Ion flows and heating at a contracting polar-cap boundary: GISMOS observations indicating viscous-like interaction on the flanks of the magnetotail

This paper complements that in this issue by Clauer et al. concerning the international GISMOS campaign of 3–5 June 1987. From a detailed study of the EISCAT data, the polar-cap boundary, as defined by an almost shear east-west convection reversal, is found to contract across the EISCAT field of view between 04 and 07 MLT. An annulus of enhanced ion temperature and non-thermal plasma is observed immediately equatorward of the contracting boundary due to the lag in the response of the neutral-wind pattern to the change in ion flows. The ion flow inside the polar cap and at the boundary is shown to be relatively smooth, compared with that in the auroral oval, at 15-second resolution. The flow at the boundary is directed poleward, with velocities which exceed that of the boundary itself. The effect of velocity shears on the beamswinging technique used to derive the ion flows has been analysed in detail and it is found that spurious flows across a moving boundary can be generated. However, these are much smaller than the observed flows into the polar cap and cannot explain the 7 kV potential difference across the observed segment of the cap boundary between 04:30–06:30 UT. The ion temperature enhancements at the two observing azimuths is used to define the boundary orientation. The results are consistent with recent observations of slow anti-sunward flow of closed field lines on the flanks of the geomagnetic tail, which appears to be generated by some form of “viscous” coupling to the magnetosheath plasma.

Ion flows and heating at a contracting polar-cap boundary

Data recorded by the POLAR experiment run on the EISCAT radar during the international GISMOS campaign of 3–5 June 1987 are studied in detail. The polar-cap boundary, as denned by an almost shear East-West convection reversal, was observed to jump southward across the EISCAT field of view in two steps at 02:00 and 03:00 Magnetic Local Time and subsequently to contract back between 04:00 and 07:00 M.L.T. An annulus of enhanced ion temperature and non-thermal plasma was observed immediately equatorward of the contracting boundary due to the lag in the response of the neutral-wind pattern to the change in ion flows. The ion flow at the boundary is shown to be relatively smooth at 15 s resolution and directed northward, with velocities which exceed that of the boundary itself. The effect of velocity shears on the beamswinging technique used to derive the ion flows is analyzed in detail and it is shown that, for certain orientations of the cap boundary, spurious flows into the cap can be generated. However, these are much smaller than the observed flows into the polar cap and cannot explain the potential difference across the observed segment of the cap boundary (extending over 2 h of M.L.T.) which is roughly 7 kV. Similarly, an observed slowing of the zonal flow near the boundary cannot be explained as an error introduced by the use of the beamswinging technique. The results could be interpreted as being due to reconnection occurring on the dawn flank of the magnetopause (mapping to the polar cap at 04:30 06:30 M.L.T.). However, they are more consistent with recent observations of slow anti-sunward flow of closed field lines on the flanks of the geomagnetic tail, which appears to be generated by some form of “viscous” coupling to the magnetosheath plasma.

Non-Maxwellian ion velocity distributions observed using EISCAT

Recent observations from the EISCAT incoherent scatter radar have revealed bursts of poleward ion flow in the dayside auroral ionosphere which are consistent with the ionospheric signature of flux transfer events at the magnetopause. These bursts frequently contain ion drifts which exceed the neutral thermal speed and, because the neutral thermospheric wind is incapable of responding sufficiently rapidly, toroidal, non-Maxwellian ion velocity distributions are expected. The EISCAT observations are made with high time resolution (15 seconds) and at a large angle to the geomagnetic field (73.5°), allowing the non-Maxwellian nature of the distribution to be observed remotely for the first time. The observed features are also strongly suggestive of a toroidal distribution: characteristic spectral shape, increased scattered power (both consistent with reduced Landau damping and enhanced electric field fluctuations) and excessively high line-of-sight ion temperatures deduced if a Maxwellian distribution is assumed. These remote sensing observations allow the evolution of the distributions to be observed. They are found to be non-Maxwellian whenever the ion drift exceeds the neutral thermal speed, indicating that such distributions can exist over the time scale of the flow burst events (several minutes).

Low-energy ion outflows from the ionosphere during a major polar cap expansion — evidence for equatorward motion of inverted-V structures

Data from the Dynamics Explorer 1 satellite and the EISCAT and Sondrestrom incoherent scatter radars, have allowed a study of low-energy ion outflows from the ionosphere into the magnetosphere during a rapid expansion of the polar cap. From the combined radar data, a 200kV increase in cross-cap potential is estimated. The upflowing ions show “X” signatures in the pitch angle-time spectrograms in the expanding midnight sector of the auroral oval. These signatures reveal low-energy (below about 60eV), light-ion beams sandwiched between two regions of ion conics and are associated with inverted-V electron precipitation. The lack of mass dispersion of the poleward edge of the event, despite great differences in the times of flight, reflects the equatorward expansion of the acceleration regions at velocities similar to those of the antisunward convection. In addition, a transient burst of upflow of 0+ is observed within the cap, possibly due to enhanced Joule heating during the event.

Superthermal ion signatures of auroral acceleration processes

The retarding ion mass spectrometer on the Dynamics Explorer 1 spacecraft has generated a unique data set which documents, among other things, the occurrence of non-Maxwellian superthermal features in the auroral topside ionosphere distribution functions. In this paper, we provide a representative sampling of the observed features and their spatial morphology as observed at altitudes in the range from a few thousand kilometers to a few earth radii. At lower altitudes, these features appear at auroral latitudes separating regions of polar cap and subauroral light ion polar wind. The most common signature is the appearance of an upgoing energetic tail having conical lobes representing significant ion heat and number flux in all species, including O+. Transverse ion heating below the observation point at several thousand kilometers is clearly associated with O+ outflows. In some events observed, transverse acceleration apparently involves nearly the entire thermal plasma, the distribution function becomes highly anisotropic with T⊥ > T∥, and may actually develop a minimum at zero velocity, i.e., become a torus having as its axis the local magnetic field direction. At higher altitudes, the localized dayside source region appears as a field aligned flow which is dispersed tailward across the polar cap according to parallel velocity by antisunward convective flow, so that upflowing low energy O+ ions appear well within the polar cap region. While this flow can appear beamlike in a given location, the energy dispersion observed implies a very broad energy distribution at the source, extending from a few tenths of an eV to in excess of 50 eV. On the nightside, upgoing ion beams are found to be latitudinally bounded by regions of ion conics whose half angles increase with increasing separation from the beam region, indicating low altitude transverse acceleration in immediate proximity to, and below, the parallel acceleration region. These observations reveal a clear distinction between classical polar wind ion outflow and O+ enhanced superthermal flows, and confirm the importance of low altitude transverse acceleration in ionospheric plasma transport, as suggested by previous observations.

Surface-enhanced Raman scattering study of alizarin red S

This paper presents the application of surface-enhanced resonance Raman spectroscopy (SERRS) for the structural study of alizarin red S (ARS) and the nature of its interaction with silver nanoparticles. SERRS data for ARS over nanostructured silver electrodes suggest a surface-induced reaction of the adsorbed dye and the formation of an ion stabilized by the dye and alkali ions adsorbed at the metal surface. We found that precoating the SERS active substrate with 1-propanethiol inhibits the surface-induced modification of ARS. In addition to preventing structural modifications of ARS, the coating also concentrates the hydrophobic dye close enough to the SERS active interface enabling the observation of excellent Raman spectra of ARS in aqueous environment at ppm levels. The influence of resonance Raman effect and of the pH on the SERS spectra of ARS was also investigated. (C) 2010 Elsevier B.V. All rights reserved.

Polyethylene terephthalate (PET) bulk film analysis using C60+, Au3+, and Au+ primary ion beams

The damage characteristics of polyethylene terephthalate (PET) have been studied under bombardment by C₆₀+, Au₃+ and Au+ primary ions. The observed damage cross-sections for the three ion beams are not dramatically different. The secondary ion yields however were significantly enhanced by the polyatomic primary ions where the secondary ion yield of the [M + H]+ is on average 5× higher for C₆₀+ than Au₃+ and 8× higher for Au₃+ than Au+. Damage accumulates under Au+ and Au₃+ bombardment while C₆₀+ bombardment shows a lack of damage accumulation throughout the depth profile of the PET thick film up to an ion dose of 1 ~ 10¹⁵ ions cm⁻². These properties of C₆₀+ bombardment suggest that the primary ion will be a useful molecular depth profiling tool.

Ion transport in polymer electrolytes containing nanoparticulate TiO2 : The influence of polymer morphology

Recent studies have shown that composite polymer electrolytes, formed by dispersing nanosized ceramic particles in polyether-based electrolytes, have improved ion transport properties as compared to their unfilled analogues. In the present study polymer electrolytes with different loadings of nano-sized ceramic particles (TiO₂) and different polymer chemistry and morphology have been investigated. Of special interest are filler induced effects on polymer, solvent and cationic mobility. Partly crystalline polymer electrolytes based on poly(ethylene oxide) have been compared to fully amorphous polymer electrolytes based on a polyether urethane, as well as gel electrolytes based on PMMA. ⁷Li pfg-NMR, linewidth and spin–spin relaxation times as well as ¹H pfg-NMR and spin–spin relaxation times, were measured as a function of temperature and composition. The ¹H spin–spin relaxation measurements reveal increased average polymer mobility with the addition of filler up to a maximum at 4 and 8 wt.% TiO₂ for the fully amorphous and the partly crystalline electrolytes, respectively. The ⁷Li linewidth measurements for the fully amorphous system show a broadening of the linewidth with addition of filler. Based on variable temperature measurements this broadening is interpreted as a result of the inhomogeneity introduced by the filler particles. Pulsed field gradient (pfg) diffusion measurements were employed to determine ion and solvent self-diffusion coefficients. In the case of the PMMA-based gel electrolyte and the fully amorphous electrolytes enhanced cation self-diffusion was observed upon addition of TiO₂.

Solid state ion transport and phase behaviour in composites of N,N-methyl propylpyrrolidinium tetrafluoroborate and amorphous polyethylene oxide

The binary and ternary addition of 2 wt.% LiBF₄ and 2 wt.% amorphous polyethylene oxide (aPEO) respectively to the plastic crystal forming salt P₁₃BF₄ (where P₁₃⁺=methylpropyl pyrrolidinium cation) was investigated with specific focus on the phase behaviour and evaluation of transport characteristics. Differential scanning calorimetry (DSC), optical thermomicroscopy, solid state nuclear magnetic resonance (NMR), and AC impedance spectroscopy were used to develop an understanding of the conduction process in the pure and mixed systems. The morphology of the ternary compound appeared as hexagonal spherulites upon solidification. Multinuclear NMR Pulsed Field Gradient measurements (¹H,¹⁹F,⁷Li) to probe both cation and anion diffusion coefficients are reported. The anion is shown to be the most diffusive (at 320 K:¹⁹F=2.5×10⁻¹¹ m² s⁻¹; 1H: 1.8×10⁻¹¹ m² s⁻¹; ⁷Li: 1.1×10⁻¹¹ m² s⁻¹) in the ternary compound, with enhanced conductivity (2.7×10⁻⁵ S cm⁻¹ at 310 K) just below the melt.

Ion diffusion in molten salt mixtures

The molten salts, 1-methyl,3-ethylimidazolium trifluoromethanesulfonate (triflate salt, MeEtImTf) and 1-methyl,3-ethylimidazolium bis(trifluoromethanesulfonimide) (imide salt, MeEtImNTf₂) are colourless ionic liquids with conductivities of the order of 10⁻² S cm⁻¹ at room temperature. DSC measurements revealed subambient melting and glass transition temperatures. Analysis of the anion and cation diffusion coefficients suggested that the cation was the dominant charge carrier and that the motion was largely independent of the anion. Haven ratios (H_Rs) of 1 and 1.6 were determined for the imide and triflate salts, respectively, at 30°C (303 K). Values greater than one imply some degree of ionic association, suggesting that aggregation is present in the triflate salt. Mixing of the salts to form binary systems resulted in enhanced conductivities which deviated from a simple law of mixtures. Thermal analysis showed no evidence of a melting point with only a glass transition observed. Corresponding diffusion measurements for the binaries appeared to show a weighted average of the diffusion coefficients of the pure components. The increased conductivity can be attributed to an increase in the number of charge carriers as a result of decreased ion association in the binary.

Lithium-ion conducting ceramic/polyether composites

Composites of a lithium ion conducting ceramic with a lithium salt based polymer electrolyte matrix are described. Conductivity measurements as a function of the lithium ion conducting ceramic phase content in the composite show that there is a significant increase in conductivity at approximately 40 vol% of the ceramic. The room temperature conductivity above this ceramic content is enhanced by at least 100% over that of the polymer electrolyte phase alone. It is believed that this additional contribution is substantially lithium ion conduction. The major barrier to ion-motion in these materials appears to be the interface between the polymer and ceramic. This interfacial resistance is strongly moisture-sensitive.

Nanoparticle enhanced conductivity in organic ionic plastic crystals : space charge versus strain induced defect mechanism

High conductivity in solid-state electrolytes is a critical requirement for many advanced energy and other electrochemical applications. Plastic crystalline materials have shown promise in this regard, and the inclusion of nanosized inorganic particles in both amorphous and crystalline materials has indicated order of magnitude enhancements in ion transport induced by space charge or other defect enhancement. In this paper we present conductivity enhancements in the plastic crystal N,N‘-ethylmethylpyrrolidinium bis(trifluoromethanesulfonyl)amide ([C₂mpyr][NTf₂]) induced by nanosized SiO₂ particles. The addition of the nanoparticles dramatically increases plasticity and ion mobility. Positron annihilation lifetime spectroscopy (PALS) measurements indicate an increase in mean defect size and defect concentration as a result of nanoparticle inclusion. The scaling of the conductivity with size suggests that a “trivial space charge” effect is operable, although a strain induced enhancement of defects (in particular extended defects) is also likely given the observed increase in plasticity.

Towards elucidating microscopic structural changes in Li-ion conductors Li1+yTi2–yAly[PO4 ]3 and Li1+yTi2–yAly[PO4 ]3–x [MO4 ]x(M=V and Nb) : X-ray and27Al and31P NMR studies

A combination of X-ray powder diffraction (XRD) and nuclear magnetic resonance (NMR) studies has demonstrated that attempted substitutions of Al, V and Nb into the framework of LiTi₂(PO₄)₃ yield several impurity phases in addition to direct substitutions of Al into Ti and V, Nb into P sites. Direct substitutions were confirmed by changes in the unit cell dimensions as indicated by the peak shifts observed in the X-ray diffractographs and by analyses of the ²⁷Al and ³¹P magic angle spinning (MAS) spectra. A major impurity phase was identified as AlPO₄ (found in at least two polymorphs) and the amount present increases with increasing Al additions. The formation of AlPO₄ appeared to be enhanced by further V but suppressed by Nb substitution. These results suggest that the presence of AlPO₄ , together with the non-stoichiometric modified LTP, may be the cause for the observed densification of this material upon sintering and the increased ionic conductivity.

Ion effects in REDOX cycling of conducting polymer based electrochromic materials

Conducting polymer based electrochromic devices were assembled with various ionic liquid (IL) based electrolytes to probe the role of the ion structure on electrochromic performance. When the IL contained the same anion as the dopant ion used in the conducting polymers an enhanced electrochromic performance was observed providing high photopic contrast at low applied potential.

Stable anode performance of an Sb–carbon nanocomposite in lithium-ion batteries and the effect of ball milling mode in the course of its preparation

Materials that alloy with lithium (Si, Ge, Sn, Sb, and P) are considered as alternatives to graphitic anodes in lithium-ion batteries. Their practical use is precluded by large volume changes (200–370%) during cycling. Embedding nanoparticles into carbon is being investigated as a way to tackle that, and ball milling is emerging as a technique to prepare nanocomposites with enhanced capacity and cyclic stability. Using Sb as a model system, we investigate the preparation of Sb–carbon nanocomposites using a reconfigurable ball mill. Four distinctive milling modes are compared. The structure of the composites varies depending on the mode. Frequent strong ball impacts are required for the optimal electrochemical performance of the nanocomposite. An outstanding stable capacity of 550 mA h g−1 for 250 cycles at a current rate of 230 mA g−1 is demonstrated in a thin electrode (1 mg cm−2) and a capacity of [similar]400 mA h g−1 can be retained at 1.15 A g−1. Some capacity fade is observed in a thicker electrode (2.5 mg cm−2), i.e. the performance is sensitive to mass loading. The electrochemical stability originates from the nanocomposite structure containing Sb nanoparticles (5–15 nm) dispersed in a carbon component.