Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “hydration levels”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Hydrolysis of Small Oxo/Hydroxo Molecules Containing High Oxidation State Actinides (Th, Pa, U, Np, Pu): A Computational Study

The energetics of hydrolysis reactions for high oxidation states of oxo/hydroxo monomeric actinide species (Th IV O 2 , Pa IV O 2 , U IV O 2 , Pa V O 2 (OH), U V O 2 (OH), U VI O 3 , Np VI O 3 , Np VII O 3 (OH), and Pu VII O 3 (OH)) were calculated at the CCSD(T) level. The first step is the formation of a Lewis acid/base adduct with H 2 O (hydration), followed by a proton transfer to form a dihydroxide molecule (hydrolysis); this process is repeated until all oxo groups are hydrolyzed. The physisorption (hydration) for each H 2 O addition was predicted to be exothermic, ca. -20 kcal/mol. The hydrolysis products are preferred energetically over the hydration products for the +IV and +V oxidation states. The compounds with An VI are a turning point in terms of favoring hydration over hydrolysis. For An VII O 3 (OH), hydration products are preferred, and only two waters can bind; the complete hydrolysis process is now endothermic, and the oxidation state for the An in An(OH) 7 is +VI with two OH groups each having one-half an electron. The natural bond order charges and the reaction energies provide insights into the nature of the hydrolysis/hydration processes. The actinide charges and bond ionicity generally decrease across the period. Here, the ionic character decreases as the oxidation state and coordination number increase so that covalency increases moving to the right in the actinide period.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Site-specific surface reactivity on MgO for atomic layer deposition via selective hydration

Atomic layer deposition (ALD) is a powerful technique for thin film synthesis, offering atomic-scale precision and conformality. While ALD of MgO has been widely studied for applications in energy storage and microelectronics, its potential as surface on which deposition may be selective and defects repaired remains underexplored. Here, we present a combined theoretical and experimental investigation of MgO surface hydration and its implications for targeted ALD growth using water and dimethyl aluminum isopropoxide (DMAI) as reactants. We perform density functional theory (DFT) calculations to examine molecular and dissociative H 2 O adsorption on MgO (100) terraces and step-edge sites, including pristine surfaces and those with Mg/O vacancies. Reaction Gibbs free energies are calculated under various conditions to quantify surface reactivity. Our findings reveal facet- and defect-dependent hydration behaviors that align with experimental ALD growth trends on MgO (100). This study provides a molecular-level understanding of MgO surface chemistry critical for optimizing ALD processes for thin film growth and defect repair.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electrodermal activity as a proxy for sweat rate monitoring during physical and mental activities

Electrodermal activity has long been used for mental activity monitoring by measuring skin conductance at specific locations, such as fingertips, with high sweat gland density. However, electrodermal activity has not been considered useful for physical activity monitoring, where large sweat volumes are generated, resulting in the accumulation of sweat at the skin–electrode interface and, thus, preventing further dynamic response to sweating events. Here we show that electrodermal activity can be used as a proxy for sweat loss measurement under both low and high physical activity levels. We use wearable sweat sensors that consist of water-permeable electrodes and microfluidic-based sweat analysers, and show that skin conductance is proportional to the instantaneous sweat loss. We demonstrate that sweat loss during exercise can be estimated by integrating skin conductance over time, which can be applied to assess the body hydration status of exercisers. From multisite measurements of skin conductance, we show that the wrist, forearm and upper arm are reflective of physical activity levels, whereas the finger is indicative of mental activity. Simultaneous measurement of two different sites selectively decouples mental and physical activities.

Biomedical engineering↗
DOE OSTI2026

Unraveling Grain Boundary Instability in Dense Proton-Conducting Oxides

The long-term stability of protonic ceramic electrolysis cell (PCEC) materials under high-steam operating conditions remains a critical barrier to device commercialization. Here, we investigate the fundamental degradation mechanisms of dense BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ (BCZYYb) electrolytes operated at 550 °C, 50% H 2 O in air. Over 1,000 h, the total electrolyte conductivity decreases by 11.1%, driven primarily by a >130% increase in grain-boundary resistivity. Post-mortem analyses reveal that damage is localized to near-surface grain boundaries extending ∼50 μm into the dense electrolyte pellet. This surface localization indicates that degradation is likely to be severe in thin, device-level electrolytes. Degradation is primarily attributed to chemo-mechanical grain-boundary weakening arising from hydration-induced chemical expansion, culminating in the formation of intergranular cracks oriented parallel to the pellet surface. These internal cracks subsequently react with steam and/or CO 2 , leading to the formation of nanoscale insulating phases, including Ba(OH) 2 , nanocrystalline BaCO 3 , and amorphous Ce/Zr/Y/Yb-containing oxides or hydroxycarbonates. After an initial degradation period of approximately 200 h, the overall conductivity stabilizes. Incorporating NiO sintering aids reduces grain-boundary density by an order of magnitude under identical sintering conditions. Although addition of NiO increases the initial resistivity by >160% at 550 °C, it substantially suppresses grain-boundary instability and mitigates chemical degradation. These findings underscore the urgent need for chemical and/or physical stabilization of BCZYYb electrolytes and offer design guidelines to enable durable, high-performance PCECs.

08 HYDROGEN↗
DOE OSTI2021

Bridging the gap between NMR measured mean silicate chain length and nano-scale silicate polymorphism of calcium silicate hydrates

Variable stoichiometry and silicate polymorphism in calcium-silicate-hydrates (C-S-H) has impeded the revelation of point defects distribution in the silicate tetrahedral network of C-S-H, which resembles tobermorite crystal structure with some bridging tetrahedra (BT) and paired tetrahedra (PT) vacancies in dreierketten chains. Here we use a computational approach to characterize silicate polymorphism by introducing the vacancy ratio of BT to PT (α) and establishing a three-term empirical mean chain length (MCL) formula for different calcium-to‑silicon ratios (Ca/Si) ranging from 1.2 to 2.3. The formula identifies BT and PT controls at low and high α respectively and allows an inverse mapping of polymorphic range based on NMR experiments. The proposed computational framework quantitatively describes silicate polymorphs and links NMR-measured MCL to C-S-H atomistic configurations at the molecular level.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Particle Size Optimization of Thermochemical Salt Hydrates for High Energy Density Thermal Storage

Thermal energy storage (TES) solutions offer opportunities to reduce energy consumption, greenhouse gas emissions, and cost. Specifically, they can help reduce the peak load and address the intermittency of renewable energy sources by time shifting the load, which are critical toward zero energy buildings. Thermochemical materials (TCMs) as a class of TES undergo a solid–gas reversible chemical reaction with water vapor to store and release energy with high storage capacities (600 kWh m −3 ) and negligible self‐discharge that makes them uniquely suited as compact, stand‐alone units for daily or seasonal storage. However, TCMs suffer from instabilities at the material (salt particles) and reactor level (packed beds of salt), resulting in poor multi‐cycle efficiency and high‐levelized cost of storage. In this study, a model is developed to predict the pulverization limit or R crit of various salt hydrates during thermal cycling. This is critical as it provides design rules to make mechanically stable TCM composites as well as enables the use of more energy‐efficient manufacturing process (solid‐state mixing) to make the composites. The model is experimentally validated on multiple TCM salt hydrates with different water content, and effect of R crit on hydration and dehydration kinetics is also investigated.

25 ENERGY STORAGE↗
DOE OSTI2021

Analysis of the Amorphous and Interphase Influence of Comononomer Loading on Polymer Properties toward Forwarding Bioadvantaged Copolyamides

In this paper we present an approach for selectively modifying the properties of semicrystalline polymers by introducing “bioadvantaged” counits. With this approach, the unique functionality of biomass can be leveraged to tailor the properties of the amorphous phase of semicrystalline polymers with minimal impact on crystallinity and thermomechanical properties. As a model case, PA 6,6 copolyamides were produced using the bioadvantaged monomer trans-3-hexenedioic acid (t3HDA). The analogous structure of t3HDA to adipic acid, a PA 6,6 monomer, allows for seamless integration. Screening over the entire composition range identified the t3HDA loading (20 mol%) beyond which properties deviate appreciably from Nylon 6,6. Once identified, copolyamides of suitable compositions were upgraded to commercial quality and fully characterized to assess the influence of counit loading and polymer structure on thermal and mechanical properties. Samples were characterized using gel permeation chromatography (GPC), proton nuclear magnetic resonance spectroscopy (1H NMR), heteronuclear single quantum coherence spectroscopy (HSQC), wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), tensile testing, flexural testing, and water absorption testing. t3HDA units were shown to hydrate during the harsh polycondensation to 3-hydroxyhexanedioic acid (3HHDA) and fully incorporate into the polymer backbone. Loading levels up to 20% were shown to have comparable thermal and mechanical properties in the dry state, yet moisture absorption—a known method for improving the toughness, yield strain, and elongation of polyamides—was enhanced by over 100% at 20% loading. This case study on bioadvantaged copolymers elucidates the governing structure-function principles that can be leveraged to forward value-added renewable polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Using Methyl Bromide for Interspecies Cell–Cell Signaling and As a Reporter in a Model Soil Consortium

Synthetic microbial communities are emerging as model systems for studying consortia-scale phenotypes. To establish synthetic biology tools for studying these communities in hard-to-image environmental materials, we evaluated whether a single member of a model soil consortium (MSC) can be programmed to report on gene expression without requiring matrix disruption. For these studies, we targeted a five member MSC that includes Dyadobacter fermentans, Ensifer adhaerens, Rhodococcus sp003130705, Streptomyces sp001905665, and Variovorax beijingensis. By coupling the expression of a methyl halide transferase to a constitutive promoter, we show that Variovorax beijingensis can be programmed to synthesize methyl halides that accumulate in the soil headspace at levels that are ≥24-fold higher than all other MSC members across a range of environmentally-relevant hydration conditions. We find that methyl halide production can report on a MSC promoter that is activated by changes in water potential, and we demonstrate that a synthetic gas signal can be read out directly using gas chromatography and indirectly using a soil-derived Methylorubrum that is programmed to produce a visual output in response to methyl halides. Finally, these tools will be useful for future studies that investigate how MSC respond to dynamic hydration conditions, such as drought and flood events induced by climate change, which can alter soil water potential and induce the release of stored carbon.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

The primary gas phase hydration shell of hydroxide

The number of water molecules in hydroxide’s primary hydration shell has been long debated to be three from the interpretation of experimental data and four from theoretical studies. Here, we provide direct evidence for the presence of a fourth water molecule in hydroxide’s primary hydration shell from a combined study based on high-resolution cryogenic experimental photoelectron spectroscopy and high-level quantum chemical computations. Well-defined spectra of OH - (H 2 O) n clusters (n = 2 to 5) yield accurate electron binding energies, which are, in turn, used as key signatures of the underlying molecular conformations. Although the smaller OH - (H 2 O) 3 and OH - (H 2 O) 4 clusters adopt close-lying conformations with similar electron binding energies that are hard to distinguish, the OH - (H 2 O) 5 cluster clearly has a predominant conformation with a four-coordinated hydroxide binding motif, a finding that unambiguously determines the gas phase coordination number of hydroxide to be four.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Observation of Potential-Induced Hydration on the Surface of Ceramic Proton Conductors Using In Situ Near-Ambient Pressure X-ray Photoelectron Spectroscopy

Interactions of ceramic proton conductors with the environment under operating conditions play an essential role on material properties and device performance. It remains unclear how the chemical environment of material, as modulated by the operating condition, affects the proton conductivity. Combining near-ambient pressure X-ray photoelectron spectroscopy and impedance spectroscopy, we investigate the chemical environment changes of oxygen and the conductivity of BaZr 0.9 Y 0.1 O 3-δ under operating condition. Changes in O 1s core level spectra indicate that adding water vapor pressure increases both hydroxyl groups and active proton sites at undercoordinated oxygen. Applying external potential further promotes this hydration effect, in particular, by increasing the amount of undercoordinated oxygen. The enhanced hydration is accompanied by improved proton conductivity. Here, this work highlights the effects of undercoordinated oxygen for improving the proton conductivity in ceramics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1976

An Atlas of extraterrestrial particles collected with NASA U-2 aircraft, 1974 - 1976

Extraterrestrial particles collected during U-2 flights in the stratosphere were divided into four groups: chondritic, iron-sulfur--nickel, mafic silicates, and others. The chondritic aggregates are typically composed of Fe, Mg, Si, C, S, Ca, and Ni. Detectable levels of He-4 implanted from the solar wind occur in some. Olivine, spinel, and possibly pyrrhotite and a hydrated layered-lattice silicate were identified. The chondritic ablation particles contain no sulfur and appear to have been melted. Magnetite, olivine, and pyroxene were identified. The iron-sulfur-nickel type particles resemble meteoritic iron sulfide with a small amount of nickel, and contain magnetite and troilite. The mafic silicate type particles are iron magnesium silicate grains with clumps of chondritic aggregate particles adhering to their surfaces. Olivine and possibly pyrrhotite and pyroxene were identified. Most of the iron-nickel type particles are spherules and include taenite and wustite. The other type particles include nickel-iron mounds on spheroidal glassy-like grains having chondritic-like elemental abundances.

Brownlee, D. E.↗
DOE OSTI2020

Thermodynamics of Metal Carbonates and Bicarbonates and Their Hydrates for Mg, Ca, Fe, and Cd Relevant to Mineral Energetics

The heats of formation of carbonate, bicarbonate and bicarbonate/hydroxide metal complexes and hydrated versions these complexes of Mg 2+ , Ca 2+ , Fe 2+ , and Cd 2+ are predicted from atomization energies using correlated molecular orbital theory at the CCSD(T) level extrapolated to the complete basis set limit following the Feller-Peterson-Dixon (FPD) approach. Using the calculated gas phase values and the available experimental solid state values, the cohesive energies of selected minerals were calculated. The gas phase decomposition energies into MO, CO 2 and H 2 O follow the order Mg ~ Ca > Cd ~ Fe, and correlate with the hardness of the metal +2 ions. Gas phase hydration energies show that the order is Mg > Fe > Ca ~ Cd. There are a number of bulk hydrated Mg and Ca complexes that occur as minerals but there are few if any for Fe and Cd, suggesting that a number of factors are important in determining the stability of the bulk mineral hydrates. The FPD heats of formation were used to benchmark a range of density functional theory exchange-correlation functionals, including those commonly used in solid state mineral calculations. None of the functionals provided chemical accuracy agreement (± 1 kcal/mol) with the FPD results The best functionals are ωB97X and ωB97X-D with mean average unsigned errors of 10 kcal/mol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Natural carbonation of portland cement with synthetic zeolite Y as a supplementary cementitious material

Risks associated with carbonation are a key limitation to greater replacement levels of ordinary portland cement (OPC) by supplementary cementitious materials (SCMs). The addition of pozzolanic SCMs in OPC alters the hydrate assemblage by forming phases like calcium-(alumina)-silicate-hydrate (C-(A)-S-H). The objective of the present study was to elucidate how such changes in hydrate assemblage influence the chemical mechanisms of carbonation in a realistic OPC system. Here, in this paper, we show that synthetic zeolite Y (faujasite) is a highly reactive pozzolan in OPC that reduces the calcium content of hydration products via prompt consumption of calcium hydroxide from the evolving phase assemblage prior to CO 2 exposure. Suppression of portlandite at moderate to high zeolite Y content led to a more damaging mechanism of carbonation by disrupting the formation of a passivating carbonate layer. Without this layer, carbonation depth and CO 2 uptake are increased. Binders containing 12–18% zeolite Y by volume consumed all the calcium hydroxide from OPC during hydration and reduced the Ca/(Si+Al) ratio of the amorphous products to near 0.67. In these cases, higher carbonation depths were observed after exposure to ambient air with decalcification of C-(A)-S-H as the main source of CO 2 buffering. Binders with either 0% or 4% zeolite Y contained calcium hydroxide in the hydrated microstructure, had higher Ca/(Si+Al) ratios, and formed a calcite-rich passivation layer that halted deep carbonation. Although the carbonated layer in the samples with 12% and 18% zeolite Y contained 70% and 76% less calcite than the OPC respectively, their higher carbonation depths resulted in total CO 2 uptakes that were 12x greater than the OPC sample. Passivation layer formation in samples with calcium hydroxide explains this finding and was further supported by thermodynamic modeling. High Si/Al zeolite additives to OPC should be balanced with the calcium content for optimal carbonation resistance.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Site-Selective Atomic Layer Deposition on Rutile TiO 2 : Selective Hydration as a Route to Target Point Defects

Routes to area-and especially site-selective atomic layer deposition (ALD) remain an enticing challenge in precision surface science, despite the potentially game-changing capability for many energy applications. An unparalleled level of surface reaction control is required to direct ALD to select sites on the same nominal material, for example, targeted growth on distinct phases, facets, step-edges, and/or defects. However, as a sequential surface synthesis method, ALD is uniquely suited to these challenges, including the possibility of selective deposition at defective surface atom arrangements. Here, we computationally identify conditions for site-selective ALD through hydration of surface defects, including oxygen vacancies and titanium interstitials on low-index rutile TiO 2 facets. First-principles computation is used to predict, as a function of temperature, the hydroxylation of defects that are targeted by proton-exchange-mediated ALD processes. In situ ellipsometric measurements of ALD Al 2 O 3 nucleation on TiO 2 (110) single crystals prepared with and without abundant oxygen vacancies demonstrate striking contrast, corroborating computational predictions and revealing a mechanistically clear path to site-selective ALD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

A quick look method of detecting water of hydration in small solar system bodies

The action of aqueous alteration of the near-subsurface material on asteroids and probably some satellites in the Solar System constitutes part of the formation history of the Solar System. The C-class asteroids (and subclasses B, G, and F) were initially believed to have undergone aqueous alteration based on their low albedos and neutral broadband visible and near-infrared colors. These spectra exhibit a sharp drop at wavelengths shorter than 0.55 microns due to a strong ferric oxide intervalence change transfer transition. This IVCT comprises multiple absorptions that are not uniquely indicative of phyllosilicates, but rather are present in the spectrum of any object containing Fe(2+) and Fe(3+) in its surface material. A definitive indication of aqueous alteration came when the broad IR absorption feature having a minimum near 3.0 microns indicative of structural hydroxyl (OH) and interlayer and and absorbed water in phyllosilicates was identified in the IR photometry of many C-class asteroids. Additional mineralogical compositional evidence of aqueously-altered asteroids has come as the result of high SNR narrowband spectrophotometry in the visible and near-infrared spectral regions taken using a CCD/spectrograph combination. An absorption feature centered at 0.7 microns indicative of an Fe(2+) - Fe(3+) charge transfer transition in oxidized iron in phyllosilicates in spectra of some low-albedo asteroids, especially C and G class, and CM2 carbonaceous chondrite meteorites was identified in the CCD spectra. The correlation and covariance of the 0.7-micron and 3.0-micron features were examined by comparing observations of asteroids common to both the CCD reflectance spectra and the 3.0-micron multicolor photometry data sets. Thirty-one pairs of observations were included in this training group. The results of the statistical study indicate that with a 95% confidence level, 84% of the objects observed either having or not having the 0.7-micron feature will correspondingly have the 3.0-micron water of hydration feature.

Vilas, F.↗
NASA NTRS1973

Rubber composition compatible with hydrazine

Formulation improves compatibility of butyl rubbers with hydrazine while reducing permeation to low levels necessary for prolonged storage in space. This is accomplished by replacing carbon-black filler with inert materials such as hydrated silica or clay. Pressure increases suggest that hydrazine is decomposed only slightly by new type of rubber.

Repar, J.↗
NASA NTRS1993

Mantle redox evolution and the oxidation state of the Archean atmosphere

Current models predict that the early atmosphere consisted mostly of CO2, N2, and H2O, along with traces of H2 and CO. Such models are based on the assumption that the redox state of the upper mantle has not changed, so that volcanic gas composition has remained approximately constant with time. We argue here that this assumption is probably incorrect: the upper mantle was originally more reduced than today, although not as reduced as the metal arrest level, and has become progressively more oxidized as a consequence of the release of reduced volcanic gases and the subduction of hydrated, oxidized seafloor. Data on the redox state of sulfide and chromite inclusions in diamonds imply that the process of mantle oxidation was slow, so that reduced conditions could have prevailed for as much as half of the earth's history. To be sure, other oxybarometers of ancient rocks give different results, so the question of when the mantle redox state has changed remains unresolved. Mantle redox evolution is intimately linked to the oxidation state of the primitive atmosphere: A reduced Archean atmosphere would have had a high hydrogen escape rate and should correspond to a changing mantle redox state; an oxidized Archean atmosphere should be associated with a constant mantle redox state. The converses of these statements are also true. Finally, our theory of mantle redox evolution may explain why the Archean atmosphere remained oxygen-deficient until approximately 2.0 billion years ago (Ga) despite a probable early origin for photosynthesis.

NASA Discipline Number 52-30↗
NASA NTRS1995

Evaluation testing of a portable vapor detector for Part-Per-Billion (PPB) level UDMH and N2H4

Trace level detection of hydrazine (N2H4), monomethyl hydrazine (MMH) and unsymmetrical dimethylhydrazine (UDMH) has been receiving increased attention over the past several years. In May 1995 the American Conference of Government Industrial Hygienists (ACGIH) lowered their acceptable threshold limit value (TLV) from 100 parts-per-billion (ppb) to 10 ppb. Several types of ppb-level detectors are being developed by the United States Air Force (USAF) Space and Missile Systems Center (SMSC). A breadboard version of a portable, lightweight hydrazine detection sensor was developed and produced by Giner Corp. for the USAF. This sensor was designed for ppb level UDMH and N2H4 vapor detection in near real-time. This instrument employs electrochemical sensing, utilizing a three electrode cell with an anion-exchange polymer electrolyte membrane as the only electrolyte in the system. The sensing, counter and reference electrodes are bonded to the membrane forming a single component. The only liquid required to maintain the sensor is deionized water which hydrates the membrane. At the request of the USAF SMSC, independent testing and evaluation of the breadboard instrument was performed at NASA's Toxic Vapor Detection Laboratory (TVDL) for response to ppb-level N2H4 and UDMH and MMH. The TVDL, located at Kennedy Space Center (KSC) has the unique ability to generate calibrated sample vapor streams of N2H4, UDMH, and MMH over a range from less than 10 ppb to thousands of parts per million (ppm) with full environmental control of relative humidity (0-90%) and temperature (0-50 C). The TVDL routinely performs these types of tests. Referenced sensors were subjected to extensive testing, including precision, linearity, response/recovery times, zero and span drift, humidity and temperature effects as well as ammonia interference. Results of these tests and general operation characteristics are reported.

Curran, Dan↗