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Oil and Natural Gas Development near and beneath Uranium Tailings Cells and Other Remediated Sites - 20358

DOE LM is responsible for maintaining remedies at more than 50 remediated sites that require active long-term surveillance and maintenance (LTS and M). Institutional controls (ICs) were established to limit human and environmental exposures to residual contamination by controlling land use, restricting access to potential hazards, and making the public aware of potential dangers from the residual contamination. ICs for each site were developed based on current and foreseeable conditions; however, these controls should evolve to mitigate potential human health and other environmental risks from unanticipated changes in activities or site conditions. Activities conducted beyond the DOE long-term care boundaries by non-DOE parties may impact the effectiveness of ICs or even the long-term stability of disposal cells and groundwater remedies. Several sites that LM manages or that will transfer to LM for LTS and M are in active oil and gas production basins. The sites are associated with uranium ore milling or nuclear test sites and have been remediated or are in the process of remediation and have no ongoing DOE mission. Particularly since 2005, hydraulic fracturing ('fracking') combined with directional drilling has dramatically increased oil and natural gas (oil/gas) production in the United States, now making it the number one hydrocarbon-producing country. Fracking has allowed production from shale and other rocks of low natural permeability that were historically not considered viable oil/gas resources. Also, because wellbores can now be drilled as many as 5 kilometers or more horizontally, hydrocarbons can be recovered from zones without having access to the surface above them. Drilling activity near Rulison, Colorado, the location of an underground nuclear detonation managed by LM, has raised public concerns that remnant radioactivity in the detonation zone could migrate to producing wells and enter the natural gas distribution system. At sites like the Falls City, Texas, Disposal site, transitioned to LM with a split estate, increased production in the region has resulted in wellbores beneath the long-term care boundary of the site. While the DOE license for Falls City was approved by the NRC in 1997 without the acquisition of the subsurface rights, NRC has raised concerns on whether this activity impacts the integrity of the cell and/or groundwater remedies. In Wyoming, LM is anticipating receiving the license for the Bear Creek site and manages the Spook site, both locations of uranium mill tailings disposal cells. These Wyoming sites are in an active region of major oil and gas development. This change in surrounding land use will require LM to work collaboratively with NRC to address these concerns. At several DOE sites radioactive waste, and often intermixed nonradioactive constituents, is permanently isolated in engineered disposal cells. At other sites, residual contamination can be present in groundwater, blast cavities, and infinite amounts within soil. Areas targeted for oil and gas development at the Texas and Wyoming sites range from depths of 2440 to 3350 meters (8000-11000 feet) below ground surface. When most site remedies were designed, oil and gas development was not considered to be an issue within the site boundary. With the more recent uses of directional drilling, fracking, and associated wastewater injections, the evaluative criteria for incoming sites and ICs for managing long-term protectiveness and regulatory compliance are changing. Although DOE surface ownership was previously thought to be a robust IC to prevent surface and subsurface development, particularly at disposal sites, that may no longer be the case. Whereas the subsurface development at Texas and Wyoming sites is currently occurring at thousands of meters beneath the surface, shallower and direct onsite development would be more of a concern for LM. The energy introduced when a well is hydraulically fractured causes microseismic events (magnitude -2 to 1.0) as the fractures propagate but does not directly cause seismic events (earthquakes) of sufficient magnitude to damage surface structures. Additionally, the extent of the hydraulic fractures is limited to the targeted depths, which are far below the surface. However, earthquakes of sufficient magnitude to damage surface structures have been attributed to the injection of wastewater into disposal wells. States that have experienced these effects have enacted regulations that limit the rate and pressures that wastewater can be injected into disposal wells. Items LM may consider are the need for monitoring the volume of water injected into nearby disposal wells and possibly installing seismic stations at sites most susceptible to damage. While the need to demonstrate that no impact from oil and gas extraction activities on a site groundwater remedy or disposal cells will vary from site to site, LM is assessing risk criteria for this activity. Though LM has not experienced an issue yet at a uranium tailings disposal site, it cannot assume that there will be none, and must address NRC concerns. LM is building on past experiences at other sites and beginning to form new processes with the hope that these concepts can be applied for other future sites. (authors)

04 OIL SHALES AND TAR SANDS↗

Uranium Mill Tailings Radiation Control Act Title II DOE Due Diligence and Lessons Learned from a Previous Site Transfer - 20352

Title II of the Uranium Mill Tailings Radiation Control Act (UMTRCA) established that a government agency will provide perpetual care for closed uranium and thorium ore-processing sites that were operating under an NRC source material license in 1978 or were licensed thereafter. Commercial owners (licensees) operating under an NRC or agreement state specific license when UMTRCA was passed are responsible for conducting reclamation of any byproduct material remaining from uranium-ore processing operations in accordance with an NRC or agreement state approved reclamation plan. Reclamation includes both surface and groundwater remedies. Upon completion of reclamation and approval by NRC, the site is required to be transferred to either the host state or the DOE for long-term surveillance and maintenance. Since UMTRCA's enactment, six Title II sites have been transferred to DOE; an additional 24 Title II sites are anticipated to be transferred before 2050. DoE's role mandated under UMTRCA Title II as the long-term care custodian is to perform 'monitoring, maintenance, and emergency measures necessary to protect the public health and safety.' UMTRCA requires that the licensee pay a long-term surveillance charge 'sufficient to cover the annual costs of site surveillance.' However, at some sites such as the Bluewater, New Mexico, Disposal Site, this mandate has required additional effort and expense by DOE, beyond the originally anticipated and intended scope within UMTRCA, but within the authority of DOE under UMTRCA. In 1997, the Bluewater site became the second UMTRCA Title II site to be transferred to DOE. The site was the location of a uranium mill operated from 1953 until 1982. The specific licensee began site reclamation in 1991, and by 1995 all tailings and contaminated materials were encapsulated in two tailings disposal cells and other disposal areas. In addition to surface contamination, milling activities impacted groundwater in the two upper aquifers. In 1989, the specific licensee attempted active groundwater remediation; however, no significant reduction in contaminant concentrations was observed. As a result, the specific licensee applied to NRC for alternate concentration limits (ACLs) in 1990, which were approved in 1996 as being protective, after additional corrective actions were performed. Since transfer of the Bluewater site to DOE, unforeseen challenges have occurred, requiring additional actions. The first challenge is the occurrence of surface depressions located on the northern section of the main tailings disposal cell. The depressions were first observed during DoE's initial inspection in 1998; however, evidence of these can be observed on satellite images taken prior to transfer. Since being first observed, the depressions have continued to grow both in depth and areal extent. Due to the design of the main tailings disposal cell, the depressions impede storm water from being effectively shed off the 101- hectare (250-acre) top slope of the main tailings disposal cell. Instead, storm water accumulates in the depressions, forming a large ephemeral pond that has stored up to 16.3 x 10{sup 6} liters (4.3 million gallons) of stormwater. The ponding poses a potential risk to the integrity of the main tailings disposal cell in the case of a large storm event, with the potential to cause the pond to overtop and erode the cover material and underlying waste. DOE has taken a number of short-term actions to monitor, measure, and reduce the ponding and is currently working with the US Army Corps of Engineers to design and construct a repair. Additional challenges are associated with groundwater at the Bluewater site. Nine wells were present on the 1335-hectare (3300-acre) site upon transfer. Groundwater compliance was called into question after the State of New Mexico reduced its uranium groundwater standard from 5.0 to 0.03 milligrams per liter in 2004, and when an ACL for uranium was exceeded in a site monitoring well in 2010. Acquiring historical groundwater data and subsequent evaluations as well as additional DOE groundwater monitoring led to installing 10 new monitoring wells and performing additional site hydrogeology recharacterization. DOE continues to evaluate groundwater conditions at the site and works with the NRC to determine regulatory requirements and a path forward. As a result of lessons learned at the Bluewater site and other Title II sites, improved processes have been implemented at a programmatic level to increase due diligence before site transfer and prevent similar issues from occurring at other UMTRCA Title II sites under long-term management. DoE's due diligence process is documented in the Process for Transition of UMTRCA Title II Disposal Sites to DOE for Long-Term Surveillance and Maintenance and is designed to ensure that DOE has no technical or compliance concerns with regulatory decisions that might compromise protectiveness following site transfer to DOE. Implementation of the due diligence process has increased DoE's role prior to site transfer and has been effective in identifying potential issues. Actions by NRC and specific licensees, in response to enhanced due diligence efforts by DOE, are expected to minimize, if not totally prevent, the need for unanticipated actions by DOE pertaining to the surface and groundwater remedies after site transfer. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Photocatalytic Oxidation of Dissolved Mn 2+ by TiO 2 and the Formation of Tunnel Structured Manganese Oxides

The redox reaction of manganese (Mn) is of great environmental, geological, and public health significance, as Mn oxides control the distribution and electron flow of numerous nutrients and contaminants in natural and engineered environments. Current understanding on the oxidation pathways of Mn(II) to Mn(III/IV) mainly focuses on biotic processes due to their much higher oxidation rates than those of abiotic processes. This study demonstrates rapid photocatalytic oxidation of Mn 2+ (aq) under circumneutral conditions catalyzed by naturally abundant semiconducting TiO 2 minerals. Notably, the photocatalytic oxidation rates are comparable to or even higher than those of reported biotic/abiotic processes. In addition, the rapid photocatalytic oxidation leads to the formation of large tunnel structured Mn oxides (todorokite and romanechite) on the surface of TiO 2 . These findings suggest that photocatalytic oxidation of Mn 2+ (aq) by natural semiconducting minerals is likely an important yet previously overlooked pathway for understanding the occurrence of natural Mn oxide coatings on rock surfaces. In addition, considering the increasing input of photoreactive engineered nanoparticles into environmental systems, this work shows the potential impacts of nanoparticles on influencing natural redox cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion Generation Using Frozen Xenon Target for Laser Ion Source

A frozen laser target that is in the gaseous phase at room temperature is advantageous for a laser ion source because it can avoid the accumulation of damage from laser irradiation by regeneration of the target surface by additional gas freezing. In this study, the possibility of forming a xenon ion beam with a current sufficient for heavy-ion inertial fusion (HIF) was investigated. The relationship between the frozen target growth and resulting ion current was analyzed to determine the optimal condition of laser irradiation that ensures stable supply of ion beams for a long time. A frozen target of xenon was formed on a mount cooled to 20 K using a Gifford McMahon cryocooler, and plasma was generated using a Nd:YAG laser. Here, the results showed that it is possible to supply a sufficient ion current for application of singly charged ions as a driver for HIF. Additionally, it was indicated that the xenon responsible for forming the plasma existed only at a certain depth from the target surface. The results imply that it is possible to obtain a stable ion supply for a long time by irradiating the target with a laser after the frozen xenon grows to a sufficient thickness.

43 PARTICLE ACCELERATORS↗

Do Melamine and Melamine-Formaldehyde Surface Modifiers Improve Fuel Cell Activity and Durability?

Precious group metal-based catalysts based on Pt- and Pt-alloys are currently used as catalysts for the kinetically sluggish Oxygen Reduction Reaction (ORR) on the cathode of fuel cells. The activity of Pt or Pt-alloy catalysts towards ORR is severely compromised by the adsorption of spectator-species such as sulfonate anions from perfluorosulfonic acid (PFSA) ionomer or Pt-O(H) ad via water activation. Considering recent evidence pointing to the improvement in ORR activity via the use of melamine organic molecule or melamine-formaldehyde copolymeric additives as surface blocking agents for the prevention of sulfonate or Pt-OH ad adsorption, we evaluated these additives in fuel cells. The catalysts were modified with either of these additives and characterized using ex situ and in situ methods to verify successful adsorption and eventual performance in fuel cells. These surface modifying agents were found to suppress Pt-OH ad formation as well as suppress ORR activity. There was no evidence to point out that these additives improved ORR activity and H 2 /air polarization performance in a fuel cell MEA on supported, polycrystalline Pt catalyst.

08 HYDROGEN↗

Image-Based Fracture Surface Defect Characterization Methods for Additively Manufactured Ti-6Al-4V Tested in Fatigue

Abstract Fatigue initiation in additively manufactured samples/parts often occurs at processed-induced defects such as lack-of-fusion (LoF), keyhole, or other morphological/microstructural defects that have unique characteristics and measurable qualities. Attempts at identifying and minimizing such defects have utilized optimized processing conditions along with in situ and ex situ characterization that includes metallography and/or X-ray computed tomography (XCT). This paper highlights the benefits of using fracture surface analyses to detect and quantify defects that may not be detected by metallography/XCT due to sectioning and resolution limits. In addition to using manual quantification of fatigue initiating LoF and keyhole defects on fracture surfaces, image-based machine learning using convolutional neural networks such as U-Net were also used to automate the process. Statistical analyses were used to identify the extreme cases of defects that initiated and accelerated fatigue and to model the distribution of defect size and shape characteristics to distinguish the type of defect. Initial results show agreement between trained machine learning models and ground truth data in defect segmentation, and the distributions of defect characteristics are distinguishable to particular process-induced defect types.

Materials Science↗

System, method, and computer program for creating an internal conforming structure

A system for creating an internal formation of a tubular structure having an inner surface via additive manufacturing. The system broadly includes a computer modeling system and an additive manufacturing system. The computer modeling system may include a processor for generating a lattice cellular component via computer-aided design software according to inputs received from a user. The processor may also generate an internal formation lattice structure based on the lattice cellular component and modify the lattice structure to follow and/or conform to the curvature of the inner surface of the outer wall of the tubular structure. The additive manufacturing system may be configured to produce the lattice structure and the tubular structure via additive manufacturing material deposited layer by layer according to the lattice structure.

42 ENGINEERING↗

Multiscale Cryo Electron Microscopy Reveals Interfacial Degradation and Stabilization in Battery Electrodes

Electrochemical interfaces are dynamic systems, evolving based on their local environment and reactant surface structures. The electrode-electrolyte interface in Li-ion batteries can be protective, limiting parasitic reactions with the electrolyte to passivate the surface [1]. Additionally, this interphase has an impact on the Li-ion transport through that layer based on its composition, bonding environment, and thickness. These parameters are challenging to collect and may vary depending on the electrode surface site investigated relative to its spatial position in a coin cell. This study will detail a multiscale cryogenic electron microscopy approach where millimeter-scale cross-sections through the coin cell batteries were made using a cryogenic stage within a fs-laser plasma focused ion beam (laser PFIB) with complementary energy dispersive X-ray spectroscopy able to detect variations in the composition at electrode interfaces [2]. Microscale cross-sectioning and lamella sample preparation of battery electrodes was conducted at the Center for Integrated Nanotechnologies using a Ga-ion focused ion beam (FIB) with air-free and cryo-transfer [3], followed by nanoscale mapping of composition and bonding within the CEI through cryo-scanning transmission electron microscopy (cryo-STEM) electron energy loss spectroscopy [4]. This multiscale approach enabled identification of millimeter-scale features of a battery stack with visualization of degradation in electrodes such as cracks in cathode particles, gas evolution, and SEI evolution; microscale interfacial characteristics, such as heterogeneity in the SEI or barrier layer and identification of electrolyte networks to the electrode surfaces; and nanoscale measurement of the CEI thickness, mapping of transition metal bonding within the cathode particles to identify loss of active materials, and identification of beneficial electrolyte additives incorporated into the CEI structure. This multiscale approach allows for a statistical understanding of the primary mechanisms and parasitic degradation pathways that impact performance by limiting the ion transport pathways within Li+ batteries.

36 MATERIALS SCIENCE↗

Exceptional Mineral Scaling Resistance from the Surface Gas Layer: Impacts of Surface Wetting Properties and the Gas Layer Charging Mechanism

Mineral scaling is a phenomenon that occurs on submerged surfaces in contact with saline solutions. In membrane desalination, heat exchangers, and marine structures, mineral scaling reduces process efficiency and eventually leads to process failure. Therefore, achieving long-term scaling resistance is beneficial to enhancing process performance and reducing operating and maintenance costs. While evidence shows that superhydrophobic surfaces may reduce mineral scaling kinetics, prolonged scaling resistance is limited due to the finite stability of the entrained gas layer present in a Cassie–Baxter wetting state. Additionally, superhydrophobic surfaces are not always feasible for all applications, but strategies for long-term scaling resistance with smooth or even hydrophilic surfaces are often overlooked. In this study, we elucidate the role of interfacial nanobubbles on the scaling kinetics of submerged surfaces of varied wetting properties, including those that do not entrain a gas layer. We show that both solution conditions and surface wetting properties that promote interfacial bubble formation enhances scaling resistance. In the absence of interfacial bubbles, scaling kinetics decrease as surface energy decreases, while the presence of bulk nanobubbles enhances the scaling resistance of the surface with any wetting property. The findings in this study allude to scaling mitigation strategies that are enabled by solution and surface properties that promote the formation and stability of interfacial gas layers and provide insights to surface and process design for greater scaling resistance.

calcite↗

Characteristics and mechanisms of hydrogen-induced quasi-cleavage fracture of lath martensitic steel

Here this study presents an in-depth characterization of the microstructures, crystallographic orientations, and dislocation characteristics beneath hydrogen-induced quasi-cleavage fracture features of an as-quenched, lath martensitic (α') 22MnB5 steel. The fracture surfaces of gaseous hydrogen-embrittled martensitic specimens were analyzed by a combination of multiple analytical tools: scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), transmission electron microscopy (TEM), and transmission Kikuchi diffraction (TKD). The dominant fracture mode in the hydrogen-affected zones was quasi-cleavage fracture, which involved significant plasticity, evidenced by plastic zones near tear ridges and a high density of dislocations beneath the quasi-cleavage facets. The martensite constituent sizes, variant orientations, and boundaries influenced the quasi-cleavage surface morphologies. Fractography revealed the occurrence of {100} α' -type cleavage across martensitic laths, developing relatively “flat” quasi-cleavage surfaces, in addition to {110} α' -type cracking likely along lath and block boundaries, and fracture along non-cleavage planes. The likelihood of the formation of the relatively “flat” quasi-cleavage surfaces increased with increasing martensitic constituent sizes. Substantial dislocation bands formed on intersecting {112} α' slip planes within a martensite block below the hydrogen-induced cleavage fractures on {100} α' planes. River markings on the quasi-cleavage surfaces were found to originate from the complex, hierarchical lath martensitic microstructure. Steps and ridges on the quasi-cleavage facets generally linked with the various martensitic boundaries, suggesting that they were produced as a result of crack deviations at those boundaries. The fracture paths and martensite quasi-cleavage mechanisms are discussed in the context of the role of hydrogen and Cottrell cleavage model.

36 MATERIALS SCIENCE↗

Corrosion characteristics of Mo and TZM alloy for plasma facing components in molten lithium at 623 K

Here, in this study, the corrosion behaviours of molybdenum (Mo) and a Mo-based alloy (TZM) were investigated using a static immersion corrosion technique. Weight loss, surface microstructure, and corrosion depth of Mo and the TZM alloy were correlated with elements. The compatibility of Mo and the TZM alloy in static liquid Li was suitable. Mo demonstrated uniform corrosion with a homogenous dissolution of free C and Mo, and TZM alloy exhibited a nonuniform corrosion behaviour with a preferential grain boundary attack caused by the selective dissolution of free C, Ti, and Zr. When the surface oxidation layer of the samples was consumed, free C from Mo and TZM diffused into molten Li to form Li 2 C 2 and then was captured by Zr, Ti, and Mo to form thermodynamically stable carbides, which resulted in the enrichment of the C layer near the sample surfaces. In addition, Ti and Zr acted as N-trappers in liquid Li; the formation of Zr and Ti nitrides resulted in the enrichment of N, Ti, and Zr elements on the surface and led to TZM corrosion increase. Thus, Zr and Ti depletion, pitting, and grain boundary corrosion were problematic for TZM under long-term exposure to liquid Li. Reducing the content of free C and nonmetallic N and increasing the amount of Ti and Zr carbides on the surface of and inside the raw TZM alloy helped improve the corrosion resistance of TZM in liquid Li.

36 MATERIALS SCIENCE↗

High-throughput surface characterization to identify porosity defects in additively manufactured 316L stainless steel

In the present study, a high throughput (HT) methodology is applied to rapidly assess the surface characteristics of 83 additively manufactured 316L stainless steel. The variation in surface roughness (S a ) showed a good correlation with a dimensionless number (π) and provided direct linkages to the internal porosity defects. Lack-of-fusion regime relates to high surface roughness (S a > 5 µm), low dimensionless number (π < 61), and the presence of cavities in between the melt pool tracks. Balling regime correlates to high surface roughness (S a > 5 µm), intermediate dimensionless number (61 < π < 146), and non-uniform melt pool track width. Keyhole regime shows low surface roughness (S a < 5 µm), high dimensionless number (π > 146), and a curved melt pool track. This approach accelerates the process parameter discovery and minimizes the porosity defects for the LPBF process. The impact of the defects on the as-processed tensile mechanical properties demonstrates that samples with porosity exhibit up to 10% less tensile strength and 30% less ductility than optimal samples.

316L stainless steel↗

Enhancing fatigue life of aluminum alloy castings through cavitation water jet peening: Experiments and simulations

This study presents an investigation into the enhancement of the fatigue life of aluminum castings through the application of cavitation water-jet peening (CWJP). CWJP harnesses the impacts of water cavitation to induce surface compressive residual stress within metallic materials. In this work, CWJP was applied to a high pressure die-cast (HPDC) Al–Si alloy A380 with three different water-jet traverse velocities. The fatigue-life improvement, evaluated in a 4-point bending configuration (stress ratio R = 0.1), was found to vary with applied stress level and ranges from 1.6 to 10 times that of the parent alloy. The data also shows that decreasing the traverse velocity results in greater compressive residual stresses within the surface layer and a concurrent increase in surface roughness. This residual stress layer extends to a depth of 400 μm below the surface, as confirmed by through-thickness residual stress and microhardness measurements. CWJP treatment effectively slows down fatigue crack propagation, as evidenced by microstructural observations of narrower striation spacing. Simulations reveal that compressive residual stresses, in addition to surface hardening during CWJP, are key to improving fatigue life. A 20% increase in surface hardness and 150 MPa compressive residual stress imposed by CWJP process provides an average 5-fold enhancement of fatigue life across different stress levels. This study demonstrates the potential of CWJP as an effective surface treatment to enhance the fatigue life of aluminum castings, such as HPDC components for automotive applications.

Al casting↗

Formation and fate of freshwater on an ice floe in the Central Arctic

The melt of snow and sea ice during the Arctic summer is a significant source of relatively fresh meltwater. The fate of this freshwater, whether in surface melt ponds or thin layers underneath the ice and in leads, impacts atmosphere–ice–ocean interactions and their subsequent coupled evolution. Here, we combine analyses of datasets from the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition (June–July 2020) for a process study on the formation and fate of sea ice freshwater on ice floes in the Central Arctic. Our freshwater budget analyses suggest that a relatively high fraction (58 %) is derived from surface melt. Additionally, the contribution from stored precipitation (snowmelt) outweighs by 5 times the input from in situ summer precipitation (rain). The magnitude and rate of local meltwater production are remarkably similar to those observed on the prior Surface Heat Budget of the Arctic Ocean (SHEBA) campaign, where the cumulative summer freshwater production totaled around 1 m during both. A relatively small fraction (10 %) of freshwater from melt remains in ponds, which is higher on more deformed second-year ice (SYI) compared to first-year ice (FYI) later in the summer. Most meltwater drains laterally and vertically, with vertical drainage enabling storage of freshwater internally in the ice by freshening brine channels. In the upper ocean, freshwater can accumulate in transient meltwater layers on the order of 0.1 to 1 m thick in leads and under the ice. The presence of such layers substantially impacts the coupled system by reducing bottom melt and allowing false bottom growth; reducing heat, nutrient, and gas exchange; and influencing ecosystem productivity. Regardless, the majority fraction of freshwater from melt is inferred to be ultimately incorporated into the upper ocean (75 %) or stored internally in the ice (14 %). Terms such as the annual sea ice freshwater production and meltwater storage in ponds could be used in future work as diagnostics for global climate and process models. For example, the range of values from the CESM2 climate model roughly encapsulate the observed total freshwater production, while storage in melt ponds is underestimated by about 50 %, suggesting pond drainage terms as a key process for investigation.

54 ENVIRONMENTAL SCIENCES↗

Developing Accelerated Test Protocols and Tuning Microstructures of the Common Materials to Improve Robustness, Reliability, and Endurance of SOFC Cells

This work is built on our prior work where we found that phase transformation in praseodymium nickelates, e.g. Pr 2 NiO 4 (PNO) and (Pr 1-x Nd x ) 2 NiO 4 (PNNO), can be electrochemically driven, and is substantially faster when compared to thermal annealing studies. The first task aims at an attempt to further accelerate the phase transformation in the oxygen electrode by alternating the current input in the cells, which lead to the development of accelerated test protocols (ATPs). ATPs showed up to 60x faster phase transformation and up to 10x faster performance degradation in (Pr 0.50 Nd 0.50 ) 2 NiO 4 electrodes, when compared to long-term operation under constant current density. Furthermore, the phase stable Nd 2 NiO 4 and (La 0.6 Sr 0.4 )(Co 0.8 Fe 0.2 )O 3 (LSCF6482) electrodes were tested in full cells under ATPs, and showed up to 10x faster performance degradation within 1,100 hours in a comparison with long-term thermal annealing studies and electrochemical operation under constant current density. The second task aims at the quantification of the contributions of cell components to the total impedance of a solid oxide fuel cell (SOFC) using electrochemical impedance spectroscopy (EIS) and distribution of relaxation times (DRT). Specifically, the role of gas composition at both anode and cathode was systematically studied, aiming at deconvoluting, identifying and quantifying the contributions of different electrode processes. This was achieved by first tuning the partial pressure of H 2 at the anode and subsequently varying the partial pressure of O 2 at the cathode. The results suggest that, while DRT offers a viable way of deconvoluting different times distributions, additional attention is needed before assigning a peak to a specific electrode process due to the significant overlap of the contributions from the cathode and the anode. Density function theory studies show that both Pr-vacancies and O-defects play a key role on the activity and stability for nickelates towards oxygen reduction reaction. The resident O-interstitials and oxygen ions in the PrO layer form peroxide (O 2 2- ) nearby Pr vacancies. The O 2 2- limits oxygen-ion transport due to the required additional energy to break its O-O bond. We further calculated the formation and segregation energies for different Ln ions (La, Pr, Nd, Pm, Sm, Gd, Tb, Dy, and Ho) in PNO and CeO 2 (111) surfaces. In addition to Nd, Pm and La are suggested as potential dopants in PNO to enhance it stability without decomposition due to their more negative formation energies, lower diffusion energies, and positive separation energies.

01 COAL, LIGNITE, AND PEAT↗

Quantitatively accounting for the effects of surface topography on the oxidation kinetics of additive manufactured Hastelloy X processed by electron beam melting

In this work, the effects of surface roughness on the high-temperature corrosion of nickel-based superalloy X produced through electron-beam melting (EBM) additive manufacturing were studied. Surface area of samples in the rough, as-fabricated condition was measured using a 2D cross-section image analysis technique and a 3D image analysis technique. To verify the accuracy of surface area measurements, oxidation testing of samples in the as-fabricated and polished conditions was performed; polished sample oxidation curves were then compared to the as-fabricated sample oxidation curves before and after being adjusted using obtained surface area measurements. It was found that the 2D technique accurately measured surface area and accounted for the overlapping features present on EBM sample surfaces, whereas the 3D technique did not. Further, it was also observed that oxidation kinetics were moderately faster on the alloy X samples in the as-fabricated condition than for the polished condition.

36 MATERIALS SCIENCE↗

Evidence for anti-synergism between ion-assisted etching and in-plasma photoassisted etching of silicon in a high-density chlorine plasma

Etching of p-Si in 60 mTorr 10%Cl2/90%Ar Faraday-shielded inductively coupled high density plasmas was investigated under both ionassisted etching (IAE) and photoassisted etching (PAE) conditions. Real-time etching rates and after-etching Si surface chemical compositions were obtained by laser interferometry and vacuum-transfer x-ray photoelectron spectroscopy (XPS), respectively. Precisely controlled ion energy distributions (IEDs) were generated by applying pulsed negative DC bias on the conductive sample stage. Above a 36 eV threshold at a total flow rate of 250 SCCM, the IAE rate increased with the square root of the ion energy. In contrast to the DC bias, etching under RF bias did not exhibit a threshold ion energy because of the wide IED. XPS spectra revealed that the surface layer under PAE conditions had a significantly lower chlorine content, composed of only SiCl. Under IAE conditions, however, silicon dangling bonds (Si•), SiCl 2 , and SiCl 3 were found on the surface, in addition to SiCl, with a relative abundance of SiCl > SiCl 2 , and SiCl 3 . The absence of higher chlorides and Si• under PAE conditions suggested that vacuum ultraviolet photons and above threshold-energy ions interact with the surface very differently. By varying the duty cycle of the pulsed DC bias, it was found that the IAE rate scaled with the energetic ion dose, but only for low duty cycles. For higher duty cycles, the apparent IAE yield fell off with an increasing Cl coverage on the surface, as the duty cycle went up, which pointed to a negative synergy (antisynergism) between PAE and IAE as the explanation. This antisynergism was further supported by the observed decrease of the total etching rate with an increasing period of the pulsed DC bias. A plausible mechanism is that increasing the pulsing period causes more near-surface damage, creating more recombination centers that lead to a higher loss rate of electron-hole pairs through recombination, thereby reducing the PAE rate.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Pulsed Light Synthesis of High Entropy Nanocatalysts with Enhanced Catalytic Activity and Prolonged Stability for Oxygen Evolution Reaction

The ability to synthesize compositionally complex nanostructures rapidly is a key to high-throughput functional materials discovery. In addition to being time-consuming, a majority of conventional materials synthesis processes closely follow thermodynamics equilibria, which limit the discovery of new classes of metastable phases such as high entropy oxides (HEO). Herein, a photonic flash synthesis of HEO nanoparticles at timescales of milliseconds is demonstrated. By leveraging the abrupt heating and cooling cycles induced by a high-power-density xenon pulsed light, mixed transition metal salt precursors undergo rapid chemical transformations. Hence, nanoparticles form within milliseconds with a strong affinity to bind to the carbon substrate. Oxygen evolution reaction (OER) activity measurements of the synthesized nanoparticles demonstrate two orders of magnitude prolonged stability at high current densities, without noticeable decay in performance, compared to commercial IrO 2 catalyst. This superior catalytic activity originates from the synergistic effect of different alloying elements mixed at a high entropic state. It is found that Cr addition influences surface activity the most by promoting higher oxidation states, favoring optimal interaction with OER intermediates. The proposed high-throughput method opens new pathways toward developing next-generation functional materials for various electronics, sensing, and environmental applications, in addition to renewable energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗