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At least 343 records · Page 19

Effect of Catalyst and Catalyst Layer Composition on Catalyst Support Durability

Polymer electrolyte membrane fuel cells (PEMFCs) are efficient, zero-emission engines for the automotive sector. However, cost and durability are major barriers for the commercialization of PEMFCs. Degradation of the carbon support in the cathode catalyst layer due to high potential excursions caused by unmitigated events like H 2 starvation, or start-up/shutdown are still a major durability issue in PEMFCs. Catalyst support durability was studied by accelerated stress tests (ASTs) that included repeated potential cycling from 1.0 to 1.5 V. The effect of catalyst layer composition on carbon corrosion was studied using membrane electrode assemblies with different catalysts (Pt, PtCo), catalyst composition (catalyst wt.%, supports), ionomer composition (loading, and equivalent weights). The corrosion of the carbon support is similar between Pt and PtCo catalysts. However, the performance degradation rate is higher for the alloy catalysts due to differences in catalyst particle size and the transition metal’s leaching accelerating the performance degradation. The carbon loss is lower for catalysts with lower initial carbon loading (or higher catalyst wt.%), which is better for durability. However, the cumulative loss of carbon is identical for electrodes with the same catalyst support irrespective of catalyst and ionomer composition in the catalyst layer.

25 ENERGY STORAGE↗

Quasi-Distributed Fiber Sensor-Based Approach for Pipeline Health Monitoring: Generating and Analyzing Physics-Based Simulation Datasets for Classification

This study presents a framework for detecting mechanical damage in pipelines, focusing on generating simulated data and sampling to emulate distributed acoustic sensing (DAS) system responses. The workflow transforms simulated ultrasonic guided wave (UGW) responses into DAS or quasi-DAS system responses to create a physically robust dataset for pipeline event classification, including welds, clips, and corrosion defects. This investigation examines the effects of sensing systems and noise on classification performance, emphasizing the importance of selecting the appropriate sensing system for a specific application. The framework shows the robustness of different sensor number deployments to experimentally relevant noise levels, demonstrating its applicability in real-world scenarios where noise is present. Overall, this study contributes to the development of a more reliable and effective method for detecting mechanical damage to pipelines by emphasizing the generation and utilization of simulated DAS system responses for pipeline classification efforts. The results on the effects of sensing systems and noise on classification performance further enhance the robustness and reliability of the framework.

36 MATERIALS SCIENCE↗

Experimental Operation of a Prototype 750C Advanced Chloride Molten Salt Bellows Valve

To achieve DOE 2030 SunShot targets that reduce the cost of liquid-based solar by an additional 40% to 70% beyond 2018 costs, a more reliable, highly manufacturable flow valve, capable of achieving operational temperatures of >700°C is required [1]. This paper investigates the development of an innovative high-temperature chloride molten salt valve, with operation up to 750°C. This valve is intended to be employed within Gen 3 CSP liquid-based thermal energy storage (TES) systems as well as Gen 4 modular salt reactor (MSR) technologies. This work details the general design and flow testing of a bellows-seal flow control valve (FCV). This design includes an integrated closed-loop thermal control system to ensure robust design for freeze-thaw cycles. The self-contained thermal management STM system, is unique in the salt valve industry since it is an integrated solution to provide a consistent, repeatable alternative to typical heat tracing. Additionally, the design includes the employment of a novel heat pipe valve stem to facilitate enhanced passive thermal management into the valve assembly. This valve stem heat pipe is designed to facilitate natural circulation within the bonnet to ensure robust operation, during both nominal and transient thermal operation. The valve body and trim will be designed using SS316H, consistent with Flowserve Corporation’s existing product base and is code qualified but will utilize clad material for materials corrosion, manufacturing cost reduction and compatibility to ensure design flexibility. A test campaign was performed in this investigation utilizing a novel 750°C ternary chloride (20%NaCl/40%MgCl2/40%KCl by mol. wt. %) molten salt flow loop. A discussion about the design and installation of the valves within this test bed is provided for this investigation. Valve test results from this study assessed Cv curves as well as multiple actuator cycles, under varying thermodynamic and operational mode conditions, which would be characteristic within a commercial molten salt facility. The results indicate nominal operation for the baseline design, though improved performance and reliability is expected with the full designed FCV.

Armijo, Kenneth (ORCID:0000000346832147)↗

Electrochemical corrosion of multiphase stainless steel-based alloy nuclear waste forms

Abstract The electrochemical corrosion behaviors of two multiphase alloys representing waste forms made with 316 L stainless steel and different amounts of surrogate metallic fuel wastes were measured and related to the microstructures. Potentiodynamic (PD) scans were performed in an acid brine solution and the corroded surfaces were characterized with scanning electron microscopy (SEM) to compare the electrochemical responses to the corrosion of specific phases. PD scans for the two multiphase alloys, 316 L stainless steel, and pure palladium were compared to understand the complex corrosion behavior of these multiphase alloys also recently classified as multi principle element alloys (MPEAs) and to determine the effects of alloying elements and noble metals present in constituent phases on the corrosion behavior.

Gattu, Vineeth Kumar (ORCID:0000000307265813)↗

Atmospheric Cold Plasma Jet Coating and Surface Treatment for Improved Adhesive Bonding Performance of Dissimilar Material Joints Subject to Harsh Environmental Exposure

The program goal was the development and demonstration of a novel material coating system using an innovative atmospheric cold microwave plasma jet to enable surface functionalization for corrosion protection, wear resistance and improved bonding strength. The technical approach was directed towards proof-of-concept demonstration of advanced point-of-manufacturing material bonding to improve adhesive joint performance subject to harsh environmental exposure. The assembled team, consisting of the researchers at the University of Illinois, end-users at General Motors and small business manufacturer Starfire Industries, successfully demonstrated a single, cost-effective, high-volume production process that meets the requirements of multi-material combinations relevant to the energy-intensive transportation industry (e.g. Al-steel, Mg-steel, Al-Mg and Al-CFRP joints for body-in-white structures) while eliminating offline pretreatment for Al and Mg alloy substrates that are energy intensive, have chemical waste disposal issues, and add cost. Technical demonstration of dissimilar material joining while maintaining bonding strength and cohesion after long-duration environmental exposure was accomplished for all materials of interest. This novel approach has broad applicability for manufacturing in automotive, aerospace, marine, railcar, and specialty consumer goods, etc.

36 MATERIALS SCIENCE↗

Microstructural, Corrosion and Mechanical Characterization of Friction-Stir Welded Joints Between Aluminum and Magnesium Alloys

Friction Stir Welding (FSW) of Aluminum-Magnesium (Al-Mg) alloys has garnered increasing attention due to its wide-ranging applications in the automotive and aerospace industries. The microstructural, corrosion, and mechanical properties of FSW Al-Mg welds under selected conditions are critical factors that must be well-investigated to ensure their durability and performance. In this study, electrochemical tests, including Open Circuit Potential (OCP), Linear Polarization Resistance (LPR), Potentiodynamic Polarization Scan (PD), and Electrochemical Impedance Spectroscopy (EIS), have been used to analyze the corrosion resistance of these welds, along with weight loss measurements through cyclic corrosion testing (CCT) and surface evolution via SEM over an 8-week period. Mechanical properties are evaluated through microindentation, nanoindentation, fatigue, and lap-shear tests. The results of the electrochemical tests reveal that the corrosion properties of the center weld zone differ from those of the two base alloys. Indentation tests indicate that the weld zone behaves differently from the base alloys. Surprisingly, the lap shear strength did not decrease significantly even after 8 weeks of cyclic corrosion testing, indicating that the joint prevented any ingress of the electrolyte. Fatigue testing showed that applying an adhesive between the Al and Mg joint improved the fatigue life to some extent, although the corrosion resistance reduced due to the discontinuous bonding of the adhesive layer. Overall, these findings highlight the importance of investigating the corrosion and mechanical properties of FSW Al-Mg welds and provide valuable insights for future modeling works.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Accurate Ultrasonic Thickness Measurement for Arbitrary Time-Variant Thermal Profile

Ultrasonic thickness measurement of mechanical structures is one of the most popular and commonly used nondestructive methods for various kinds of process control and corrosion monitoring. With ultrasonic propagation speed being temperature-dependent, the thickness measurement can be performed reliably only when the thermal profile is completely known. Most conventional techniques assume the temperature of the test structure is uniform and at room temperature across its thickness. Such assumptions may lead to large errors in the thickness measurement, especially when there are significant temperature variations across the thickness. State-of-the-art techniques use external temperature measurements or implement iterative methods to compensate for the unknown thermal profiles. However, such techniques produce unsatisfactory results when the heat distribution is complex or varies rapidly with time. In this work, we propose a two-sensors technique, using both compressive and shear excitations, with a non-iterative rapid data processing method for accurate thickness measurement under arbitrary time-variant thermal profile. The independent behavior of shear and compressive waves is used to formulate a real-time thickness estimation technique. The developed technique is experimentally validated on a steel plate with fixed acoustic sensors. Test results show that the error in thickness estimation can be reduced by up to 98% compared to conventional thickness gauging methods.

36 MATERIALS SCIENCE↗

Rapid synthesis of phase-engineered tungsten carbide electrocatalysts via flash joule heating for high-current-density hydrogen evolution

Fabricating durable and high-performance electrocatalysts operating at high current densities for industrial acidic hydrogen evolution remains a daunting challenge. Tailoring the phase composition of electrocatalysts is a promising strategy to harness synergistic effects and improve charge transfer, thereby optimizing their performance. Here, this work presents a fast, green method based on flash joule heating (FJH) to synthesize phase-engineered tungsten carbide electrocatalysts for the acidic hydrogen evolution reaction (HER) at high current densities. Tungsten carbide electrodes with varying FJH treatment durations (3, 10, 30, and 60 s) are fabricated to fine-tune the mixture of tungsten monocarbide (WC) and tungsten semicarbide (W 2 C) phases. Results show that samples with a 30-s treatment (TC-3) exhibit an optimal balance between these phases, leading to a low overpotential of 180.97 and 387 mV at current densities of 10 mA/cm 2 and 4 A/cm 2 , respectively. TC-3 exhibits significantly lower charge transfer resistance compared to the other electrocatalysts, which can be attributed to its optimal phase ratio. Notably, the TC-3 electrocatalyst remains stable for over 9 days at 4 A/cm 2 due to their controlled phases and excellent corrosion-resistant properties. This work highlights a new method to fabricate cost-effective, high-performance tungsten carbide electrocatalysts with well-controlled phase compositions.

Acidic hydrogen evolution reaction↗

Mitigate Stress Corrosion Cracking (SCC) in High-strength Al Castings (CRADA 508)

Development of high strength, corrosion resistant, aluminum alloys is important to a number of industries, including automotive, aerospace, power, etc. Understanding how processing methods such as casting, chemistry, additives and recycle content affect an alloy’s microstructure and performance in real world environments is crucial to their implementation. One major concern is how the repeated exposure to saline solutions can be detrimental to the structural integrity of aluminum alloy components. This study was undertaken as a collaboration between Eck Industries and PNNL to investigate the stress corrosion cracking (SCC) and corrosion behavior of aluminum alloys. This work examines the SCC response of three different materials set. First is cast A206 Al alloy produced by three different casting techniques (i.e., permanent mold, and sand casting with and without chill) and with or without nano forming additives as potential grain refiners. The second materials set comprises Al alloy tubes extruded by PNNL’s ShAPE process and produced using raw material with three different ratios of twitch and pre-consumer Al 6061 scrap. Finally, the third materials set comprises two Al-Si-Mg-Fe alloys with controlled Si% and Fe% to mimic recycle grade Al alloys. The corrosion behavior of these materials was characterized using SCC testing and scanning electrochemical cell microscopy (SECCM) technique; mechanical behavior was characterized using tensile testing, and microstructure was characterized using optical and electron microscopy techniques. Of the A206 Al alloys, the samples with nano forming additives performed poorly compared to those without. The best SCC performance (i.e. least degradation in mechanical properties) was demonstrated by A206 alloy sand cast with chill while the permanent mold sample showed the worst SCC performance. The SECCM was performed on A206 alloy sand cast with chill to understand the effect of microstructure and determine the location-dependent corrosion properties on grain boundaries (GB) and inside grains (IG) on the sample. The corrosion potential and current measured on GB and IG at various points on the sample established that the GB locations are more cathodic and corrosive than the IG locations. Further work needs to be conducted to investigate the mechanisms behind the observed dependence of SCC on casting technique and nano forming additives. Among the ShAPE extruded tubes, SECCM data suggests the decreasing order of tendency to corrode as follows: 100% twitch > 75% twitch > 50% twitch. Finally, both variants of the Al-Si-Mg-Fe alloys showed a large volume fraction of Fe- and Si-containing intermetallics and additional work is needed to discern differences in their respective corrosion responses. In summary, correlating local electrochemical behavior (e.g. via SECCM) with micro/nanostructure, in conjunction with bulk mechanical behavior, can help identify the right fabrication method and alloy chemistry to minimize SCC issues in Al alloys.

36 MATERIALS SCIENCE↗

Optimized purification methods for metallic contaminant removal from directly recycled Li-ion battery cathodes

Metallic contaminants pose a significant challenge to the viability of directly recycling Li-ion batteries. To date, few strategies exist to selectively remove metallic impurities from mixtures of shredded end-of-life material (black mass; BM) without concurrently damaging the structure and electrochemical performance of the target active material. We herein present tailored methods to selectively ionize two major contaminants—Al and Cu—while retaining a representative cathode (LiNi 0.33 Mn 0.33 Co 0.33 O 2 ; NMC-111) intact. This BM purification process is conducted at moderate temperatures in a KOH-based solution matrix. We rationally evaluate approaches to increase both the kinetic corrosion rate and the thermodynamic solubility of Al 0 and Cu 0 , and evaluate the impact of these treatment conditions on the structure, chemistry, and electrochemical performance of NMC. Specifically, we explore the impacts of chloride-based salts, a strong chelating agent, elevated temperature, and sonication on the rate and extent of contaminant corrosion, while concurrently evaluating the effects on NMC. The reported BM purification process is then demonstrated on samples of “simulated BM” containing a practically relevant 1 wt% concentration of Al or Cu. Increasing the kinetic energy of the purifying solution matrix through elevated temperature and sonication accelerates the corrosion of metallic Al and Cu, such that ∼100% corrosion of 75 μm Al and Cu particles is achieved within 2.5 hr. Further, we determine that effective mass transport of ionized species critically impacts the efficacy of Cu corrosion, and that saturated Cl – hinders rather than accelerates Cu corrosion by increasing solution viscosity and introducing competitive pathways for Cu surface passivation. The purification conditions do not induce bulk structural damage to NMC, and electrochemical capacity is maintained in half-cell format. Testing in full cells suggests that a limited quantity of residual surface species are present after treatment, which initially disrupt electrochemical behavior at the graphite anode but are subsequently consumed. Process demonstration on simulated BM suggests that contaminated samples—which prior to treatment show catastrophic electrochemical performance—can be recovered to pristine electrochemical capacity. The reported BM purification method offers a compelling and commercially viable solution to address contamination, particularly in the “fine” fraction of BM where contaminant sizes are on the same order of magnitude as NMC and where traditional separation approaches are unfeasible. Thus, this optimized BM purification technique offers a pathway towards viable direct recycling of BM feedstocks that would otherwise be unusable.

25 ENERGY STORAGE↗

Determining Drying Conditions to Mitigate Hanford Double Shell Storage Tank Underside Corrosion — Phase 1

The Hanford Site in Washington State has legacy radiological waste that is being retrieved from single shell tanks (SSTs) and transferred to newer, double shell tanks (DSTs) for eventual closure of the SSTs. The waste is maintained in the DSTs until eventual immobilization can be performed at the Waste Treatment and Immobilization Plant (WTP), currently under construction. Until full immobilization is complete, extended service of the DSTs must be ensured by mitigating corrosion of the steel tank walls and buried steel pipelines. A Pit Air Supply System has been developed to mitigate corrosion of the leak detection pits connected to the concrete foundations of the DSTs. The objectives for the present study are: (i) to corrode steel specimens in an electrolytic simulant to form artificial pits with specific pit depths, and (ii) to determine the temperature and humidity levels that will mitigate further pit growth. Experimental work and results will be presented to evaluate conditions associated with the PASS system and predict corrosion rates when the PASS is operating.

Atmospheric Corrosion↗

A hybrid meshfree discretization to improve the numerical performance of peridynamic models

Efficient and accurate calculation of spatial integrals is of major interest in the numerical implementation of peridynamics (PD). The standard way to perform this calculation is a particle-based approach that discretizes the strong form of the PD governing equation. This approach has rapidly been adopted by the PD community since it offers some advantages. Additionally, it is computationally cheaper than other available schemes, can conveniently handle material separation, and effectively deals with nonlinear PD models. Nevertheless, PD models are still computationally very expensive compared with those based on the classical continuum mechanics theory, particularly for large-scale problems in three dimensions. This results from the nonlocal nature of the PD theory which leads to interactions of each node of a discretized body with multiple surrounding nodes. Here, we propose a new approach to significantly boost the numerical efficiency of PD models. We propose a discretization scheme that employs a simple collocation procedure and is truly meshfree; i.e., it does not depend on any background integration cells. In contrast to the standard scheme, the proposed scheme requires a much smaller set of neighboring nodes (keeping the same physical length scale) to achieve a specific accuracy and is thus computationally more efficient. Our new scheme is applicable to the case of linear PD models and within neighborhoods where the solution can be approximated by smooth basis functions. Therefore, to fully exploit the advantages of both the standard and the proposed schemes, a hybrid discretization is presented that combines both approaches within an adaptive framework. The high performance of the developed framework is illustrated by several numerical examples, including brittle fracture and corrosion problems in two and three dimensions.

42 ENGINEERING↗

Highly reversible Zn metal anode enabled by sustainable hydroxyl chemistry

Rechargeable Zn metal batteries (RZMBs) may provide a more sustainable and lower-cost alternative to established battery technologies in meeting energy storage applications of the future. However, the most promising electrolytes for RZMBs are generally aqueous and require high concentrations of salt(s) to bring efficiencies toward commercially viable levels and mitigate water-originated parasitic reactions including hydrogen evolution and corrosion. Electrolytes based on nonaqueous solvents are promising for avoiding these issues, although full cell performance demonstrations with solvents other than water have been very limited. To address these challenges, we investigated MeOH as an alternative electrolyte solvent. These MeOH-based electrolytes exhibited exceptional Zn reversibility over a wide temperature range, with a Coulombic efficiency > 99.5% at 50% Zn utilization without cell short-circuit behavior for > 1,800 h. More important, this remarkable performance translates well to Zn || metal-free organic cathode full cells, supporting < 6% capacity decay after > 800 cycles at –40°C.

25 ENERGY STORAGE↗

Deliquescence of Eutectic LiCl-KCl Diluted with NaCl for Interim Waste Salt Storage

Molten eutectic LiCl-KCl salt is a widely used electrolyte for electrorefining uranium from spent nuclear fuel. Due to the hygroscopic nature of this salt, such operations must be performed under controlled atmospheric conditions, and waste salts require careful storage to avoid deliquescence and corrosion of container materials. This study investigated a potential processing path for reducing the degree of deliquescence through dilution to varying extents with NaCl. Here, the hydration behavior of LiCl-KCl salts diluted with NaCl was evaluated in terms of mass gain due to water absorption, degree of deliquescence (including first appearances of standing water), and evidence of corrosion to stainless steel containers in a humid air environment (40°C, 20% relative humidity). In this humid air environment, pure eutectic LiCl-KCl exhibited a 50 mass % increase due to water absorption and showed evidence of standing water after 24 h. Waste salt diluted with NaCl required loadings of 89 mass % NaCl in order to prevent deliquescence and exhibited a 3 mass % increase due to water absorption. After periodic observation for 48 h, standing water was observed near all ingots with the exception of the 89 mass % NaCl samples. Dilution with 89% NaCl was also found to reduce evidence of corrosion when stored in stainless steel crucibles. While dilution with NaCl greatly decreases steady-state hydration, the storage volume is increased ~10× through this procedure.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Carbonated Brine Injection for a Pilot Site as a Low-Risk Geologic Carbon Storage Strategy: A Simulation Study

This technical report presents a preliminary study for CBI implementation in the Pena Creek pilot site in Dimmit County, Texas, targeting the Edwards Limestone Formation for SWD, in collaboration with NGL Energy Partners. The objective of this study is to find the conservative CO 2 molality for safe storage and potential risks for CBI at this pilot site. Geomodel was performed to get site-specific reservoir geology information. Reservoir modeling was performed to investigate dissolved CO 2 molality and pressure changes at relevant injection conditions. Wellbore corrosion and compatibility was discussed with corrosion modeling. Dissolved CO 2 long-term fate in the reservoir was examined with reactive transport modeling. This plan would set the scientific foundation as the initial step for future implementation in the field.

58 GEOSCIENCES↗

Origins of wear-induced tungsten corrosion defects in semiconductor manufacturing during tungsten chemical mechanical polishing

During chemical mechanical polishing (CMP) process optimization, a unique corrosion defect was identified in the tungsten (W) contact plugs, which were investigated to develop practical solutions to improve CMP mass productivity. The corrosion defect occurred in the absence of external incident energy and was observed to occur only at the W plugs connected to the P + /n-well close to the wafer edge. To examine the root cause of the corrosion, a series of experiments was carried out at each W CMP step, using in-line defect inspection. Additional experiments were conducted using on-line inductively coupled plasma mass spectrometry (ICP-MS) to understand pH- and potential-dependent electrochemical dissolution behaviors of W. Experimentally, W corrosion was confirmed to be exacerbated if the surface oxide of the W plugs is removed by the deionized water (DIW) rinsing step under wafer pressurization, then exposed to DIW and alkaline cleaning solution. Although the DIW rinsing step is commonly performed to clean polishing pads right after the main polishing, a small amount of applied pressure (0.5 psi) without slurry supply can lead to corrosion defects. Finally, this wear-induced corrosion of the W plugs can be prevented by removing the applied pressure during the post DIW rinsing step of W CMP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Testing- and Model- Based Optimization of Coal-fired Primary Heater Design for Indirect Supercritical CO 2 Power Cycles (Final Scientific and Technical Report)

The overall objective of this project was to perform the R&D necessary to mitigate the risk associated with the design of a primary heat exchanger for a solid-fired combustion system coupled with an indirect-fired closed-loop Brayton Cycle utilizing supercritical CO 2 . The key technological hurdle was the coupling of a solid-fuel firing system with the primary heater, which poses a singular challenge, which is the management of burner performance and operational conditions in a way to manage heat exchanger tube metal temperatures and temperature ramp rates in the absence of fluid phase change on the inside of the tubes. We designed and built the first ever pseudo power system employing a simple recuperated supercritical CO 2 closed-loop Brayton Cycle coupled to a solid-fuel fired system. Advanced coupled CFD and process modeling were used to design the primary heat exchanger (PHX), which consisted of both radiative and convective sections, to limit tube metal temperatures resulting from the heat release profile of the solid fuel flame near the radiative tubes. The heat exchanger was designed to produce finished CO 2 temperatures of 600 °C a pressure of 20.7 MPa and CO 2 flow of 5.5 kg/s. The constructed PHX was capable of 1.2 MWth heat uptake. During design of the PHX, the modeling showed that most variables influencing flame shape (burner stoichiometric ratio and register velocities and swirl) were not suitable to manage heat flux to the metal surfaces. This is because they substantially increased adiabatic flame temperature through the influence of localized stoichiometric ratio. Excess air and firing rate were the two most powerful variables that could be used to control tube surface temperatures. The coupled system was operated for a total of 407 hours, with the longest continuous run of 248 hours. For 62% of the operational time, the unit was unmanned and in automatic control. The fuels used for the testing included natural gas, two Utah Bituminous coals, woody biomass, and bagasse. During the testing we were able to verify the 1.2 MWth heat uptake and we operated at a finished CO 2 temperature of 607 °C and a pressure of 20.3 MPa simultaneously. The real-time corrosion rate of the Super 304H tube CO 2 surface in the region of the radiative section of the PHX were measured, at an approximate temperature of 550 °C. The two key variables related to corrosion rate are the pressure and flow rate of the CO 2 . A technoeconomic analysis was performed at a scale of 120 MWE. The updated analysis showed that the efficiency of an sCO 2 power producing plant will be related to the pressure drop of the PHX.

01 COAL, LIGNITE, AND PEAT↗