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At least 325 records · Page 18

The Skylab barium plasma injection experiments. II - Evidence for a double layer

Television observations of a barium-plasma flux tube extending from near 4500 km to near 10,000 km during a magnetic substorm and dawn-sector auroral display indicated several interesting anomalous events. Beyond 5500 km, there was a rapid increase in brightness accompanied by flux-tube splitting and diffusion, leaving behind a truncated single flux tube. From the orientation of the flux tube compared with theoretical field models, the presence of a substantial field-aligned current sheet is deduced. A suggested explanation of these phenomena is given in terms of a plasma potential double layer.

Wescott, E. M.↗

Concentration of simple aldehydes by sulfite-containing double-layer hydroxide minerals: implications for biopoesis

Environmental conditions play an important role in conceptual studies of prebiotically relevant chemical reactions that could have led to functional biomolecules. The necessary source compounds are likely to have been present in dilute solution, raising the question of how to achieve selective concentration and to reach activation. With the assumption of an initial 'RNA World', the questions of production, concentration, and interaction of aldehydes and aldehyde phosphates, potential precursors of sugar phosphates, come into the foreground. As a possible concentration process for simple, uncharged aldehydes, we investigated their adduct formation with sulfite ion bound in the interlayer of positively charged expanding-sheet-structure double-layer hydroxide minerals. Minerals of this type, initially with chloride as interlayer counter anion, have previously been shown to induce concentration and subsequent aldolization of aldehyde phosphates to form tetrose, pentose, and hexose phosphates. The reversible uptake of the simple aldehydes formaldehyde, glycolaldehyde, and glyceraldehyde by adduct formation with the immobilized sulfite ions is characterized by equilibrium constants of K=1.5, 9, and 11, respectively. This translates into an observable uptake at concentrations exceeding 50 mM.

NASA Discipline Exobiology↗

Double layers in contactor plasmas

The concept of using a hollow cathode to establish a low impedance contact between a spacecraft and the ambient plasma continues to gain in popularity, and is often then referred to as a plasma contactor. A growing number of studies indicate that large contact currents can be supported with small potential difference between the contactor and the ambient plasma. Results will be presented from a simple one-dimensional spherical model that obtains potentials from the solution of Poisson's equation, and particle densities from a turning point formalism that includes particle angular momentum. The neglect of collisions and magnetic field limits the realism. However, the results illustrate the effect of double layers that can form at the interface between contactor and ambient plasmas, when there is any voltage differential between the contactor and the ambient. The I-V characteristic of this model shows the usual space charge depends upon collection when the contactor flux is lower than some threshold; independence of I from variation in V when the flux is slightly greater than that threshold, and (numerical ?) instability for excessive flux suggesting the possibility of negative resistance. Even if a real I-V characteristic does not exhibit negative resistance, flat spots or high resistance regions may still be troublesome (or useful) to the total circuit.

Cooke, David L.↗

Some aspects of double layer formation in a plasma constrained by a magnetic mirror

The shift from wave-generated anomalous resistivity toward the more large-scale effects of magnetic confinement of current carrying plasmas was inspired by the more extensive data on auroral particle distribution functions that were made available, data that may often seem consistent with a dissipation-free acceleration of auroral electrons over an extended altitude range. Efforts to interpret these data have brought new vigor to the concept that a smooth and static electric field can be self-consistently generated by suitable pitch angle anisotropies among the high altitude particle populations, different for electrons and ions, and that such an electric field is both necessary and sufficient to maintain the plasma in a quasi-neutral steady state. Certain aspects of this concept are reviewed and criticized, both from a general theoretical standpoint and from the standpoint of what is known about the magnetospheric environment. It is argued that this concept has flaws and that the actual physical problem is considerably more complicated, requiring a more complex electric field, possibly including double layer structures.

Lennartsson, W.↗

Structure and Dynamics of Polymeric Canopies in Nanoscale Ionic Materials: An Electrical Double Layer Perspective

Nanoscale ionic materials (NIMs) are an emerging class of materials consisting of charged nanoparticles and polymeric canopies attaching to them dynamically by electrostatic interactions. Using molecular simulations, we examine the structure and dynamics of the polymeric canopies in model NIMs in which the canopy thickness is much smaller than the nanoparticle diameter. Without added electrolyte ions, the charged terminal groups of polymers adsorb strongly on charged walls, thereby electrostatically “grafting” polymers to the wall. These polymers are highly stretched. They rarely desorb from the wall, but maintain modest in-plane mobility. When electrolyte ion pairs are introduced, the counterions adsorb on the wall, causing some electrostatically “grafted” polymers to desorb. The desorbed polymers, however, are less than the adsorbed counter-ions, which leads to an overscreening of wall charges. The desorbed polymers’ charged terminal groups do not distribute uniformly across the canopy but are depleted in some regions; they adopt conformation similar to those in bulk and exchange with the “grafted” polymers rapidly, hence dilating the canopy and accelerating its dynamics. We understand these results by taking the canopy as an electrical double layer, and highlight the importance of the interplay of electrostatic and entropic effects in determining its structure and dynamics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Toggling Stereochemical Activity through Interstitial Positioning of Cations between 2D V 2 O 5 Double Layers

The 5/6s 2 lone-pair electrons of p-block cations in their lower oxidation states are a versatile electronic and geometric structure motif that can underpin lattice anharmonicity and often engender electronic and structural instabilities that underpin the function of active elements in nonlinear optics, thermochromics, thermoelectrics, neuromorphic computing, and photocatalysis. In contrast to periodic solids where lone-pair-bearing cations are part of the structural framework, installing lone-pair-bearing cations in the interstitial sites of intercalation hosts provides a means of a systematically modulating electronic structure through the choice of the group and the period of the inserted cation while preserving the overall framework connectivity. The extent of stereochemical activity and the energy positioning of lone-pair-derived mid-gap states depend on the cation identity, stoichiometry, and strength of anion hybridization. V 2 O 5 polymorphs are versatile insertion hosts that can accommodate a broad range of s-, p-, and d-block cations. However, the insertion of lone-pair-bearing cations remains largely underexplored. In this article, we examine the implications of varying the 6s 2 cations situated in interlayer sites between condensed [V 4 O 10 ] n double layers. Systematic modulations of lattice distortions, electronic structure, and magnetic ordering are observed with increasing strength of stereochemical activity from group 12 to group 14 cations. We compare and contrast p-block-layered M x V 2 O 5 (M = Hg, Tl, and Pb) compounds and map the significance of local off-centering arising from the stereochemical activity of lone-pair cations to the emergence of filled antibonding lone-pair 6s 2 –O 2p-hybridized mid-gap states mediated by second-order Jahn–Teller distortions. Crystallographic studies of cation coordination environments and the resulting modulation of V–V interactions have been used in conjunction with variable-energy hard X-ray photoelectron spectroscopy measurements, first-principles electronic structure calculations, and crystal orbital Hamilton population analyses to decipher the origins of stereochemical activity. Magnetic susceptibility measurements reveal antiferromagnetic signatures for all the three compounds. However, the differences in V–V interactions significantly affect the energy balance of the superexchange interactions, resulting in an ordering temperature of 160 and 260 K for Hg 0.5 V 2 O 5 and δ-Tl 0.5 V 2 O 5 , respectively, as compared to 7 K for δ-Pb 0.5 V 2 O 5 . In δ-Pb 0.5 V 2 O 5 , the strong stereochemical activity of electron lone pairs and the resulting electrostatic repulsions enforce superlattice ordering, which strongly modifies the electronic localization patterns along the [V 4 O 10 ] slabs, resulting in disrupted magnetic ordering and an anomalously low ordering temperature. The results demonstrate a versatile strategy for toggling the stereochemical activity of electron lone pairs to modify the electronic structure near the Fermi level and to mediate superexchange interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electron-acoustic solitons and double layers in the inner magnetosphere: ELECTRON-ACOUSTIC SOLITONS

The Van Allen Probes observe generally two types of electrostatic solitary waves (ESW) contributing to the broadband electrostatic wave activity in the nightside inner magnetosphere. ESW with symmetric bipolar parallel electric field are electron phase space holes. The nature of ESW with asymmetric bipolar (and almost unipolar) parallel electric field has remained puzzling. To address their nature, we consider a particular event observed by Van Allen Probes to argue that during the broadband wave activity electrons with energy above 200 eV provide the dominant contribution to the total electron density, while the density of cold electrons (below a few eV) is less than a few tenths of the total electron density. We show that velocities of the asymmetric ESW are close to velocity of electron-acoustic waves (existing due to the presence of cold and hot electrons) and follow the Korteweg-de Vries (KdV) dispersion relation derived for the observed plasma conditions (electron energy spectrum is a power law between about 100 eV and 10 keV and Maxwellian above 10 keV). The ESW spatial scales are in general agreement with the KdV theory. We interpret the asymmetric ESW in terms of electron-acoustic solitons and double layers (shocks waves).

79 ASTRONOMY AND ASTROPHYSICS↗

Ion-cyclotron turbulence and diagonal double layers in a magnetospheric plasma

A survey of current concepts regarding electrostatic ion-cyclotron turbulence (theory and experiment), and regarding inclined double potential layers in the magnetospheric plasma is presented. Anomalous resistance governed by electrostatic ion-cyclotron turbulence, and one-dimensional and two-dimensional models of double electrostatic layers in the magnetospheric plasma are examined.

Liperovskiy, V. A.↗

Lithium aluminum–layered double hydroxide chlorides ( LDH ): Formation enthalpies and energetics for lithium ion capture

Layered aluminum double hydroxide chloride sorbents, LiCl∙Al 2 (OH)6. n H 2 O, Li-LDH, have shown promising application in selective Li extraction from geothermal brines. Maintaining LiCl uptake capacity and retaining a long cycle life are critical to widespread application of sorbent materials. To elucidate the energetics of Li capture, enthalpies of LDH with different Li content have been measured by acid solution calorimetry. The formation enthalpies generally become less exothermic as the Li content increases, which indicates that Li intercalation destabilizes the structure, and the enthalpies seem to approach a limit after the Li content x = 2Li/Al exceeds 1. To improve stability, metal doping of the aluminum LDH structure with iron was performed. Introduction of a metal with greater electron density but a similar ionic radius was postulated to improve the stability of the LDH crystal structure. Here, the calorimetric results from Fe-doped LDH samples corroborate this as they are more exothermic than LDH-lacking Fe. This suggests that Fe doping is an effective way to stabilize the LDH phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diffusion Through Single And Double Layer Shields And Induced Voltages From Low Frequency Electromagnetic Environments

The diffusion through shells consisting of either a single conducting or double conducting layers are examined. Exterior drives resulting from Electromagnetic Radiation (EMR), Electromagnetic Pulse (EMP), nearby (indirect) lightning, and DC (low frequency) magnetic fields are used. Both the interior field and the induced voltage from a maximally oriented and sized single turn loop are estimated. It is shown that the loop voltage with the empty cavity bounds the case where the center region is excluded by a conducting object. The cases of interior magnetic and electric fields from an exterior magnetic drive and the interior electric field from an exterior electric drive are both solved; the magnetic interior field from an exterior magnetic drive is the only case that results in a nonzero low frequency penetration.

42 ENGINEERING↗

Hollow nanoparticles with hybrid double layers

The present invention discloses the morphology of hollow, double-shelled submicrometer particles generated through a rapid aerosol-based process. The inner shell is an essentially hydrophobic carbon layer of nanoscale dimension (5-20 nm), and the outer shell is a hydrophilic silica layer of approximately 5-40 nm, with the shell thickness being a function of the particle size. The particles are synthesized by exploiting concepts of salt bridging to lock in a surfactant (CTAB) and carbon precursors together with iron species in the interior of a droplet. This deliberate negation of surfactant templating allows a silica shell to form extremely rapidly, sealing in the organic species in the particle interior. Subsequent pyrolysis results in a buildup of internal pressure, forcing carbonaceous species against the silica wall to form an inner shell of carbon. The incorporation of magnetic iron oxide into the shells opens up applications in external stimuli-responsive nanomaterials.

John, Vijay T.↗

Local, global, and nonlinear screening in twisted double-layer graphene

Significance Using scanning tunneling microscopy and numerical simulations we demonstrate that a graphene buffer sheet placed underneath an atomically thin layer is an extremely effective method to increase the quality of 2D electron systems without modifying their electronic structure and without compromising the gating capabilities. We show that owing to its remarkable nonlinear screening capability the graphene buffer layer provides better shielding from substrate-induced perturbations than either increasing the distance to the substrate or doubling the carrier density, or even than using a graphene bilayer.

36 MATERIALS SCIENCE↗

Study on a Novel Binary Zn{sub n}Eu Layered Double Hydroxide with Excellent Fluorescence

A group of binary Zn{sub n}Eu-LDHs with Zn{sup 2+}/Eu{sup 3+} molar ratios of 5.0, 6.0, 7.0, and 8.0 have been obtained in ammonia water media by hydrothermal treatment. The structure, composition, and fluorescent property of samples have been investigated using various techniques. Compositional analyses revealed that the composition of samples was in agreement with that of the initial reactants. X-ray diffraction (XRD) suggested that the Zn{sub n}Eu-LDHs exhibited typical layered structure with orthorhombic symmetry. All the Zn{sub n}Eu-LDHs appeared strong red emissions attributed to {sup 5}D{sub 0} → {sup 7}F{sub J} (J = 1, 2) transitions of Eu{sup 3+}. Moreover, the intensity of emissions due to {sup 5}D{sub 0} → {sup 7}F{sub J} (J = 1, 2) transitions of Eu{sup 3+} tended to increase with the Zn{sup 2+}/Eu{sup 3+} molar ratio varied from 8.0, 7.0 to 6.0, then decreased as the Zn{sup 2+}/Eu{sup 3+} molar ratio reduced to 5.0. The strongest fluorescence was found to be at Zn{sup 2+}/Eu{sup 3+} molar ratio of 6.0. Further the fluorescence decay spectra show that the Zn{sub n}Eu-LDH have similar behavior of fluorescent decay and decayed more slowly than that of the Eu(OH){sub 3}. These results indicate that the novel binary Zn{sub n}Eu-LDHs have better fluorescent property and may be potential application as fluorescent materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Double layer hydroxide minerals as host structures for bioorganic molecules

A central problem in molecular evolution concerns the selective concentration from dilute, multicomponent solution of source molecules into a reactive environment, where formation of larger molecular assemblages can take place. Minerals consisting of positively charged, separable metal hydroxide sheets have proven capable of these functions. This common structural type is represented by minerals such as pyroaurite (Mg-Fe(3+) hydroxide), hydrotalcite (Mg-Al), green rust Fe(2+)-Fe(3+) and others. Effective interlayer sorption is demonstrated for orthophosphate and condensed phosphates, anionic alkyl compounds, polypeptides, nucleic acids, cyanide complexes and glycolaldehyde phosphate, the latter shown to readily oligomerize to form and selectively retain racemic hexose -2, 4, 6-phosphates, preferentially of altrose (Pitsch, et al, 1993). The selective aldomerization and retention effects correlate with the charge distribution in the host mineral structure and the stereochemistry of the substrate molecules. Interaction between nucleic acid bases, and between the cyanide groups of glycolaldehyde phosphate nitrile at the low water activity in the mineral interlayer is indicated by doubling of the monomeric separation of the hydroxide mineral sheets.

Lee, Ton↗