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At least 1,261 records · Page 70
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Oxygen Deficiency and Migration-Mediated Electric Polarization in Magnetic Fe,Co-Substituted SrTiO3−δ

We use density functional theory (DFT) calculations to show that oxygen vacancies (vO) and mobility induce noncentrosymmetric polar structures in SrTi1−x−yFexCoyO3−δ (STFC, x=y=0.125) with δ={0.125,0.25}, enhance the saturation magnetization, and give rise to large changes in the electric polarization |ΔP|. We present an intuitive set of rules to describe the properties of STFC, which are based on the interplay between (Co/Fe)-vO defects, magnetic cation coordination, and topological vacancy disorder. STFC structures consist of layered crystals with sheets of linearly organized O4,5,6-coordinated Fe–Co pairs, sandwiched with layers of O5-coordinated Ti. (Co/Fe)-vO defects are the source of crystal distortions, cation off-centering and bending of the oxygen octahedra which, considering the charge redistribution mediated by vO and the cations’ electronegativity and valence states, triggers an effective electric polarization. Oxygen migration for δ=0.125 leads to |ΔP|>∼10 µC/cm2 due to quantum-of-polarization differences between δ=0.125 structures. Increasing the oxygen deficiency to δ=0.25 yields |ΔP|, the O migration of which resolved polarization for δ=0.25 is >∼3 µC/cm2. Magnetism is dominated by the Fe,Co spin states for δ=0.125, and there is a contribution from Ti magnetic moments (∼1 μB) for δ=0.25. Magnetic and electric order parameters change for variations of δ or oxygen migration for a given oxygen deficiency. Our results capture characteristics observed in the end members of the series SrTi(Co,Fe)O3, and suggest the existence of a broader set of rules for oxygen-deficient multiferroic oxides.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Evaluation of Electrodialysis Desalination Performance of Novel Bioinspired and Conventional Ion Exchange Membranes with Sodium Chloride Feed Solutions

Electrodialysis (ED) desalination performance of different conventional and laboratory-scale ion exchange membranes (IEMs) has been evaluated by many researchers, but most of these studies used their own sets of experimental parameters such as feed solution compositions and concentrations, superficial velocities of the process streams (diluate, concentrate, and electrode rinse), applied electrical voltages, and types of IEMs. Thus, direct comparison of ED desalination performance of different IEMs is virtually impossible. While the use of different conventional IEMs in ED has been reported, the use of bioinspired ion exchange membrane has not been reported yet. The goal of this study was to evaluate the ED desalination performance differences between novel laboratory‑scale bioinspired IEM and conventional IEMs by determining (i) limiting current density, (ii) current density, (iii) current efficiency, (iv) salinity reduction in diluate stream, (v) normalized specific energy consumption, and (vi) water flux by osmosis as a function of (a) initial concentration of NaCl feed solution (diluate and concentrate streams), (b) superficial velocity of feed solution, and (c) applied stack voltage per cell-pair of membranes. A laboratory‑scale single stage batch-recycle electrodialysis experimental apparatus was assembled with five cell‑pairs of IEMs with an active cross-sectional area of 7.84 cm2. In this study, seven combinations of IEMs (commercial and laboratory-made) were compared: (i) Neosepta AMX/CMX, (ii) PCA PCSA/PCSK, (iii) Fujifilm Type 1 AEM/CEM, (iv) SUEZ AR204SZRA/CR67HMR, (v) Ralex AMH-PES/CMH-PES, (vi) Neosepta AMX/Bare Polycarbonate membrane (Polycarb), and (vii) Neosepta AMX/Sandia novel bioinspired cation exchange membrane (SandiaCEM). ED desalination performance with the Sandia novel bioinspired cation exchange membrane (SandiaCEM) was found to be competitive with commercial Neosepta CMX cation exchange membrane.

42 ENGINEERING↗
DOE OSTI2022

Bacterial Membranes Are More Perturbed by the Asymmetric Versus Symmetric Loading of Amphiphilic Molecules

Characterizing the biophysical properties of bacterial membranes is critical for understanding the protective nature of the microbial envelope, interaction of biological membranes with exogenous materials, and designing new antibacterial agents. Presented here are molecular dynamics simulations for two cationic quaternary ammonium compounds, and the anionic and nonionic form of a fatty acid molecule interacting with a Staphylococcus aureus bacterial inner membrane. The effect of the tested materials on the properties of the model membranes are evaluated with respect to various structural properties such as the lateral pressure profile, lipid tail order parameter, and the bilayer’s electrostatic potential. Conducting asymmetric loading of molecules in only one leaflet, it was observed that anionic and cationic amphiphiles have a large impact on the Staphylococcus aureus membrane’s electrostatic potential and lateral pressure profile as compared to a symmetric distribution. Nonintuitively, we find that the cationic and anionic molecules induce a similar change in the electrostatic potential, which points to the complexity of membrane interfaces, and how asymmetry can induce biophysical consequences. Finally, we link changes in membrane structure to the rate of electroporation for the membranes, and again find a crucial impact of introducing asymmetry to the system. Understanding these physical mechanisms provides critical insights and viable pathways for the rational design of membrane-active molecules, where controlling the localization is key.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Single-Well Push–Pull Tracer Test Analyses to Determine Aquifer Reactive Transport Parameters at a Former Uranium Mill Site (Grand Junction, Colorado)

At a former uranium mill site where tailings have been removed, prior work has determined several potential ongoing secondary uranium sources. These include locations with uranium sorbed to organic carbon, uranium in the unsaturated zone, and uranium associated with the presence of gypsum. To better understand uranium mobility controls at the site, four single-well push–pull tests (with a drift phase) were completed with the goal of deriving aquifer flow and contaminant transport parameters for inclusion in a future sitewide reactive transport model. This goes beyond the traditional use of a constant sorption distribution coefficient (K d ) and allows for the evaluation of alternative remedial injection fluids, which can produce variable K d values. Dispersion was first removed from the resulting data to determine possible reactions before conducting reactive transport simulations. These initial analyses indicated the potential need to include cation exchange, uranium sorption, and gypsum dissolution. A reactive transport model using multiple layers to account for partially penetrating wells was completed using the PHT-USG reactive transport modeling code and calibrated using PEST. The model results quantify the hydraulic conductivity and dispersion parameters using the injected tracer concentrations. Uranium sorption, cation exchange, and gypsum dissolution parameters were quantified by comparing the simulated versus observed geochemistry. All simulations required some cation exchange and calcite equilibrium, and one simulation required gypsum dissolution to improve the model fit for calcium and sulfate. Uranium sorption parameters were not strongly influenced by the other parameter values but were highly influenced by uranium concentrations during the drift phase, with possible kinetic rate limitations. Thus, a future recommendation for such push–pull tests is to collect more geochemical data during the drift phase. The final uranium sorption parameters were within the range of values determined from prior column testing. The flow and transport parameters derived from these single-well push–pull tests will provide initial parameters for any future sitewide reactive transport model.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Structure-Related Electronic and Magnetic Properties in Ultrathin Epitaxial Ni x Fe 3–x O 4 Films on MgO(001)

Off-stoichiometric Ni x Fe 3–x O 4 ultrathin films (x < 2.1) with varying Ni content x and thickness 16 (±2) nm were grown on MgO(001) by reactive molecular beam epitaxy. Synchrotron-based high-resolution X-ray diffraction measurements reveal vertical compressive strain for all films, resulting from a lateral pseudomorphic adaption of the film to the substrate lattice without any strain relaxation. Complete crystallinity with smooth interfaces and surfaces is obtained independent of the Ni content x. For x < 1 an expected successive conversion from Fe 3 O 4 to NiFe 2 O 4 is observed, whereas local transformation into NiO structures is observed for films with Ni content x > 1. However, angle-resolved hard X-ray photoelectron spectroscopy measurements indicate homogeneous cationic distributions without strictly separated phases independent of the Ni content, while X-ray absorption spectroscopy shows that also for x > 1, not all Fe 2+ cations are substituted by Ni 2+ cations. The ferrimagnetic behavior, as observed by superconducting quantum interference device magnetometry, is characterized by decreasing saturation magnetization due to the formation of antiferromagnetic NiO parts.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Design and Gas Separation Performance of Imidazolium Poly(ILs) Containing Multivalent Imidazolium Fillers and Crosslinking Agents

This work introduces a series of vinyl-imidazolium-based polyelectrolyte composites, which were structurally modified via impregnation with multivalent imidazolium-benzene ionic liquids (ILs) or crosslinked with novel cationic crosslinkers which possess internal imidazolium cations and vinylimidazolium cations at the periphery. A set of eight [C4vim][Tf2N]-based membranes were prepared via UV-initiated free radical polymerization, including four composites containing di-, tri-, tetra-, and hexa-imidazolium benzene ILs and four crosslinked derivatives which utilized tri- and tetra- vinylimidazolium benzene crosslinking agents. Structural and functional characterizations were performed, and pure gas permeation data were collected to better understand the effects of “free” ILs dispersed in the polymeric matrix versus integrated ionic crosslinks on the transport behaviors of these thin films. These imidazolium PIL:IL composites exhibited moderately high CO2 permeabilities (~20–40 Barrer), a 4–7× increase relative to corresponding neat PIL, with excellent selectivities against N2 or CH4. The addition of imidazolium-benzene fillers with increased imidazolium content were shown to correspondingly enhance CO2 solubility (di- < tri- < tetra- < hexa-), with the [C4vim][Tf2N]: [Hexa(Im+)Benz ][Tf2N] composite showing the highest CO2 permeability (PCO2 = 38.4 Barrer), while maintaining modest selectivities (αCO2/CH4 = 20.2, αCO2/N2 = 23.6). Additionally, these metrics were similarly improved with the integration of more ionic content bonded to the polymeric matrix; increased PCO2 with increased wt% of the tri- and tetra-vinylimidazolium benzene crosslinking agent was observed. This study demonstrates the intriguing interactions and effects of ionic additives or crosslinkers within a PIL matrix, revealing the potential for the tuning of the properties and transport behaviors of ionic polymers using ionic liquid-inspired small molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Mobile barrier mechanisms for Na + -coupled symport in an MFS sugar transporter

While many 3D structures of cation-coupled transporters have been determined, the mechanistic details governing the obligatory coupling and functional regulations still remain elusive. The bacterial melibiose transporter (MelB) is a prototype of major facilitator superfamily transporters. With a conformation-selective nanobody, we determined a low-sugar affinity inward-facing Na + -bound cryoEM structure. The available outward-facing sugar-bound structures showed that the N- and C-terminal residues of the inner barrier contribute to the sugar selectivity. The inward-open conformation shows that the sugar selectivity pocket is also broken when the inner barrier is broken. Isothermal titration calorimetry measurements revealed that this inward-facing conformation trapped by this nanobody exhibited a greatly decreased sugar-binding affinity, suggesting the mechanisms for substrate intracellular release and accumulation. While the inner/outer barrier shift directly regulates the sugar-binding affinity, it has little or no effect on the cation binding, which is supported by molecular dynamics simulations. Furthermore, the hydron/deuterium exchange mass spectrometry analyses allowed us to identify dynamic regions; some regions are involved in the functionally important inner barrier-specific salt-bridge network, which indicates their critical roles in the barrier switching mechanisms for transport. These complementary results provided structural and dynamic insights into the mobile barrier mechanism for cation-coupled symport.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1974

Matrix isolation technique for the study of some factors affecting the partitioning of trace elements

The factors that affect the preferred positions of cations in ionic solid solutions were investigated utilizing vibrational spectroscopy. Solid solutions of the sulfate and chromate ions codoped with La(+3) and Ca(+2) in a KBr host lattice were examined as a function of the polyvalent cation concentration. The cation-anion pairing process was found to be random for Ca(+2), whereas the formation of La(+3)-SO4(-2) ion pairs with a C2 sub v bonding geometry is highly preferential to any type of La(+3)-CrO4(-2) ion pair formation. The relative populations of ion pair site configurations are discussed in terms of an energy-entropy competition model which can be applied to the partition of trace elements during magmatic processes.

Grzybowski, J. M.↗
NASA NTRS1978

Implications of liquid-liquid distribution coefficients to mineral-liquid partitioning

In order to evaluate the influence of a silicate liquid structure on mineral-liquid partitioning, element partitioning data is obtained for coexisting anhydrous immiscible granitic and ferrobasaltic magmas. It is found that: (1) mineral-liquid distribution coefficients indicate the competition of crystal and liquid for cation incorporation, (2) increased polymerization of the residual liquid during crystal-liquid fractionation increases the mineral-liquid distribution coefficients for high-charge-density cations, (3) incompatible element ratios of low- and high-charge-density cations may vary during crystal-liquid fractionation because of changes in the melt composition and structure, (4) relative solubilities of REE's in melts do not vary with melt polymerization, (5) the changes of Sm/Eu ratios during crystal-liquid fractionation depend on the melt composition, and (6) minor components and volatiles can significantly influence the silicate melt structure and the mineral-liquid distribution coefficients.

Ryerson, F. J.↗
NASA NTRS1982

Mineral Separation in a CELSS by Ion-exchange Chromatography

Operational parameters pertinent to ion exchange chromatography separation were identified. The experiments were performed with 9 mm diameter ion exchange columns and conventional column accessories. The cation separation beds were packed with AG 50W-X2 strong acid cation exchange resin in H(+) form and 200-400 dry mesh particle size. The stripper beds used in some experiments were packed with AG 1-XB strong base cation exchange resin in OH(-) form and 200-400 dry mesh particle size.

Ballou, E. V.↗
NASA NTRS1985

Hibonite: Crystal Chemistry and Origin of Blue Coloration in Meteoritic Assemblages

The blue color and optical spectra of hibonite, a common constituent of refractory inclusions in carbonaceous chondrites, are discussed. Because they may be manifestations of exotic cation species stabilized in unusual coordination sites in the hibonite crystalstructure. Hibonite, ideally CaAl12O19, is conducive to atomic substitution of host Ca2+ and Al3+ ions by a variety of lanthanide and first series transition elements. The latter cations are responsible for the colors of many rock-forming minerals as a result of intraelectronic or intervalence transitions. The visible-region spectra of most oxide and silicate minerals are generally well understood. Assignments of absorption bands in meteoritic hibonite optical spectra due to uncertainties of cation valencies and complexities in the crystal structure are examined. The crystal chemistry of hibonite is reviewed, Mossbauer spectral measurements of iron-bearing hibonite and electronic transitions that may be responsible for the blue coloration of meteoritic hibonites are discussed.

Burns, R. G.↗
NASA NTRS1985

Crystal Chemistry of Meteoritic Hibonites

The characteristics of cation vacancies and site occupancies of natural hibonites in meteors are discussed. Note is taken of the effect of the specific locations of the hibonites in the matrices on the crystal chemistry, electronic stabilities, and spectral features of the metal ions which replace the Al(3+). Hibonites form beta-alumina hexagonal cells with 26 cation sites. Fe cations are found in octahedral, tetrahedral, and five-fold coordinates. Fe(2+) is found in face-shared Al(3) octahedra, a siting explained in terms of ionic radius and crystal field stabilization energy criteria. Spectral colors are attributed to V(3+) and Ti(3+) field transitions at 400 and 700 nm, respectively, although the 700 nm line may arise from transitions of Ti(3+) to Ti(4+) or Fe(2+) to Fe(3+) during heating. Excesses of Mg-26 can be traced to decay of nebular Al-26.

Burns, R. G.↗
NASA NTRS1984

Crystal chemistry of meteoritic hibonites

The characteristics of cation vacancies and site occupancies of natural hibonites in meteors are discussed. Note is taken of the effect of the specific locations of the hibonites in the matrices on the crystal chemistry, electronic stabilities, and spectral features of the metal ions which replace the Al(3+). Hibonites form beta-alumina hexagonal cells with 26 cation sites. Fe cations are found in octahedral, tetrahedral, and five-fold coordinations. Fe(2+) is found in face-shared Al(3) octahedra, a siting explained in terms of ionic radius and crystal field stabilization energy criteria. Spectral colors are attributed to V(3+) and Ti(3+) field transitions at 400 and 700 nm, respectively, although the 700 nm line may arise from transitions of Ti(3+) to Ti(4+) or Fe(2+) to Fe(3+) during heating. Excesses of Mg-26 can be traced to decay of nebular Al-26.

Burns, R. G.↗
NASA NTRS1985

pH profile of the adsorption of nucleotides onto montmorillonite. I - Selected homoionic clays

The effect of pH and adsorbed ions on the adsorption of purine and pyrimidine nucleotides on montmorillonite clay was studied experimentally. The specific nucleotides examined were: 5 prime-AMP; 3-prime AMP; and 5 prime-CMP. The pH of the clay samples was adjusted to various levels in the 2-12 pH range using microliter volumes of concentrated acid (1N HCl) and base (1NHNaOH). It was found that preferential adsorption among nulceotides was dependent on the pH level and on the characteristics of the substituted metal cation and anion exchange mechanisms. Below pH 4, adsorption was attributed to cation and anion exchange mechanisms. Above pH 4, however, adsorption was attributed to the complexation mechanisms occurring between the metal cations in the clay exchange site and in the biomolecule. The possible role of homoionic clays in the concentration mechanisms of biomonomers in the prebiotic environment is discussed.

Lawless, J. G.↗
NASA NTRS1986

The evolution and growth of Al2O3 scales on beta-NiAl

The formation and growth of Al2O3 scales on (beta)-NiAl were studied using electron microscopy and other analytical techniques to gain an understanding of the oxidation properties of (beta)-NiAl and of alumina-forming alloys, in general. The transient and mature stages of oxidation were studied as well as the transformation stage during which the oxide scale transforms from metastable Al2O3 phases to the thermodynamically stable alpha-Al2O3 phase. The transient oxidation stages were studied at 800 deg C and for short times at 1100C. At 800C, the scales consist predominantly of delta-Al2O3 which forms by cation vacancy ordering in the defective spinel lattice of gamma-Al2O3. At 1100C, a fast-growth morphology of theta-Al2O3 forms as a surface layer over delta-Al2O3. For both oxidation temperatures, the scales are often epitaxially oriented with respect to the metal. The transient scales grow by outward cation diffusion as evidenced by surface growth morphologies. The transformation to alpha-Al2O3 occurs within 1 hour at 1100C by a nucleation and radial growth process. The large volume decrease associated with the transformation results in a highly strained alpha-Al2O3 microstructure. A change in scale growth mechanism from outward cation to inward anion diffusion allows transient surface morphologies to be smoothed by surface diffusion. The mature stage of oxidation involves the growth of an alpha-Al2O3 scale having the lacey morphology formed as a result of the gamma yields alpha transformation. Growth of the scale occurs by counterdiffusion along grain boundaries resulting in ridges formed by impingement of alpha-Al2O3 nuclei during the transformation stage. Also scale growth occurs by inward oxygen diffusion through healed cracks; the cracks result from transformation stresses. The measured growth rates of scales having the lacey morphology are an order of magnitude less than fine-grained alpha-Al2O3 scales. Metal orientations were found to have a large effect on oxide morpholoies during all stages of oxidation.

Doychak, J. K.↗
NASA NTRS1987

Clarification Procedure for Gels

Procedure developed to obtain transparent gels with consistencies suitable for crystal growth, by replacing sodium ions in silicate solution with potassium ions. Clarification process uses cation-exchange resin to replace sodium ions in stock solution with potassium ions, placed in 1M solution of soluble potassium salt. Slurry stirred for several hours to allow potassium ions to replace all other cations on resin. Supernatant solution decanted through filter, and beads rinsed with distilled water. Rinsing removes excess salt but leaves cation-exchange beads fully charged with potassium ions.

Barber, Patrick G.↗
NASA NTRS1989

Manufactured soils for plant growth at a lunar base

Advantages and disadvantages of synthetic soils are discussed. It is pointed out that synthetic soils may provide the proper physical and chemical properties necessary to maximize plant growth, such as a toxic-free composition and cation exchange capacities. The importance of nutrient retention, aeration, moisture retention, and mechanical support as qualities for synthetic soils are stressed. Zeoponics, or the cultivation of plants in zeolite substrates that both contain essential plant-growth cations on their exchange sites and have minor amounts of mineral phases and/or anion-exchange resins that supply essential plant growth ions, is discussed. It is suggested that synthetic zeolites at lunar bases could provide adsorption media for separation of various gases, act as catalysts and as molecular sieves, and serve as cation exchangers in sewage-effluent treatment, radioactive-waste disposal, and pollution control. A flow chart of a potential zeoponics system illustrates this process.

Ming, Douglas W.↗
NASA NTRS1992

Is a pyrene-like molecular ion the cause of the 4,430-A diffuse interstellar absorption band?

The diffuse interstellar band (DIB) absorption features of astronomical spectra are suggested by recent results to be separable from the grains that cause visual extinction. Attention is presently given to laboratory measurements of the optical spectrum of the pyrene cation C16H10(+), which is one of the polycyclic aromatic hydrocarbon (PAH) molecular candidates proposed as carriers for DIBs. This ion exhibits an intense but strangely broad continuum similar to that of the naphthalene cation, so that this may be a common feature of all PAH cations and the basis of an explanation for PAHs' converting of an interstellar radiation fraction as large as that from the UV and visible range down to the IR.

Salama, F.↗