar year (CY) 2025. Monitoring and surveillance of the facilities used by the DOE are conducted to verify protection of public health and safety and the environment. The report is a key component of the DOE’s effort to keep the public informed of environmental conditions at the WVDP. The quality assurance protocols applied to the environmental monitoring program ensure the validity and accuracy of the monitoring data. In addition to demonstrating compliance with environmental laws, regulations, and directives, the evaluation of data collected in 2025 continued to indicate that WVDP activities posed no threat to public health or safety, or to the environment.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2022

Insights Into the Aerodynamic Versus Radiometric Surface Temperature Debate in Thermal-Based Evaporation Modeling

Global evaporation monitoring from Earth observation thermal infrared satellite missions is historically challenged due to the unavailability of any direct measurements of aerodynamic temperature. State-of-the-art one-source evaporation models use remotely sensed radiometric surface temperature as a substitute for the aerodynamic temperature and apply empirical corrections to accommodate for their inequality. This introduces substantial uncertainty in operational drought mapping over complex landscapes. By employing a non-parametric model, we show that evaporation can be directly retrieved from thermal satellite data without the need of any empirical correction. Independent evaluation of evaporation in a broad spectrum of biome and aridity yielded statistically significant results when compared with eddy covariance observations. While our simplified model provides a new perspective to advance spatio-temporal evaporation mapping from any thermal remote sensing mission, the direct retrieval of aerodynamic temperature also generates the highly required insight on the critical role of biophysical interactions in global evaporation research.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

A reduced-order modeling of a tubular solar reactor for long duration thermochemical energy storage

The storage of solar energy in a solid form, referred to as a “solar fuel”, can be achieved through a process known as endothermic solar thermochemistry. This process transforms the absorbed solar energy into a stable and retrievable form that can be stored for extended periods of time. This paper presents a low–order heat transfer model of a counter–current tubular falling bed reactor designed to produce thermally reduced magnesium manganese oxide pellets for long duration thermochemical energy storage. The energy required for the endothermic reduction was supplied by concentrated solar energy or renewable electricity via indirect heating of the gas and solid reactants flowing in a ceramic tube. The counter-current gas flow enhances the mixing of the solid particles with the heat recuperation zone, allowing the gas and particles to enter and exit the tubular reactor close to room temperature. Further, the reactor was vertically oriented and was heated circumferentially by an adjustable level heat flux along a finite segment of its length. The temperature distribution of the reactor in response to transient changes along the tube was modeled by considering conduction, convection, and radiation heat transfer. Governing equations for the heat transfer model were solved by discretizing the reactor tube into a finite number of control volumes and using an energy balance for the heat exchange between the reactor wall, gas, and particles within the control volume. The energy absorbed during this endothermic reaction was modeled numerically by fitting the data of the chemical conversion rate with the corresponding temperature of particles in the heating zone. The numerical model has been experimentally validated using a reactor prototype made of a 121.92 cm alumina tube heated by a 7kW electric tube–furnace. The alumina tube receives magnesium manganese oxide pellets of 3.66±0.516 mm in diameter from the top, and a counter–current gas flow from the bottom. The reactor wall temperature was monitored by six thermocouples installed along the reactor tube length. The experimental procedure was numerically simulated, and the temperature variation along the reactor tube was compared with a matrix of experimental runs for a range of particles mass flowrates (0.75–1.25g/s) and corresponding gas flowrates (36–65 SLPM). The reactor system was heated gradually from room temperature to a steady state temperature of 1673K, and then cooled down to room temperature. The heating and cooling processes were simulated, and the numerical and experimental results were compared throughout processes. The numerical model showed similar trends to the experimental results, with an error of 0.69 to 7.9% for the particle inlet and 0.7 to 7.9% for the gas inlet during steady-state operation. The proposed numerical model can be implemented as a simplified physical model to design a feedback control system to regulate reactor temperature.

14 SOLAR ENERGY↗