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At least 919 records · Page 51

Understanding_the_deactivation_mechanisms_of_ethanol_conversion_over_Cu-Y_Beta_catalyst

Direct conversion of bioethanol to C₃⁺olefins is a promising pathway for sustainable aviation fuel (SAF) production, but catalyst deactivation limits long-term operation. The stability and deactivation mechanisms of multifunctional Cu–Y/Beta zeolite catalysts were investigated for ethanol-to-olefins conversion over 300 h time-on-stream in the presence of H2. Catalytic testing reveals progressive losses in ethanol conversion and C₃⁺ olefin selectivity accompanied by increased acetaldehyde formation. The catalyst testing studies correlate with a suite of characterizations of fresh, spent, and regenerated catalysts to identify the deactivation factors. The loss of Y Lewis acid sites is the primary deactivation element. Reversible acid site deactivation is caused by coke deposition, which blocks Y-derived Lewis acid sites responsible for aldol condensation, MPV reduction, and alcohol dehydration. Minor irreversible deactivation is observed and possibly results from hydrothermal dehydroxylation of Y–silanol interactions, resulting in permanent loss of Lewis acidity without zeolite framework degradation or Y aggregation. Cu sites undergo limited agglomeration into small nanoparticles but contribute insignificantly to catalyst deactivation, under the investigated time frame. Oxidative regeneration removes coke and redistributes Cu sites, leading to full recovery of the initial catalytic performance though the Y Lewis acid sites are unable to fully recover. These findings establish Lewis acid site degradation as the primary deactivation mechanism impacting long-term catalyst stability

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding the Cathode Electrochemistry of Humidified Solid‐State Lithium‐Oxygen Batteries

Lithium-oxygen batteries (LOBs) possess a high theoretical energy density, making them potential candidates for next-generation energy storage. However, challenges such as reactive oxygen species-induced component degradation hinder their practical use. Inorganic solid-state electrolytes offer an alternative to degradation-prone aprotic electrolytes, while also protecting lithium anodes from potential atmospheric reactants. Here, this study explores the cathode electrochemistry of solid-state LOBs using humidified oxygen, which forms an aqueous catholyte during initial cycling, thereby improving cathode-electrolyte contact. To quantitatively analyze the cathode electrochemistry, a ‘Humidity-Incorporated’ Differential Electrochemical Gas Monitoring System (HiDEMS) is developed to control humidity and monitor gas consumption and evolution in real time. When studying a Li-O 2 cell that employs a NASICON-type Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) solid electrolyte and a porous carbon cathode, a shift in discharge products from Li 2 O 2 to LiOH is observed over repeated cycles. While Li 2 O 2 evolves O 2 during charging, LiOH oxidation leads to minimal O 2 release and increased CO 2 production, originating from oxidation of carbon electrodes. Further, dissolution of Al and P from LATP is observed, likely driven by the formation of the alkaline catholyte. The findings highlight the need for carbon-free cathode materials and more stable solid-state conductors to minimize side reactions and improve rechargeability in humidified solid-state Li-O 2 batteries.

LATP degradation↗

Intermediate Temperature Strength Degradation in SiC/SiC Composites

Woven silicon carbide fiber-reinforced, silicon carbide matrix composites are leading candidate materials for an advanced jet engine combustor liner application. Although the use temperature in the hot region for this application is expected to exceed 1200 C, a potential life-limiting concern for this composite system exists at intermediate temperatures (800 +/- 200 C), where significant time-dependent strength degradation has been observed under stress-rupture loading. A number of factors control the degree of stress-rupture strength degradation, the major factor being the nature of the interphase separating the fiber and the matrix. BN interphases are superior to carbon interphases due to the slower oxidation kinetics of BN. A model for the intermediate temperature stress-rupture of SiC/BN/SiC composites is presented based on the observed mechanistic process that leads to strength degradation for the simple case of through-thickness matrix cracks. The approach taken has much in common with that used by Curtin and coworkers, for two different composite systems. The predictions of the model are in good agreement with the rupture data for stress-rupture of both precracked and as-produced composites. Also, three approaches that dramatically improve the intermediate temperature stress-rupture properties are described: Si-doped BN, fiber spreading, and 'outside debonding'.

Morscher, Gregory N.↗

Morphological Degradation of Oxygen Evolution Reaction-Electrocatalyzing Nickel Selenides at Industrially Relevant Current Densities

We investigated electrodeposited nanoparticulate nickel selenide (pre)catalysts that transform into nickel oxides/ oxyhydroxides under oxygen evolution reaction conditions in alkaline solutions. Previous studies of this transformation were conducted at lower current densities than those of industrial relevance (≥1 A cm −2 ). We used ultramicroelectrodes (UMEs) to achieve such current densities, benefiting from their small size, ensuring low absolute currents and low ohmic drop but high current densities. Morphological degradation of the catalyst material was only observed at current densities exceeding 1 A cm −2 but not for smaller ones. Using X-ray absorption, Xray photoemission spectroscopy, and X-ray diffraction, we confirmed that the degradation was accompanied by the literature-known transformation of nanoparticulate Ni 3 Se 2 (bulk)/NiSe (surface) into nickel oxyhydroxide. The transformation of the precatalyst goes along with a significant improvement in the charge transfer kinetics observed by decreasing Tafel slopes with ongoing experimental time extracted from cyclic voltammetry (CV) experiments and electrochemical impedance spectroscopy (EIS) in the high-frequency range. However, these kinetic improvements are accompanied by limitations in mass transport concluded from decreasing current responses at high overpotentials in CVs and increasing impedance in the low-frequency range of the EIS spectra after extended CV cycling. These mass transport limitations originated from morphological degradations at the UME exceeding 1 A cm −2 which we proved by applying identical location scanning electron microscopy. This has not been reported in studies that have been limited to lower current densities before. Our findings showcase how UMEs can be used to study (pre)catalysts (herein nickel selenides) under current densities of industrial relevance in the absence of ohmic drop-related ambiguities, combined with in-depth materials characterization studies, e.g., identical location microscopy and advanced spectroscopic methods. This approach enables direct evaluation and comparison of catalyst materials and thus demonstrates how to overcome long-standing limitations of electrocatalyst design and testing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nickel-incorporated Oxide Composites for Fiber-Optic Based Gas Sensing

Numerous high-value applications within the energy sector involve environmental conditions that are incompatible with traditional sensor technology due to degradation of electrical interconnects, packaging, or the sensors themselves. These can include chemically harsh conditions, high temperature operation, or the presence of electromagnetic interference due to high voltage. The fiber optic platform, constructed of robust, electrically insulating glass or single crystal oxides, offers a versatile and often low cost per node solution to this problem, especially with the integration of distributed sensing techniques such as optical time-domain and frequency-domain reflectometry (OTDR, OFDR). A major challenge of gas and chemical sensing on the optical fiber platform is the fabrication of robust and stable sensing materials that interact quickly and reversibly to the presence of the target analytes. In this work, we discuss the utilization of nickel-incorporated oxides on evanescent-field optical fiber sensors for gas sensing under harsh conditions relevant to multiple energy infrastructure applications. This paper will discuss a Ni/GDC (Ni / Gd-doped ceria) based sensing layer targeting conditions relevant for high-temperature (up to at least 800 oC) hydrogen sensing applications (e.g., for operation within a solid oxide fuel cell or electrolyzer). The impact of hydrogen at elevated temperatures on the optical properties of Ni/GDC will be shown and the material mechanisms for the optical response will be discussed.

gas sensors↗

Nickel-incorporated Oxide Composites for Fiber-Optic Based Gas Sensing

Numerous high-value applications within the energy sector involve environmental conditions that are incompatible with traditional sensor technology due to degradation of electrical interconnects, packaging, or the sensors themselves. These can include chemically harsh conditions, high temperature operation, or the presence of electromagnetic interference due to high voltage. The fiber optic platform, constructed of robust, electrically insulating glass or single crystal oxides, offers a versatile and often low cost per node solution to this problem, especially with the integration of distributed sensing techniques such as optical time-domain and frequency-domain reflectometry (OTDR, OFDR). A major challenge of gas and chemical sensing on the optical fiber platform is the fabrication of robust and stable sensing materials that interact quickly and reversibly to the presence of the target analytes. In this work, we discuss the utilization of nickel-incorporated oxides on evanescent-field optical fiber sensors for gas sensing under harsh conditions relevant to multiple energy infrastructure applications. This paper will discuss a Ni/GDC (Ni / Gd-doped ceria) based sensing layer targeting conditions relevant for high-temperature (up to at least 800oC) hydrogen sensing applications (e.g., for operation within a solid oxide fuel cell or electrolyzer). The impact of hydrogen at elevated temperatures on the optical properties of Ni/GDC will be shown and the material mechanisms for the optical response will be discussed.

gas sensors↗

A Subunit of ESCRT-III, MoIst1, Is Involved in Fungal Development, Pathogenicity, and Autophagy in Magnaporthe oryzae

The culprit of rice blast, Magnaporthe oryzae , is a filamentous fungus that seriously affects the yield and quality of rice worldwide. MoIst1, a subunit of ESCRT-III, is involved in identified ubiquitinated proteins and transports them into the intraluminal vesicles of multivesicular bodies (MVBs) for degradation in lysosomes. Here, we identify and characterize MoIst1 in M. oryzae . Disruption of MoIst1 leads to a significant decrease in sporulation and formation of appressoria, defects in response to oxidative stress, cell wall stress, hyperosmotic stress, and reduced pathogenicity. Deletion of MoIst1 also caused the decreased Pmk1 phosphorylation levels, appressorium formation, the delayed translocation and degradation of lipid droplets and glycogen, resulting in a decreased appressorium turgor. In addition, deletion of MoIst1 leads to an abnormal autophagy. In summary, our results indicate that MoIst1 is involved in sporulation, appressorium development, plant penetration, pathogenicity, and autophagy in M. oryzae .

Sun, Lixiao↗

Degradation Characterization of Unsteady Pressure-Sensitive Paint Under Various Pressures

The lifetime and intensity techniques are two distinct methods used to measure the surface pressure of wind tunnel models with pressure-sensitive paint (PSP). When exposed to 405 nm light for extended periods, both the luminescence and the lifetime ratio were observed to decrease, affecting perceived pressure values. To help further the implementation of the uPSP, this paper describes the efforts to characterize the degradation of both the intensity of the paint and its lifetime ratio, as well as the change in intensity calibration. It was found that the paint degrades at different rates depending on the partial pressure of oxygen during excitation. It was also found that the calibration curves exhibit greater changes when under higher oxygen concentrations, both indicating photodegradation due to photodecomposition and photo-oxidation processes. These effects are observed on models in a subsonic 14” × 14” wind tunnel. The work provides insight into the dynamic degradation behavior of PSP and uPSP, paving the way to reduce the error in pressure measurements obtained through these techniques.

Pressure-Sensitive Paint↗

Electrochemical cleaning: An in-Situ method to reverse chromium poisoning in solid oxide fuel cell cathodes

Chromium poisoning is one of the primary factors that affect solid oxide fuel cell (SOFC) durability. In this study, an electrochemical cleaning method has been employed to reverse the effects of chromium poisoning. Two cells were fabricated and poisoned under identical conditions by operating them at 800°C in the presence of a Cr source. Both poisoned cells exhibited a significant reduction in maximum power density and an increase in polarization resistance. One of the poisoned cells, designated as the baseline cell, was cooled to room temperature after poisoning. Microstructural observation of the baseline cell showed significant contamination of the cathode active layer by chromium oxide and (Cr,Mn) spinel deposits. The other poisoned cell was electrochemically cleaned for two hours under a mild electrolytic condition. As a result of the electrochemical cleaning process, the chromium oxide deposits were substantially removed leading to a significant reduction of Cr concentration in the cathode, especially at the cathode/electrolyte interface. Furthermore, a substantial fraction of the cell performance loss was also reversed. To the best of our knowledge, this is a first demonstration of reversing the effects of chromium poisoning using a rapid in-situ process.

30 DIRECT ENERGY CONVERSION↗

Enhancing the Multifunctional Photocatalytic Activity of Sustainable Magnetic Nanoparticles

The development of efficient photocatalytic materials has intensified in response to increasing emphasis on sustainable energy conversion and environmental restoration. However, the excessive use and indiscriminate release of heavy metals from photocatalytic nanoparticles pose potential environmental risks. This study provides insights into optimizing visible-light-active photocatalysts to enhance their photocatalytic properties and stability. Specifically, cobalt doping and controlled pH modulation are employed on the modified Fe 3 O 4 , forming two distinct samples: Co@Fe 3 O 4 -B (base-treated) and Co@Fe 3 O 4 -A (acid-treated) nanoparticles. Microscopic characterization reveals that Co@Fe 3 O 4 -A undergoes a phase transition to hematite, whereas Co@Fe 3 O 4 -B retains its mixed-phase configuration. Spectroscopic analyses confirm that the cobalt dopants decorate the outskirts of each nanoparticle, forming a core–shell structure. However, Co@Fe 3 O 4 -B exhibit Co 2+ states with a high oxygen vacancy content, whereas Co@Fe 3 O 4 -A contain mixed Co 2+/3+ states. The high density of defect states in the Co@Fe 3 O 4 -B results in superior photocatalytic efficiency, achieving near-complete oxidation of furfuraldehyde (97% conversion) and 5-hydroxymethylfurfural (94% conversion), as well as effective degradation of toluene (78% conversion). This study demonstrates that the combined approach of doping and pH treatment is promising for the surface-defect engineering of photocatalysts, enhancing their multifunctional performance and reusability for sustainable energy conversion.

Fe3 O4 nanoparticles↗

Persistent and partially mobile oxygen vacancies in Li-rich layered oxides

Increasing the energy density of layered oxide battery electrodes is challenging as accessing high states of delithiation often triggers voltage degradation and oxygen release. Here we utilize transmission-based X-ray absorption spectromicroscopy and ptychography on mechanically cross-sectioned Li 1.18–x Ni 0.21 Mn 0.53 Co 0.08 O 2–δ electrodes to quantitatively profile the oxygen deficiency over cycling at the nanoscale. The oxygen deficiency penetrates into the bulk of individual primary particles (~200 nm) and is well-described by oxygen vacancy diffusion. Using an array of characterization techniques, we demonstrate that, surprisingly, bulk oxygen vacancies that persist within the native layered phase are indeed responsible for the observed spectroscopic changes. We additionally show that the arrangement of primary particles within secondary particles (~5 μm) causes considerable heterogeneity in the extent of oxygen release between primary particles. Finally, our work merges an ensemble of length-spanning characterization methods and informs promising approaches to mitigate the deleterious effects of oxygen release in lithium-ion battery electrodes.

25 ENERGY STORAGE↗

Exploring the Performance and Reliability of Screen-Printable Fire-Through Copper Paste on PERC Solar Cells

In this work, we present the performance and reliability of a fire-through copper (Cu) paste which has been screen printed on c-Si solar cell with passivated emitter rear contact (PERC). The Cu paste is fired through silicon nitride (SiN) anti-reflection coating at a peak temperature of 630 degrees C . SEM images of the Cu paste show a Cu core with ~200 nm oxide shell around the particles. This conductive oxide layer acts as a diffusion barrier between Cu and Si and prevents the degradation of cell performance during accelerated aging conditions. An efficiency of 19.250% has been achieved with Voc=654mV,FF= 76.68%, Jsc=38.40 m.A/cm 2 for champion PERC cells. Accelerated testing of the PERC mini-modules in damp heat chamber with 85 degrees C and 85% humidity have demonstrated that the devices are operational even after 1,500 hours. Devices with screen printed Ag contacts on the front side have been studied in parallel to the Cu contacts for comparison.

copper↗

Effects of temperature and hold times on low cycle fatigue of Astroloy

Low cycle fatigue (LCF) and creep-fatigue-environment interactions of HIP Astroloy were studied at 650 C and 725 C. The results showed that the model proposed by Kaisand and Mowbray (1979) was successful in predicting the magnitude and trend of the fatigue crack growth rate from LCF data. Raising the temperature from 650 C to 725 C did not change the fracture mode, while employing tensile hold caused a change in fracture mode and was more damaging than raising the temperature by 75 C. All samples displayed multiple fracture origins, which is initiated transgranularly in continuous cycling tests and intergranularly in hold time tests. An examination of the secondary crack showed no apparent creep damage. Oxidation in high purity argon appeared to be the major factor in LCF life degradation due to hold time.

Choe, S. J.↗

An empirical approach to predicting long term behavior of metal particle based recording media

Alpha iron particles used for magnetic recording are prepared through a series of dehydration and reduction steps of alpha-Fe2O3-H2O resulting in acicular, polycrystalline, body centered cubic (bcc) alpha-Fe particles that are single magnetic domains. Since fine iron particles are pyrophoric by nature, stabilization processes had to be developed in order for iron particles to be considered as a viable recording medium for long term archival (i.e., 25+ years) information storage. The primary means of establishing stability is through passivation or controlled oxidation of the iron particle's surface. A study was undertaken to examine the degradation in magnetic properties as a function of both temperature and humidity on silicon-containing iron particles between 50-120 C and 3-89 percent relative humidity. The methodology to which experimental data was collected and analyzed leading to predictive capability is discussed.

Hadad, Allan S.↗

Isothermal Damage and Fatigue Behavior of SCS-6/Timetal 21S [0/90](Sub S) Composite at 650 Deg C

The isothermal fatigue damage and life behaviors of SCS-6/Timetal 21S (0/90)s were investigated at 650 C. Strain ratcheting and degradation of the composite's static elastic modulus were carefully monitored as functions of cycles to indicate damage progression. Extensive fractographic and metallographic analyses were conducted to determine damage/failure mechanisms. Resulting fatigue lives show considerable reductions in comparison to (0) reinforced titanium matrix composites subjected to comparable conditions. Notable stiffness degradations were found to occur after the first cycle of loading, even at relatively low maximum stress levels, where cyclic lives are greater than 25,000 cycles. This was attributed to the extremely weak fiber/matrix bond which fails under relatively low transverse loads. Stiffness degradations incurred on first cycle loadings and degradations thereafter were found to increase with increasing maximum stress. Environmental effects associated with oxidation of the (90) fiber interfaces clearly played a role in the damage mechanisms as fracture surfaces revealed environment assisted matrix cracking along the (90) fibers. Metallographic analysis indicated that all observable matrix fatigue cracks initiated at the (90) fiber/matrix interfaces. Global de-bonding in the loading direction was found along the (90) fibers. No surface initiated cracks were evident and minimal if any (0) fiber cracking was visible.

Castelli, Michael G.↗

The surface properties of fluorinated polyimides exposed to VUV and atomic oxygen

The effect of atomic oxygen flux and VUV radiation alone and in combination on the surface of fluorinated polyimide films was studied using XPS spectroscopy. Exposure of fluorinated polyimides to VUV radiation alone caused no observable damage to the polymer surface, while an atomic oxygen flux resulted in substantial oxidation of the surface. On the other hand, exposure to VUV radiation and atomic oxygen in combination caused extensive oxidation of the polymer surface after only 2 minutes of exposure. The amount of oxidized carbon on the polymer surface indicated that there is aromatic ring opening oxidation. The changes in the O1s/C1s, N1s/C1s, and F1s/C1s ratios suggested that an ablative degradation process is highly favorable. A synergistic effect of VUV radiation in the presence of atomic oxygen is clearly evidenced from the XPS study. The atomic oxygen could be considered as the main factor in the degradation process of fluorinated polyimide films exposed to a low earth orbit environment.

Forsythe, John S.↗

Thermally Stable Ohmic Contacts on Silicon Carbide Developed for High- Temperature Sensors and Electronics

The NASA aerospace program, in particular, requires breakthrough instrumentation inside the combustion chambers of engines for the purpose of, among other things, improving computational fluid dynamics code validation and active engine behavioral control (combustion, flow, stall, and noise). This environment can be as high as 600 degrees Celsius, which is beyond the capability of silicon and gallium arsenide devices. Silicon-carbide- (SiC-) based devices appear to be the most technologically mature among wide-bandgap semiconductors with the proven capability to function at temperatures above 500 degrees Celsius. However, the contact metalization of SiC degrades severely beyond this temperature because of factors such as the interdiffusion between layers, oxidation of the contact, and compositional and microstructural changes at the metal/semiconductor interface. These mechanisms have been proven to be device killers. Very costly and weight-adding packaging schemes that include vacuum sealing are sometimes adopted as a solution.

Okojie, Robert S.↗