Enhancing the phase stability of ceramics under radiation via multilayer engineering
This study provides a strategy to improve the phase stability of ceramic material under radiation through interface engineering.
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This study provides a strategy to improve the phase stability of ceramic material under radiation through interface engineering.
This study examines the activity of chemisorbed CO 2 species in the microenvironment formed by bifunctional ionic liquids (ILs) in the reactive capture and conversion (RCC) of CO 2 to CO on silver. Comparative electroanalytical measurements with imidazolium based ILs were performed to probe the impact of electrostatic interactions, anion and cation basicity, and hydrogen bonding on RCC. Particularly, ILs with 1-ethyl-3-methylimidazolium ([EMIM]+) and 1-ethyl-2,3-dimethylimidazolium ([EMMIM]+) cations and aprotic heterocyclic anions of 2-cyanopyrrolide ([2-CNpyr]) and 1,2,4-triazolide ([124-Triz]) were examined for RCC. It was found that anion–CO 2 carbamate complexes facilitate RCC at significantly lower overpotentials compared to cation–CO 2 carboxylate complexes. Additionally, [EMIM]+ was found to better stabilize anion–CO 2 complexes at the interface than [EMMIM]+. Furthermore, it was found that 2-CNpyrH that naturally forms during CO 2 absorption competes for electrode surface adsorption with the anion–CO 2 carbamate complex, thereby reducing the electrochemical activity of the anion–CO 2 complex. These results highlight the importance of IL structure in tuning the interfacial interactions and suggest that ILs with anion-dominated CO 2 chemisorption enhances CO 2 utilization in RCC applications.
In this project, a holistic analysis of architecture, stabilization, and cost/efficiency analysis in hybrid AC and DC distribution grids are conducted. Particularly, versatile and cost-efficient multiport converters are developed to not only integrate solar sources and other DERs in DC grids, but also facilitate the interactive operation of DC sub-grids and conventional AC distribution grids. Meanwhile, a universal and extended impedance-based stabilization approach with a decentralized and adaptive virtual impedance loop is developed in hybrid AC and DC distribution grids, which comprehensively covers the active stabilization of DC sections, AC sections, and interface inverters interlinking both AC and DC sections. Furthermore, to quantitatively evaluate the cost and efficiency of hybrid AC and DC distribution grids and quantify the improvement of hybrid AC and DC grids over conventional pure AC grids, the project team develops an alpha-version tool to monitor and calculate the efficiency and cost of the DC, AC, or hybrid AC and DC grids.
This work investigates the influence of sodium promotion on Ag/m-ZrO 2 catalysts for methanol steam reforming (MSR), focusing on activity, selectivity, surface chemistry, and mechanistic pathways. Temperature programmed reduction (TPR), XANES/EXAFS, CO 2 TPD, DRIFTS, and temperature programmed surface reaction methods were combined with fixed bed MSR testing to develop an integrated structure–function understanding of Na-modified Ag-ZrO 2 interfaces. Na addition systematically increases surface basicity, stabilizes strongly basic O 2− sites, and weakens the ν(CH) vibrational mode of surface formate, thereby facilitating C–H bond scission and accelerating decarboxylation to CO 2 . At moderate promoter levels (0.5–1.0 wt.% Na), the catalysts show significantly enhanced CO 2 selectivity and increased conversion relative to unpromoted Ag/m-ZrO 2 , while CH 4 formation remains negligible. Excessive Na (≥1.8 wt.%) leads to slower formate decomposition, greater carbonate stabilization, and suppressed conversion, revealing a narrow optimum around 1 wt.% Na. Short-term stability testing demonstrates steady conversion and product selectivity for both unpromoted and Na-promoted catalysts, with the latter maintaining markedly higher CO 2 selectivity. Although Pt/YSZ retains far superior intrinsic activity at ~10× higher space velocity, Ag offers a cost-advantaged alternative where lower cost metals are desirable. Collectively, these findings show that Na promotion enables tunable MSR selectivity on Ag/m-ZrO 2 by directing formate decomposition toward the CO 2 -forming pathway.
Oxygen can be extracted from carbon dioxide via thermal dissociation at elevated temperatures. However, temperatures in excess of 1000 K are needed to effect significant levels of dissociation. The experiments reported here have examined the feasibility of using a glow-discharge in low-pressure carbon dioxide to produce increased atomic oxygen yields at lower temperatures (on the order of 800 K). The experiments have shown that when silver membranes are used simultaneously as anodes for the glow discharge and as permeable membranes for oxygen separation, oxygen yields which are comparable to the permeation rates for pure oxygen, can be produced. Since the silver membrane can be employed as the electrode interface between Mars atmosphere and a stabilized-zirconia electrochemical pump, glow-discharge enhancement can be considered as a complementary technology which can be used with the zirconia-based oxygen extraction systems described previously by others. Not only can glow-discharge be used to increase oxygen yields at lowered temperatures, but it can also be considered as a possible way to avoid filtration and compression of Mars atmosphere, since the glow-discharge can be sustained in Mars ambient pressures.
The research summarized in this report has involved a combined theoretical and computational study of fluid flow that results from the random acceleration environment present onboard space orbiters, also known as g-jitter. We have focused on a statistical description of the observed g-jitter, on the flows that such an acceleration field can induce in a number of experimental configurations of interest, and on extending previously developed methodology to boundary layer flows. Narrow band noise has been shown to describe many of the features of acceleration data collected during space missions. The scale of baroclinically induced flows when the driving acceleration is random is not given by the Rayleigh number. Spatially uniform g-jitter induces additional hydrodynamic forces among suspended particles in incompressible fluids. Stochastic modulation of the control parameter shifts the location of the onset of an oscillatory instability. Random vibration of solid boundaries leads to separation of boundary layers. Steady streaming ahead of a modulated solid-melt interface enhances solute transport, and modifies the stability boundaries of a planar front.
Finite element analysis was vital to the design and optimization of the kinematic mounts for the Near Infrared Camera (NIRCam) instrument The design had to meet dueling structural requirements driven by 12G launch loads, a survivability of bulk cool down from room temperature to 22 K, minimum first mode of 50 Hz and mass allocation constraints. Additionally the design has to meet stability and Integrated Science Instrument Module (ISIM) interfaces when cooled to 22K.
In the adjoining letter, Dessler [1961] argues that the interface between the solar wind and the geomagnetic field is stable and cannot, therefore, generate hydromagnetic waves. According to our interpretation, his argument may be paraphrased as follows: He observes that, for many sudden commencement geomagnetic storms, surface magnetograms show no marked change in the level of disturbances from the period before the sudden commencement until well into the initial phase of the storm. He applies the attenuation factors calculated by Francis and Karplus [1960] to the measurements of the 1 cps component of the magnetic disturbances obtained at the surface. From this calculation, he concludes that, during the initial phase of these geomagnetic storms, the amplitudes of hydromagnetic disturbances above the ionosphere are less than 1. Assuming that the sudden commencement indicates the presence of a solar wind, he further concludes that hydromagnetie disturbances are not generated in the region between the geomagnetic field and the solar wind and that this interface is, therefore, inherently stable. He subsequently accounts for the hydromagnetie disturbances which are frequently observed at the earth as having been produced by fluctuations in the energy density of the impinging solar wind.
Understanding how supported metal nanoparticles dynamically evolve under reaction conditions is critical for controlling their catalytic function. Here, the mechanism behind the dynamic disintegration of Pt nanoparticles (NPs) supported on CeOx-TiO2 (CT) during CO oxidation is elucidated, leading to the formation of single atoms (SAs) and/or sub-nanometer clusters. Density functional theory (DFT) calculations reveal that strong Pt-CO interactions weaken Pt─Pt cohesion, while electronic coupling between Pt and Ce ions stabilizes Pt-CO* intermediates at the oxide interface. Surface oxygen vacancies kinetically trap Pt-CO*, but the vacancies are replenished under oxygen-rich conditions, enabling Pt-CO* surface diffusion and subsequent structural reorganization. In situ spectroscopic analyses confirm the oxygen-driven transformation of Pt NPs, correlating with a threefold increase in mass-specific activity at 150 °C. These findings demonstrate that interfacial oxygen dynamics and metal-support interactions can be leveraged to induce nanoparticle disintegration and optimize catalytic performance, highlighting the catalytic potential of interface-engineered Pt nanostructures.
Sulfide electrolyte all-solid-state lithium batteries (ASLBs) with uncoated Li-Ni x Mn y Co 1–x–y O 2 (NMC) cathodes suffer from a large capacity loss during initial cycling and an increase in cell impedance. Decomposition reactions are known to occur at the Li 6 PS 5 Cl-NMC111 interface due to incompatibility between the two materials. If a stabilizing coating is applied to the NMC, it delivers full capacity during initial charge. However, the loss in capacity during discharge still occurs. The interface was studied by μ XANES and through EIS analysis. A chemically-formed interphase was detected by μ XANES, evident from reduction of Co at an uncoated NMC particle surface. This interphase was produced by decomposition at rest. To study the effect of the interphase on electrochemically active surface area, piecewise in situ EIS was performed and the data was modeled using a transmission line model (TLM). The charge transfer resistance R CT was used to estimate the volume specific active surface area (a act ). The median value for a act was 296 cm –1 , a factor of 7.5 lower than the theoretical value of 2216 cm –1 . This provided evidence of a lower electrochemically active surface area in the ASLB.
2D-on-3D (2D/3D) perovskite heterostructures with engineered energy landscapes offer the potential to realize efficient and stable inverted solar cells. However, managing the energy landscape using 2D perovskites with thicker inorganic layers n > 1 necessitates the usage of the chemically unstable methylammonium MA + . Here, we synthesized formamidinium (FA)-rich and pure-FA n = 3 Ruddlesden-Popper (RPP) and Dion-Jacobson perovskite (DJP) single crystals by identifying ligands with suitably lattice-matched organic and inorganic components of the 2D lattice. These crystals were translated onto 3D perovskites as capping layers, forming 2D/3D hetero-bilayers (HBs). Degradation studies revealed that HBs with butylammonium-based RPPs as capping layers rapidly phase segregate into non-perovskites under combined extrinsic stressors, compromising the underlying 3D layer, whereas FA-rich DJPs based on 3-aminomethylpiperidine retain their phase stability. The DJP HBs also possess a favorable energy landscape and electron transport at the 2D/3D interface, enabling inverted solar cells with a champion PCE of 25.33% and remarkable stability.
Metal halide perovskites are promising for optoelectronic device applications; however, their poor stability under solar illumination remains a primary concern. While the intrinsic photostability of isolated neat perovskite samples has been widely discussed, it is important to explore how charge transport layers—employed in most devices—impact photostability. Here, in this paper, we study the effect of organic hole transport layers (HTLs) on light-induced halide segregation and photoluminescence (PL) quenching at perovskite/organic HTL interfaces. By employing a series of organic HTLs, we demonstrate that the HTL’s highest occupied molecular orbital energy dictates behavior; furthermore, we reveal the key role of halogen loss from the perovskite and subsequent permeation into organic HTLs, where it acts as a PL quencher at the interface and introduces additional mass transport pathways to facilitate halide phase separation. In doing so, we both reveal the microscopic mechanism of non-radiative recombination at perovskite/organic HTL interfaces and detail the chemical rationale for closely matching the perovskite/organic HTL energetics to maximize solar cell efficiency and stability.
W-ZrC composites were successfully prepared by reactive melt infiltration (RMI) of stoichiometric and excess amounts of Zr 2 Cu into sintered and un-sintered WC preforms made from binder jet 3D printing. The focus of this work was to study the conversion of reactant powders and liquid infiltrant with varying preform density and infiltrant amount by controlling the processing time to reach high conversion yield while understanding the phase composition, microstructure, and hardness. To investigate the effect of time, the reactive melt infiltration was conducted at 1400 °C for 2, 4 and 8 h in a furnace with 96% Ar - 4% H2 gas atmosphere. The increase in reaction time from 2 to 8 h increased the W and W 2 C phase contents and decreased the ZrC phase content when using sintered WC preforms. Samples prepared from un-sintered WC preforms exhibited improved reactive melt infiltration compared to sintered samples, and there was no detectable W 2 C phase and nearly full consumption of WC. Similar to sintered WC samples, the content of W and ZrC phases increased with the increase in time from 2 to 8 h. The interfaces and phases at reaction interfaces were investigated using electron diffraction analysis and S/TEM-EDS to understand material stability; the phases were identified and consistent with XRD analysis. Additionally, there was no Cu present at the interfaces. Increasing the amount of infiltrant led to better reactive melt infiltration. In general, the hardness increased with reaction time and the highest Vickers hardness was found in the W-ZrC sample formed from sintered WC reacted with excess Zr 2 Cu. Finally, this research addresses the critical comparison of sintering and RMI time and shows that by using un-sintered samples for 8 h we are able to achieve W-ZrC composites with fewer undesired phases.
The building blocks of a computer algorithm developed for the time-accurate flow analysis of rotating machines are described. The flow model is a finite volume method utilizing a high resolution approximate Riemann solver for interface flux definitions. This block LU implicit numerical scheme possesses apparent unconditional stability. Multi-block composite gridding is used to orderly partition the field into a specified arrangement. Block interfaces, including dynamic interfaces, are treated such as to mimic interior block communication. Special attention is given to the reduction of in-core memory requirements by placing the burden on secondary storage media. Broad applicability is implied, although the results presented are restricted to that of an even blade count configuration. Several other configurations are presently under investigation, the results of which will appear in subsequent publications.
Transport layer and interface optimization is critical for improving the performance and stability of perovskite solar cells (PSCs) but is restricted by the conventional fabrication approach of sequential layer deposition. While the bottom transport layer is processed with minimum constraints, the narrow thermal and chemical stability window of the halide perovskite (HP) layer severely restricts the choice of top transport layer and its processing conditions. To overcome these limitations, we demonstrate lamination of HPs—where two transport layer-perovskite half-stacks are independently processed and diffusion-bonded at the HP-HP interface—as an alternative fabrication strategy that enables self-encapsulated solar cells. Power conversion efficiencies (PCE) of >21% are realized using cells that incorporate a novel transport layer combination along with dual-interface passivation via self-assembled monolayers, both of which are uniquely enabled by the lamination approach. This is the highest reported PCE for any laminated PSC encapsulated between glass substrates. We further show that this approach expands the processing window beyond traditional fabrication processes and is adaptable for different transport layer compositions. The laminated PSCs retained >75% of their initial PCE after 1000 h of 1-sun illumination at 40 °C in air using an all-inorganic transport layer configuration without additional encapsulation. Furthermore, a laminated 1 cm 2 device maintained a V oc of 1.16 V. Finally, the scalable lamination strategy in this study enables the implementation of new transport layers and interfacial engineering approaches for improving performance and stability.
The Ca 2+ solvation structure at the electrolyte/electrode interface is of central importance to understand electroreduction stability and solid–electrolyte interphase (SEI) formation for the novel multivalent Ca battery systems. Here, using an exemplar electrolyte, the concentration-dependent solvation structure of Ca(BH 4 ) 2 -tetrahydrofuran on a gold model electrode has been investigated with various electrolyte concentrations via electrochemical quartz crystal microbalance with dissipation (EQCM-D) and X-ray photoelectron spectroscopy (XPS). For the first time, in situ EQCM-D results prove that the prevalent species adsorbed at the interface is CaBH 4 + across all concentrations. As the salt concentration increases, the number of BH 4 – anions associated with Ca 2+ increases, and much larger solvated complexes such as CaBH 4 + ·4THF or Ca(BH 4 ) 3 – ·4THF form at the interface at high concentrations prior to Ca plating. Different interfacial chemistries lead to the formation of SEIs with different components demonstrated by XPS. High electrolyte concentrations reduce the solvent decomposition and promote the formation of thick, uniform, and inorganic-rich (i.e., CaO) SEI layers, which contribute to improved Ca plating efficiency and current density in electrochemical measurements.
The science and technologies of emulsion droplets have been a long‐term focus of extensive research endeavors for their practical utility across a breadth of industries, including pharmaceutical products, oil recovery processes, and the food sciences. However, with advances in materials chemistry and characterization tools, new emerging areas are arising with a focus on “smart droplets”. The versatility of emulsion droplets across is based on their ability to partition and create isolated systems with properties defined by the liquid–liquid interface, while preparative routes allow manipulation of droplet size, stability, and encapsulated contents. As described in this article, significant efforts are being devoted to creating new types of droplets by “activating” this interface through the incorporation of reactive structures that trigger droplet response to applied or environmental stimuli (e.g., pH, temperature, salt, or external fields). Moreover, parallels between droplets and live cells inspire efforts to conceive systems that resemble biological motifs or that can produce cellular behaviors that imitate biology (e.g., swarming, communication, or motion). Here, the authors highlight recent advances in smart droplets, with emphasis on organic, polymer, and/or particle surfactants that give rise to inter‐droplet communication (via aggregation, fusion, division, or mass transfer), droplet vehicles for controlled delivery, autonomous droplet motion, and tunable emulsion inversion. Especially emphasized is the macromolecular design to produce reactive and functional surfactants, which are crucial to responsive droplet behavior and their underlying mechanisms. More generally, the exquisite interplay between materials science and biology inspires the review of this research area that provides unique opportunities for insight and inspiration into the capabilities of new droplet designs.
A stratified interface is stable to the buoyancy reversal instability for surprisingly large values of D (buoyancy reversal parameter). A new instability mechanism is proposed, which considers the mixing process at the interface. For the type of density curves studied here, under strong perturbations, the mixed parcel must have a buoyancy reversal comparable to the initial stratification before the interface is unstable. This is in accord with a simple model of the interface mixing process, as well as aircraft observations of long-live marine stratocumulus clouds. These clouds' remarkable longevity in the face of finite D indicates that they can be stable (Hanson, 1984; Albrecht et al., 1985; Siems et al., 1989). It is suggested that buoyancy reversal as well as the disturbance must be large for Cloudtop Entrainment Stability. The effect of buoyancy reversal (evaporative cooling) does not always enhance the entrainment rate over that in the inert case, but it may be negligible if Ri (Richardson number) is large (Ri is larger than 50) and D is small (D is smaller than 0.5). This work may shed some light on the fundamental mechanism of the breakup process of the subtropical stratocumulus clouds into tradewind cumulus. These results may also be related to the instability in the Weddell Sea off of Antarctica.