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The failure of nickel-cadmium storage batteries due to severe gassing during charging is discussed. In order to increase the life of such cells, nongassing positive and negative electrodes are used. The gassing characteristics of nickel electrodes were evaluated as a function of their loading, charge rate, and charge temperature.
Spatial variations of density and temperature along a magnetic field line are evaluated for a plasma undergoing adiabatic motion in a rotating magnetosphere. The effects of centrifugal and gravitational forces are accounted for, as is anisotropy in the pitch angle distribution functions of individual species. A polarization electric field is invoked to eliminate the net electric charge density resulting from the aforementioned mass dependent forces and different anisotropies. The position of maximum density in a two-component, electron-ion plasma is determined both in the absence and in the presence of the polarization effect and compared. A scale height, generalized to include anisotropies, is derived for the density fall-off. The polarization electric field is also included in the parallel guiding center equation; equilibrium points are determined and compared in both individual and average senses with the position of density maximum. Finally a transverse (to magnetic field lines) electric component is deduced as a consequence of dissimilar charge neutralization on adjacent field lines. The E x B velocity resultant from such a 'fringing' electric field is calculated and compared with the magnitude of other drifts.
Due to their simplicity and versatility of design, straight strip or rectangular pad anode structures are frequently employed with micro-pattern gas detectors to reconstruct high precision space points for various tracking applications. The particle impact point is typically determined by interpolating the charge collected by several neighboring strips. However, to effectively extract the inherent positional information, the lateral spacing of the straight strips must be comparable to or preferably smaller than the full extent of the incident charge cloud. In contrast, highly interleaved anode patterns, such as zigzags, can adequately sample the incident charge with a pitch appreciably larger than the charge cloud.
Mesospheric ionization and its variability are examined. Data were obtained primarily by the parachute-borne blunt probe technique conducted in coordinated rocket experiments at White Sands Missile Range, New Mexico and Wallops Island, Virginia. Electrical conductivity measurements and deduced charge density values from ten rocket launches are presented and discussed. Positive ion conductivity and electron density were found to be relatively invariant with height between 45 and 60 km. Variations in positive conductivity of a factor of two and enhancements in negative conductivity by as much as a factor of four were measured by the blunt probe. A simple lumped parameter ion chemistry model is shown to satisfactorily explain the charge density values for the undisturbed lower D-region. Implications of the data in terms of this model are considered. The principal loss mechanism for positive ions in the 45 to 60 km. region is concluded to be dissociative recombination. Electron densities deduced from the conductivity data are explained by detachment involving a minor neutral constituent which is mixed between 65 and 45 km. and then cuts off sharply below 45 km. A correlation study involving blunt probe measurements shows relatively good agreement between variations in positive conductivity and temperature.
Iron redox cycling between low-valent oxidation states of Fe II and Fe III drives crucial processes in nature. The Fe II/III redox couple charge compensates the cycling of lithium iron phosphate, a positive electrode (cathode) for lithium-ion batteries. High-valent iron redox couples, involving formal oxidation higher than Fe III , could deliver higher electrochemical potentials and energy densities. However, because of the instability of high-valent Fe electrodes, they have proven difficult to probe and exploit in intercalation systems. Here, in this study, we report and characterize a formal Fe III/V redox couple by revisiting the charge compensation mechanism of (de)lithiation in Li 4 FeSbO 6 . Valence-sensitive experimental and computational core-level spectroscopy reveal a direct transition from Fe III (3d 5 ) to a negative-charge-transfer FeV (3d 5 L 2 ) ground state on delithiation, without forming Fe IV , or oxygen dimers. We identify that the cation ordering in Li 4 FeSbO 6 drives a templated phase transition to stabilize the unique Fe V species and demonstrate that disrupting cation ordering suppresses the Fe III/V redox couple. Exhibiting resistance to calendar aging, high operating potential and low voltage hysteresis, the Fe III/V redox couple in Li 4 FeSbO 6 provides a framework for developing sustainable, Fe-based intercalation cathodes for high-voltage applications.
We have solved the Heisenberg equation of motion for the time evolution of the position and momentum operators for a non-relativistic spinless charged particle in the presence of a weakly non-uniform electric and magnetic field. It is shown that the drift velocity operator obtained in this study agrees with the classical counterpart, and that, using the time dependent operators, the variances in position and momentum grow with time. The expansion rate of variance in position and momentum are dependent on the magnetic gradient scale length, however, independent of the electric gradient scale length. In the presence of a weakly non-uniform electric and magnetic field, the theoretical expansion rates of variance expansion are in good agreement with the numerical analysis. It is analytically shown that the variance in position reaches the square of the interparticle separation, which is the characteristic time much shorter than the proton collision time of plasma fusion. After this time, the wavefunctions of the neighboring particles would overlap, as a result, the conventional classical analysis may lose its validity. The broad distribution of individual particle in space means that their Coulomb interactions with other particles become weaker than that expected in classical mechanics.
The Mu2e experiment at Fermilab is designed to search for charged-lepton flavor violation by looking for muon to electron conversions in the field of the nucleus. The concept of the experiment is to generate a low momentum muon beam, stopping the muons in a target and measuring the momentum of the outgoing electrons. The implementation of this approach utilizes a complex magnetic field composed of graded solenoidal and toroidal fields. The location of the solenoid cold mass relative to external fiducials is needed for alignment as well as monitoring coil movements during cool down and magnet excitation. This study describes a novel design of a Cold Mass Position Monitor System (CMPS) that will be implemented for the Mu2e experiment.
Initial measurements from the ULECA sensor of the Max-Planck-Institut/University of Maryland experiment on ISEE 1 are reported. ULECA is an electrostatic deflection - total energy sensor consisting of a collimator, a deflection analyzer, and an array of solid-state detectors. The position of a given detector, which determines the energy per charge of an incident particle, together with the measured energy, determines the particle's charge state. It is found that a rich variety of phenomena are operative in the transthermal energy regime (about 10 keV/Q to 100 keV/Q) covered by ULECA. Specifically, observations are presented of locally accelerated protons, alpha particles, and heavier ions in the magnetosheath and upstream of earth's bow shock. Preliminary analysis indicates that the behavior of these locally accelerated particles is most similar at the same energy per charge.
Conjugated organic chromophores composed of linked donor (D) and acceptor (A) moieties have attracted considerable attention for photoelectrochemical applications. In this work, we compare the optoelectronic properties and photoelectrochemical performance of two D–A–D structural isomers with thiophene-X-carboxylic acid (X denotes 3 and 2 positions) derivatives and 2,1,3-benzothiadiazole as the D and A moieties, respectively. 5,5′-(Benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-3-carboxylic acid), BTD1, and 5,5′-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carboxylic acid), BTD2, were employed in the study to understand how structural isomers affect surface attachments within chromophore–catalyst assemblies and their influence on charge-transfer dynamics. Crystal structures revealed that varying the position of the −COOH anchoring group causes the molecules to either contort out of a plane (BTD1) or adopt a near-perfect planar conformation (BTD2). BTD1 and BTD2 were co-loaded with either a water oxidation catalyst, [Ru(2,6-bis(1-methylbenzimidazol-2-yl)pyridine)-(4,4′-((HO) 2 OPCH 2 )2-2,2′-bipyridine)(OH 2 )] 2 , RuCt 2+ , or proton reduction catalyst [Ni(P 2 Ph N 2 C 6 H 4 CH 2 PO 3 H 2 ) 2 ] 2+ , NiCt 2+ , on oxide electrodes to facilitate photodriven water splitting reactions. Emission quenching measurements indicate that both BTD1 and BTD2 inject electrons into n-type SnO 2 |TiO 2 electrodes and holes into p-type NiO semiconductors from their respective excited states at high efficiencies >60%. Photocurrent densities of chromophore–catalyst assemblies obtained using linear sweep voltammetry (LSV) show that BTD2-sensitized photoanodes generate significantly more photocurrent than BTD1-sensitized electrodes; however, both exhibit similar performances at the photocathode. Photoelectrocatyltic measurements demonstrate that both BTD1 and BTD2 performed similarly, generating Faradaic efficiencies of 39 and 38% at the anode or 61 and 79% at the cathode. Transient absorption measurements suggest that the differences between the LSV and photoelectrocatalytic measurements result from the differences in quantum yields of the photogenerated redox equivalents, which is also a reflection of the varying metal oxide surface conformation. Our findings suggest that BTD2 should be investigated further in photocathodic studies since it has the structural advantage of being incorporated into diverse types of chromophore–catalyst assemblies.
The structure of the bacterial photosynthetic reaction center (RC) reveals symmetry-related electron transfer (ET) pathways, but only one path is used in native RCs. Analogous mutations have been made in two Rhodobacter (R.) species. A glutamic acid at position 133 in the M subunit increases transmembrane charge separation via the naturally inactive (B-side) path through impacts on primary ET in mutant R. sphaeroidesRCs. Prior work showed that the analogous substitution in the R. capsulatusRC also increases B-side activity, but mainly affects secondary ET. Finally, the overall yields of transmembrane ET are similar, but enabled in fundamentally different ways.
Low-temperature non-thermal plasmas produce highly reactive chemical environments made up of electrons, ions, radicals, and vibrationally excited molecules. These reactive species, when combined with catalysts, can help drive thermodynamically unfavorable chemical reactions at low temperatures and atmospheric pressure. The conversion of methane (CH 4 ) to produce other value-added chemicals is a good model system because of its applicability to a wide range of industries. To effectively create these plasma catalytic systems, a fundamental understanding of the plasma-phase chemistry alone is imperative. While there have been many studies on methane plasmas and how certain operating conditions (i.e., gas composition and power) affect the plasma, there is limited understanding on how changing bulk reaction temperature affects the plasma properties and ensuing plasma chemistry. Here, in this work, we use a dielectric barrier discharge to investigate the effects of temperature on the reaction chemistry and the plasma’s electrical properties in various methane-gas mixtures. Results show that increasing temperature leads to a reduction in methane conversion as well as changes to both the gas and dielectric material pre-breakdown, which manifests itself in temperature-dependent electrical properties of the plasma. Experiments at various temperatures and power show a positive correlation between key electrical plasma properties (average charge and lifetime per filament) and the measured methane conversion as a function of temperature.
A systematic investigation on tuning the charge carrier concentration by substitution of the Ru position in RuIn{sub 3} is performed. Samples with nominal composition Ru{sub 0.95}T{sub 0.05}In{sub 3} (T=Re, Rh, Ir) were synthesized via liquid–solid-reaction and subsequent spark plasma sintering treatment. The chemical composition was characterized by X-ray, metallographic and microstructure analysis revealing solid solutions in the samples with Rh and Ir, whereas Re cannot be incorporated in RuIn{sub 3}. Minor oxide impurities in the commercially available starting elements, the homogeneity range of RuIn{sub 3} and the redox potentials of the participating elements are the key for interpreting the observed lattice parameters and the corresponding composition. Both, substitutions with Rh or Ir and Re inclusions in RuIn{sub 3} lead independently to a significant decrease of the total thermal conductivity down to approximately one half of the value observed for binary RuIn{sub 3}, prepared with commercially available starting materials. The electrical resistivity was reduced by substitution and the temperature dependence changes from semiconductor-like, for RuIn{sub 3}, to metal-like in the substitution derivatives. At the same time the sign change in the thermopower at high temperatures, characteristic for binary RuIn{sub 3}, is suppressed, attaining only electrons as majority carriers. - Graphical abstract: Microstructure (perpendicular to the pressure axis; polarized light) of polycrystalline Ru{sub 0.95}Rh{sub 0.05}In{sub 3} (a), Ru{sub 0.95}Ir{sub 0.05}In{sub 3} (b) and Ru{sub 0.95}Re{sub 0.05}In{sub 3} (c) samples after SPS treatment. - Highlights: • Substitution solid solutions of RuIn{sub 3} were prepared via liquid–solid-reaction. • Chemistry of oxide impurities is crucial for explanation of experimental results. • Thermodynamic calculations support the observation of In{sub 2}O{sub 3} or ZnO as impurities. • Electrical resistivity is reduced by substitution. • Temperature dependence of resistivity changes from semiconductor- to metal-like.
Highlights: • TiO{sub 2}:Nb (1.2 at.%) multilayer films were deposited by sol–gel method on glass and Si. • 5 and 10 layers TiO{sub 2}:Nb films crystallize only in the anatase phase. • E{sub g} values are within 3.24–3.32 eV showing a decrease with increasing the layer number. • The specific resistivity, effective donor and sheet energy densities were obtained. • Nb donor compensation by acceptor levels in TiO{sub 2}:Nb film was suggested. - Abstract: Thin films of 5 and 10-layered sol–gel TiO{sub 2} were doped with 1.2 at.% Nb and their structural, optical and electrical properties were investigated. The films crystallized only in anatase phase, as evidenced by X-ray diffraction and selected area electron diffraction analyses. High resolution transmission electron microscopy revealed nanosized crystallites with amorphous boundaries. Current-voltage measurements on metal-TiO{sub 2}–Si structures showed the formation of n{sup +}–n heterojunction at the TiO{sub 2}–Si interface with a rectification ratio of 10{sup 4}. The effective donor density varies between 10{sup 16} and 10{sup 17} cm{sup −3}, depending on film thickness. The sheet energy densities under forward and reverse bias are in the order of 10{sup 12} and 10{sup 10} cm{sup −2} eV{sup −1}, respectively. These values and the high specific resistivity (10{sup 4} Ω cm) support the existence of compensating acceptor levels in these films. It was established that the conduction mechanism is based on space charge limited current via deep levels with different energy positions in the band gap.
The SIGMA project aims to develop a p-type segmented inverted coaxial point contact germanium detector for gamma-ray tracking and imaging. Here the performance of the first prototype of this type of detector is reported. The measurements performed verified the size and shape of the crystal and determined the location of the complex active volumes of the detector segments. The latter determines the charge collection times that are related to the position of interaction. Good agreement is found between the results and the specified crystal design. The energy resolution of the point contact has been measured to be 0.84 keV and 2.21 keV at 122 keV and 1332 keV, respectively.
Solution-processed organic electronic devices often consist of layers of polar and non-polar polymers. In addition, either of these layers could be doped with small molecular dopants. It is extremely important for device stability to understand the diffusion behavior of these molecular dopants under the thermal stress and whether the dopants have preference for the polar or the non-polar polymer layers. In this work, a widely used molecular dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) was chosen to investigate dopant site preference upon thermal annealing between the polar thiophene poly(thiophene-3-[2-(2-methoxy-ethoxy)ethoxy]-2,5-diyl) (S–P3MEET) and non-polar thiophene poly(3-hexylthiophene) (P3HT). F4TCNQ is able to p-type dope both P3HT and S–P3MEET. Further doping studies of S–P3MEET using near edge X-ray absorption fine structure spectroscopy, conductivity measurements and atomic force microscopy show that the F4TCNQ additive competes for doping sites with the covalently attached dopants on the S–P3MEET. Calorimetry measurements reveal that the F4TCNQ interacts strongly with the side-chains of the S–P3MEET, increasing the melting temperature of the side-chains by 30 °C with 5 wt% dopant loading. Next, the thermal stability of doping in the polar/non-polar (S–P3MEET/P3HT) bilayer architectures was investigated. Steady-state absorbance and fluorescence results show that F4TCNQ binds much more strongly in S–P3MEET than P3HT and very little F4TCNQ is found in the P3HT layer after annealing. In combination with reflectometry measurements, we show that F4TCNQ remains in the SP3MEET layer with annealing to 210 °C even though the sublimation temperature for neat F4TCNQ is about 80 °C. In contrast, F4TCNQ slowly diffuses out of P3HT at room temperature. We attribute this difference in binding the F4TCNQ anion to the ability of the ethyl-oxy side-chains of the S–P3MEET to orient around the charged dopant molecule and thereby to stabilize its position. Furthermore, this study suggests that polar side-chains could be engineered to increase the thermal stability of molecular dopant position.
The continued development and application of surfactant-encapsulated polyoxometalates (SEPs) relies on understanding the ordering and organization of species at their interface and how these are impacted by the various local environments to which they are exposed. In this paper, we report on the equilibrium properties of two common SEPs adsorbed to the air–water interface and probed with surface-specific vibrational sum-frequency generation (SFG) spectroscopy. These results reveal clear shifts in vibrational band positions, the magnitude of which scales with the charge of the SEP core, which is indicative of a static field effect on the surfactant coating and the associated local chemical environment. This static field also induces ordering in surrounding water molecules that is mediated by charge screening via the surface-bound surfactants. From these SFG measurements, we are able to show that Mo 132 -based SEPs are more polar than Mo 72 V 30 SEPs. Disorder in the surfactant chain packing at the highly curved SEP surfaces is attributed to large conic volumes that can be sampled without interactions with neighboring chains. Measurements of adsorption isotherms yield free energies of adsorption to the air–water interface of -46.8 ± 0.4 and -44.8 ± 1.2 kJ/mol for the Mo 132 and Mo 72 V 30 SEPs, respectively, indicating a strong propensity for the fluid surface. Finally, the influence of intermolecular interactions on the surface adsorption energies is discussed.
Scalable quantum processors require tunable two-qubit gates that are fast, coherent and long-range. The Heisenberg exchange interaction offers fast and coherent couplings for spin qubits, but is intrinsically short-ranged. Here, we demonstrate that its range can be increased by employing a multielectron quantum dot as a mediator, while preserving speed and coherence of the resulting spin-spin coupling. We do this by placing a large quantum dot with 50–100 electrons between a pair of two-electron double quantum dots that can be operated and measured simultaneously. Two-spin correlations identify coherent spin-exchange processes across the multielectron quantum dot. We further show that different physical regimes of the mediated exchange interaction allow a reduced susceptibility to charge noise at sweet spots, as well as positive and negative coupling strengths up to several gigahertz. These properties make multielectron dots attractive as scalable, voltage-controlled coherent coupling elements.
Abstract not provided