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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.

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At least 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

A Novel Eco-Biosorbent for Decontamination of Hazardous Dye from Aqueous Medium

A novel multi-component biosorbent consisted of pine, oak, hornbeam and fir sawdust biomasses was used to eliminate a common hazardous dye (Malachite green, MG) from aqueous solution. The influences of different parameters like solution pH, biosorbent amount, dye concentration and contact time on the removal process were thoroughly studied to evaluate optimum biosorption conditions. The pseudo-first-order, pseudo-second-order, Elovich, logistic and intra-particle diffusion models were used to describe the biosorption kinetics. Logistic model represented the kinetic experimental data well. The experimental equilibrium biosorption data were analyzed by Freundlich, Langmuir and Dubinin–Radushkevich isotherms. Freundlich model fitted better with the experimental data compared to others. In addition, the mean free energy obtained from Dubinin–Radushkevich model and the standard Gibbs free energy change indicated that the nature of biosorption was feasible, spontaneous and physical type. Overall, the novel eco-biosorbent could be used as a promising biosorbent to remove such unsafe dye molecules from aqueous environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Adsorption Efficiency of Polyaspartate-Montmorillonite Composite Towards the Removal of Pb(II) and Cd(II) from Aqueous Solution

The selective modification of sodium montmorillonite (Na{sup +}-Mt) surface with polyionene followed by poly (succinimde-co-aspartate) has been considered. Na{sup +}-Mt was allowed to react with well characterized polyionene in two fold excess. The resulting polyionene/Mt (IC) was further modified with poly (succinimide-co-aspartate) through an ion exchange process. The obtained polyaspartate/Mt (IPS) composite was characterized by elemental analysis, X-ray diffraction, FTIR spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and BET surface analyzer. The adsorption efficiency of IPS composite was investigated for the removal of Pb(II) and Cd(II) from aqueous solution under different experimental conditions including initial metal ions concentration, temperature and single and binary mixture systems of metal ions. The experimental data were analyzed by Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich models. Langmuir model reveals that the monolayer adsorption capacity of IPS was 92.59 and 67.57 mg/g for Pb(II) and Cd(II), respectively. The modification of parent Na{sup +}-Mt enhanced their adsorption capacity by about 87.91 and 29.84% for Pb(II) and Cd(II), respectively, due to inclusion of extra active sites of polyaspartate. The mean sorption energy, E calculated from Dubinin–Radushkevich isotherm were 2.75 and 1.98 kJ/mol for the adsorption of Pb(II) and Cd(II), respectively, indicating physical adsorption process. Also, The thermodynamic parameters were calculated and indicated that the adsorption was spontaneous and exothermic process. The mechanism of cation exchange and complexation of metal ions was suggested. IPS composite has a considerable potential for the removal of heavy metal ions from aqueous solution and wastewater stream.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Removal of Congo Red from Aqueous Solution by Hydroxyapatite Nanoparticles Loaded on Zein as an Efficient and Green Adsorbent: Response Surface Methodology and Artificial Neural Network-Genetic Algorithm

This study is based on the application of hydroxyapatite nanoparticles loaded on Zein (Zein/nHAp) as an efficient adsorbent for the removal of Congo red from aqueous solutions. The properties of the adsorbent were characterized using various techniques including FT-IR, XRD, FE-SEM, and BET. The influence of five parameters such as pH, temperature, contact time, initial dye concentration, and adsorbent dosage on the removal percentage of the dye was investigated. The optimum conditions of 5.83, 34.32 °C, 5.20 min, 392.10 ppm, and 0.007 g were achieved for pH, temperature, contact time, initial dye concentration, and adsorbent dosage, respectively. The maximum removal percentage of 99.48% was obtained under the optimum condition that exhibited high adsorption potential of the used adsorbent. Central composite design (CCD) under response surface methodology and artificial neural network-genetic algorithm (ANN-GA) were utilized for optimization of parameters. Comparison of the results of the two models in terms of coefficient of determination (R{sup 2}) and mean absolute percentage error confirmed the prediction potential of CCD and ANN-GA. Higher ability and accuracy of ANN-GA in prediction was found based on given results. The experimental equilibrium data were studied by Langmuir, Freundlich, Temkin and Dubinin-Radushkevic isotherm models and explored that the data well presented by Langmuir model with maximum adsorption capacity of 416.66 mg/g. The adsorption kinetic was well-fitted by the pseudo-second-order model. The thermodynamics of the adsorption displayed spontaneous and endothermic nature of the process. Regeneration investigation showed that Zein/nHAp can impressively be reused, indicating that the adsorbent was a promising one for the removal of Congo red from aqueous solution. Graphical Abstract: .

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Highly Efficient Removal of Lead Ions from Aqueous Solutions Using Chitosan/Rice Husk Ash/Nano Alumina with a Focus on Optimization by Response Surface Methodology: Isotherm, Kinetic, and Thermodynamic Studies

In the present study, an adsorbent named chitosan/rice husk ash/nano-γ alumina was prepared and used for the removal of lead ions from aqueous solutions. It was characterized by FESEM, FTIR, XRD, and BET. The important and interactive effects of some considered parameters, such as the initial lead ion concentration, pH, adsorbent mass and contact time, were estimated and optimized by using the central composite design (CCD). The Maximum adsorption efficiency of lead ions under optimum conditions, including the pH of 5, adsorbent mass of 0.01 g, the initial lead ion concentration of 30 ppm, and the contact time of 105 min, was achieved to be 90.98%. The adsorption kinetic was consistent with the pseudo-second-order model (R{sup 2} = 0.9967). The lead adsorption isotherms were well fitted to the Langmuir model, indicating the maximum adsorption capacity of 181.82 mg g{sup −1}. Thermodynamic parameters (R{sup 2}: 0.9200, ΔH°: − 22871.81 kJ mol{sup −1}, ΔG{sup °}: − 10.63 kJ mol{sup −1}, and ΔS{sup °}: 118.37 kJ mol{sup −1} K{sup −1}) were calculated and indicating adsorption process was exothermic and spontaneous in the temperature range of 283.15–313.15 k. The maintenance above 70% capacity of the adsorbent was observed by the regeneration study of chitosan/rice husk ash/nano-γ alumina after six cycles. Comparison of adsorption efficiency of the studied adsorbent and other adsorbents in the removal of lead ions was also done in this paper. Consequently, the excellent properties of the presented nanocomposite could make it an ideal adsorbent for the removal of lead ions from aqueous solutions. Graphical Abstract: .

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Removal of Methylene Blue from Aqueous Solutions Using Poly(vinyl alcohol)/Montmorillonite Nanocomposite Hydrogels: Taguchi Optimization

Nanocomposite hydrogel adsorbents on the basis of poly(vinyl alcohol) containing 0, 4, 8 and 12 wt% (based on dry basis) of montmorillonite were prepared using a cyclic freezing–thawing process. The capabilities of the adsorbents in adsorbing of a cationic dye, methylene blue, were studied in aqueous solutions having different temperatures, pH and concentrations. The Taguchi method was utilized to optimize the controllable factors, including the montmorillonite loading level, the solution temperature and pH and also the methylene blue concentration in adsorption solution. The prepared nanocomposite hydrogel adsorbents were characterized by Fourier transform infrared spectroscopy and their gel content and swelling values were also measured. The results showed that the gel content and swelling of nanocomposite hydrogel adsorbents had a direct and inverse dependency to the loading level of incorporated montmorillonite to adsorbent, respectively. The successful dye adsorption by the prepared nanocomposite hydrogel adsorbents was confirmed by the Fourier transform infrared spectroscopy. Based on the Taguchi method, the optimized conditions for methylene blue adsorption were found as: montmorillonite loading level of 12 wt%, adsorption temperature of 50 °C, pH of the aqueous solution of 9 and methylene blue concentration in adsorption solution of 5 mg/L. The percentage contribution of each parameter on the removal of methylene blue was determined using the Analysis of Variance method and the following order was found: temperature > concentration of methylene blue in solution > montmorillonite loading level in adsorbent > pH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Adsorption of Zn(II) and Pb(II) Ions from Aqueous Solution Using Chitosan Cross-Linked Formaldehyde Adsorbent to Protect the Environment

Synthesis of chitosan cross-linked formaldehyde was successfully prepared from shrimp chitosan. Characterization of the adsorbent using functional properties such as Fourier transform infrared spectroscopy and scanning electron microscope shows the present of amide and hydroxyl groups at their respective position, also the morphological structure of the adsorbent. Adsorption study of the above adsorbent was carry out for the removal of Zn(II) and Pb(II) from aqueous solution. The effect of cross-linked chitosan dosage, initial concentration, contact time, temperature and pH of the solution for the removal of Zn(II) and Pb(II) were discussed. The optimum dosage required for the removal of Zn(II) and Pb(II) were found to be at 0.4 g at the maximum temperature of 25 °C and the percentage removal were 20.34 and 13.54% respectively. The time required for equilibrium to be reached was 50 min. Effectiveness of the cross-linked adsorbent was observed to increase by increase in contact time. Further studies were also done on isotherms and kinetics of Zn(II) and Pb(II) removal from aqueous solution using chitosan cross-linked formaldehyde. Adsorption Isotherm study conducted from the cross-linked absorbent, shows that the Langmuir plot for the removal of Zn(II) was best fitted with R{sup 2} value of 0.9934, and the adsorption process follows the pseudo second order kinetics with an R{sup 2} value of 0.996. This adsorption process was established to be reversible with an R{sub L} values of zinc (0.8232) and lead (0.8853) respectively. Therefore this implies a successfully reduction in the adsorption of zinc and lead ions from cross-linked formaldehyde solution to protect our environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Solubility Measurements of Crystalline NiO in Aqueous Solution as a Function of Temperature and pH

Abstract Results of solubility experiments involving crystalline nickel oxide (bunsenite) in aqueous solutions are reported as functions of temperature (0 to 350 C) and pH at pressures slightly exceeding (with one exception) saturation vapor pressure. These experiments were carried out in either flow-through reactors or a hydrogen-electrode concentration cell for mildly acidic to near neutral pH solutions. The results were treated successfully with a thermodynamic model incorporating only the unhydrolyzed aqueous nickel species (viz., Ni2+ ) and the neutrally charged hydrolyzed species (viz., Ni(OH)02 ). The thermodynamic quantities obtained at 25 C and infinite dilution are, with 2 uncertainties: log10Ko s0 = (12.40 0.29), rGo m = (70.8 1.7) kJ mol 1; rHo m = (105.6 1.3) kJ mol 1; rSo m = (116.6 3.2) J K 1 mol 1; rCo p,m = (0 13) J K 1 mol 1; and log10Ko s2 = (8.76 0.15); rGo m = (50.0 1.7) kJ mol 1; rHo m = (17.7 1.7) kJ mol 1; rSo m = (108 7) J K 1 mol 1; rCo p,m = (108 3) J K 1 mol 1. These results are internally consistent, but the latter set differs from those gleaned from previous studies recorded in the literature. The corresponding thermodynamic quantities for the formation of Ni2+ and Ni(OH)02 are also estimated. Moreover, the Ni(OH) 3 anion was never observed, even in relatively strong basic solutions (mOH = 0.1 mol kg 1), contrary to the conclusions drawn from all but one previous study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Disperse aqueous systems based on (S)-lysine in a wide range of concentrations and physiologically important temperatures

It was shown for the first time using a complex of physicochemical methods (dynamic and electrophoretic light scattering, nanoparticle tracking analysis, transmission electron and atomic force microscopy, conductometry, pH-metry) that in a temperature range of 25—60 °С (S)-lysine aqueous solutions (1•10{sup –17}—1•10{sup –2} mol L{sup –1}) are disperse systems, where the nature and parameters of the disperse phase change with dilution, which affects the nonmonotonic dependences of the specific conductivity and pH of the system. Nanoassociates hundreds of nanometers in size were found to contain ordered water structures that are responsible for the size and ζ-potential of the disperse phase in the aqueous systems and also participate in the formation of spatially organized systems on the support.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Uptake of aqueous heavy metal ions (Co2+, Cu2+ and Zn2+) by calcium-aluminium-silicate-hydrate gels

Highlights: • C-A-S-H gels containing metal ions (Co{sup 2+}, Cu{sup 2+} or Zn{sup 2+}) were precipitated by a sol-gel technique. • Uptake mechanism and immobilization capacity of divalent metal ions by C-A-S-H are elucidated. • Up to ~55–60 mol% of Zn can be incorporated in defective tobermorite-type C-A-S-H. • Metal uptake by C-A-S-H is controlled mainly by isomorphous substitution for Ca ions. • Crystal-chemical features of C-A-S-H gels and implications for practical application are discussed. Calcium-aluminium-silicate-hydrate (C-A-S-H) gels containing heavy metal ions (Me: Co{sup 2+}, Cu{sup 2+} or Zn{sup 2+}) were precipitated at different Me/Si molar ratios to study the uptake mechanism and immobilization capacity. Aqueous solution chemistry and solid-phase characterization using XRD, FTIR, ESEM-EDX, TEM-HAADF and TG-DSC methods reveal threshold values for ion substitution of ~55–60 mol% for Zn, ~30–40 mol% for Co and ~25–30 mol% for Cu in defective tobermorite-type C-A-S-H with (Ca + Me)/(Si + Al) molar ratios from 0.86 to 1.04. At higher aqueous Me concentrations, Me (chloride) hydroxides start to co-precipitate. The uptake mechanism of Me ions by C-A-S-H is based on (i) isomorphous substitution of Me for Ca in the CaO layer, (ii) ion exchange in the interlayer, (iii) tetrahedral substitution (Zn) within the dreierketten chains and (iv) surface adsorption onto the C-A-S-H gel structure. Systematics in crystal-chemistry of Me-bearing C-A-S-H and implications for application and performance in natural and man-made settings are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2012

The effects of aqueous bicarbonate and calcium ions on uranium biosorption by Arthrobacter G975 strain

Uranium(VI) biosorptionwas investigated using carbonate-free and carbonate amended synthetic groundwater (SGW) under conditions relevant to Ca-rich carbonate-bearing subsurface environments. SGW was amended with bicarbonate concentrations ranging between 0.5 and 5 mM and a G975 Arthrobacter oxydans strain, a soil bacterium previously isolated from Hanford Site soil. Selected treatments were amended with 5 mMof calcium to evaluate its effect on U(VI) biosorption. The study confirmed that Arthrobacter sp. G975 can effectively remove soluble U(VI) ions from aqueous solution. The Langmuir, Linear, and Freundlich isotherms were fitted to the experimental data. Based on a higher correlation coefficient, the data was better fit by the Langmuir model. The presence of calciumand bicarbonate ions in SGWaffects the sorption behavior of U(VI) due to the formation of highly soluble and stable uranyl-carbonate and calciumuranyl carbonate complexes that reduce adsorption of U(VI). Increasing aqueous bicarbonate concentrations exponentially reduced the U(VI) microbial adsorption compared to values obtained in carbonate-free solutions. The differences in U(VI) uptake generated by calcium additions in bicarbonate-free solutionswere small enough to conclude that calciumwas not a governing factor in biosorption. Results suggest that in the presence of bicarbonate and calcium, the damage to bacterial cells caused by U(VI) toxicity was reduced, yielding similar values for TOC degradation and cell density compared to U(VI)-free controls.

42 ENGINEERING↗
DOE OSTI2011

Basalt Reactivity Variability with Reservoir Depth in Supercritical CO2 and Aqueous Phases

Long term storage of CO{sub 2} in geologic formations is currently considered the most attractive option to reduce greenhouse gas emissions while continuing to utilize fossil fuels for energy production. Injected CO{sub 2} is expected to reside as a buoyant water-saturated supercritical fluid in contact with reservoir rock, the caprock system, and related formation waters. As was reported for the first time at the GHGT-9 conference, experiments with basalts demonstrated surprisingly rapid carbonate mineral formation occurring with samples suspended in the scCO{sub 2} phase. Those experiments were limited to a few temperatures and CO{sub 2} pressures representing relatively shallow (1 km) reservoir depths. Because continental flood basalts can extend to depths of 5 km or more, in this paper we extend the earlier results across a pressure-temperature range representative of these greater depths. Different basalt samples, including well cuttings from the borehole used in a pilot-scale basalt sequestration project (Eastern Washington, U.S.) and core samples from the Central Atlantic Magmatic Province (CAMP), were exposed to aqueous solutions in equilibrium with scCO{sub 2} and water-rich scCO{sub 2} at six different pressures and temperatures for select periods of time (30 to 180 days). Conditions corresponding to a shallow injection of CO{sub 2} (7.4 MPa, 34 C) indicate limited reactivity with basalt; surface carbonate precipitates were not easily identified on post-reacted basalt grains. Basalts exposed under identical times appeared increasingly more reacted with simulated depths. Tests, conducted at higher pressures (12.0 MPa) and temperatures (55 C), reveal a wide variety of surface precipitates forming in both fluid phases. Under shallow conditions tiny clusters of aragonite needles began forming in the wet scCO{sub 2} fluid, whereas in the CO{sub 2} saturated water, cation substituted calcite developed thin radiating coatings. Although these types of coatings were sparse, conditions corresponding to deeper depths showed increasing carbonate precipitation. Basalts exposed to aqueous dissolved CO{sub 2} (25.5 MPa, 116 C) for 30 days were coated in tiny nodules of precipitate ({approx}100 {micro}m in diameter) that were identified by micro x-ray diffraction as ankerite, [Ca(Fe,Mg)(CO{sub 3}){sub 2}], a variety of dolomite commonly associated with hydrothermal and metamorphic environments. Surface characterization by SEM revealed well-developed round nodules composed of discrete individual platelets. In contrast, reaction products forming on the basalt in the corresponding wet scCO{sub 2} phase had completely different morphology, appearing in an optical microscope as a surface coating instead of discrete nodules. Examination by SEM revealed layers of discrete platelets forming a cover over a few discrete nodules. Longer test durations (180 days) produced severe iron staining along with minerals structures similar to rhodochrosite and kutnohorite. These preliminary experiments show strong evidence of the faster rate of increase in mineralization reactions taking place in the scCO{sub 2} phase, transformation reactions that are just beginning to be explored in detail.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Carbon-encapsulated niobium carbonitride with high volumetric capacitance and wide potential windows in aqueous pseudocapacitors

Electrochemical capacitors deliver high power and have long operational lives; yet, their energy densities are limited. Compared to carbon-based electrical double-layer capacitors, pseudocapacitors with an aqueous electrolyte are predicated to provide both high gravimetric and volumetric capacitance while being cost-effective and eco-friendly. However, their narrow operational potential windows limit the practical delivery of energy. In this study, we synthesized novel NbCxN1-x nanoparticles encapsulated in a uniform carbon layer. This pseudocapacitive material exhibits a high volumetric capacitance, a wide potential window stability (~345 F cm –3 , 2.1 V, in 1 M of Li 2 SO 4 ), and a long cycling life (>10 000 cycles). Moreover, the symmetric cells (2.2 V, in 1 M of Li 2 SO 4 ) exhibit high energy density as well as excellent cyclability and rate performances. These results offer new chances for the design of aqueous energy storage devices having a wide applied potential difference and excellent performance.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Aqueous solution-based synthesis approach for carbon-disordered rocksalt composite cathode development and its limitations

Disordered rocksalt cathodes exhibit high specific capacities and high energy density; however, their low electronic conductivity poses a great challenge. Herein, we explored an aqueous-solution-based synthesis route that involves controlling the surface charges of Li 1.2 Mn 0.6 Ti 0.2 O 1.8 F 0.2 (LMTOF) to be anchored by a few-layer reduced graphene oxide (rGO) for the first time. The uniform rGO wrapping on the surface of the LMTOF particles is achieved by electrostatic attraction between the negatively charged rGO and positively charged LMTOF particles. Although the initial specific capacity of rGO-LMTOF composite increased by 58 % compared to the pristine LMTOF, the composite experienced a severe capacity fade over cycling. The synthesis process in an aqueous medium resulted in Li + /H + exchange and TM dissolution as evidenced from inductively coupled plasmon analysis and X-ray diffraction analysis. Therefore, this work suggests the search for alternative media or conditions for the synthesis of carbon-disordered rock salt cathode composite.

25 ENERGY STORAGE↗
DOE OSTI2021

Iron-iminopyridine complexes as charge carriers for non-aqueous redox flow battery applications

Non-aqueous redox flow batteries (RFBs) have been gaining increased attention in the energy storage arena. Some of their attractive features include the promise for high energy densities, wider voltage windows compared to aqueous systems, as well as wider operating temperature ranges. One of the major challenges in the development of these systems is the lack of electroactive materials that can undergo reversible redox events within the larger potential window of organic solvents. In this paper, we present the design, synthesis, and measurement of electrochemical properties of some iron-based imine- and iminopyridine complexes as promising candidates for RFB applications. Synthesized complexes afforded three reversible redox couples over a ~3 V range. The redox events were also computationally explored and are in good agreement with experimental data. Theoretical calculations show that the redox event at the positive potential can be characterized as metal-centered event corresponding to Fe 3+ → Fe 2+ reduction, while the two redox events at negative potentials are associated with the consecutive reductions of iminopyridine or diimine moieties. This work has led to the identification of a promising anolyte material, [tris(imino)pyridine)Fe][OTf] 2 (1), which is soluble in acetonitrile and is synthesized in two simple steps. This species shows outstanding performance when cycled between 1.0 V and 2.35 V, with 93% coulombic efficiency, 84% energy efficiency, and a capacity decay rate of 0.61% per cycle at 5 mA cm –2 . Further modifications to this kind of charge carrier may lead to the development of high energy density materials for grid scale energy storage applications.

25 ENERGY STORAGE↗
DOE OSTI2018

Removal of priority and emerging pollutants from aqueous media by adsorption onto synthetic organo-funtionalized high-charge swelling micas

Highlights: • Adsorption occurs in the interlayer space (C{sub 18}-Mica-4: 49.9 Å). • Pollutants remained sorbed into C{sub 18}-Mica-4 at least 7 days after treatment. • No sample pH adjustment neither NaCl addition is required. • Removal rates from 70% to 100% for most of the 18 pollutants in 24 h. • Applicability to wastewater, surface and tap water samples demonstrated. In this work, the removal of different types of emerging pollutants (four perfluoroalkyl compounds, two preservatives, three surfactants and nine pharmaceutical compounds) from aqueous solution by adsorption onto two novel synthetic clays, a high-charge swelling mica (Na-Mica-4) and an organo-functionalized mica (C{sub 18}-Mica−4), was evaluated. Na-Mica-4 and C{sub 18}-Mica− 4 were prepared and characterized by X-Ray diffraction, Zeta potential, specific surface area, thermogravimetric analysis and transmission electron microscopy, before and after adsorption experiments. The influence of the aqueous sample pH, salt addition and extraction time in the removal were evaluated. The results showed the high adsorption affinity of C{sub 18}-Mica-4 for most of the emerging pollutants analysed after a removal time of 24 h (14 out of 18 pollutants were effectively removed [70–100%]). A high correlation was observed between the log K{sub ow} of the selected emerging pollutants and the adsorption onto C{sub 18}-Mica-4. The results also indicate that adsorption occurs in the interlayer space. While the removal rates with Na-Mica-4 were in the range 8–97% after seven days, some of the compounds, perfluorobutanoic acid and most of pharmaceutically active compounds, were not adsorbed onto the high-charge mica. C{sub 18}-Mica− 4 was effectively used for the removal of contaminants from four types of water samples.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Toward the understanding of hydration phenomena in aqueous electrolytes from the interplay of theory, molecular simulation, and experiment

We confront the microstructural analysis of aqueous electrolytes and present a detailed account of the fundamentals underlying the neutron scattering with isotopic substitution (NDIS) approach for the experimental determination of ion coordination numbers in systems involving both halides anions and oxyanions. We place particular emphasis on the frequently overlooked ion-pairing phenomenon, identify its microstructural signature in the neutron-weighted distribution functions, and suggest novel techniques to deal with either the estimation of the ion-pairing magnitude or the correction of its effects on the experimentally measured coordination numbers. We illustrate the underlying ideas by applying these new developments to the interpretation of four NDIS test-cases via molecular simulation, as convenient dry runs for the actual scattering experiments, for representative aqueous electrolyte solutions at ambient conditions involving metal halides and nitrates.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2011

Monte Carlo Simulations of the Dissolution of Borosilicate and Aluminoborosilicate Glasses in Dilute Aqueous Solutions

The aim of this study was to provide atomic-level insights into the dissolution behavior of borosilicate and aluminoborosilicate glasses to complement and help interpret previous experimental work on the NeB glass series studied by Pierce et al. [Pierce E. M., Reed L. R., Shaw W. J., McGrail B. P., Icenhower J. P., Windisch C. F., Cordova E. A. and Broady J. (2010) Experimental determination of the effect of the ratio of B/Al on glass dissolution along the nepheline (NaAlSiO4) - Malinkoite (NaBSiO4) join. Geochim. Cosmochim. Acta 74, 2634-2654]. The composition of these glasses was 50 mol% SiO2 - 25 mol% Na2O - (25-x) mol% Al2O3 - x mol% B2O3, with x varying from 0 to 20 mol%. In the first part of this work, the different structural features of these glasses (e.g., presence of non-bridging oxygens, partition of boron between trigonal and tetrahedral bonding environments, and formation of boroxol rings), identified in the study of Pierce et al., were implemented in the Monte Carlo program. Their effects on the dissolution of borosilicate and aluminosilicate glasses were then evaluated individually and led to the following conclusions. (1) The dependence of the dissolution rate on the amount of non-bridging oxygens was found to be linear at all Si/B ratios and the accelerating effect of non-bridging oxygens was shown to increase with increasing Si/B ratio. (2) The formation of boroxol rings and of clusters of boroxol rings resulted in an increase of the dissolution rate at all Si/B ratios and, again, the extent of the rate increase was strongly dependent on the Si/B ratio. (3) For aluminosilicate glasses, the implementation of the aluminum avoidance rule was found to increase the rate of dissolution relative to that obtained for a random distribution. In the second part of this work, Monte Carlo simulations were performed to model the dissolution of the NeB glasses in dilute conditions. One of the conclusions that emerged from the study of Pierce et al. was that either the rupture of the Al-O bonds or that of the Si-O bonds was the rate-limiting step controlling the dissolution of the NeB glasses. The Monte Carlo simulations carried out in this work enabled us to refine this conclusion. Indeed, the simulations showed that, at low B/Al ratios, the rupture of both Al-O-Si and Si-O-Si linkages contributed to the dissolution rate whereas, at high B/Al ratios, the dissolution rate was independent of the rupture of Al-O-Si linkages and was controlled by S1 sites (silicon sites at the glass-water interface with one bond to nearest-neighbor sites) and dissolution via detachment of clusters.

aluminosilicates↗
DOE OSTI2017

Formation of an ultracarbonaceous Antarctic micrometeorite through minimal aqueous alteration in a small porous icy body

A comprehensive study of the organic chemistry and mineralogy of an ultracarbonaceous micrometeorite (UCAMM D05IB80) collected from near the Dome Fuji Station, Antarctica, was carried out to understand the genetic relationship among organic materials, silicates, and water. The micrometeorite is composed of a dense aggregate of ~5 µm-sized hollow ellipsoidal organic material containing submicrometer-sized phases such as glass with embedded metal and sulfides (GEMS) and mineral grains. There is a wide area of organic material (~15 × 15 μm) in its interior. Low-Ca pyroxene is much more abundant than olivine and shows various Mg/(Mg + Fe) ratios ranging from ~1.0 to 0.78, which is common to previous works on UCAMMs. By contrast, GEMS grains in this UCAMM have unusual chemical compositions. They are depleted in both Mg and S, which suggests that these elements were leached out from the GEMS grains during very weak aqueous alteration, without the formation of phyllosilicates. The organic materials have two textures—smooth and globular with an irregular outline—and these are composed of imine, nitrile and/or aromatic nitrogen heterocycles, and amide. The ratio of nitrogen to carbon (N/C) in the smooth region of the organics is ~0.15, which is five times higher than that of insoluble organic macromolecules in types 1 and 2 carbonaceous chondritic meteorites. In addition, the UCAMM organic materials are soluble in epoxy and are thus hydrophilic; this polar nature indicates that they are very primitive. The surface of the material is coated with an inorganic layer, a few nanometers thick, that consists of C, O, Si, S, and Fe. Sulfur is also contained in the interior, implying the presence of organosulfur moieties. There are no isotopic anomalies of D, 13 C, or 15 N in the organic material. Interstellar photochemistry alone would not be sufficient to explain the N/C ratio of the UCAMM organics; therefore, we imply that a very small amount of fluid on a comet must have been necessary for the formation of the UCAMM. The GEMS grains depleted in Mg and S in the UCAMM prove a very weak degree of aqueous alteration; weaker than that of carbonaceous chondrites. Short-duration weak alteration probably caused by planetesimal shock locally melted cometary ice grains and released water that dissolved the organics; the fluid would likely have not mobilized because of the very low thermal conductivity of the porous icy body. This event enabled the formation of the large organic puddle of the UCAMM, as well as organic matter sulfurization, formation of thin membrane-like layers of minerals, and deformation of organic nanoglobules.

58 GEOSCIENCES↗