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At least 361 records · Page 20

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NASA NTRS2002

Infrared Spectra of Hydrated Magnesium Salts and their Role in the Search for Possible Life Conditions on Jupiter Moons

Recent observations from the Galileo satellite indicate that three of the Jupiter moons, Europa, Ganymede, and Callisto, may have subsurface oceans. Possible existence of such ocean and the nature of its composition are of great interest to astrobiologists. Data from Galileo's NIMS spectrometer indicate the possibility of hydrated salts on Europa's surface. To aid in the design of future missions, we investigated infrared spectra of MgSO4-nH20, n=1-3 using ab initio calculations. Geometry, energetics, dipole moments, vibrational frequencies and infrared intensities of pure and hydrated MgSO4 salts were determined. Significant differences are found between vibrational spectra of water molecules in complexes with MgSO4 and pure water. Some of the O-H stretching frequencies in the complexes are shifted to the red by up to 1,500 - 2,000 per cm. In addition, the SO2 stretching vibrations are found at lower frequency regions than the water vibrations. The calculated bands of water and SO2 fragments can serve as markers for the existence of the salt-water complexes on the surface of Jupiter's moon.

Chaban, Galina↗

NASA NTRS1997

A blast of gas in the latest Paleocene: simulating first-order effects of massive dissociation of oceanic methane hydrate

Carbonate and organic matter deposited during the latest Paleocene thermal maximum is characterized by a remarkable -2.5% excursion in delta 13C that occurred over approximately 10(4) yr and returned to near initial values in an exponential pattern over approximately 2 x 10(5) yr. It has been hypothesized that this excursion signifies transfer of 1.4 to 2.8 x 10(18) g of CH4 from oceanic hydrates to the combined ocean-atmosphere inorganic carbon reservoir. A scenario with 1.12 x 10(18) g of CH4 is numerically simulated here within the framework of the present-day global carbon cycle to test the plausibility of the hypothesis. We find that (1) the delta 13C of the deep ocean, shallow ocean, and atmosphere decreases by -2.3% over 10(4) yr and returns to initial values in an exponential pattern over approximately 2 x 10(5) yr; (2) the depth of the lysocline shoals by up to 400 m over 10(4) yr, and this rise is most pronounced in one ocean region; and (3) global surface temperature increases by approximately 2 degrees C over 10(4) yr and returns to initial values over approximately 2 x 10(6) yr. The first effect is quantitatively consistent with the geologic record; the latter two effects are qualitatively consistent with observations. Thus, significant CH4 release from oceanic hydrates is a plausible explanation for observed carbon cycle perturbations during the thermal maximum. This conclusion is of broad interest because the flux of CH4 invoked during the maximum is of similar magnitude to that released to the atmosphere from present-day anthropogenic CH4 sources.

Non-NASA Center↗

NASA NTRS2012

Mineralogy and Oxygen Isotope Compositions of Two C-Rich Hydrated Interplanetary Dust Particles

Oxygen isotopic compositions of chondrites reflect mixing between a O-16-rich reservoir and a O-17,O-18-rich reservoir produced via mass-independent fractionation. The composition of the O-16-rich reservoir is reasonably well constrained, but material representing the O-17,O-18-rich end-member is rare. Self-shielding models predict that cometary water, presumed to represent this reservoir, should be enriched in O-17 and O-18 18O by > 200%. Hydrated interplanetary dust particles (IDPs) rich in carbonaceous matter may be derived from comets; such particles likely contain the products of reaction between O-16-poor water and anhydrous silicates that formed in the inner solar system. Here we present mineralogy and oxygen isotope compositions of two C-rich hydrated IDPs, L2083E47 and L2071E35.

Snead, C. J.↗

NASA NTRS2013

ADR salt pill design and crystal growth process for hydrated magnetic salts

A process is provided for producing a salt pill for use in very low temperature adiabatic demagnetization refrigerators (ADRs). The method can include providing a thermal bus in a housing. The thermal bus can include an array of thermally conductive metal conductors. A hydrated salt can be grown on the array of thermally conductive metal conductors. Thermal conductance can be provided to the hydrated salt.

Shirron, Peter J.↗

NASA NTRS2016

Coordinates Analyses of Hydrated Interplanetary Dust Particles: Samples of Primitive Solar System Bodies

Interplanetary dust particles (IDPs) collected in the stratosphere fall into two major groups: an anhydrous group termed the "chondritic-porous (CP) IDPs and a hydrated group, the "chondritic-smooth (CS) IDPs, although rare IDPs with mineralogies intermediate between these two groups are known [1]. The CP-IDPs are widely believed to be derived from cometary sources [e.g. 2]. The hydrated CS-IDPs show mineralogical similarities to heavily aqueously altered carbonaceous chondrites (e.g. CI chondrites), but only a few have been directly linked to carbonaceous meteorite parent bodies [e.g. 3, 4]. Most CS-IDPs show distinct chemical [5] and oxygen isotopic composition differences [6-8] from primitive carbonaceous chondrites. Here, we report on our coordinated analyses of a suite of carbon-rich CS-IDPs focusing on their bulk compositions, mineralogy, mineral chemistry, and isotopic compositions.

Keller, L. P.↗

NASA NTRS2016

Performing Mineral Hydration Experiments in the CheMin Diffractometer on Mars

Laboratory work is the cornerstone of experimental planetary geochemistry, mineralogy, and petrology, but much is to be gained by "experiments" while on a planet surface. Earth-bound experiments are often limited in ability to control multiple conditions relevant to planetary bodies (e.g. cycles in temperature and vapor pressure of water), but observations on-planet provide a unique opportunity where conditions are native to the planet and those affected by sampling and analysis can be constrained. The CheMin XRD instrument on Mars Science Laboratory has been able to test mineral hydration in samples held for up to 300 Mars days (sols). Clay minerals sampled at Yellowknife Bay early in the mission had both collapsed (10 Å) and expanded (13.2 Å) basal spacing. Collapsed interlayers were expected, but larger spacing was not; it was uncertain whether larger basal spacing would collapse on prolonged exposure to warmer conditions inside CheMin. Observation over several hundred sols showed no collapse, with the conclusion that expanded interlayer spacing was due to partial intercalation by metal-hydroxyl groups that resist dehydration. More recently, a sample of the Murray Formation, Oudam, provided the first XRD detection of gypsum and a chance to observe gypsum stability. Laboratory work suggests gypsum should be stable at Mars surface conditions, and indeed gypsum has been observed from orbit at higher latitudes and in thick veins at Yellowknife Bay by Mastcam reflectance spectra. Laboratory experiments have shown that on dehydration the gypsum would not become X-ray amorphous but would rather transform to a water-deficient bassanite structure. Over a period of 37 sols, it was observed that the Oudam sample in CheMin transformed from an assemblage of gypsum+anhydrite, to gypsum+bassanite+anhydrite, and finally to bassanite+anhydrite. Mg-sulfates were also anticipated but have not been observed in CheMin despite chemical evidence for their presence. Unlike gypsum, hydrated Mg-sulfates can transition to an X-ray amorphous form. Crystalline Mg-sulfates are expected higher in the section on Mount Sharp, where it should be possible to determine whether they persist or are destabilized after sampling, providing further insight into hydrous mineral stability at Mars near-equatorial conditions.

Vaniman, D. T.↗

NASA NTRS2019

Spectral Properties of Hydrated Poorly Crystalline Materials for Spectral Analysis of the Moon and Mars

Visible/near-infrared (VNIR) reflectance spectra of both Mars [1] and the Moon [2] include hydration bands that vary across the planet and are not well explained in some cases. Poorly crystalline phases have been found at ~30-70 wt.% by CheMin in Gale crater, Mars in all samples measured to date [3]. Here we report on VNIR reflectance spectra of a large collection of amorphous and poorly crystalline materials. These include opal, allophane, imogolite, iron hydroxides/ oxyhydroxides (FeOx), and several synthetic materials containing Si, Al and/or Fe. All of these contain hydration bands due to water and OH that can be used to identify these materials remotely on planetary bodies.

Bishop, J. L.↗

NASA NTRS2020

Aqueous Alteration in the Kuiper Belt: Evidence from Hydrated Interplanetary Dust Particles

Edgeworth-Kuiper belt objects (EKBOs) formed in the outer reaches of the protoplanetary disk and thus avoided much of the high tempera-ture processing experienced by bodies in the inner solar system. For this reason, they contain a wealth of information on the nature of nebular solids and the chemical conditions in the earliest solar system. Astronomical observations of EKBOs have been limited largely to the surface chemistry of the ices covering these small and difficult to observe bodies. The mineralogy of EKBO objects are poorly known, but clues regarding their mineralogical makeup come from studies of samples from short period comets (e.g. Wild2), and interplanetary dust particles (IDPs) produced by collisions in the Kuiper belt. Interplanetary dust particles from objects in the solar system (mainly comets and asteroids) spiral in to-wards the Sun under the influence of Poynting-Robertson (PR) drag forces and accumulate solar flare energetic particle tracks. Recent work has shown that the observed solar flare track densities (~1010-1011/sq.cm) in these IDPs are ~two orders of magnitude higher than expected if they were derived from main belt asteroids or Jupiter family comets and thus require an origin from outer solar system source bodies such as EKBOs. The track-rich IDPs include representatives from the two major groups of IDPs: the chondritic-porous, anhydrous IDPs and the chondritic-smooth, hydrated IDPs, although rare IDPs with mineralogies intermediate between these two groups are known. Here, we report on the mineralogy, composition, organic matter content, and isotopic characteristics of track-rich hydrated IDPs, and implications for aqueous alteration in outer solar system bodies.

Keller, L. P.↗

NASA NTRS2020

Telescopic Observations of Lunar Hydration: Variations and Abundance

Prior to 2009, the Moon was believed to be anhydrous. However, observations by three spacecraft revealed a hydrated surface by reporting a 3 μm absorption band attributed to hydroxyl and possibly molecular water. The Moon Mineralogy Mapper (M3) spectrometer, onboard the Chandrayaan-1 spacecraft is mainly used to study the lunar 3 μm band but its spectral range ends at 3 μm. The limited wavelength range of M3 has allowed observed variations in the 3 μm band to be called into question due to uncertainties in thermal corrections. To investigate the validity of variations in the lunar 3 μm band, we used the SpeX infrared spectrograph at the NASA InfraRed Telescope Facility at Maunakea Observatory in Hawaiʻi. With SpeX, we are able to obtain lunar data over a wavelength range of 1.67 to 4.2 μm at 1 – 2 km spatial resolution. The long wavelengths provide strong constraints on thermal emission corrections. We confirm that the 3 μm band varies with lunar time of day as well as with latitude and composition. Each observation reveals strong variations in abundances of hydroxyl and possibly molecular water. The data reveal a decrease in abundance with increasing lunar local time, an asymmetric trend about the equator that favors the southern latitudes, and higher concentrations in highland regions. The longer wavelengths provided by SpeX have allowed us to examine variations in the 3 μm band and provide definitive evidence that the variations are due to changes in hydration.

C. I. Honniball↗

NASA NTRSDate not supplied

The Carbonate Mineralogy of Hydrated Interplanetary Dust Particles

Hydrated interplanetary dust particles (IDPs) are a major component of the stratospheric dust population and are widely believed to be derived from asteroidal parent bodies. Recent work has shown that many, if not most, hydrated IDPs represent samples of outer solar system parent bodies, namely Kuiper Belt objects (KBOs) [1]. Coordinated analyses of these IDPs provide important constraints on the nature and extent of water:rock interactions in these outer solar system parent bodies.

Lindsay P. Keller↗

DOE OSTI2025

Effect of Sulfonation Level on the Percolated Morphology and Proton Conductivity of Hydrated Fluorine-Free Copolymers: Experiments and Simulations

Using all-atom molecular dynamics simulations and a variety of experimental methods, we previously reported on a linear polyethylene with pendant phenyl sulfonated groups precisely on every fifth carbon along the backbone. With increasing relative humidity this fluorine-free polymer self-assembled to form nanoscale water channels and exhibited exceptional proton conductivity. Expanding upon those findings, here we explore partially sulfonated random copolymers, referred to as p 5PhSH-Y. Using either acetyl sulfate or sulfuric acid, a wide range of sulfonation levels were prepared ( Y = 34−98%) corresponding to ion-exchange capacities (IEC) of 2.0−4.4 mmol/g. Combining experimental techniques and all-atom molecular dynamics simulations, we study the effect of Y on water uptake, nanoscale morphology, and the proton/water transport properties of p5PhSH- Y . The proton conductivity of p 5PhSH- Y increases with relative humidity and with Y and achieves values in excess of 0.1 S/cm. These high conductivities are attributed to high IEC and welldeveloped nanoscale percolated hydrophilic domains made possible by the flexible backbone. We quantitatively describe the nature of the water channels using the characteristic distance, channel width distribution, the area per sulfonate group at the hydrophilic/ hydrophobic interface, and the fractal dimension. Notably, the channel widths and the areas per sulfonate group are nominally independent of the level of sulfonation, while depending significantly on the level of hydration. The fractal dimension of the water channels correlates strongly with the water diffusion coefficients calculated from the molecular dynamics (MD) simulations. These findings demonstrate that the p 5PhSH- Y hydrocarbon copolymers can be modified to tune properties, particularly proton conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Carbonation dynamics of hydrated alite revealed by electron microscopy

CO 2 sequestration in concrete is crucial to relieve the environmental burden, while the carbonation mechanisms remain unclear. Here, we explored the carbonation dynamics of alite hydrates through electron microscopy. We discovered that calcite is the main phase of carbonate crystals throughout the entire carbonation period in the alite system. Further, the shape evolution of calcite crystals was captured: spindle carbonates initially formed on C-S-H substrate and then transformed into rhombohedrons; Intermediate states such as polyhedral particles and layered rhomboids were also observed. Based on our quantitative calculations, the growth rate of calcite particles was determined approximately 0.2 μm/day, which may be affected by the relative concentration between calcium ions and CO 2 source. A direct relation between the microstructure and mechanical properties of calcite was uncovered using atomic force microscopy. Furthermore, we found that the morphology development of calcite crystals during carbonation may be explained by the surface energy variation of different facets. This work suggests a unique approach to track carbonation kinetics and provides new opportunities to unveil underlying carbonation mechanisms at the nanoscale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Hydration behavior of cements with reduced clinker factor in mixture with sulfoaluminate binder

CO{sub 2} regulation and raw material availability will strongly influence the future cement market and a wider use of composite cements containing limestone and pozzolan or slag is expected. In the present paper, the possibility to combine Portland cements (PCs) with reduced clinker factor with sulfoaluminate cement (CSA), is explored. Low Portland clinker cements are prepared in laboratory using different supplementary cementitious materials (limestone, slag, pozzolan and fly ash) and mixed with a sulfoaluminate cement: the hydration behavior of the resulting binders is investigated up to 90 days through a multi-technique approach involving X-ray diffraction, differential scanning calorimetry and nuclear magnetic resonance spectroscopy. Understanding the interaction mechanisms between SCMs and CSA/PC blends will support the development of innovative high performing binders based on CEM III or CEM V, or even on new standardized CEM II. Results highlight that slag is particularly suitable promoting late strength development.

36 MATERIALS SCIENCE↗

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 OSTI2021

Effect of a liquid-type temperature rise inhibitor on cement hydration

A liquid-type temperature rise inhibitor (L-TRI) based on modified sorbitol was developed to solve the thermal cracking issue by modulating the heat release from cement hydration during the early age. Both the exothermic process and phase evolution of cement pastes blended with/without L-TRI were investigated by the combination of isothermal calorimetry, in-situ XRD, ICP-OES and SEM. Also, the adsorption of the L-TRI in the cement paste was identified by total organic carbon analysis. The testing results suggested that the L-TRI affected the heat flow curve in two ways. It prolonged the induction period as a retarding effect. It also reduced the heat flow during the acceleration period and decreased the maximum heat flow as a depressing effect. The retarding effect was mainly caused by the complexation of unabsorbed molecules in the pore solution, and the depressing effect was caused by inhibiting the growth of C-S-H.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Effect of PCEs with different structures on hydration and properties of cementitious materials with low water-to-binder ratio

Polycarboxylate ethers (PCEs) with different structures and densities of anchor groups in the backbone were synthesized and characterized. The surface tension of their solutions, their adsorption on cementitious particles and zeta potential of cement-silica fume pastes with PCEs were measured. Their effects on hydration and properties of cement-silica fume paste with low water-to-binder ratio were examined. Results indicated that the adsorption kinetics of theses PCEs on cementitious particles are fitted the pseudo-second-order model. The introduction of long silane chain on PCE decreased its electrostatic adsorption, while PCE was adsorbed onto the surface of particles via both chemical and electrostatic adsorption, when silicon hydroxyl is directly connected to its backbone. In the presence of PCE with higher adsorbed amount, pastes exhibited lower yield stress and higher flowability, and higher strength at 7 d and 28 d. The low plastic viscosity, autogenous and drying shrinkage were related to the low surface tension of PCE solution.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Iron incorporation in synthetic precipitated calcium silicate hydrates

Effect of Fe{sup 3+} on the precipitation of synthetic calcium silicate hydrates (C-S-H) under controlled conditions has been evaluated. Using extremely basic either initial calcium nitrate or sodium silicate solutions (pH > 11), incipient formation of ferrihydrite in both solutions was observed. In this case both C-S-H and iron-containing siliceous hydrogarnet are formed. For pH < 11, ferrihydrite was absent. Only C-S-H is formed. The presence of magnetically dilute Fe{sup 3+} in the C-S-H was shown by EPR and the atomic Fe/Si ratio of the C-S-H phase was shown to be between 0.01% and 0.1% by measuring and modelling the {sup 29}Si spin-lattice relaxation in NMR experiments. A uniform distribution of Fe{sup 3+} when C-S-H precipitates in the absence of initial ferrihydrite is obtained. When initial ferrihydrite is present, a non-uniform distribution of Fe{sup 3+} is found and the concentration of Fe{sup 3+} in the C-S-H is merely 3% of the overall iron concentration, suggesting the initial formation of ferrihydrite restricts the incorporation of iron into C-S-H.

36 MATERIALS SCIENCE↗

DOE OSTI2021

New insights into creep characteristics of calcium silicate hydrates at molecular level

The fundamental mechanisms under concrete creep are far from being fully understood, especially at the molecular level. Hereby, a calcium-silicate-hydrate (C-S-H) molecular model is developed to explain, for the first time, the creep characteristics at various stress states, temperature levels and water contents, which are not accessible experimentally. Rather tensile and compressive loadings, C-S-H only creeps under shear loadings originating from the sliding of the calcium silicate layers over each other as the interlayer component (water and ions) acts as a lubricator. A heterogeneous creep characteristic is observed. Elevated temperature reduces the interlayer lubricator viscosity and weakens the interfacial adhesion between the layers and the interlayer lubricator, which accelerates C-S-H creep. The removal of interlayer water enhances the creep resistance, resulting from the reduced interlayer space and enhanced interfacial adhesion. The atomic-level mechanisms explain the inter-CSH-particle behaviours at the microscale, which bridges the gap between atomistic simulation and microcosmic phenomenon.

36 MATERIALS SCIENCE↗