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Distribution of nickel(II) ions adsorbed at the muscovite mica (001)-water interface determined by in-situ resonant anomalous X-ray reflectivity

Mineral-water interfaces mediate adsorption, ion exchange, and secondary mineral formation that control element mobility in natural and engineered systems. Reliable prediction and control of these processes require a fundamental understanding of the interfacial structure that links adsorbed ion speciation to macroscopic sorption capacity and strength. Here, we determine atomic-scale changes in hydration and distribution of Ni(II) at the muscovite mica (001)-water interface using in situ high-resolution X-ray reflectivity (XR) and resonant anomalous X-ray reflectivity (RAXR) at 1 mM NiCl2 and pH 5.7. XR reveals reorganization of the primary hydration structure relative to that in deionized water: the water layer adsorbed in the cavity sites at a height of ~1.3 Å disappears, while distinct solution layers emerge at ~2.3, ~4.1, and ~5.6 Å above the basal oxygen plane. RAXR resolves three interfacial Ni(II) species: a dominant outer-sphere complex at 3.65 Å (~80% of the total coverage), a minor inner-sphere complex at 0.75 Å, and a low-coverage, more distant outer-sphere species at 5.63 Å. These three adsorbed Ni(II) species account for a total Ni(II) coverage of 0.54 ± 0.02 ion per unit cell area that compensates for the surface charge. These results highlight the role of interfacial hydration in controlling the speciation and stability of adsorbate cations on the negatively charged mica surface, providing quantitative insight into predicting the geochemical behavior of divalent metal cations in the aqueous environments.

Lee, Sang Soo

Electrical double layers at the oil/water interface

This review presents the historical development and current status of the theory of the electrical double layer at a liquid/liquid interface. It gives rigorous thermodynamic definitions of all basic concepts related to liquid interfaces and to the electrical double layer. The difference between the surface of a solid electrode and the interface of two immiscible electrolyte solutions (ITIES) is analyzed in connection to their electrical properties. The most important classical relationships for the electrical double layer are presented and critically discussed. The generalized adsorption isotherm is derived. After a short review of the classical Gouy-Chapman and Verwey-Niessen models, more recent developments of the double layer theory are presented. These include effects of variable dielectric permittivity, nonlocal electrostatics, hydration forces, the modified Poisson-Boltzmann equation and the ion-dipole plasma. The relative merits of different theories are estimated by comparing them with computer simulation of the ITIES and electrical double layer. Special attention is given to the structure of ITIES and its variation due to adsorption of ions and amphiphilic molecules.

Non-NASA Center

Origin of Martian channels - Clathrates and water

Criticism is directed at the suggestion that Martian channels may have been eroded by liquid water produced by the depressurization of CO2 hydrate. The release of pre-existing subsurface liquid water, such as that trapped under a permafrost layer, by meteorite impact or tectonic activity could produce sufficient flow and would not require heat transfer. The presence of water in a CO2 hydrate is shown to be detrimental to its release from an underground reservoir.

Peale, S. J.

Sulfates on Mars: Indicators of Aqueous Processes

Recent analyses by MER instruments at Meridiani Planum and Gusev crater and the OMEGA instrument on Mars Express have provided detailed information about the presence of sulfates on Mars [1,2,3]. We are evaluating these recent data in an integrated multi-disciplinary study of visible-near-infrared, mid-IR and Mossbauer spectra of several sulfate minerals and sulfate-rich analog sites. Our analyses suggest that hydrated iron sulfates may account for features observed in Mossbauer and mid-IR spectra of Martian soils [4]. The sulfate minerals kieserite, gypsum and other hydrated sulfates have been identified in OMEGA spectra in the layered terrains in Valles Marineris and Terra Meridiani [2]. These recent discoveries emphasize the importance of studying sulfate minerals as tracers of aqueous processes. The sulfate-rich rock outcrops observed in Meridiani Planum may have formed in an acidic environment similar to acid rock drainage environments on Earth [5]. Because microorganisms typically are involved in the oxidation of sulfides to sulfates in terrestrial sites, sulfate-rich rock outcrops on Mars may be a good location to search for evidence of past life on that planet. Whether or not life evolved on Mars, following the trail of sulfate minerals will lead to a better understanding of aqueous processes and chemical weathering.

Bishop, Janice L.

Phyllosilicate and Hydrated Sulfate Deposits in Meridiani

Several phyllosilicate and hydrated sulfate deposits in Meridiani have been mapped in detail with high resolution MRO CRISM [1] data. Previous studies have documented extensive exposures of outcrop in Meridiani (fig 1), or etched terrain (ET), that has been interpreted to be sedimentary in origin [e.g., 2,3]. These deposits have been mapped at a regional scale with OMEGA data and show enhanced hydration (1.9 m absorption) in several areas [4]. However, hydrated sulfate detections were restricted to valley exposures in northern Meridiani ET [5]. New high resolution CRISM images show that hydrated sulfates are present in several spatially isolated exposures throughout the ET (fig 1). The hydrated sulfate deposits in the valley are vertically heterogeneous with layers of mono and polyhydrated sulfates and are morphologically distinct from other areas of the ET. We are currently mapping the detailed spatial distribution of sulfates and searching for distinct geochemical horizons that may be traced back to differential ground water recharge and/or evaporative loss rates. The high resolution CRISM data has allowed us to map out several phyllosilicate deposits within the fluvially dissected Noachian cratered terrain (DCT) to the south and west of the hematite-bearing plains (Ph) and ET (fig 1). In Miyamoto crater, phyllosilicates are located within ~30km of the edge of Ph, which is presumably underlain by acid sulfate deposits similar to those explored by Opportunity. The deposits within this crater may record the transition from fluvial conditions which produced and/or preserved phyllosilicates deposits to a progressively acid sulfate dominated groundwater system in which large accumulations of sulfate-rich evaporites were deposited .

Wiseman, S. M.

Carbonation of Alkaline Earth Metal Hydroxides: Structure across Nano- to Mesoscales

The conversion of gaseous CO 2 into a solid constitution through mineralization is an active area of carbon capture, and alkaline earth metal hydroxides (M(OH) 2 , M = Ca 2+ , Mg 2+ ) are frontrunners in this area. As model systems, nanolime samples are excellent templates for the study of this reaction. Here, we have examined these under ambient pressure conditions with controlled humidity and CO 2 . Utilizing a broad range of analytical methods, we first established the purity and structures of the selected materials. We then examined the structural changes due to carbonation, using infrared spectroscopy, X-ray scattering, and neutron scattering. The resulting structural changes are resolved from nanoscale to mesoscale and from early-stage to late-stage carbonation. Ca(OH) 2 and Mg(OH) 2 are found to behave quite differently. As expected from prior work, the carbonation of Ca(OH) 2 is kinetically favored. Further, our structure studies suggest this is due to a facile reaction at the fractal interface of the particles. From early- to late-stage carbonation, there is a consistent increase in the fractal roughness. This is in contrast to Mg(OH) 2 where the same surface evolves into a smooth conformal coating. For this material the major reacting component is at the mesoscale, suggesting globular particle growth or evolving macro-porosity. Because neutron scattering is sensitive to hydrogen content, we expected a significant change as M(OH) 2 evolves to MCO 3 . Such a change is found for Ca(OH) 2 but not for Mg(OH) 2 , providing evidence for the formation of hydrated carbonates for the later material. The formation of a conformal layer along with water-rich carbonate formation is an impediment to the use of Mg(OH) 2 for carbon capture. For energy-efficient carbon capture, it would be desirable to enhance carbonation rates for Mg(OH) 2 , and one possible route would be the use of anhydrous fluids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Ice particulates in the mesosphere

The observations of noctilucent clouds, the measurements of hydrated and of large immobile ions, and the light-scattering layer detected by the OGO-6 satellite suggest the presence of particulates, probably ice, in the mesosphere. The correlation between temperature and positive ion conductivity where the vapor pressure over ice becomes greater than atmospheric pressure in the stratopause region indicates the presence of ice crystals throughout the mesosphere over a wide range of latitudes during all seasons. Between one and ten billion ice crystals per cubic meter of order 10 nanometers in diameter can dominate ionization loss processes in the mesosphere, and can explain a variety of experimental observations, including observed solar angle dependence and seasonal variability of electron density.

Chesworth, E. T.

Damage to cellular DNA from particulate radiations, the efficacy of its processing and the radiosensitivity of mammalian cells. Emphasis on DNA double strand breaks and chromatin breaks

For several years, it has been evident that cellular radiation biology is in a necessary period of consolidation and transition (Lett 1987, 1990; Lett et al. 1986, 1987). Both changes are moving apace, and have been stimulated by studies with heavy charged particles. From the standpoint of radiation chemistry, there is now a consensus of opinion that the DNA hydration shell must be distinguished from bulk water in the cell nucleus and treated as an integral part of DNA (chromatin) (Lett 1987). Concomitantly, sentiment is strengthening for the abandonment of the classical notions of "direct" and "indirect" action (Fielden and O'Neill 1991; O'Neill 1991; O'Neill et al. 1991; Schulte-Frohlinde and Bothe 1991 and references therein). A layer of water molecules outside, or in the outer edge of, the DNA (chromatin) hydration shell influences cellular radiosensitivity in ways not fully understood. Charge and energy transfer processes facilitated by, or involving, DNA hydration must be considered in rigorous theories of radiation action on cells. The induction and processing of double stand breaks (DSBs) in DNA (chromatin) seem to be the predominant determinants of the radiotoxicity of normally radioresistant mammalian cells, the survival curves of which reflect the patterns of damage induced and the damage present after processing ceases, and can be modelled in formal terms by the use of reaction (enzyme) kinetics. Incongruities such as sublethal damage are neither scientifically sound nor relevant to cellular radiation biology (Calkins 1991; Lett 1990; Lett et al. 1987a). Increases in linear energy transfer (LET infinity) up to 100-200 keV micron-1 cause increases in the extents of neighboring chemical and physical damage in DNA denoted by the general term DSB. Those changes are accompanied by decreasing abilities of cells normally radioresistant to sparsely ionizing radiations to process DSBs in DNA and chromatin and to recover from radiation exposure, so they make significant contributions to the relative biological effectiveness (RBE) of a given radiation.(ABSTRACT TRUNCATED AT 400 WORDS).

Non-NASA Center

Complex Dependence of Calcite Crack Kinetics on Salinity: The Role of DLVO and Hydration Forces

Abstract Subcritical crack growth (SCG) plays an important role in many geological processes such as delayed earth rupture and rock weathering. The complex dependency of SCG on the in‐crack fluid chemistry, however, is still poorly understood. In this study, we utilize the newly developed surface force‐based fracture theory (SFFT) to elucidate the relative contributions of surface forces and solute transport to the crack growth kinetics of calcite in NaCl solutions. Expanding on Barenblatt's cohesive crack model, SFFT introduces an effective stress intensity at the crack tip that encompasses all the relevant intermolecular forces across the crack in addition to the external far‐field stresses. The nonlinear system of equations portraying the crack opening profile, the solute distribution in a propagating crack, and the crack growth velocity are numerically solved via an implicit scheme. After carefully calibrating the model for calcite‐water systems, the SFFT is used to predict the SCG response of calcite at different NaCl concentrations, based on various hypotheses. These predictions are then compared to existing SCG data from the literature. We demonstrate that the experimentally observed variation of SCG rate with NaCl concentration cannot be explained solely by DLVO forces (electrostatic and Van der Waals interactions). This can be remediated by introducing an exponentially decaying hydration force with a nonlinear, nonmonotonic dependence on NaCl concentration. Furthermore, we demonstrate that accounting for both diffusive and advective transport of ions is important in explaining the absence of a stage‐II SCG response for calcite in electrolyte solutions. Plain Language Summary Subcritical crack growth (SCG) refers to the slow propagation of cracks in materials under a stress below the threshold for catastrophic failure. SCG is a key process in many geological events, for example, delayed earth ruptures and rock weathering. New initiatives such as underground CO 2 and H 2 storage in carbonate reservoirs further call for better understanding of SCG in carbonate minerals subjected to varying fluid chemistry. This study examines the SCG of calcite, a key mineral found in carbonate rocks, intergranular cement in sandstones, and filling material in mineral veins and faults, determining their deformation and strength. A mathematical model is developed to describe how the crack opens and propagates, how solutes (like salts) distribute within the crack, and how the crack surfaces interact with each other. We used the model to predict calcite SCG in water at different salt concentrations and compared it with experimental data. Our results revealed that the hydration force is the dominating factor in determining the complex, non‐linear dependency of SCG on salinity. We also found that both the movement of ions by diffusion and by bulk water flow are crucial for explaining the SCG rates, especially when the cracks grow quickly. Key Points Surface Force‐Based Fracture Theory predicts the complex subcritical crack growth patterns of calcite crystals immersed in NaCl solutions Results highlight the dominant role of hydration forces in altering the fracture behavior of calcite compared to VdW and electric double‐layer forces Advective solute transport explains the absence of stages‐II and ‐III subcritical crack growth responses in solid‐liquid systems

DLVO

Cyclic moisture reactivation of calcium sorbents for long duration thermochemical energy storage

The transition to a flexible and reliable energy infrastructure, using electro-thermal energy generation technologies such as geothermal, concentrated solar power, and nuclear, usually demands simultaneous advancement of thermal energy storage (TES) to support on-demand electricity generation and industrial applications while mitigating the inherent intermittency of renewable energy sources and power outages from direct energy generation. Among TES technologies, thermochemical energy storage (TCES) based on calcium looping emerges as a compelling high-power energy storage candidate due to its high reaction enthalpy, compatibility with elevated operating temperatures, and abundance of low-cost materials. However, the long-term durability of calcium-based sorbents for TCES is hindered by surface sintering and particle aggregation, leading to performance degradation over repeated thermal cycles. This study explores a moisture hydration-based strategy to regenerate a degraded calcium sorbent and mitigate performance degradation for long duration TCES. The addition of moisture transforms calcium oxide into calcium hydroxide and produces intercalation water layers, associated with a regenerated surface area and reduced calcium oxide crystallite size. Both these effects are beneficial in restoring the sorbents' reactivity for carbonization. Additionally, an optimized hydration-assisted reactivation protocol balances the recovered energy storage capacity with heating penalty required for moisture removal from hydrated samples, resulting in an enhanced energy storage capacity up to 176% compared to benchmark sorbents that undergo cycling without reactivation after 60 cycles. In conclusion, these results highlight the potential of hydration-assisted reactivation to enhance the long-term performance of TCES, providing an effective pathway to advancing electro-thermal storage technologies.

36 MATERIALS SCIENCE

A model for diagenesis in proto-planetary bodies

A model is proposed which eases the thermal constraints imposed by earlier models of low-temperature aqueous alteration in primitive extraterrestrial materials in which formation of an aqueous medium promoting these alterations required complete melting of the water-ice. It is argued that low-temperature alterations in a protoplanetary body such as the formation of hydrated silicates will occur because of the presence of an interfacial water layer.

Rietmeijer, F. J. M.

Space Weathering Impact on Solar System Surfaces and Planetary Mission Science

We often look "through a glass, darkly" at solar system bodies with tenuous atmospheres and direct surface exposure to the local space environment. Space weathering exposure acts via universal space-surface interaction processes to produce a thin patina of outer material covering, potentially obscuring endogenic surface materials of greatest interest for understanding origins and interior evolution. Examples of obscuring exogenic layers are radiation crusts on cometary nuclei and iogenic components of sulfate hydrate deposits on the trailing hemisphere of Europa. Weathering processes include plasma ion implantation into surfaces, sputtering by charged particles and solar ultraviolet photons, photolytic chemistry driven by UV irradiation, and radiolytic chemistry evolving from products of charged particle irradiation. Regolith structure from impacts, and underlying deeper structures from internal evolution, affects efficacy of certain surface interactions, e.g. sputtering as affected by porosity and surface irradiation dosage as partly attenuated by local topographic shielding. These processes should be regarded for mission science planning as potentially enabling, e.g. since direct surface sputtering, and resultant surface-bound exospheres, can provide in-situ samples of surface composition to ion and neutral mass spectrometers on orbital spacecraft. Sample return for highest sensitivity compOSitional and structural analyses at Earth will usually be precluded by limited range of surface sampling, long times for return, and high cost. Targeted advancements in instrument technology would be more cost efficient for local remote and in-situ sample analysis. More realistic laboratory simulations, e.g. for bulk samples, are needed to interpret mission science observations of weathered surfaces. Space environment effects on mission spacecraft and science operations must also be specified and mitigated from the hourly to monthly changes in space weather and from longer term (e.g., solar cycle) evolution of space climate. Capable instrumentation on planetary missions can and should be planned to contribute to knowledge of interplanetary space environments. Evolving data system technologies such as virtual observatories should be explored for more interdisciplinary application to the science of planetary surface, atmospheric, magnetospheric, and interplanetary interactions.

Cooper, John F.

Large Primtive Asteroids: Thermal and Dynamical Context

Primitiveasteroids, most of which are located in the outer belt and Jupiter’s Trojan clouds, provide information related to the origin and evolution of the solar system and the conditions in which the solar nebula was formed. These asteroids are widely thought to be the origin of the least-altered car-bonaceous chondrite that allow us to put crucial con-straints on the current dynamical and thermal theories of the formation and evolution of the early solar sys-tem. The nature of surface composition of large and low-albedo asteroids, like (1) Ceres, (10) Hygiea and (52) Europa, is still under intense debate and different interpretations have beenput forth to explain the ab-sorption features in these objects (e.g.,[1, 2, 3,4,5,6]). Laboratory and spectroscopic experiments on me-teorites that represent all nine carbonaceous chondrite types also found no spectral matches for these large asteroids (e.g.,[7]). Previous studies of asteroid Ceres (the largest primitive asteroid in the solar system) have been conducted to constrain and estimate its surface composition (e.g., [2, 5]). Using linear mixing,[2]found hydroxide brucite, serpentines, and carbonates, to be consistent with Ceres’ ground-based spectra.[5]estimated the surface composition of Ceres and found evidence of widespread NH3-phyllosilicates across its surface using best-fit solutions to Dawn’s NIR spectra. The presence of NH3-phyllosilicates implies that mate-rial from the outer solar system was incorporated into large primitive asteroids, either during their formation at great heliocentric distance or by incorporation of material transported into the Main Belt region. Here we presentnew largeand primitive asteroidsthat share the same spectral similaritieswith the largest asteroid in the solar system, Ceres.We also present the context of these new observations in terms oftheirthermal and dynamicalevolution.Large Primitive Asteroids: Dynamical and Thermal Context:Orbital Distribution of LargePrimitiveAsteroids: Constraining the mineralogy and surface composition of large primitive asteroids will place crucial con-straints on existing dynamical and thermal theories of the formation of the early solar system. We identified several additional asteroids in the Europa-like group in addition to asteroids Europa, Euphrosyne, and Patien-tia, that wereidentified in [8]using NASA IRTFtele-scope (e.g.,Figure 1). These new asteroids along with the already-observed Ceres-and Europa-like group members are localized in the 2.8 < a < 3.4 AU region and characterized by larger sizes, showing an interest-ing orbital distribution (Figure 2). Ceres-likeand Eu-ropa-like groups, which include the largest asteroids in the solar system, show an interesting orbital distribu-tion. These groups are located in the 2.6 < a < 3.6 AU region that contains the snow-line. The snow-line’s location may have been driftedinwards due to the disk’s cooling and evolution[9,10]. Recent dynamical models[11,12]suggested that a substantial fraction of primitive asteroids originated between or beyond the giant planets (a > 5 AU), where water ice would have been stable, and then implanted in the outer Main Belt region because of the giant planets’ growth.Figure 1. Two asteroids, 94 Aurora and 423 Diotima, showing spectra similar to asteroids (1)Ceres and (52)Europa.Thermal modeling and evolution of primitive aster-oids:Primitive water-rich asteroids are thought to be originally composed of mixtures of anhydrous materi-als and water ice that waslater melted by heating sources such as the decay of 26Al, reacting with anhy-drous materials to form H2O/OH-rich minerals. Calcu-lations of the evolution of the temperature and struc-ture of icy planetesimals were performedusing a 1D finite differences thermal evolution model[13, 14] for 26Al-heated planetesimals. In particular, thermally activated compaction due to hot pressing of bodies with an initially unconsolidated porous structure is included. An ice-rich initial composition that leads to a material dominated by phyllosilicates upon aqueous alteration (with 25 vol% H2O and a rock fraction that contains 85 vol% phyllosilicates and 15 vol% olivine upon aque-ous alteration, similar to CIand CM chondrites) was assumed. Atypical initial porosity of 40%[15] is re-duced following the change of the strain rate that is calculated as Voigt approximation from the strain rates of components[16]. Material properties (thermal con-ductivity, density, heat capacity, etc.) correspond to the composition assumed and are adjusted with tempera-ture and porosity. Melting of the water ice as well as water-rock separation are included[14]. Both short-and long-lived radionuclides are consideredas heat sources. Figure 3 shows the maximum temperature calculated as a function of radius and accretion time. A variety of internal structures is obtained, ranging from primordial (no melting of water ice) over partially melted or partially differentiated (melting of water ice, hydration, formation of a rocky core and water ocean below an undifferentiated layer) to completely differ-entiated ones (rocky core, water mantle, Enceladus-like case). The heating and differentiation of planetesi-mals is determined by the availability of 26Al, i.e., by the accretion time t0 relative to the formation of the calcium-aluminum-rich inclusions (CAIs), such that maximum temperatures and structures vary stronglyfor t0< 6 Myr rel. to CAIs. However, for a later accre-tion only the size of the body determines its maximum tempera-ture and structure due to the nearly constant heating by long-lived radionuclides. Average densities of Ceres-and Europa-like group membersimply high-ly porous interiors and, consequently, relatively late accretion at t0> 3 Myr rel. to CAIs with a maximum temperature of < 600 K (Figure3)

D Takir

Formation of Tropopause Cirrus clouds by Typhoon-induced gravity waves during the Asian Summer Monsoon: A Case Study from the BATAL 2017 Campaign

Cirrus clouds in the Tropical Tropopause Layer (TTL) have a net warming impact on Earth’s climate and they regulate the amount of water vapor entering the lower stratosphere through dehydration process near the cold-point tropopause. During the Boreal summer, Asian Summer Monsoon (ASM) is an important source of cirrus clouds and humidity in the TTL owing to frequent deep convection. However, better representation of convection and TTL cirrus clouds in global climate models is needed for accurate assessment of their response to changing climate. In this study, we investigate the mechanisms involved in the formation of a tropopause cirrus cloud layer observed during the Balloon measurement campaigns of the Asian Tropopause Aerosol Layer (BATAL) over Hyderabad (17.47 °N, 78.58 °E), India on 23 August 2017. A subvisible cirrus cloud layer (optical thickness ~0.025) was detected by a backscatter sonde (COBALD) onboard a balloon near the cold-point tropopause (CPT, temperature~ -86.4 ° C, altitude~17.9 km) which was later confirmed by the CATS lidar on the ISS. Simultaneous measurements from an optical particle counter (Boulder Counter) revealed the presence of ice crystals smaller than 50 microns in this layer. The formation mechanism responsible for this tropopause cirrus is investigated using a technique combining three-dimensional back-trajectories, satellite observations, and ERA5 reanalysis data. Satellite observations revealed that the overshooting convection associated with a category-3 typhoon Hato, which hit Macau and Hong Kong on 23 August 2017 injected ice into the lower stratosphere. This caused a hydration patch that followed the ASM anticyclone subsequently moving towards Hyderabad. The presence of tropopause cirrus cloud layers in the cold temperature anomalies and updrafts along the back-trajectories indicated towards the role of typhoon-induced gravity waves in their formation. This case study highlights the role of typhoons in influencing the formation of tropopause cirrus clouds through stratospheric hydration and gravity waves in the ASM anticyclone.

Amit Kumar Pandit

Bonding by Hydroxide-Catalyzed Hydration and Dehydration

A simple, inexpensive method for bonding solid objects exploits hydroxide-catalyzed hydration and dehydration to form silicate-like networks in thin surface and interfacial layers between the objects. The method can be practiced at room temperature or over a wide range of temperatures. The method was developed especially to enable the formation of precise, reliable bonds between precise optical components. The bonds thus formed exhibit the precision and transparency of bonds formed by the conventional optical-contact method and the strength and reliability of high-temperature frit bonds. The method also lends itself to numerous non-optical applications in which there are requirements for precise bonds and/or requirements for bonds, whether precise or imprecise, that can reliably withstand severe environmental conditions. Categories of such non-optical applications include forming composite materials, coating substrates, forming laminate structures, and preparing objects of defined geometry and composition. The method is applicable to materials that either (1) can form silicate-like networks in the sense that they have silicate-like molecular structures that are extensible into silicate-like networks or (2) can be chemically linked to silicate-like networks by means of hydroxide-catalyzed hydration and dehydration. When hydrated, a material of either type features surface hydroxyl (-OH) groups. In this method, a silicate-like network that bonds two substrates can be formed either by a bonding material alone or by the bonding material together with material from either or both of the substrates. Typically, an aqueous hydroxide bonding solution is dispensed and allowed to flow between the mating surfaces by capillary action. If the surface figures of the substrates do not match precisely, bonding could be improved by including a filling material in the bonding solution. Preferably, the filling material should include at least one ingredient that can be hydrated to have exposed hydroxyl groups and that can be chemically linked, by hydroxide catalysis, to a silicate-like network. The silicate-like network could be generated in situ from the filling material and/or substrate material, or could be originally present in the bonding material.

Gwo, Dz-Hung

Synthesis and Characterization of Layered Actinide (U, Np, Pu) Oxide and Hydroxide Phases

Systematic structural comparisons across the early actinides remain limited by the scarcity of well-defined transuranic layered oxide and oxyhydroxide phases. Here, we report the synthesis and single-crystal characterization of new layered actinide compounds spanning U, Np, and Pu obtained under mild hydrothermal conditions in concentrated alkali hydroxide media. These include hydrated oxides α-Cs 2 U 2 O 7 •0.5H 2 O and Rb 2 An 2 O 7 •0.5H 2 O (An = Np, Pu), oxy-hydroxides Rb 6 [(AnO 2 ) 6 O 8 (OH) 2 ]•xH 2 O x = 0, 0.5 (An = U, Np) and Rb 4 [(UO 2 ) 5 O 6 (OH) 2 ]•2H 2 O, as well as nitrate-intercalated compounds Cs 6 [(AnO 2 ) 3 O 4 (OH) 2 ](NO 3 ) 2 (An = Np, Pu). Single-crystal X-ray diffraction studies reveal extended two-dimensional architectures constructed from edge- and vertex-sharing actinyl polyhedra, with systematic evolution in equatorial coordination, hydration, and anionic sheet topology across the U–Np–Pu series. Incorporation of nitrate anions within the interlayer region of Cs 6 [(AnO 2 ) 3 O 4 (OH) 2 ](NO 3 ) 2 establishes a previously unobserved structural motif in layered transuranic oxyhydroxides, demonstrating an additional pathway for anion-mediated framework stabilization. Correlation of crystallographic metrics with single-crystal Raman spectroscopy provides new vibrational benchmarks linking differences in An═O yl bond lengths to the equatorial coordination and the interstitial cations. These findings expand the structural hierarchy of layered actinide materials and address clarifying periodic trends governing topology, bonding, and vibrational signatures in high-valent 5ƒ oxide systems.

actinides

Subsurface Cl-bearing salts as potential contributors to recurring slope lineae (RSL) on Mars

We report laboratory experimental results that support a brine-related hypothesis for the recurring slope lineae (RSL) on Mars in which the subsurface Cl-salts, i.e., hydrous chlorides and oxychlorine salts (HyCOS) are the potential source materials. Our experiments revealed that within the observed RSL temperature window TRSL (250–300 K), the deliquescence of HyCOS could occur in relative humidity ranges (RH≥22%–46%) much lower than those for hydrous (Mg, Fe)-sulfates (RH≥75%–96%). In addition, we demonstrated that the RH values kept by common HyCOS and hydrous sulfates in enclosures have a general trend as RH(sulfates) > RH(perchlorates) > RH(chlorides) (with same type of cation) in wide T range. It means that the required RH range for a Cl-bearing salt to deliquescence can be satisfied by a co-existing salt of different type, e.g., in the subsurface layers of mixed salts on Mars. Furthermore, we found a strong temperature dependence of the deliquescence rates for all tested HyCOS, e.g., a duration of 1–5 sols for all HyCOS at the high end (300 K) of TRSL, and of 20–70 sols for all tested HyCOS (except NaClO4·H2O) at the low end (250 K) of TRSL, which is consistent with the observed seasonal behavior of RSL on Mars. From a mass-balance point of view, the currently observed evidences on Mars do not support a fully-brine-wetted track model, thus we suggest a brine-triggered granular-flow model for the most RSL. Considering the recurrence of RSL in consecutive martian years, our experimental results support the rehydration of remnant HyCOS layers during a martian cold season through H2O vapor-to-salt direct interaction. We found that the evidences of HyCOS rehydration under Mars relevant P-T-RH conditions are detectable in a few minutes by in situ Raman spectroscopy. This rehydration would facilitate the recharge of H2O back into subsurface HyCOS, which could serve as the source material to trigger RSL in a subsequent warm season. The major limiting factor for this rehydration is the H2O supply, i.e., the H2O vapor density carried by current Mars atmospheric circulation and the diffusion rate of H2O vapor into the salt-rich subsurface in a cold season. In a worst-case scenario, these H2O supplies can support a maximum increase of hydration degrees of two for totally dehydrated HyCOS, whereas the full rehydration of subsurface HyCOS layers can be easily reached during a>30° obliquity period that has H2O vapor density 10× to 20× times the value of current obliquity. Overall, our results imply the existence of a large amount of Cl-bearing salts in the subsurface at RSL sites.

Alian Wang

Mineral Trends in Early Hesperian Lacustrine Mudstone at Gale Crater, Mars

The Mars Science Laboratory Curiosity rover landed in Gale crater in August 2012 to study the layered sediments of lower Aeolis Mons (i.e., Mount Sharp), which have signatures of phyllosilicates, hydrated sulfates, and iron oxides in orbital visible/near-infrared observations. The observed mineralogy within the stratigraphy, from phyllosilicates in lower units to sulfates in higher units, suggests an evolution in the environments in which these secondary phases formed. Curiosity is currently investigating the sedimentary structures, geochemistry, and mineralogy of the Murray formation, the lowest exposed unit of Mount Sharp. The Murray formation is dominated by laminated lacustrine mudstone and is approx.200 m thick. Curiosity previously investigated lacustrine mudstone early in the mission at Yellowknife Bay, which represents the lowest studied stratigraphic unit. Here, we present the minerals identified in lacus-trine mudstone from Yellowknife Bay and the Murray formation. We discuss trends in mineralogy within the stratigraphy and the implications for ancient lacustrine environments, diagenesis, and sediment sources.

Rampe, E. B.