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At least 1,063 records · Page 59

Metal-supported solid oxide fuel cells operating with reformed natural gas and sulfur

The performance, long-term durability, and thermal cycling tolerance of metal supported solid oxide fuel cells (MS-SOFCs) operating with natural gas reformate fuels is assessed. Symmetric MS-SOFCs with composite SDC-Ni anode catalysts and PrO x cathode catalysts are operated with simulated natural gas steam-reformate and partial-oxidation-reformate fuels with 1 ppm and 5 ppm of sulfur. Cells are operated for 1000 h with initial degradation rates similar to humidified H 2 , and initial performance differences attributed to the lower H 2 concentration in reformate fuels. Additionally, cells tolerate many aggressive thermal cycles with sulfur present, with minimal impact on performance. Post mortem analysis suggests that Ni particle coarsening and Cr deposition are sources of degradation, while carbon and sulfur deposition are not observed. Overall, MS-SOFCs operate successfully with reformed natural gas.

08 HYDROGEN↗

Structural dependence of hydrogen evolution reaction on transition metal catalysts sputtered at different temperatures in alkaline media

In the present article, we studied the catalytic activity of magnetron sputtered Mo, V, Ni, and Co thin films for hydrogen evolution reaction (HER) in the alkaline electrolyte. Here, we find that the HER potentials (η 10 ) of the Mo and V thin film catalysts sputtered at 800 °C shift positive with respect to those of the film catalysts sputtered at 25°C. For Mo metal the observed shift of η 10 was 280 mV and for V metal observed shift of η 10 was 390 mV. On the other hand, minimal effect of sputtering temperature on both Ni and Co thin film catalyst activity for HER was observed. Structural analysis reveals that Mo and V prepared at 800 °C have uncommon face centered cubic (fcc, 0.74 packing density) structure as opposed to room-temperature sputtered Mo and V thin films which have common body centered cubic (bcc, 0.68 packing density) structure, resulting in significant increases of the packing densities when they are prepared at 800 °C. On the other hand, the high-temperature prepared thin films of Ni and Co retained fcc structures, resulting in no density changes compared to the room-temperature prepared fcc Ni and hexagonal close packed (hcp, 0.74 packing density) Co. Impedance spectroscopy shows that fcc Mo is a better catalyst than fcc Ni, which is considered an industry standard for non-noble pure metal-based catalysts in alkaline media. Stability tests also suggest that fcc Mo thin film catalysts prepared at 800 °C are more durable than fcc Ni thin films. Our study points out that structure phases of catalysts can be a key factor governing the activities of transition metals for HER in alkaline media.

08 HYDROGEN↗

Direct utilization of gaseous fuels in metal supported solid oxide fuel cells

Direct utilization and internal reforming of gaseous fuels is investigated on symmetric-architecture metal supported solid oxide fuel cells (MS-SOFCs) with thin ceramic electrolyte and scaffold backbone layers, and low cost ferritic stainless steel supports on both sides. Infiltrated Pr-oxide and Ni/samarium-doped ceria catalysts are added to the cathode and anode electrodes, respectively. Initial performance and durability is evaluated for MS-SOFCs operating with natural gas, propane, ammonia, and dimethyl ether at 700 °C. Cells for natural gas and propane utilize a novel high entropy alloy (HEA) catalyst for internal reforming with performance and degradation rates similar to H 2 (0.5W cm -2 and ~12%/100 h). In conclusion, initial testing with sulfur shows reversible degradation for levels found in natural gas and irreversible degradation for higher levels found in commercial propane. Overall, MS-SOFCs show successful fuel flexibility.

08 HYDROGEN↗

Capacity Assessment and Cost Analysis of Geologic Storage of Hydrogen: A Case Study in Intermountain-West Region USA

Hydrogen is an integral component of the current energy transition roadmap to decarbonize the economy and create an environmentally-sustainable future. However, surface storage options (e.g., tanks) do not provide the required capacity or durability to deploy a regional or nationwide hydrogen economy. In this study, we have analyzed the techno-economic feasibility of the geologic storage of hydrogen in depleted gas reservoirs, salt caverns, and saline aquifers in the Intermountain-West (I-WEST) region. We have identified the most favorable candidate sites for hydrogen storage and estimated the volumetric storage capacity. Our results show that the geologic storage of hydrogen can provide at least 72% of total energy consumption of the I-WEST region in 2020. We also calculated the capital and levelized costs of each storage option. We found that a depleted gas reservoir is the most cost-effective candidate among the three geologic storage options. Interestingly, the cushion gas type plays a significant role in the storage cost when we consider hydrogen storage in saline aquifers. The levelized costs of hydrogen storage in depleted gas reservoirs, salt caverns, and saline aquifers with large-scale storage capacity are approximately $\$$1.15, $\$$2.50, and $\$$3.27 per kg of H 2 , respectively. Here, this work provides essential guidance for the geologic hydrogen storage in the I-WEST region.

08 HYDROGEN↗

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↗

Grid-responsive hydrogen production: Capital utilization and current density vs. efficiency in variable electricity markets

To achieve low-cost hydrogen production from water electrolyzers, grid tied electrolysis may need to operate dynamically to minimize the cost of supplying energy to the electrolyzer stack and produce hydrogen during low-cost hours and turn off/down during high-cost hours. Operating systems in this way can decrease capital utilization (capacity factor) and electricity costs. This strategy would shift the dominant cost drivers away from electricity (and thus efficiency) to the capital costs of the system, due to the underutilized capital when operating at low-capacity factors. Increasing the operational current density of the system could, in effect, reduce the capital cost of the system while producing hydrogen at a lower efficiency on a per unit energy basis. In the variable electricity cost profiles analyzed in this paper, increasing the current density for liquid alkaline from 0.5 A/cm2 to 1.5 Ac/m2 and proton exchange membrane electrolyzers from 2 A/cm2 to 4 A/cm2 resulted in substantial reductions in the levelized cost of hydrogen. Additionally, as capacity factors and electricity costs decrease, the optimal operating current density of the electrolyzer systems analyzed increases. These findings suggest R&D efforts should focus on increasing the operational current densities, reducing the turn down ratios, and understanding the durability implications of those strategies on low-temperature liquid alkaline and proton exchange membrane electrolyzers.

08 HYDROGEN↗

Patterns and Predictors of Failure in Recurrent or Refractory Large B-Cell Lymphomas After Chimeric Antigen Receptor T-Cell Therapy

Chimeric antigen receptor T-cell (CAR T) therapy is capable of eliciting durable responses in patients with relapsed/refractory (R/R) lymphomas. However, most treated patients relapse. Patterns of failure after CAR T have not been previously characterized, and may provide insights into the mechanisms of resistance guiding future treatment strategies.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Prospective Clinical Investigation of the Efficacy of Combination Radiation Therapy With Immune Checkpoint Inhibition

Immune checkpoint inhibitors (ICIs) lead to durable responses in a subset of patients with cancer, but most patients do not respond to ICI, prompting interest in combining immunotherapy with other therapeutic regimens. Preclinical evidence supports the potential for therapeutic synergy between immunotherapy and radiation therapy through modulation of the tumor microenvironment and antitumor immune responses. Local therapy also has the potential to overcome localized sites of relative immune suppression and resistance. Prospective clinical trials have been initiated to test these hypotheses in the clinic as well as to investigate the toxicities and adverse events associated with combination immunotherapy and radiation therapy. In this review, we discuss the emerging results from prospective clinical trials of combination immunotherapy and radiation therapy, the safety and efficacy of their combination, concordance with preclinical and retrospective data, and some of the remaining open questions to be addressed by future clinical trials.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Adaptively remeshed multiphysical modeling of resistance forge welding with experimental validation of residual stress fields and measurement processes

Welding processes used in the production of pressure vessels impart residual stresses in the manufactured component. Computational modeling is critical to predicting these residual stress fields and understanding how they interact with notches and flaws to impact pressure vessel durability. Here, in this work, we present a finite element model for a resistance forge weld and validate it using laboratory measurements. Extensive microstructural changes, near-melt temperatures, and large localized deformations along the weld interface pose significant challenges to Lagrangian finite element modeling. The proposed modeling approach overcomes these roadblocks in order to provide a high-fidelity simulation that can predict the residual stress state in the manufactured pressure vessel; a rich microstructural constitutive model accounts for material recrystallization dynamics, a frictional-to-tied contact model is coordinated with the constitutive model to represent interfacial bonding, and adaptive remeshing is employed to alleviate severe mesh distortion. An interrupted-weld approach is applied to the simulation to facilitate comparison to displacement measures. Several techniques are employed for residual stress measurement in order to validate the finite element model: neutron diffraction, the contour method, and the slitting method. Model-measurement comparisons are supplemented with detailed simulations that reflect the configurations of the residual-stress measurement processes themselves. The model results show general agreement with experimental measurements, and we observe some similarities in the features around the weld region. Factors that contribute to model-measurement differences are identified. Finally, we conclude with some discussion of the model development and residual stress measurement strategies, including how to best leverage the efforts put forth here for other weld problems.

36 MATERIALS SCIENCE↗

Analysis of anion exchange membrane water electrolyzer performance and its evolution over time

Understanding water, evolved gas, and ionic transport in membrane-electrode-assemblies (MEAs) is essential for the development of high performance and durable anion exchange membrane water electrolyzers (AEMWEs). This study evaluates the MEA conditioning process, operating conditions, and short-term stability in a 1 M potassium hydroxide (KOH) electrolyte, focusing on the underlying transport phenomena. We observe a significant initial voltage loss in continuous cell operation, which could be associated with gas bubble accumulation, transport layer or flow field passivation, and changes in the catalyst oxidation state. Further, we investigate the effects of materials and operational configurations, including the membrane type and thickness, and the electrolyte flow rate, including KOH being fed to both electrodes as well as to the anode only. Furthermore, the effect of membrane drying temperature on ex situ as well as in situ electrochemical performance is evaluated. Finally, we discuss 700 h of AEMWE operation at 1 A/cm 2 , highlighting the underlying degradation phenomena.

25 ENERGY STORAGE↗

Bioinspired nonwetting surfaces for corrosion inhibition over a range of temperature and corrosivity

Applications of superhydrophobic (SHS) and lubricant infused surfaces (LIS) involve exposure to corrosive environments from the acidic to the basic, at a range of temperatures, that are not fully characterized. Here, we present for the first time a multifactorial study of the effects of surface fabrication method, surface modification, surface functionalization time, temperature and pH of the immersion medium on the corrosion performance of nonwetting copper surfaces. Bioinspired SHS and LIS fabricated using facile methods of etching and electrodeposition are systematically assessed using potentiodynamic polarization measurements for their corrosion resistance in saline solution (pH ≈7) over a temperature range 23–85°C. SHS and LIS are shown to exhibit diminished corrosion rate, by up to two orders of magnitude, compared to bare copper surface. An Arrhenius model is developed for the first time, describing the temperature- dependent corrosion rate of SHS and LIS. Electrochemical impedance spectroscopy is used to show that corrosion resistance of LIS is larger by three orders of magnitude in extremely acidic (pH = 1) and by an order magnitude in extremely alkaline (pH = 14) media compared to bare copper surface. Etched LIS are generally more resistant to corrosion compared to SHS at all temperatures with excellent microstructural durability.

42 ENGINEERING↗

Engineering surface segregation of perovskite oxide through wet exsolution for CO catalytic oxidation

Cation segregation occurring near the surface or interfaces of solid catalysts plays an important role in catalytic reactions. Unfortunately, the native surface of perovskite oxides is dominated by passivated A-site segregation, which severely hampers the catalytic activity and durability of the system. To address this issue, we present a wet exsolution method to reconstruct surface segregation in perovskite cobalt oxide. Here, under reduction etching treatment of glycol solution, inert surface Sr segregation was transformed into active Co 3 O 4 segregation. By varying the reaction time, we achieved differing coverage of the active Co 3 O 4 segregation on the La 0.5 Sr 0.5 CoO 3-δ (LSCO) perovskite oxide surface. This study reveals that CO oxidation activity exhibits a volcano-shaped dependence on the coverage of Co 3 O 4 segregation at the surface of a perovskite cobalt oxide. Furthermore, we find that a suitable coverage of Co 3 O 4 segregation can dramatically improve the catalytic activity of the perovskite catalyst by enhancing interface interactions. Co K-edge, Co L-edge, and O K-edge X-ray absorption spectra confirm that the synergistic effect optimizes the covalence of the metal-oxygen bond at the surface and interface. This work not only contributes to the design of perovskite-type catalysts, but also provides important insight into the relationship between surface segregation and catalytic activity.

36 MATERIALS SCIENCE↗

Microbial interactions with phosphorus containing glasses representative of vitrified radioactive waste

The presence of phosphorous in borosilicate glass (at 0.1 – 1.3 mol % P 2 O 5 ) and in iron-phosphate glass (at 53 mol % P 2 O 5 ) stimulated the growth and metabolic activity of anaerobic bacteria in model systems. Dissolution of these phosphorous containing glasses was either inhibited or accelerated by microbial metabolic activity, depending on the solution chemistry and the glass composition. The breakdown of organic carbon to volatile fatty acids increased glass dissolution. The interaction of microbially reduced Fe(II) with phosphorus-containing glass under anoxic conditions decreased dissolution rates, whereas the interaction of Fe(III) with phosphorous-containing glass under oxic conditions increased glass dissolution. Phosphorous addition to borosilicate glasses did not significantly affect the microbial species present, however, the diversity of the microbial community was enhanced on the surface of the iron phosphate glass. Results demonstrate the potential for microbes to influence the geochemistry of radioactive waste disposal environments with implication for wasteform durability.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Design, performance, and cost savings of using GF-PC additively manufactured tooling for stamping of HSS 590 sheet metal

Conventional sheet metal forming tooling in the automotive industry is made up of hardened steel and used for mass-production. Prototype tooling made of metal is durable, but it is only used for a small number of parts despite its high cost, contributing heavily to the vehicle development cost. Additive Manufacturing (AM) offers a low-cost alternative for fabricating tooling suitable for low-volume production. Here, this study investigates the feasibility of using AM polymer composite tooling for the stamping of 1.5mm thickness HSS 590 steel sheets through a two-pronged approach – experimental and numerical analysis. Sheet metal stamping experiments were conducted with glass fiber reinforced polycarbonate (GF-PC) AM polymer tooling and their performance was evaluated based on various metrics such as tool deformation and part accuracy. Finite element simulations of the stamping process were performed, which accurately captured the tool deformations seen in experiments with the use of anisotropic material models. The effective use of simulations in optimizing process parameters to achieve the desired final part geometry is also demonstrated. The GF-PC AM polymer composite tooling was found to be well suited for low volume production applications with potential cost savings.

36 MATERIALS SCIENCE↗

Nanoscopic structure of borosilicate glass with additives for nuclear waste vitrification

In this report we investigated the nanoscopic structure of borosilicate glasses as a host for high-level radioactive liquid waste (HLLW) in the presence of the additives Na 2 O and CaO/ZnO with and without Li 2 O. These additives have been used to lower the glass melting point, suppress the macroscopic phase separation, and increase the chemical durability of glasses. Small-angle neutron scattering was used to elucidate the effect of the additives on the nanoscopic structure along with macro- and atomic-scale observations obtained using neutron imaging and X-ray diffraction, respectively. The borosilicate glass made without Na 2 O formed a microphase-separated structure of SiO 2 - and B 2 O 3 -rich domains approximately 100 nm in size, and the material was homogeneous at length scales up to millimeters. With the addition of increasing amounts of Na 2 O, the domain spacing decreased. Introducing CaO/ZnO additives induced inhomogeneities in the glass, such as void structures several nanometers in size, although the inhomogeneity was suppressed by the coaddition of Li 2 O. These results provide insights into the performance of host glasses for HLLW vitrification. Incorporating HLLW into glasses is likely to cause changes in the nanoscopic structure of host glasses similar to those revealed here.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Glass Design Using Machine Learning Property Models with Prediction Uncertainties: Nuclear Waste Glass Formulation

The United States Department of Energy is responsible for managing the legacy nuclear waste stored in underground tanks at the Hanford Site. The waste will be separately vitrified as low-activity waste and high-level waste fractions. Waste glass formulation algorithms have been traditionally developed using partial quadratic mixture property-composition models. Recently, machine learning (ML) techniques have been used to predict glass properties and discover new glass materials for nuclear waste vitrification, and these advancements can be utilized to improve waste glass composition design. In this proof-of-principle study, ML algorithms such as Gaussian process regression (GPR) were used to interpolate glass properties (e.g., viscosity, electrical conductivity, chemical durability). After selecting appropriate sets of GPR hyper-parameters for each property, an optimization program was developed to formulate glass compositions to maximize waste loading while simultaneously satisfying property within constraints. The results of the ML-based waste loadings and glass compositions were compared to those obtained using the traditional methods. Comparing to the previous glass design framework, the ML-based optimization methods offer improved glass designs and a streamlined approach to generation of optimally designed data and near real-time updates.

glass formulation, machine learning, constraints, ↗

Low Activity Waste Glass Optimization with Property Models from Machine Learning, Part 2: Experimental Validation and Active Learning

The United States Department of Energy is responsible for managing legacy nuclear waste stored in underground tanks at the Hanford Site. To treat the waste, it is planned as the current baseline to separately vitrify low-activity waste (LAW) and high-level waste fractions. Previously, machine learning (ML) based glass property models (e.g., chemical durability, viscosity, electrical conductivity and SO3 solubility) were developed with prediction uncertainties. A waste glass optimization approach was then established to enable the capability of using these ML models in LAW glass formulation. In this study, the previous ML models were first experimentally validated, and the results were incorporated back into the database to update the ML models. The updated models and formulations showed increased waste loading while reducing the failure rate, demonstrating improved predictive accuracy, reduced uncertainties, and the effectiveness of active learning in guiding high-dimensional, nonlinear LAW glass design. This represents the first experimental validation of ML based LAW glass formulation, with practical benefits such as higher waste loading, shorter mission duration, and lower operational risk.

Lu, Xiaonan (ORCID:0000000179708148)↗