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At least 451 records · Page 25

Evaluation of Selected Solid Lubricating Films

An investigation was conducted to examine the friction and wear properties of bonded molybdenum disulfide (MoS2), magnetron-sputtered MoS2, ion-plated silver, ion-plated lead, magnetron-sputtered diamondlike carbon (MS DLC), and plasma-assisted, chemical-vapor-deposited DLC (PACVD DLC) films in sliding contact with 6-mm-diameter AISI 440C stainless steel balls. Unidirectional ball-on-disk sliding friction experiments were conducted with a load of 5.9 N and a sliding velocity of 0.2 m/s at room temperature in three environments: ultrahigh vacuum (vacuum pressure, 7 x 10(exp -7) Pa), humid air (relative humidity, approx. 20 percent), and dry nitrogen (relative humidity, less than 1 percent). The main criteria for judging the performance of the solid lubricating films were coefficient of friction and wear rate, which had to be less than 0.3 and on the order of 10(exp -6) cubic mm/N(dot)m or less, respectively. The bonded MoS2 and magnetron-sputtered MoS2 films met the criteria in all three environments. The ion-plated lead and silver films met the criteria only in ultrahigh vacuum but failed in humid air and in dry nitrogen. The MS DLC and PACVD DLC films met the requirements in humid air and dry nitrogen but failed in ultrahigh vacuum.

Miyoshi, Kazuhisa↗

Durability Evaluation of Selected Solid Lubricating Films

An investigation was conducted to examine the coefficients of friction, wear rates, and durability of bonded molybdenum disulfide (MoS2), magnetron-sputtered MoS2, ion-plated silver, ion-plated lead, magnetron-sputtered diamondlike carbon (MS DLC), and plasma-assisted, chemical-vapor-deposited DLC (PACVD DLC) films in sliding contact with 6-mm-diameter AISI 440C stainless steel balls. Unidirectional ball-on-disk sliding friction experiments were conducted with a load of 5.9 N and a sliding velocity of 0.2 m/s at room temperature in three environments: ultrahigh vacuum (vacuum pressure, 7 x 10(exp -7) Pa), humid air (relative humidity, approx. 20 percent), and dry nitrogen (relative humidity, less than 1 percent). The main criteria for judging the performance of the solid lubricating films were coefficient of friction and wear rate, which had to be less than 0.3 and on the order of 10(exp -6) cu mm/N.m or less, respectively. The bonded MoS2 and magnetron-sputtered MoS2 films met the criteria in all three environments. The ion-plated lead and silver films met the criteria only in ultrahigh vacuum but failed in humid air and in dry nitrogen. The MS DLC and PACVD DLC films met the requirements in humid air and dry nitrogen but failed in ultrahigh vacuum.

Miyoshi, Kazuhisa↗

The Sensitivity of West African Squall Line Water Budgets to Land Cover

This study used a two-dimensional coupled land/atmosphere (cloud-resolving) model to investigate the influence of land cover on the water budgets of squall lines in the Sahel. Study simulations used the same initial sounding and one of three different land covers, a sparsely vegetated semi-desert, a grassy savanna, and a dense evergreen broadleaf forest. All simulations began at midnight and ran for 24 hours to capture a full diurnal cycle. In the morning, the latent heat flux, boundary layer mixing ratio, and moist static energy in the boundary layer exhibited notable variations among the three land covers. The broadleaf forest had the highest latent heat flux, the shallowest, moistest, slowest growing boundary layer, and significantly more moist static energy per unit area than the savanna and semi-desert. Although all simulations produced squall lines by early afternoon, the broadleaf forest had the most intense, longest-lived squall lines with 29% more rainfall than the savanna and 37% more than the semi-desert. The sensitivity of the results to vegetation density, initial sounding humidity, and grid resolution was also assessed. There were greater differences in rainfall among land cover types than among simulations of the same land cover with varying amounts of vegetation. Small changes in humidity were equivalent in effect to large changes in land cover, producing large changes in the condensate and rainfall. Decreasing the humidity had a greater effect on rainfall volume than increasing the humidity. Reducing the grid resolution from 1.5 km to 0.5 km decreased the temperature and humidity of the cold pools and increased the rain volume.

Mohr, Karen I.↗

Evaporation/SST Sensitivity Over the Tropical Oceans During ENSO Events as Estimated from the da Silva, Young, Levitus Surface Marine Data Set

The da Silva, Young and Levitus Surface Marine Atlas, based on observations from the Comprehensive Ocean Atmosphere Data Set (COADS) Release 1, has been used to investigate the relationship between evaporation and sea-surface temperature (SST) over the global oceans. For the period 1950 to 1987 SST, surface latent heat flux, and other related variables have been filtered to minimize data uncertainties and to focus upon interannual variations associated with warm (El Nino) and cold (La Nina) ENSO events. Compositing procedures have enabled identification of systematic variations in latent heat fluxes accompanying these events and the relationship to spatial anomalies in ocean surface wind speed and humidity. The evaporation response associated with ENSO sea surface temperature (SST) variability is systematic in nature and composed of offsetting contributions from the surface wind and humidity variations. During warm events exceeding 1.0 S.D. delta SST, increases in the surface humidity deficit, delta(qs-qa), between the surface and 2m height dominate regions of positive SST anomalies and lead to increases in evaporation of almost 2 Wm (exp -2) at deltaSST = 0.23 K. Despite the increases in specific humidity, relative humidity decreases slightly in regions of elevated SSTs. For the most part, variations in wind speed are consistent with previous investigations. Weakening of the equatorial easterlies (and generation of westerlies) between 160 degrees E and 140 degrees W dominates during the early phases of warm events. Elevated wind speeds in adjacent subtropical regions and in the eastern equatorial Pacific subsequently develop too. The net contribution of these winds, which reflect adjustments in Hadley and Walker circulation components is toward reduced evaporation. Results for cold periods are approximately similar, but opposite in sign to warm events, though evidence of different temporal evolution is noted.

Robertson, F. R.↗

Tropical Ocean Evaporation/SST Sensitivity and It's Link to Water and Energy Budget Variations During ENSO

The continuing debate over feedback mechanisms governing tropical sea surface temperatures (SSTs) and tropical climate in general has highlighted the diversity of potential checks and balances within the climate system. Competing feedbacks due to changes in surface evaporation, water vapor, and cloud long- and shortwave radiative properties each may serve critical roles in stabilizing or destabilizing the climate system. It is also intriguing that even those climate variations having origins internal to the climate system - changes in ocean heat transport for example, apparently require complementary equilibrating effects by changes in atmospheric energy fluxes. Perhaps the best observational evidence of this is the relatively invariant nature of tropically averaged net radiation exiting the top-of-atmosphere (TOA) as measured by broadband satellite sensors over the past two decades. Thus, analyzing how these feedback mechanisms are operating within the context of current interannual variability may offer considerable insight for anticipating future climate change. In this paper we focus primarily on interannual variations of ocean evaporative fluxes and their significance for coupled water and energy cycles within the tropical climate system. In particular, we use both the da Silva estimates of surface fluxes (based on the Comprehensive Ocean Atmosphere Data Set, COADS) and numerical simulations from several global climate models to examine evaporation sensitivity to perturbations in SST associated with warm and cold ENSO events. The specific questions we address are as follows: (1) What recurring patterns of surface wind and humidity anomalies are present during ENSO and how do they combine to yield systematic evaporation anomalies?, (2) What is the resulting tropical ocean mean evaporation-SST sensitivity associated with this climate perturbation?, and (3) What role does this evaporation play in tropical heat and water balance over tropical oceanic regions? We use the da Silva ocean flux data to identify composite structure of departures of latent heat flux from climatology. We also show how these patterns arise out of associated wind and humidity anomaly distributions. Our preliminary work shows that evaporation sensitivity estimates from the da Silva / COADS data, computed for the tropical oceans (30 degrees N/S) are in the neighborhood of 5 to 6 W/square m K. Model estimates are also quite close to this figure. This rate is only slightly less than a rate corresponding to constant relative humidity; however, substantial regional departures from constant relative humidity are present. These patterns are robust and we relate the associated wind and humidity fluctuations noted in previous investigations to the derived evaporation anomalies. Finally, these results are interpreted with other data from the Earth radiation Budget Experiment (ERBE), Global Precipitation Climatology Project (GPCP) and NASA's Surface Radiation Budget (SRB) data set to characterize the tropical energetics of ENSO-related climate variability.

Robertson, Franklin R.↗

Auto Emission Testing

The photos show automobile engines being tested for nitrous oxide emissions, as required by the Environmental Protection Agency (EPA), at the Research and Engineering Division of Ford Motor Company, Dearborn. Michigan. NASA technical information helped the company develop a means of calculating emissions test results. Nitrous oxide emission readings vary with relative humidity in the test facility. EPA uses a standard humidity measurement, but the agency allows manufacturers to test under different humidity conditions, then apply a correction factor to adjust the results to the EPA standard. NASA's Dryden Flight Research Center developed analytic equations which provide a simple, computer-programmable method of correcting for humidity variations. A Ford engineer read a NASA Tech Brief describing the Dryden development and requested more detailed information in the form of a technical support package, which NASA routinely supplies to industry on request. Ford's Emissions Test Laboratory now uses the Dryden equations for humidity-adjusted emissions data reported to EPA.

Source record↗

Water Vapor Measurements by Howard University Raman Lidar during the WAVES 2006 Campaign

Retrieval of water vapor mixing ratio using the Howard University Raman Lidar is presented with emphasis on three aspects: i) performance of the lidar against collocated radiosondes and Raman lidar, ii) investigation of the atmospheric state variables when poor agreement between lidar and radiosondes values occurred and iii) a comparison with satellite-based measurements. The measurements were acquired during the Water Vapor Validation Experiment Sondes/Satellites 2006 field campaign. Ensemble averaging of water vapor mixing ratio data from ten night-time comparisons with Vaisala RS92 radiosondes shows on average an agreement within 10 % up to approx. 8 km. A similar analysis of lidar-to-lidar data of over 700 profiles revealed an agreement to within 20 % over the first 7 km (10 % below 4 km). A grid analysis, defined in the temperature - relative humidity space, was developed to characterize the lidar - radiosonde agreement and quantitatively localizes regions of strong and weak correlations as a function of altitude, temperature or relative humidity. Three main regions of weak correlation emerge: i) regions of low relative humidity and low temperature, ii) moderate relative humidity at low temperatures and iii) low relative humidity at moderate temperatures. Comparison of Atmospheric InfraRed Sounder and Tropospheric Emission Sounder satellites retrievals of moisture with that of Howard University Raman Lidar showed a general agreement in the trend but the formers miss a lot of the details in atmospheric structure due to their low resolution. A relative difference of about 20 % is usually found between lidar and satellites measurements.

Adam, M.↗

Characteristics of Mesoscale Organization in WRF Simulations of Convection during TWP-ICE

Compared to satellite-derived heating profiles, the Goddard Institute for Space Studies general circulation model (GCM) convective heating is too deep and its stratiform upper-level heating is too weak. This deficiency highlights the need for GCMs to parameterize the mesoscale organization of convection. Cloud-resolving model simulations of convection near Darwin, Australia, in weak wind shear environments of different humidities are used to characterize mesoscale organization processes and to provide parameterization guidance. Downdraft cold pools appear to stimulate further deep convection both through their effect on eddy size and vertical velocity. Anomalously humid air surrounds updrafts, reducing the efficacy of entrainment. Recovery of cold pool properties to ambient conditions over 5-6 h proceeds differently over land and ocean. Over ocean increased surface fluxes restore the cold pool to prestorm conditions. Over land surface fluxes are suppressed in the cold pool region; temperature decreases and humidity increases, and both then remain nearly constant, while the undisturbed environment cools diurnally. The upper-troposphere stratiform rain region area lags convection by 5-6 h under humid active monsoon conditions but by only 1-2 h during drier break periods, suggesting that mesoscale organization is more readily sustained in a humid environment. Stratiform region hydrometeor mixing ratio lags convection by 0-2 h, suggesting that it is strongly influenced by detrainment from convective updrafts. Small stratiform region temperature anomalies suggest that a mesoscale updraft parameterization initialized with properties of buoyant detrained air and evolving to a balance between diabatic heating and adiabatic cooling might be a plausible approach for GCMs.

Del Genio, Anthony D.↗

Impact of Convectively Detrained Ice Crystals on the Tropical Upper Troposphere and Lower Stratosphere

The role of convectively detrained ice crystals on the humidity of the tropical upper troposphere and lower stratosphere (UTLS) is investigated in simulations of cirrus clouds along trajectories launched from the 378K potential temperature level in the tropics. The one-dimensional (vertical) cloud model tracks individual ice crystals through their lifecycle beginning with detrainment from convection, followed by deposition growth, sedimentation and sublimation. Convective influence of the parcels is diagnosed by tracing the trajectories through time-dependent fields of convective cloud-top height adjusted to match the CloudSAT and CALIPSO statistics. Model simulations of UTLS water vapor and cloud fields are evaluated and constrained by comparison with Aura MLS and CALIPSO measurements. Preliminary results indicate sensitivity of the detrained ice crystal lifecycle to atmospheric conditions downstream of convection. Specifically, cooling (high relative humidity and supersaturation) downstream of convection leads to deposition growth and sedimentation of detrained ice crystals, resulting in net dehydration of the UTLS. In contrast, warming (low relative humidity and subsaturation) downstream of convection leads to sublimation of detrained ice crystals and subsequent hydration. As such, the impact of detrained ice crystals on the humidity of the UTLS exhibits distinct spatial variability. Detrained ice crystals predominantly dehydrate the UTLS in the tropical mean. Sensitivities to the convectively detrained ice crystal size and concentration are also examined using measurements from the StatoClim aircraft campaign. The importance of convectively detrained ice crystals will be discussed within the context of the overall contribution of convection to the lower stratospheric humidity.

Ueyama, Rei↗

Evaporation from the Southern Ocean Estimated on the Basis of AIRS Satellite Data

Evaporation plays an important role in the global water and energy cycles and, hence, in climate change. Evaporation over the Southern Ocean, where the Antarctic sea ice coverage has a large annual cycle, is poorly quantified. In this study, daily evaporation is estimated for the Southern Ocean with a sea‐ice‐specific algorithm, using surface temperature and air humidity from National Aeronautics and Space Administration's Atmospheric Infrared Sounder (AIRS), and wind speeds from Modern‐Era Retrospective Analysis for Research and Applications, Version 2 (MERRA‐2), reanalysis during 2003–2016. An uncertainty of 34% was found in the evaporation product. The results indicate that annual evaporation has considerable interannual and regional variability, but with a decreasing trend during the study period over most of the Southern Ocean. There are, however, areas where evaporation has increased, specifically in the Ross Sea in winter and summer, with smaller positive trends in spring and fall. Overall, the changes in the difference between the surface specific humidity and the air specific humidity, and to a much lesser extent in the wind speed, are the main drivers for the changes in evaporation throughout the year. During spring and fall months, changes to the sea ice cover, which alter the surface specific humidity, are the main drivers for the change, but in summer and winter the main driver is the air‐specific humidity. Air masses originating from the Antarctic continent (south) are associated with cold and dry conditions, which increase evaporation, whereas air masses from lower latitudes in the Southern Ocean (north) are associated with warm and moist conditions, decreasing evaporation. Comparisons with other reanalysis evaporation products produce similar trends, although annual averages differ.

Boisvert, Linette↗

Statistical Analysis of Factors Riving Surface Ozone Variability over Continental South Africa

Statistical relationships between surface ozone (O3) concentration, precursor species and meteorological conditions in continental South Africa were examined from data obtained from measurement stations in north-eastern South Africa. Three multivariate statistical methods were applied in the investigation, i.e. multiple linear regression (MLR), principal component analysis (PCA) and –regression (PCR), and generalised additive model (GAM) analysis. The daily maximum 8-h moving average O3 concentrations were considered in these statistical models (dependent variable). MLR models indicated that meteorology and precursor species concentrations are able to explain ~50% of the variability in daily maximum O3 levels. MLR analysis revealed that atmospheric carbon monoxide (CO), temperature and relative humidity were the strongest factors affecting the daily O3 variability. In summer, daily O3 variances were mostly associated with relative humidity, while winter O3 levels were mostly linked to temperature and CO. PCA indicated that CO, temperature and relative humidity were not strongly collinear. GAM also identified CO, temperature and relative humidity as the strongest factors affecting the daily variation of O3. Partial residual plots found that temperature, radiation and nitrogen oxides most likely have a non-linear relationship with O3,while the relationship with relative humidity and CO is probably linear. An inter-comparison between O3 levels modelled with the three statistical models compared to measured O3 concentrations showed that the GAM model offered a slight improvement over the MLR model. These findings emphasise the critical role of regional-scale O3 precursors coupled with meteorological conditions in daily variances of O3 levels in continental South Africa.

multiple linear regression (MLR)↗

An international study on THM modelling of the full-scale heater experiment at Mont Terri laboratory

We present results from an international model comparison study of the Full-Scale Emplacement (FE) experiment in Opalinus Clay at the Mont Terri Laboratory, Switzerland. Based on a provided parameter set the teams decided which parameters they adopted for their models, whether they considered the excavation and the ventilation phase in addition to the heating phase and if they included technical features like the shotcrete or the EDZ. The teams were able to reproduce the measured parameters temperature, relative humidity and pore pressure. The modelled results for temperature agree very closely between the teams especially in the sensors in Opalinus Clay. All teams were able to reproduce the redistribution of water in the bentonite backfill due to heating. The evolution of the relative humidity showed similar trends with differences in the intensity of the dry out effect. To model the pore pressure evolution is more complex because it comprises the full interaction of the coupled THM processes. The spread between the pore pressure modelled by the teams was larger, with some teams overestimating the pressure increase due to heating and some teams overestimating the extent of drainage. The agreement of modelled results with measurements improves with larger distance to the heater. We conclude that the EDZ and the shotcrete potentially influence the behaviour of the rock causing higher differences closer to the heater. Further research is needed to better implement those influences into the models. Based on the calibrated models, the future evolution of temperature, relative humidity and pore pressure was predicted over the next 10 years following a change of the heat power applied in 2023 and 2024. Again, the predicted temperatures agree very closely between the teams. Most teams do not expect an increase in relative humidity during the next 10 years after the initial dry-out.

58 GEOSCIENCES↗

A multiphase flow model of water droplets dielectrophoretic-induced air dehumidification phenomena

Air humidity in indoor spaces plays a critical role in human comfort and health. Dehumidification systems are used for building humidity controls, but they can take significant energy consumption, especially in geographic locations with high outdoor humidity and warm climates. Consequently, there is a growing demand for innovative dehumidification processes that consume minimal energy. Dielectrophoretic air dehumidification represents one such promising approach. However, it has not garnered significant attention due to the absence of engineering models and simulation tools capable of evaluating its performance and limitations at large-scale airflows. A new numerical multiphase CFD model, which is also experimentally validated, is developed in a customized Reacting Foam solver based on OpenFOAM® version 9. The newly developed model seeks to decrease substantial energy consumption and lower costs by leveraging the dielectrophoretic phenomenon to regulate moisture levels in the air. The solver integrates a hybrid Eulerian-Lagrangian framework to track the droplet's trajectory and growth rate while solving the continuum equations for the moist air. An electrospray produces electrically charged droplets, which grow during their in-flight trajectories as water vapor condenses onto their surfaces. The role of electrostatic forces in promoting vapor condensation within a high-gradient electrical field is investigated, and the dielectrophoretic vapor nucleation process on charged water droplets is discussed. The CFD model was validated against results from the literature and from proof-of-concept experiments conducted by the authors, which showed a 2 % air dehumidification with a single electrospray and airflow rate of 5 cubic feet per minute. The simulation results indicated that augmenting the number of electrically charged spray droplets increased the dehumidification of the air to 25 %. The initial mean droplet diameter, the orientation of the injector and relative humidity significantly influence the assessment of dehumidification. As a result, scaling up this approach to larger airflow volumes is identified as a potential future research direction.

42 ENGINEERING↗

Coupled neutronics, thermochemistry, corrosion modeling and sensitivity analyses for isotopic evolution in molten salt reactors

This study presents a computational methodology for analyzing isotopic evolution and associated uncertainties in molten salt reactors (MSRs), focusing on both fluoride- and chloride-based fuel salts. The primary goal is to enhance the understanding of isotopic behavior in MSRs and provide data to support future experimental efforts. The methodology integrates transport-coupled depletion calculations using OpenMC, equilibrium thermodynamics modeling with Thermochimica, and a corrosion model. Sensitivity analyses are performed to evaluate the impact of power density, air ingress, and humidity content on isotopic evolution in MSR concepts. This study examines representative F- and Cl-based MSR designs, highlighting the dominant influence of power density on isotopic composition, which significantly affects isotope production and depletion rates, accounting for approximately 76% of the observed variance in element concentration. Air ingress and humidity content also affect the redox potential, solubility of heavier elements, and corrosion rates, thereby altering the expected isotopic evolution in the reactor. On average, air ingress accounts for around 17% of the variance in element concentrations, while humidity explains the remaining 7%. These variances differ significantly from element to element, depending on the element’s role in depletion, redox potential evolution, and galvanic corrosion. The findings indicate that power density, air ingress, and humidity content are all critical factors for optimizing reactor design and operational strategies. Furthermore, the study provides expected ranges for key impurities in the fuel salt, which are crucial for guiding future experimental studies and refining MSR designs. Finally, this study demonstrates the importance of modeling depletion coupled with the evolution of redox potential and chemical interactions in MSR fuel salts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Hygrothermal aging effects on polyimide and acrylate-based adhesive materials in high-performance flat-flex cable assemblies

Flat-flex assemblies are widely used across a diverse range of technologies, including consumer electronics, automotive systems, aerospace and defense applications, and medical devices, due to their compact form factor and flexibility. However, environmental stressors like temperature and humidity are known to degrade performance over time, though the main mechanisms for degradation remain unknown. Here, in this work, we examined the aging behavior of copper/polyimide/adhesive laminate systems under varying temperature and humidity conditions, focusing on material degradation and its effects on mechanical and dielectric properties. Results show that peel strength and breakdown voltage decrease with exposure time, temperature, and humidity; spectroscopic characterization revealed that the adhesive, and not the polyimide, is the weak link in the material stack-up. The adhesive, identified as a butyl acrylate-acrylonitrile (BA-AN) copolymer, exhibited age-related spectral changes that correlated with exposure severity and duration. Hydrolysis at BA ester and AN nitrile groups was identified as the primary degradation mechanism, producing amides, acids, and alcohols. We developed a mechanistic model that connects kinetic parameters for BA-AN spectral band decay to peel strength and breakdown voltage, and implicates hydrolysis at the AN moiety, not BA, in performance decrements. Modeling predictions at ambient conditions indicate faster decline in peel strength than dielectric strength at early times, followed by plateauing of both properties at longer times. These findings provide critical insights into laminate aging mechanisms and highlight the importance of addressing BA-AN degradation to improve the long-term reliability of these systems in high-humidity environments.

organic↗

Formation and degradation mechanism of methylammonium lead iodide perovskite thin film fabricated by electrospray technique

Electrospray deposition technique has been reported previously for fabricating effective and stable perovskite thin film, leading to efficient perovskite solar cells. Here, in this work, a comprehensive investigation of the formation mechanism of methylammonium lead iodide perovskite (CH 3 NH 3 PbI 3 ) film by electrospray technique is demonstrated and compared to the formation mechanism through the conventional spin coating technique. In the electrospray process, charged MAI nanoparticles are gradually introduced onto the PbI 2 film, intercalating within the PbI 2 structure to produce the perovskite film. In contrast, the spin-coating method involves supplying the MAI solution in bulk, leading to perovskite crystal formation through the dissolution of the PbI 2 layer by the MAI solution, followed by recrystallization into perovskite oriented in the [110] direction, 30° inclined to the substrate. The impact of charge and the electric field on the formation of perovskite film using the electrospray is explored. Furthermore, the intrinsic stability of perovskite films is monitored in real-time in a highly humid environment (≥80 % relative humidity (RH)) using in-situ Grazing Incidence Wide Angle X-ray Scattering (GIWAXS), and a degradation mechanism is proposed to enhance the durability of the perovskite-based devices. The study further delves into the comparison of the stability of electrosprayed and spin-coated perovskite film, and the impact of humidity level and the presence of a hole-transporting layer on the stability of the perovskite layer. Overall, this work provides a detailed understanding of the formation and humidity-induced degradation mechanism of electrosprayed perovskite films, offering insights that can extend to various applications of perovskite materials.

14 SOLAR ENERGY↗

Evaluating Autoxidation Radical Scavengers and Additives to Enhance Aminopolymer Sorbent Stability

Solid amine sorbents have shown promise in the removal of ultradilute CO 2 from the atmosphere. Despite being a promising candidate material type for this application, these sorbents are prone to degradation during long-term exposure to environmental components such as CO 2 , O 2 , and H 2 O, with amine oxidation being a particularly challenging problem. In this study, we investigate the potency of different radical scavengers and additives in mitigating the degradation of a model poly- (ethylenimine) (PEI)/Al 2 O 3 sorbent under direct air capture (DAC)-relevant conditions. The results reveal that a 4,4′-bis(α,α- dimethylbenzyl)diphenylamine (BDDPA)-incorporated PEI/Al 2 O 3 sorbent showed the most resistance toward oxidative degradation at varying exposure times and BDDPA loadings under CO 2 -free air (21% O 2 /balance N 2 ) at 120 °C. Interestingly, under humid (∼43% relative humidity (RH) at 26 °C) and dry 0.04% CO 2 -air, the BDDPA/PEI/Al 2 O 3 sorbent showed enhanced sorbent stability both at 70 and 120 °C after 4.5 h of exposure. Under humid CO 2 -free air, at 120 °C, the antioxidant performance slightly declined (in comparison to the dry CO 2 -free air condition) but displayed a much higher stability than the pristine sorbent. Overall, the ability of BDDPA to inhibit sorbent degradation under dry and humid, CO 2 -free and CO 2 -containing (0.04%) air at intermediate (70 °C) and elevated (120 °C) temperatures is promising in prolonging sorbent stability and underscores the importance of performing accelerated oxidation studies in the presence of all species that are expected to be present in DAC processes to identify suitable stabilization treatments for sorbent materials.

36 MATERIALS SCIENCE↗

Balancing moisture and oxygen can match the crystallization dynamics of inert halide perovskite processing

Understanding crystallization in ambient environments is essential for scaling the fabrication of halide perovskite solar cells. Antisolvent-free perovskite deposition offers improved compatibility with high-throughput processing but introduces distinct crystallization dynamics relative to the more ubiquitous use of antisolvents in lab-scale perovskite fabrication. These dynamics are driven by interactions between solutes, solvent and the deposition environment. Using in situ wide-angle X-ray scattering during spin-coating and annealing, we demonstrate how relative humidity (RH) and oxygen, can be tuned to drive polytype evolution during ambient crystallization of formamidinium lead iodide to match that of inert synthesis and achieve comparable film and device quality. In an inert (N 2 ) environment, we find that perovskite films follow a well-established 2H → 3C phase transformation with a short period of coexistence of the 4H and 6H phase during heating. During crystallization in dry air (RH 0%), the added presence of oxygen leads to the dominance of 4H intermediate for an extended duration, establishing a 2H → 4H → 3C pathway. Introducing low humidity (RH 10%) suppresses the 4H phase to a short-lived intermediate above 100 °C, facilitating a more direct transition to the desired 3C phase and almost replicating the crystallization behavior observed under inert conditions. Interestingly, films crystallized under RH 10% show a lower onset temperature for the perovskite 3C phase than under N 2 . At higher humidity (RH 40%), the strong interaction of oxygen and moisture with iodoplumbates appears to stabilize higher order polytypes (4H and 6H). Devices fabricated under RH 10% achieve higher efficiency and enhanced stability compared to those produced under inert atmosphere. These findings provide mechanistic insight into crystallization pathways in different environments and provide a framework to transfer processes from inert to ambient conditions. The results highlight the critical role of controlled humidity in tuning antisolvent-free perovskite crystallization for scalable processing.

Hossain, Maimur [Univ. of California, San Diego, C↗