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At least 163 records · Page 9

Development of Analysis Methods that Integrate Numeric and Textual Equipment Reliability Data

Within the Light Water Reactor Sustainability (LWRS) program, the Risk-Informed Systems Analysis (RISA) Pathway is performing collaborative research on the development and deployment of technologies designed to assist operating nuclear power plants (NPPs) to reduce operating costs improve plant reliability and availability. One of the RISA research areas is focusing on the development of methods and tools designed to optimize plant operations (e.g., maintenance/replacement schedules, optimal maintenance postures for plant structures, systems, and components [SSCs]) in a manner that is more cost effective than current approaches and makes better use of available SSC health data. The Risk-Informed Asset Management (RIAM) project targets this research area by creating a direct bridge between component equipment reliability (ER) data and system engineer decision making regarding maintenance activity scheduling and component aging management. In this respect, one challenge that NPP system engineers are facing is that the amount of ER data being continuously generated is not only extremely large in size, but it comes in different forms: textual (e.g., condition or maintenance reports) and numeric (e.g., generated by monitoring systems). All these data elements provide them with valuable insights and information regarding: 1) the discovery of anomalous behaviors or degradation trends, 2) the identification of the possible causes behind such behaviors/trends, and 3) the prediction of their direct consequences. However, several challenges have proved to be roadblocks to this process. While some of these challenges are technical in nature (i.e., data are often distributed over several physical servers/databases), others are conceptual in nature: data elements come in different formats (e.g., numeric or textual), and measured values have different scales (e.g., vibration spectra and oil temperature). The activities performed by the RIAM project during FY23 directly tackles the need to simultaneously integrate the analysis of ER data in all its forms, numeric and textual. Note that such task has never been performed before due to the complexity of the systems under consideration but, most importantly, because of the technical challenges behind the harmonization of ER data formats and the lack of adequate computational methods to analyze them. Our approach borrows ideas and concepts from the medical field where integration of several data sources is vital to assist medical practitioners to perform correct diagnosis and indicate optimal treatments. In our view a NPP asset is equivalent to a patient in a medical context. The main difference is the complexity of a human body is a magnitude more complex when compared to typical assets commonly present in NPPs (e.g., centrifugal pumps, or motor operated valves). This simplifies our first requirement when analyzing heterogenous ER data formats: to put data into “context”. Context is here intended as the additional piece of information that is needed by ER data analysis tools to understand what these data elements are referring to, i.e., which king of knowledge they are generating. In our context, this knowledge can be translated into models that capture the form and functional architecture of assets/systems, their dependencies, and how they interact. These models actually emulate the knowledge that that NPP system engineers possess about assets and systems; this is their key of success when analyzing ER data, their challenge is ability to handle large amount of data. Here, we employ model-based system engineering (MBSE) models of systems and assets to represent and capture their architecture and functional, i.e. cause-effect, relations. Then, ER data elements are processed by identifying first of all which elements of the developed MBSE elements they are referring to. For numeric ER data this task is fairly easy since it is possible to precisely pinpoint what MBSE elements the corresponding sensor are observing (e.g., bearing temperature of a centrifugal pump). Task is much harder for textual data since the information contained in issue or maintenance reports needs to “be understood” by a computational tool. Here we called this process as “knowledge extraction”. Once again, we borrow the experience in the medical field where methods to extract knowledge from textual data have been developed in the past decade. The missing element for us is the availability of a complete dictionary of NPP related concepts (in addition to the MBSE models presented earlier) that can put “text into context”. In FY23, such dictionary has been developed along with all the computational elements required for knowledge extraction. Lastly, once numeric and textual ER data elements have been processed and “understood”, then the last step is the discovery of possible cause-effect relations among them. This is performed by observing if a logical connection through the MBSE models exists, and if the

97 MATHEMATICS AND COMPUTING↗

Allosteric control of electron transfer in nitrogenase and nitrogenase-like enzymes (Final Report)

More than a third of all known proteins to date are either oxidoreductases or metalloproteins. The diversity of metal cofactors and redox centers in these proteins make them attractive candidates for engineering protein-based biocatalysts, biosensors, and biofuel cells, among other necessary tools for the bioeconomy. Many of these enzymes function as large multi-subunit complexes arranged as symmetric or asymmetric assemblies, and the purpose of this architecture is unclear. The goal of the project was to address this fundamental question by investigating the mechanism of action of two oxidoreductases: Nitrogenase and DPOR (Dark-Operative Protochlorophyllide Oxidoreductase, a nitrogenase-like oxidoreductase). Nitrogenase and DPOR play key roles in nitrogen fixation and photosynthesis, processes essential to sustaining life. Both proteins are arranged as two symmetrical halves with each half capable of substrate reduction. For more than half a century, substrate reduction by nitrogenase has been presumed to occur independently within the two identical halves. Funded by this DOE grant we have now shown that both nitrogenase and DPOR function asymmetrically. Electron transfer in one half suppresses activity in the other. Thus, we have demonstrated that the two halves do not function in an independent manner; rather, catalytic events in one-half allosterically suppress activity and electron transfer (ET) in the other. This alternating-site mechanism has significant implications on our current understanding of substrate reduction by these enzymes and offers a new mechanistic paradigm for the reactions they catalyze. Our work now provides a mechanistic map of the how the two symmetric catalytic halves work together to establish and maintain the sequential-site mechanism through multiple ET cycles to achieve substrate reduction. There is substantive need for bio-inspired tools that enable reduction of nitrogen and other substrates, as well as photosynthesis, for energy and food production. Understanding the workings of enzymes like nitrogenase and DPOR that mediate multi-electron redox chemistry is vital for designing such synthetic tools. The timing of our research coincides with the biotechnological breakthrough of light-driven artificial N2 reduction by nitrogenase, achieved using the native enzyme with both halves arranged in a mirror-like architecture as catalyst. Together with such discoveries, our research now reveal unknown facets of the reaction mechanism and hold promise for designing more effective catalysts.

59 BASIC BIOLOGICAL SCIENCES↗

An Alternative Humans to Mars Approach: Reducing Mission Mass with Multiple Mars Flyby Trajectories and Minimal Capability Investments

Mars flyby trajectories and Earth return trajectories have the potential to enable lower- cost and sustainable human exploration of Mars. Flyby and return trajectories are true minimum energy paths with low to zero post-Earth departure maneuvers. By emplacing the large crew vehicles required for human transit on these paths, the total fuel cost can be reduced. The traditional full-up repeating Earth-Mars-Earth cycler concept requires significant infrastructure, but a Mars only flyby approach minimizes mission mass and maximizes opportunities to build-up missions in a stepwise manner. In this paper multiple strategies for sending a crew of 4 to Mars orbit and back are examined. With pre-emplaced assets in Mars orbit, a transit habitat and a minimally functional Mars taxi, a complete Mars mission can be accomplished in 3 SLS launches and 2 Mars Flyby's, including Orion. While some years are better than others, ample opportunities exist within a given 15-year Earth-Mars alignment cycle. Building up a mission cadence over time, this approach can translate to Mars surface access. Risk reduction, which is always a concern for human missions, is mitigated by the use of flybys with Earth return (some of which are true free returns) capability.

Whitley, Ryan J.↗

Transpiring Cooling of a Scram-Jet Engine Combustion Chamber

The peak cold-wall heating rate generated in a combustion chamber of a scram-jet engine can exceed 2000 Btu/sq ft sec (approx. 2344 W/sq cm). Therefore, a very effective heat dissipation mechanism is required to sustain such a high heating load. This research focused on the transpiration cooling mechanism that appears to be a promising approach to remove a large amount of heat from the engine wall. The transpiration cooling mechanism has two aspects. First, initial computations suggest that there is a reduction, as much as 75%, in the heat flux incident on the combustion chamber wall due to the transpirant modifying the combustor boundary layer. Secondly, the heat reaching the combustor wall is removed from the structure in a very effective manner by the transpirant. It is the second of these two mechanisms that is investigated experimentally in the subject paper. A transpiration cooling experiment using a radiant heating method, that provided a heat flux as high as 200 Btu/sq ft sec ( approx. 234 W/sq cm) on the surface of a specimen, was performed. The experiment utilized an arc-lamp facility (60-kW radiant power output) to provide a uniform heat flux to a test specimen. For safety reasons, helium gas was used as the transpirant in the experiments. The specimens were 1.9-cm diameter sintered, powdered-stainless-steel tubes of various porosities and a 2.54cm square tube with perforated multi-layered walls. A 15-cm portion of each specimen was heated. The cooling effectivenes and efficiencies by transpiration for each specimen were obtained using the experimental results. During the testing, various test specimens displayed a choking phenomenon in which the transpirant flow was limited as the heat flux was increased. The paper includes a preliminary analysis of the transpiration cooling mechanism and a scaling conversion study that translates the results from helium tests into the case when a hydrogen medium is used.

Choi, Sang H.↗

Nitric Oxide Production from Nitrite plus Ascorbate during Ischemia upon Hippocampal Glutamate NMDA Receptor Stimulation

Nitric oxide (•NO), a diffusible free radical, is an intercellular messenger, playing a crucial role in several key brain physiological processes, including in neurovascular coupling (NVC). In the brain, glutamatergic activation of the neuronal nitric oxide synthase (nNOS) enzyme constitutes its main synthesis pathway. However, when oxygen (O2) supply is compromised, such as in stroke, ischemia, and aging, such •NO production pathway may be seriously impaired. In this context, evidence suggests that, as already observed in the gastric compartment, the reduction of nitrite by dietary compounds (such as ascorbate and polyphenols) or by specific enzymes may occur in the brain, constituting an important rescuing or complementary mechanism of •NO production. Here, using microsensors selective for •NO, we show that nitrite enhanced the •NO production in a concentration-dependent manner and in the presence of ascorbate evoked by N-methyl-D-aspartate (NMDA) and glutamate stimulation of rat hippocampal slices. Additionally, nitrite potentiated the •NO production induced by oxygen-glucose deprivation (OGD). Overall, these observations support the notion of a redox interaction of ascorbate with nitrite yielding •NO upon neuronal glutamatergic activation and given the critical role of NO as the direct mediator of neurovascular coupling may represents a key physiological mechanism by which •NO production for cerebral blood flow (CBF) responses to neuronal activation is sustained under hypoxic/acidic conditions in the brain.

Nunes, Carla (ORCID:0000000274521592)↗

A comprehensive review on the loss of wellbore integrity due to cement failure and available remedial methods

With the recent abrupt fluctuations in oil pricing and the need of complying with environmental and social requirements, nowadays it is an urgent call for the oil and gas industry to produce the hydrocarbon without any loss as well as in a safe manner. Cements are placed in the annular space of casing to provide zonal isolation in between wellbore and surface during the operational life cycle of the well or even after the abandonment. But this is not what happens most of the time. Cement degrades or loses its integrity through debonding either from the casing or formation and generates cracks or fractures due to varied reasons throughout the life of the well. Multiple causes contribute to the loss of wellbore integrity – either by physical, mechanical, or chemical processes. These failures lead to sustained casing pressure (SCP) and contamination of surrounding environment. To combat this issue or to restore the well integrity, multiple remedial actions have also been either implemented in the industry or proposed based on experimental research to prevent the damage or to seal the leakage in the cement sheath. Here, this paper will provide an extensive review of the underlying reasons of cement failure and the available remedial actions to minimize the loss of well integrity issue. These information are not only useful to know about the different corrective options available for us to implement in industry but also it will provide us a knowledge base regarding how we can enhance the performance of the exiting systems to battle the cement integrity problem more efficiently.

02 PETROLEUM↗

Scaleup of Microwave Powder Bed Fusion for Lunar Infrastructure Construction

NASA and its partners are seeking to establish a sustainable and permanent presence on the Moon. Like explorers on Earth, making use of natural resources upon arrival at the destination will be paramount. In-situ resource utilization of the lunar regolith will enable efficient construction of lunar infrastructure. Transforming the granular regolith into a solid can be achieved in many ways. One method is to use microwave energy to sinter the regolith into various structures. The lunar regolith has a low thermal conductivity, but microwaves can volumetrically heat it to bind the granular particles together in an energy efficient manner. One concept that is being developed and evaluated to sinter the regolith into infrastructure uses the Moon’s surface as a powder bed. Regolith would be added to the sintered lunar structure to build up layers to create structures such as landing pads, blast shields, roads, etc. Microwave systems, concept of operations, and sintering protocols are being developed to create a sub-element structure targeted for a lunar demonstration mission.

microwave↗

Temporal responsiveness of adipose-derived stem/stromal cell immune plasticity

Highlights: • Adipose-derived stem cells modulate immune responses in a plastic manner. • The persistence of pro- and anti-inflammatory phenotypes was explored over time. • IL-6 was present at all time points; IDO1 was induced after cytokine stimulation. • Phenotypes persisted 96–168 h after returning to control conditions. • Macrophages showed reaction to ASC culture but without time effect. We determined the role of time in adipose-derived stem/stromal cell (ASC) response to a model inflammatory environment. ASCs and other mesenchymal stem/stromal cells exhibit immune plasticity. We evaluated the persistence of pro- and anti-inflammatory phenotypes for ASCs exposed to a sustained or pulse inflammatory stimulus. Using qPCR, flow cytometry, and immunocytochemistry, we monitored the temporal expression and up-regulation patterns of a pro-inflammatory gene (caspase 1), a pleiotropic gene/protein (interleukin 6, IL-6), and an anti-inflammatory gene/protein (indoleamine 2, 3-dioxygenase, IDO1) after exposing ASCs to the cytokines tumor necrosis factor-α and interferon-γ. In response to sustained cytokine stimulation, we discovered that time played a role in the balance of pro- and anti-inflammatory ASC phenotypes. IL-6 was present at all time points for both cytokine-stimulated and non-stimulated conditions, whereas IDO1 was heterogeneously up-regulated in stimulated conditions at later time points. After a pulse stimulus, ASC immunoresponse remained consistent for 96–168 h. As a final measure of immune plasticity, we cultured cytokine-stimulated ASCs with blood-derived macrophages to observe macrophage polarization. While the presence of ASCs altered macrophage phenotype, there was no dependency on the length of ASC cytokine exposure time.

60 APPLIED LIFE SCIENCES↗

Porous materials for hydrogen storage

Hydrogen is a clean energy carrier and a promising candidate to realize carbon-neutral systems for a sustainable future because the combustion of hydrogen produces only water. The large-scale implementation of hydrogen, particularly in zero-emission hydrogen-powered fuel-cell automobiles, requires efficient hydrogen storage systems; however, the current on-board hydrogen storage technologies mainly rely on costly and potentially unsafe high-pressure compression strategies that reach pressures of up to 700 bar. Recently, solid-state porous materials, such as metal-organic frameworks, have emerged as sorbents that can conceivably store comparable amounts of hydrogen in a safer and more efficient manner relative to the current high-pressure storage technologies. Here this review summarizes the current progress on the development of state-of-the-art porous materials and their composites for hydrogen storage. We hope this work will inspire efforts toward creating next-generation hydrogen storage materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Convective Generation of Cirrus Near the Tropopause

The July 2004 CRYSTAL-FACE field program, based from Key West, Florida, showed that long-lived thin tropopause cirrus (TTC) layers were common above thunderstorm anvils. This paper investigates the origins of these cloud using airborne measurements. The horizontal dimensions of the TTC were nearly identical to the convectively formed anvil beneath. However, the TTC did not appear to have originated from convective detrainment. Rather it appears to have formed in stably stratified air derived from high altitudes near the tropopause. The TTC was separated from the anvil by approx. 1 km, it lacked precipitation particles, and it was strongly depleted in HDO. Nonetheless, compared to surrounding clear air near the tropopause, the TTC was enriched in moisture and trace gases in a manner consistent with it having mixed with the same convective airmass that produced the anvil. Unlike surrounding air, the TTC had embedded a monochromatic gravity wave with a wavelength of 2 km and an amplitude of several hundred meters. Combined, this evidence, supported by a photograph from CRYSTAL-FACE, leads to the conjecture that the TTC originated as a pileus cloud layer, which formed near the tropopause ahead of vigorous convective uplift. We hypothesize that the pileus was penetrated by the convection, moistened through mixing, and once the convection subsided, it was sustained by radiative cooling due to the presence of the anvil layer beneath.

Garrett, T. J.↗

Human Systems Integration in the Federal Government

Human Systems Integration principles and methods can be used to help integrate people, technology, and organizations in an effective and efficient manner. Over the past decade, a wide range of tools, techniques, and technologies have been developed by federal agencies to achieve significant cost and performance benefits. In this discussion, we will explore trends in military human systems integration and learn about the critical role being played by human performance and effectiveness research. We will also examine case studies on the planning and design of future human space flight vehicles, the national air space system and the first nuclear reactors to be built in the United States in over 30 years. And with an eye toward sustaining the discipline s principles and methods, we ll take a look at educating and training the next generation of human systems integration practitioners.

Jones, Patricia M.↗

Harnessing autocatalytic reactions in polymerization and depolymerization

Abstract Autocatalysis and its relevance to various polymeric systems are discussed by taking inspiration from biology. A number of research directions related to synthesis, characterization, and multi-scale modeling are discussed in order to harness autocatalytic reactions in a useful manner for different applications ranging from chemical upcycling of polymers (depolymerization and reconstruction after depolymerization), self-generating micelles and vesicles, and polymer membranes. Overall, a concerted effort involving in situ experiments, multi-scale modeling, and machine learning algorithms is proposed to understand the mechanisms of physical and chemical autocatalysis. It is argued that a control of the autocatalytic behavior in polymeric systems can revolutionize areas such as kinetic control of the self-assembly of polymeric materials, synthesis of self-healing and self-immolative polymers, as next generation of materials for a sustainable circular economy. Graphic Abstract

36 MATERIALS SCIENCE↗

Airport Traffic Conflict Detection and Resolution Algorithm Evaluation

A conflict detection and resolution (CD&R) concept for the terminal maneuvering area (TMA) was evaluated in a fast-time batch simulation study at the National Aeronautics and Space Administration (NASA) Langley Research Center. The CD&R concept is being designed to enhance surface situation awareness and provide cockpit alerts of potential conflicts during runway, taxi, and low altitude air-to-air operations. The purpose of the study was to evaluate the performance of aircraft-based CD&R algorithms in the TMA, as a function of surveillance accuracy. This paper gives an overview of the CD&R concept, simulation study, and results. The Next Generation Air Transportation System (NextGen) concept for the year 2025 and beyond envisions the movement of large numbers of people and goods in a safe, efficient, and reliable manner [1]. NextGen will remove many of the constraints in the current air transportation system, support a wider range of operations, and provide an overall system capacity up to three times that of current operating levels. Emerging NextGen operational concepts [2], such as four-dimensional trajectory based airborne and surface operations, equivalent visual operations, and super density arrival and departure operations, require a different approach to air traffic management and as a result, a dramatic shift in the tasks, roles, and responsibilities for the flight deck and air traffic control (ATC) to ensure a safe, sustainable air transportation system.

Jones, Denise R.↗

Effectiveness of Redundant Communications Systems in Maintaining Operational Control of Small Unmanned Aircraft

As a part of NASA’s Unmanned Aircraft System (UAS) Traffic Management (UTM) research, a test was performed to evaluate the effectiveness of the redundant Command and Control (C2) communications system for maintaining operational control of small UAS in the airspace over a rural area. In the test, operators set up a primary and a secondary UAS C2 communications system, sent a maneuver command to an Unmanned Aircraft (UA) with and without a functioning primary system, then verified the execution of the sent command to confirm the operator control. Operators reported that the tested redundancy configurations were effective in maintaining operational control in the test airspace over rural locations. Since the next phase of UTM research focuses on operations in an urban area where an increased level of Radio Frequency (RF) activities occur compared to a rural area, four recommendations are provided to sustain the effectiveness of redundancy in urban operations. First, the operator should not include C2 systems that use the industrial, scientific, and medical (ISM) radio bands in redundancy configurations. Second, the operator should verify the RF characteristics of the intended operation area and examine the area’s radio noise floor. Third, the operator should monitor the availability, quality, and reliability of communications services used by a redundant system. Fourth, the small UAS community should adopt a standard set of contingency steps to handle the loss of C2 communications so that such events are managed in a consistent manner across the airspace. The insights from the test will be used to accommodate the FAA’s UAS integration effort.

Jung, Jaewoo↗

Building Operations Efficiencies into NASA's Ares I Crew Launch Vehicle Design

The U.S. Vision for Space Exploration guides the National Aeronautics and Space Administration s (NASA's) challenging missions that expand humanity s boundaries and open new routes to the space frontier. With the Agency's commitment to complete the International Space Station (ISS) and to retire the venerable Space Shuttle by 2010, the NASA Administrator commissioned the Exploration Systems Architecture Study (ESAS) in mid 2005 to analyze options for safe, simple, cost-efficient launch solutions that could deliver human-rated space transportation capabilities in a timely manner within fixed budget guidelines. The Exploration Launch Projects Office, chartered in October 2005, has been conducting systems engineering studies and business planning over the past few months to successively refine the design configurations and better align vehicle concepts with customer and stakeholder requirements, such as significantly reduced life-cycle costs. As the Agency begins the process of replacing the Shuttle with a new generation of spacecraft destined for missions beyond low-Earth orbit to the Moon and Mars, NASA is designing the follow-on crew and cargo launch systems for maximum operational efficiencies. To sustain the long-term exploration of space, it is imperative to reduce the $4.5 billion NASA typically spends on space transportation each year. This paper gives top-level information about how the follow-on Ares I Crew Launch Vehicle (CLV) is being designed for improved safety and reliability, coupled with reduced operations costs.

Dumbacher, Daniel↗

Building Operations Efficiencies into NASA's Ares I Crew Launch Vehicle Design

The U.S. Vision for Space Exploration guides the National Aeronautics and Space Administration's (NASA's) challenging missions that expand humanity's boundaries and open new routes to the space frontier. With the Agency's commitment to complete the International Space Station (ISS) and to retire the venerable Space Shuttle by 2010, the NASA Administrator commissioned the Exploration Systems Architecture Study (ESAS) in 2005 to analyze options for safe, simple, cost-efficient launch solutions that could deliver human-rated space transportation capabilities in a timely manner within fixed budget guidelines. The Exploration Launch Projects (ELP) Office, chartered by the Constellation Program in October 2005, has been conducting systems engineering studies and business planning to successively refine the design configurations and better align vehicle concepts with customer and stakeholder requirements, such as significantly reduced life-cycle costs. As the Agency begins the process of replacing the Shuttle with a new generation of spacecraft destined for missions beyond low-Earth orbit to the Moon and Mars, NASA is designing the follow-on crew and cargo launch systems for maximum operational efficiencies. To sustain the long-term exploration of space, it is imperative to reduce the $4 billion NASA typically spends on space transportation each year. This paper gives toplevel information about how the follow-on Ares I Crew Launch Vehicle (CLV) is being designed for improved safety and reliability, coupled with reduced operations costs. These methods include carefully developing operational requirements; conducting operability design and analysis; using the latest information technology tools to design and simulate the vehicle; and developing a learning culture across the workforce to ensure a smooth transition between Space Shuttle operations and Ares vehicle development.

Dumbacher, Daniel L.↗

Process intensification education contributes to sustainable development goals. Part 1

In 2015 all the United Nations (UN) member states adopted 17 sustainable development goals (UN-SDG) as part of the 2030 Agenda, which is a 15-year plan to meet ambitious targets to eradicate poverty, protect the environment, and improve the quality of life around the world. Although the global community has progressed, the pace of implementation must accelerate to reach the UN-SDG time-line. For this to happen, professionals, institutions, companies, governments and the general public must become cognizant of the challenges that our world faces and the potential technological solutions at hand, including those provided by chemical engineering. Process intensification (PI) is a recent engineering approach with demonstrated potential to significantly improve process efficiency and safety while reducing cost. It offers opportunities for attaining the UN-SDG goals in a cost-effective and timely manner. However, the pedagogical tools to educate undergraduate, graduate students, and professionals active in the field of PI lack clarity and focus. This paper sets out the state-of-the-art, main discussion points and guidelines for enhanced PI teaching, deliberated by experts in PI with either an academic or industrial background, as well as representatives from government and specialists in pedagogy gathered at the Lorentz Center (Leiden, The Netherlands) in June 2019 with the aim of uniting the efforts on education in PI and produce guidelines. In this Part 1, we discuss the societal and industrial needs for an educational strategy in the framework of PI. The terminology and background information on PI, as it relates to educational implementation in industry and academia, are provided as a preamble to Part 2, which presents practical examples that will help educating on Process Intensification.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Morphology selection in dealloying: A phase field study of the coupling among kinetic mechanisms

A phase field model is used to investigate how the corrosion rate and morphology of a dealloying metal is controlled by the kinetic rates of bulk solid diffusion, interfacial diffusivity, and interface dissolution. A specific focus is investigating the manner by which variations in these kinetic parameters synergistically influence the onset of a morphological instability at the solid-liquid interface, which is known to precede rapid dealloying corrosion towards highly topologically complex structures such as bicontinuous porous solids. This work demonstrates that this instability can be suppressed by either an increase of interdiffusion in the solid alloy, or by a decreasing rate of dissolution at the solid-liquid interface. When the instability is suppressed, the result is a relatively planar, passivated dealloying front. Importantly, however, coupled changes in kinetic parameters can also promote the morphological instability and sustain fine-scale ligament and pore formation. Finally, the relevance of the solid-liquid interfacial diffusion for determining the rate of dealloying and ligament formation is highlighted. By elucidating the mechanistic influence of bulk and interfacial kinetic factors on the dealloyed morphology, this work helps to rationalize the contrasting morphologies observed in various dealloying systems.

Diffusion↗