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At least 217 records · Page 12

Development of a framework for sequential Bayesian design of experiments: Application to a pilot-scale solvent-based CO 2 capture process

In this paper, a methodology is developed for sequential design of experiments (SDoE) for process systems and applied to a solvent-based CO 2 capture system. In this approach, the prior knowledge of the system is used to prioritize process data collection at specific operating conditions. These data are then incorporated into a Bayesian inference methodology for updating a stochastic model by refining estimations of its underlying parameters, and the updated model is then used to generate the next set of test runs. Thus, the new knowledge obtained from the data is used to guide subsequent iterations of the experimental runs, ensuring that the overall data collection is maximally informative given that most experimental campaigns, especially at pilot or higher-scale plants, are costly, time-consuming, and resource-limited. The test run objective for this work was to minimize the maximum model prediction uncertainty for key output variables, but the methodology is generic and can be readily applied to other test run objectives. This methodology is applied to an aqueous monoethanolamine (MEA) pilot plant campaign at the National Carbon Capture Center (NCCC) in Wilsonville, Alabama, USA. The SDoE framework was utilized for two iterations, while collecting 18 sets of data representing different process conditions, and this resulted in an overall average reduction in uncertainty of approximately 50% in the prediction of CO 2 capture percentage. Moreover, 11 additional data sets were obtained with variation of absorber packing height for further model validation. This work shows the capability of the SDoE framework to maximize learning given limited resources, allowing for the reduction of model uncertainty, which is of great importance for many applications including reduction of technical risk associated with scale-up and economic analysis.

20 FOSSIL-FUELED POWER PLANTS↗

Fault Protection Design and Testing for the Cassini Spacecraft in a "Mixed" Thruster Configuration

NASA's Cassini Spacecraft, launched on October 15th, 1997 and arrived at Saturn on June 30th, 2004, is the largest and most ambitious interplanetary spacecraft in history. In order to meet the challenging attitude control and navigation requirements of the orbit profile at Saturn, Cassini is equipped with a monopropellant thruster based Reaction Control System (RCS), a bipropellant Main Engine Assembly (MEA) and a Reaction Wheel Assembly (RWA). In 2008, after 11 years of reliable service, several RCS thrusters began to show signs of end of life degradation, which led the operations team to successfully perform the swap from the A-branch to the B-branch RCS system. If similar degradation begins to occur on any of the B-branch thrusters, Cassini might have to assume a "mixed" thruster configuration, where a subset of both A and B branch thrusters will be designated as prime. The Cassini Fault Protection FSW was recently updated to handle this scenario. The design, implementation, and testing of this update is described in this paper.

propellant↗

Mapping of Heterogeneous Catalyst Degradation in Polymer Electrolyte Fuel Cells

Pt catalysts in polymer electrolyte fuel cells degrade heterogeneously as the catalyst particles are exposed to local variations throughout the catalyst layer during operation. State-of-the-art analytical techniques for studying degradation of Pt catalysts do not possess fine spatial resolution to elucidate such non-uniform degradation behavior at a large electrode level. A new methodology is developed to spatially resolve and quantify the heterogeneous Pt catalyst degradation over a large area (several cm ) of aged MEAs based on synchrotron X-ray microdiffraction. PEFC single cells are aged using voltage cycling as an accelerated stress test and the degradation heterogeneity at a micrometer length scale is visualized by mapping Pt catalyst particle size after voltage cycling. It is demonstrated in detail that the Pt catalyst particle size growth is non-uniform and follows the flow field geometry. The Pt particle size growth is greater in the area under the flow field land, while it is minimal in the area under the flow field channel. Additional non-uniformity is observed with the Pt particle size increasing more rapidly at the air outlet area than the Pt particle size at the inlet area.

36 MATERIALS SCIENCE↗

Tri‐Metallic Catalyst for Oxygen Evolution Reaction Enables Continuous Operation of Anion Exchange Membrane Electrolyzer at 1A cm −2 for Hundreds of Hours

Abstract Although numerous efforts are made to synthesize active electrocatalysts for green hydrogen production; catalyst stability, and facile synthesis to scale up the production are still challenging. Herein, the production of novel non‐PGM catalysts for the oxygen reduction reaction (OER) in an alkaline aqueous medium is reported, which is based on the synthesis of a trimetallic metal–organic framework (MOF) precursors. Fine‐tuning of the composition of the metal centers (Ni, Co, and Fe) shows a great effect on OER activity after the MOF undergoes dynamic chemical and structural transformations under OER conditions. In situ characterization reveals the origin of OER activity enhancement as metals’ oxidation state increases, inducing compressive mechanical strain on metal centers, enhancing the electronic conductivity through the formation of oxygen vacancies, and stronger metal–oxygen covalency. Catalysts are used in membrane electrode assembly (MEA) setup within an industrial full‐cell anion exchange membrane electrolyzer (AEMEC), showing a stable performance for 550 h without noticeable decay at 750 and 1000 mA cm −2 industrial level current densities.

Chemistry↗

Probing Electrode Transformation under Dynamic Operation for Alkaline Water Electrolysis

Alkaline water electrolyzers (AWEs) play a pivotal role in the realm of large-scale hydrogen production. However, AWEs face significant challenges in electrode degradation particularly under dynamic operating conditions, induced by reverse current phenomenon during frequent startup/shutdown. Herein, this study aims to rationalize the degradation mechanisms of AWEs under these conditions. A three-electrode membrane electrode assembly (MEA) setup is first utilized to decouple polarization behaviors of anode and cathode in AWEs. Following a proposed accelerated stress testing protocol, the setup allows for tracking individual electrode performance transformations during frequent reverse current operation. Integrating operando cell studies with in situ and post-mortem characterizations, it is showed that continuous formation of highly active species, nickel (oxy)hydroxides, improves the anode performance for oxygen evolution reaction. On the contrary, irreversible oxidation of nickel to β-nickel hydroxide results in a severe degradation of cathode, leading to material dissolution, poor electrical conductivity and loss of catalytic activity for hydrogen evolution reaction. These results provide insights in nickel-based electrode transformation mechanisms for alkaline water electrolysis and indicate that cathode with higher redox reversibility can potentially improve durability of AWEs under dynamic conditions.

08 HYDROGEN↗

Sulfonated Diels–Alder Poly(Phenylene)s in Membrane Electrode Assemblies for Fuel Cells

The transition to environmentally sustainable materials in fuel cells requires alternatives to persistent polyfluoroalkyl substances (PFAS) like Nafion. This study investigates the performance-limiting factors of membrane electrode assemblies (MEAs) utilizing sulfonated Diels–Alder poly(phenylene)s (sDAPPs) as PFAS-free polymer electrolytes. Among the configurations evaluated, the greatest performance loss occurred when sDAPP is used as the cathode binder, primarily due to phenyl group adsorption on catalyst surfaces, which reduces oxygen reduction reaction activity and impedes oxygen transport. Additional performance degradation arises from membrane-electrode interfacial incompatibility and insufficient ionomer hydrophobicity. By addressing ionomer adsorption and improving interfacial contact, an sDAPP-based cathode achieved a current density of 1.57 A cm −2 at 0.6 V under fully humidified H 2 /air conditions at 80 °C and 150 kPa abs . These results offer key insights for advancing high-performance, PFAS-free fuel cell technologies.

08 HYDROGEN↗

Selection of solvents for integrated CO 2 absorption and electrochemical reduction systems

Abstract Solvent‐based electrochemical CO 2 reduction (CO 2 R) enables the production of chemicals or fuels using CO 2 from a preceding absorption process. Employing previously tested CO 2 capture solvents does not ensure their suitability for either CO 2 R or integrated CO 2 absorption‐reduction. We propose solvent selection criteria that include the CO 2 solubility, kinetic constant, ionic conductivity, concentration of the bicarbonate, carbamate, and solvent cation in the CO 2 ‐loaded solution, and sustainability indicators. They are implemented for solvent selection (a) from novel, aqueous mixtures of N ‐methylcyclohexylamine (MCA) with piperazine (PZ), 2‐amino‐2‐methyl‐1‐propanol (AMP), potassium hydroxide (KOH), and potassium chloride (KCl) and (b) from aqueous monoethanolamine (MEA), AMP, KOH, MCA, and PZ solutions. Versions of a modified Kent‐Eisenberg model for strong bases, carbamate, and non‐carbamate‐forming amine solutions are developed and parameterized through experimental equilibrium measurements. CO 2 R experimental results are presented for solutions of KOH and MCA + KOH, as these indicate desired trade‐offs for CO 2 absorption and reduction.

Amines↗

Impact of Advances in Anion Exchange Membranes and Ionomers on Alkaline Fuel Cells

Abstract The operation of low‐temperature electrochemical energy conversion systems (fuel cells, electrolyzers) at high pH values is of perennial interest due to the possibility of moving away from expensive platinum group metal catalysts and reducing cost. Historically, the anion exchange membranes (AEMs) and ionomers have been hampered by performance (ionic conductivity, mechanical strength) and chemical stability issues. In this context, select developments over the past decade in alternate AEM chemistries, water management methods, and production of membrane electrode assemblies (MEAs) that have enabled a significant leap in performance of alkaline fuel cells are examined. These developments are linked to performance improvements in alkaline H 2 /O 2 fuel cells and also consider developments in alkaline fuel cells using nitrogen‐containing fuels (ammonia, hydrazine), carbon‐containing fuels (alcohols, glycols), and boron‐containing fuels (sodium borohydride, ammonia borane). Finally, current challenges and bottlenecks are identified, and potential solutions are proposed.

Chemistry↗

Durability of Pt-Alloy Catalyst for Heavy-Duty Polymer Electrolyte Fuel Cell Applications under Realistic Conditions

As an emerging technology, polymer electrolyte fuel cells (PEFCs) powered by clean hydrogen can be a great source of renewable power generation with flexible utilization because of high gravimetric energy density of hydrogen. To be used in real-life applications, PEFCs need to maintain their performance for long-term use under a wide range of conditions. Therefore, it's important to understand the degradation of the PEFC under protocols that are closely related to the catalyst lifetime. Alloying Pt with transitional metal improves catalyst activity. It is also crucial to understand Pt alloys degradation mechanisms to improve their durability. To study durability of Pt alloys, accelerated stress tests (ASTs) are performed on Pt-Co catalyst supported on two types of carbon. Two different AST protocols were being studied: Membrane Electrolyte Assembly (MEA) AST based on the protocol introduced by the Million Mile Fuel Cell Truck consortium in 2023 and Catalyst AST, adopted from the U.S. Department of Energy (DoE).

25 ENERGY STORAGE↗

Integrated Capture and Conversion of CO 2 to Methane Using a Water-lean, Post-Combustion CO 2 Capture Solvent

Integrated Carbon Capture and Conversion of CO 2 into materials (IC3M) is an attractive solution to meet the global energy demand, reduce our dependence on fossil fuels and lower CO 2 emissions. In this work, using a water-lean post combustion capture solvent, (N-(2-ethoxyethyl)-3-morpholinopropan-1-amine) (2-EEMPA), >90% conversion of captured CO2 to hydrocarbons, mostly methane, is achieved in the presence of a heterogenous Ru catalysts under relatively mild reaction conditions (170 °C and <15 bar H 2 pressure). The catalytic performance was better in 2-EEMPA than aqueous 5M monoethanol amine (MEA). Operando NMR study showed in-situ formation of N-formamide intermediate, which underwent further hydrogenation to form methane and other higher hydrocarbons. The technoeconomic analyses (TEA) showed that the proposed integrated process can potentially improve the thermal efficiency by 5% and reduce the total capital investment and minimum synthetic natural gas (SNG) selling price by 32% and 12% respectively compared to conventional Sabatier process, highlighting the energetic and economic benefits of integrated capture and conversion. Methane derived from CO 2 and renewable H 2 source is an attractive fuel, and it has a great potential as a renewable hydrogen carrier as an environmentally responsible carbon capture and utilization approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of cryogenic temperature and grain size on fatigue-crack propagation in the medium-entropy CrCoNi alloy

CrCoNi-based high-entropy alloys have demonstrated outstanding mechanical properties, particularly at cryogenic temperatures. Here we investigate the fatigue-crack propagation properties of the equiatomic, single-phase, face-centered cubic, medium-entropy alloy (MEA), CrCoNi, that displays exceptional strength, ductility and toughness, all of which are enhanced at cryogenic temperatures. Fatigue-crack growth is examined, at a load ratio of 0.1 over a wide range of growth rates, from ~10 –11 to >10 –7 m/cycle, at room (293 K) and cryogenic (198 K, 77 K) temperatures for two grain sizes (~7 and 68 µm), with emphasis on near-threshold behavior. We find that the ΔK th fatigue thresholds are increased with decreasing temperature and increasing grain size: from 5.7 MPa√m at 293 K to 8 MPa√m at 77 K in the fine-grained alloy, and from 9.4 MPa√m at 293 K to 13.7 MPa√m at 77 K in the coarse-grained alloy. Mechanistically, transgranular cracking at 293 K transitions to a mixture of intergranular and transgranular at cryogenic temperatures, where the increased propensity of nano-twins appears to inhibit growth rates by deflecting the crack path. However, the main factor affecting near-threshold behavior is roughness-induced crack closure from interference between the crack flanks, which is enhanced by the rougher fracture surfaces at low temperatures, particularly in the coarser-grained microstructure. Here, fatigue-crack propagation behavior in CrCoNi is comparable to nickel-based superalloys but is superior to that of the high-entropy CrMnFeCoNi (Cantor) alloy and many high-strength steels, making the CrCoNi alloy an excellent candidate material for safety-critical applications, particularly involving low temperatures.

36 MATERIALS SCIENCE↗

Intra-annual variations of regional total column ozone, aerosol optical depth, and water vapor from ground-based, satellite-based and model-based observations

The Microtops II ozonometer has been deployed to continuously measure the total column ozone (TCO), pre-cipitable water content (PWC) and aerosol optical thickness (AOT) at Atigre village (16.74° N, 74.37° E, 604 m above sea level, masl) located on the southeastern slope of Indian western Ghats. The Microtops II ozonometer measurements during the period from September 2017 to June 2018 were analyzed along with the retrieved products of Ozone Monitoring Instrument (OMI) and Moderate Resolution Imaging Spectroradiometer (MODIS) onboard NASA's Terra satellites and also the ERA-interim reanalysis model. We found that the TCO (or PWC) data from the OMI (or MODIS) and the ERA reanalysis model data products are in good agreement. The mea-surements showed strong seasonal variability such that TCO was lowest in the winter season but increased in the summer season, and both PWC and AOT were lowest in the post-monsoon season and increased in the summer season. In continuous ERA-interim reanalysis TCO observations, we found the three types of periodicities in the daily mean TCO as well as PWC (i) The weekly (7 days), (ii) quasi-biweekly (14 to 16 days), (iii) Madden Julian Oscillations (MJO) (30–60 days) oscillations. These oscillations depend on the periodic weather changes in the troposphere. We also observe that the average day to day variability in daily mean TCO observations in the observational period is about 1.4%, 1.1%, 2.62% in the Microtops II ozonometer, ERA-interim reanalysis, and OMI data respectively. We found the positive correlation between daily mean AOT and PWC in all seasons (except monsoon), which is maximum in the winter season, showing the hygroscopic nature of aerosols. The sources of water vapor and aerosol at our location are also studied using back-trajectory analysis.

Nade, Dada R.↗

Evaluation of IrO 2 catalysts doped with Ti and Nb at industrially relevant electrolyzer conditions: A comprehensive study

A series of commercial Oxygen Evolution Reaction (OER) IrO 2 -based materials doped with acid-stable titanium and niobium species were comprehensively characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS), and X-ray Scattering. Electrocatalysts were integrated into Membrane Electrode Assembly (MEA) using a fabrication method developed under the US DOE H2NEW consortium. An electrolysis performance in a commercial setup as well as a laboratory screening system was performed at conditions relevant to industrial application. According to the comprehensive characterizations, the studied materials are closer to doped iridium oxides rather than core–shell structures. In an electrolysis cell, the IrO 2 /TiO x catalyst slightly outperforms the IrO 2 /NbO x based on the activity. It was demonstrated that the operation of electrolysis cells at elevated temperatures and the implementation of thinner Nafion-type membranes allows for substantially increased performance, which is consistent with the literature report. Finally, this work provides valuable baselines including characterization and performance for guiding future research in this direction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Porous transport electrodes for oxygen evolution reaction in proton exchange membrane water electrolysis -cells: Materials, designs, and diagnoses

H 2 production using proton exchange membrane (PEM) water electrolysis (PEMWE) cells has received considerable attention because of the high efficiencies of these cells and no harmful emissions from the related process. In PEMWE cells, porous transport electrodes (PTEs) composed of a catalyst layer (CL) comprising O 2 evolution reaction (OER) catalysts, porous transport layer (PTL), and PEM play key roles in the stack performance and lifetime. Herein, Ir-based and non-precious-metal OER catalysts that are highly active and stable at low pH values and high anodic potentials are reviewed to understand their OER mechanisms. Various strategies are proposed for engineering CLs and PTLs to improve the interfacial properties and mass transfers of reactants and products to and from the active sites. Additionally, diagnoses of PTEs is significantly crucial for interpreting electrochemical processes and addressing their current challenges. Therefore, half-cell analyses, including diffusion electrode (DE), floating electrode (FE), and modified rotating disk electrode (MRDE) techniques, are explored, and membrane electrode assembly (MEA)-based analyses, such as the polarization technique, electrochemical impedance spectroscopy, and magnetic field analysis, are established. In conclusion, this study aims to provide an overview of recent technologies used for the engineering and diagnostic tools of PEMWE cells and insights into the advanced components and systems to be developed in this field.

Diagnosis of PEMWE Cells↗

Novel PtNi single-atom–nanocluster (SA–NC) ensembles promote Tafel kinetics and ampere-class AEM hydrogen evolution

The development of efficient, durable, and low-PGM electrocatalysts for the hydrogen evolution reaction (HER) in alkaline media is critical for next-generation electrolysis technologies. We report a facile two-step synthesis of highly dispersed PtNi and PtNi-nitride nanoclusters (NCs) (~2.3 nm) with ultralow Pt content (0.5 at.%) anchored on N-doped Vulcan carbon. Structural and compositional characterization via XAS, XPS, HAADF-STEM, HRTEM, and EDS mapping established key structure–activity relationships across varying Pt/Ni ratios and pyrolysis temperatures. The Pt0.5Ni0.5/C-750 catalyst, an ensemble of PtNi M-N-C type single-atom (SA) moieties with neighboring PtNi nanoclusters (NC), exhibited superior HER performance in alkaline media, achieving overpotentials of 30, 115, and 210 mV at 10, 100, and 500 mA cm−2, respectively. Despite at a lower Pt content, this novel SA–NC ensemble outperformed commercial Pt/C by ~36%. A standardized literature comparison with contemporary Pt- and Ru-doped analogues reveals the as-prepared Pt0.5Ni0.5/C-750 to sit at the apex of Tafel-limited kinetics and low overpotential at 100 mA cm−2. Tafel-limited Tafel slopes in both alkaline and acidic regimes confirm favorable proton recombination kinetics. Mass activities at 200 mV reached 13.8 and 18.84 A mgPt−1 in alkaline and acidic media, respectively. However, excessive nitridation (e.g., at 650 °C) adversely altered Pt electronic structure and HER kinetics. While Ni enhanced alkaline HER, acidic HER favored Ni-free analogues. Pt0.5Ni0.5/C-750 also demonstrated robust temperature responsiveness and 300-h operational stability at high current densities (0.5–1.0 A cm−2) in MEA tests. This work presents a scalable strategy for designing thermally responsive, durable, and compositionally tunable NC catalysts with neighboring SA moieties for alkaline electrolysis.

AEMWE↗

Effect of chloride ingress on self-healing recovery of smart cementitious composite incorporating crystalline admixture and MgO expansive agent

Highlights: • Crack closure under wet/dry cycles in chloride solution is higher than the one in distilled water. • Element analysis shows that calcium is vital for crack healing either in water or chloride solution. • AFm is consumed by chloride ion to form Fs, and Fs were decomposed to AH{sub 3} by carbonation. • Soluble reactive silica reacts with calcium hydrate to form C-S-H gel to heal concrete cracks. • Expansion of magnesium hydroxide facilitates crack self-healing by interconnected network. In this study, the effect of chloride environment containing various concentrations of chloride ion (Cl{sup −}) on self-healing performance of pre-cracked cementitious composite containing crystalline admixture (CA) and MgO expansive agent (MEA) was investigated under wet-dry cycles in chloride solutions. The results revealed that the Cl{sup −} changed the mineralogy of self-healing products, and consequently, affected the crack closure ratio and mechanical strength recovery. When self-healing occurred in distilled water, a large amount of ettringite (AFt) were detected, whereas in Cl{sup −} solution, monosulfate (AFm) was consumed by Cl{sup −} to form Friedel's salt (Fs), and then the Fs was decomposed to Al(OH){sub 3}(AH{sub 3}) due to carbonation. During the multiphase conversion process, hydroxide (OH{sup −}) was released into crack solution, therefore the dissolved carbon dioxide (CO{sub 2}) concentration was increased. The carbonation of the crystals formed in cracks was accelerated with the volume expansion, which achieved rapid crack sealing but contributed little to the mechanical performance recovery.

36 MATERIALS SCIENCE↗