Enhanced cycling performance and high energy density of LiFePO4 based lithium ion batteries

LiFePO4 attracts a lot of attention as cathode materials for the next generation of lithium ion batteries. However, LiFePO4 has a poor rate capability attributed to low electronic conductivity and low density. There is seldom data reported on lithium ion batteries with LiFePO4 as cathode and graphite as anode. According to our experimental results, the capacity fading on cycling is surprisingly negligible at 1664 cycles for the cell type 042040. It delivers a capacity of 1170 mAh for 18650 cell type at 4.5C discharge rate. It is confirmed that lithium ion batteries with LiFePO4 as cathode are suitable for electric vehicle application. (c) 2007 Elsevier B.V. All rights reserved.

A new type of boundary integral-equation for plane problems of elasticity including rotational forces

Based on the idea proposed by Hu [Scientia Sinica Series A XXX, 385-390 (1987)], a new type of boundary integral equation for plane problems of elasticity including rotational forces is derived and its boundary element formulation is presented. Numerical results for a rotating hollow disk are given to demonstrate the accuracy of the new type of boundary integral equation.

The mechanism of energy storage by shearing the solar magnetic field

In this paper, a complete set of MHD equations have been solved by numerical calculations in an attempt to study the dynamical evolutionary processes of the initial equilibrium configuration and to discuss the energy storage mechanism of the solar atmosphere by shearing the magnetic field. The initial equilibrium configuration with an arch bipolar potential field obtained from the numerical solution is similar to the configuration in the vicinity of typical solar flare before its eruption. From the magnetic induction equation in the set of MHD equations and dealing with the non-linear coupling effects between the flow field and magnetic field, the quantitative relationship has been derived for their dynamical evolution. Results show that plasma shear motion at the bottom of the solar atmosphere causes the magnetic field to shear; meanwhile the magnetic field energy is stored in local regions. With the increase of time the local magnetic energy increases and it may reach an order of 4×10^25 J during a day. Thus the local storage of magnetic energy is large enough to trigger a big solar flare and can be considered as the energy source of solar flares. The energy storage mechanism by shearing the magnetic field can well explain the slow changes in solar active regions.

A consistent model of isolated force-free magnetic arches

The magnetic flux tube concentrating strong magnetic field is the basic configuration of magneticfield in the solar atmosphere. In the present paper, the equilibrium of isolated magnetic flux tube inthe solar atmosphere is discussed. In the viewpoint of mathematics, the boundary condition is nonlinearand the position of boundary needs to be determined by the physical condition although the equation ofmagnetic potential is linear for the linear force-free field. Analytical solutions to the arches of bothuniform circular cross-section and non-uniform cross section have been obtained. The results show thatthe nonlinear problem may have or not have any solution according to different azimuthal components of the magnetic field; the number of solutions to the nonlinear problem is four at most, and two in some cases. In the present paper, the analytical solutions to the approximations of both fat and slender arches are given in detail, and the general features of magnetic arch structure are shown.

A study of populations of the anchoveta, Cetengraulis mysticetus, based on meristic characters

ENGLISH: This study was undertaken to determine whether meristic characters indicate that more than one major population of anchovetas occurs in the range of the species from Mexico to Peru. Interest in this species lies in the fact that it is the principal bait fish used to catch yellowfin and skipjack tunas in the Eastern Pacific. Specimens examined were from collections made by California tuna fishing vessels at six major baiting localities covering nearly the entire range of the species, namely, Almejas Bay on the outer coast of Baja California, Guaymas and Ahome Point in the Gulf of California, Gulf of Fonseca, Gulf of Panama, and Gulf of Guayaquil. Four meristic characters were selected for study: vertebrae, dorsal fin rays, anal fin rays, and gill rakers on the first gill arch. Vertebral counts, using X-ray film, were taken from a total of 1,500 fish, 250 each from each of the six localities. For the other characters, 125 anchovetas were examined from each locality for a total of 750, the counts being made with the aid of a binocular microscope. Specimens were between 80 and 165 mm. standard length. SPANISH: Este estudio ha sido hecho con el propósito de determinar si los caracteres numéricos de las anchovetas indican que existe más de una población de este pez en la zona en que se encuentra la especie, comprendida entre México y Perú. El interés en dicha especie radica en el hecho de que éste es el pez de carnada usado principalmente para la pesca de los atunes "aleta amarilla" y "barrilete" en el Pacífico Oriental. Los especímenes que han sido examinados, se tomaron de las muestras recogidas por los barcos atuneros de California en seis de las mejores localidades en que se pesca la anchoveta, las cuales comprenden casi toda la zona en donde se encuentra la especie, a saber, Bahía de Almejas en la costa exterior de Baja California, Guaymas y Punta Ahorne en el Golfo de California, el Golfo de Fonseca, el Golfo de Panamá y el Golfo de Guayaquil. Cuatro caracteres numéricos fueron escogidos para su estudio: los que presentan 1) las vértebras, 2) los radios de la aleta dorsal, 3) los radios de la aleta anal y 4) las branquispinas del primer arco branquial. Mediante el uso de películas con rayos X, se contaron las vértebras en un total de 1,500 peces, es decir, 250 de cada una de las seis mencionadas localidades. En relación con los otros caracteres, se examinaron 125 anchovetas de cada área, o sea, un total de 750 ejemplares, habiendo sido hecho el conteo por medio de un microscopio binocular. Los especímenes tenían un largo standard entre 80 y 165 milímetros. (PDF contains 24 pages.)

Measurements Of In Situ Stress And Mining-Induced Stress In Beiminghe Iron Mine Of China

In order to obtain the distribution rules of in situ stress and mining-induced stress of Beiminghe Iron Mine, the stress relief method by overcoring was used to measure the in situ stress, and the MC type bore-hole stress gauge was adopted to measure the mining-induced stress. In the in situ stress measuring, the technique of improved hollow inclusion cells was adopted, which can realize complete temperature compensation. Based on the measuring results, the distribution model of in situ stress was established and analyzed. The in situ stress measuring result shows that the maximum horizontal stress is 1.75-2.45 times of vertical stress and almost 1.83 times of the minimum horizontal stress in this mineral field. And the mining-induced stress measuring result shows that, according to the magnitude of front abutment pressure the stress region can be separated into stress-relaxed area, stress-concentrated area and initial stress area. At the -50 m mining level of this mine, the range of stress-relaxed area is 0-3 m before mining face; the range of stress-concentrated area is 3-55 m before mining face, and the maximum mining-induced stress is 16.5-17.5 MPa, which is 15-20 m from the mining face. The coefficient of stress concentration is 1.85.

Fluctuation characteristics of arc voltage and jet flow in a non-transferred dc plasma generated at reduced pressure

A torch with a set of inter-electrode inserts between the cathode and the anode/nozzle with a wide nozzle exit was designed to generate plasma jets at chamber pressures of 500–10 000 Pa. The variation of the arc voltage was examined with the change in working parameters such as gas flow rate and chamber pressure. The fluctuation in the arc voltage was recorded with an oscilloscope, and the plasma jet fluctuation near the torch exit was observed with a high-speed video camera and detected with a double-electrostatic probe. Results show that the 300 Hz wave originated from the tri-phase rectified power supply was always detected under all generating conditions. Helmholtz oscillations over 3000 Hz was detected superposed on the 300 Hz wave at gas flow rates higher than 8.8 slm with a peak to valley amplitude lower than 5% of the average voltage value. No appreciable voltage fluctuation caused by the irregular arc root movement is detected, and mechanisms for the arc voltage and jet flow fluctuations are discussed.

Nonlinear laser focusing using a conical guide and generation of energetic ions

Using conventional methods, a laser pulse can be focused down to around 6-8 mu m, but further reduction of the spot size has proven to be difficult. Here it is shown by particle-in-cell simulation that with a hollow cone an intense laser pulse can be reduced to a tiny, highly localized, spot of around 1 mu m radius, accompanied by much enhanced light intensity. The pulse shaping and focusing effect is due to a nonlinear laser-plasma interaction on the inner surface of the cone. When a thin foil is attached to the tip of the cone, the cone-focused light pulse compresses and accelerates the ions in its path and can punch through the thin target, creating highly localized energetic ion bunches of high density.

Multiple quasi-phase-matching for enhanced generation of selected high harmonics in aperiodic modulated fibers

A technique for enhanced generation of selected high harmonics in a gas medium, in a high ionization limit, is proposed in this paper. An aperiodically corrugated hollow-core fiber is employed to modulate the intensity of the fundamental laser pulse along the direction of propagation, resulting in multiple quasi-phase-matched high harmonic emissions at the cutoff region. Simulated annealing (SA) algorithm is applied for optimizing the aperiodic hollow-core fiber. Our simulation shows that the yield of selected harmonics is increased equally by up to 2 orders of magnitude compared with no modulation and this permits flexible control of the quasi-phase-matched emission of selected harmonics by appropriate corrugation. (c) 2007 Optical Society of America.

A multi-scale approach to shaping carbon nanotube structures for hollow microneedles

The concept of a carbon nanotube microneedle array is explored in this thesis from multiple perspectives including microneedle fabrication, physical aspects of transdermal delivery, and in vivo transdermal drug delivery experiments. Starting with standard techniques in carbon nanotube (CNT) fabrication, including catalyst patterning and chemical vapor deposition, vertically-aligned carbon nanotubes are utilized as a scaffold to define the shape of the hollow microneedle. Passive, scalable techniques based on capillary action and unique photolithographic methods are utilized to produce a CNT-polymer composite microneedle. Specific examples of CNT-polyimide and CNT-epoxy microneedles are investigated. Further analysis of the transport properties of polymer resins reveals general requirements for applying arbitrary polymers to the fabrication process.

The bottom-up fabrication approach embodied by vertically-aligned carbon nanotubes allows for more direct construction of complex high-aspect ratio features than standard top-down fabrication approaches, making microneedles an ideal application for CNTs. However, current vertically-aligned CNT fabrication techniques only allow for the production of extruded geometries with a constant cross-sectional area, such as cylinders. To rectify this limitation, isotropic oxygen etching is introduced as a novel fabrication technique to create true 3D CNT geometry. Oxygen etching is utilized to create a conical geometry from a cylindrical CNT structure as well as create complex shape transformations in other CNT geometries.

CNT-polymer composite microneedles are anchored onto a common polymer base less than 50 µm thick, which allows for the microneedles to be incorporated into multiple drug delivery platforms, including modified hypodermic syringes and silicone skin patches. Cylindrical microneedles are fabricated with 100 µm outer diameter and height of 200-250 µm with a central cavity, or lumen, diameter of 30 µm to facilitate liquid drug flow. In vitro delivery experiments in swine skin demonstrate the ability of the microneedles to successfully penetrate the skin and deliver aqueous solutions.

An in vivo study was performed to assess the ability of the CNT-polymer microneedles to deliver drugs transdermally. CNT-polymer microneedles are attached to a hand actuated silicone skin patch that holds a liquid reservoir of drugs. Fentanyl, a potent analgesic, was administered to New Zealand White Rabbits through 3 routes of delivery: topical patch, CNT-polymer microneedles, and subcutaneous hypodermic injection. Results demonstrate that the CNT-polymer microneedles have a similar onset of action as the topical patch. CNT-polymer microneedles were also vetted as a painless delivery approach compared to hypodermic injection. Comparative analysis with contemporary microneedle designs demonstrates that the delivery achieved through CNT-polymer microneedles is akin to current hollow microneedle architectures. The inherent advantage of applying a bottom-up fabrication approach alongside similar delivery performance to contemporary microneedle designs demonstrates that the CNT-polymer composite microneedle is a viable architecture in the emerging field of painless transdermal delivery.

Quantum Mechanics Studies of Fuel Cell Catalysts and Proton Conducting Ceramics with Validation by Experiment

We carried out quantum mechanics (QM) studies aimed at improving the performance of hydrogen fuel cells. This led to predictions of improved materials, some of which were subsequently validated with experiments by our collaborators.

In part I, the challenge was to find a replacement for the Pt cathode that would lead to improved performance for the Oxygen Reduction Reaction (ORR) while remaining stable under operational conditions and decreasing cost. Our design strategy was to find an alloy with composition Pt3M that would lead to surface segregation such that the top layer would be pure Pt, with the second and subsequent layers richer in M. Under operating conditions we expect the surface to have significant O and/or OH chemisorbed on the surface, and hence we searched for M that would remain segregated under these conditions. Using QM we examined surface segregation for 28 Pt₃M alloys, where M is a transition metal. We found that only Pt₃Os and Pt₃Ir showed significant surface segregation when O and OH are chemisorbed on the catalyst surfaces. This result indicates that Pt₃Os and Pt3Ir favor formation of a Pt-skin surface layer structure that would resist the acidic electrolyte corrosion during fuel cell operation environments. We chose to focus on Os because the phase diagram for Pt-Ir indicated that Pt-Ir could not form a homogeneous alloy at lower temperature. To determine the performance for ORR, we used QM to examine all intermediates, reaction pathways, and reaction barriers involved in the processes for which protons from the anode reactions react with O₂ to form H₂O. These QM calculations used our Poisson-Boltzmann implicit solvation model include the effects of the solvent (water with dielectric constant 78 with pH 7 at 298K). We found that the rate determination step (RDS) was the O_ad hydration reaction (O_ad + H₂O_ad -> OH_ad + OH_ad) in both cases, but that the barrier for pure Pt of 0.50 eV is reduced to 0.48 eV for Pt₃Os, which at 80 degrees C would increase the rate by 218%. We collaborated with the Pu-Wei Wu’s group to carry out experiments, where we found that the dealloying process-treated Pt2Os catalyst showed two-fold higher activity at 25 degrees C than pure Pt and that the alloy had 272% improved stability, validating our theoretical predictions.

We also carried out similar QM studies followed by experimental validation for the Os/Pt core-shell catalyst fabricated by the underpotential deposition (UPD) method. The QM results indicated that the RDS for ORR is a compromise between the OOH formation step (0.37 eV for Pt, 0.23 eV for Pt_2ML/Os core-shell) and H₂O formation steps (0.32 eV for Pt, 0.22 eV for Pt_2ML/Os core-shell). We found that Pt_2ML/Os has the highest activity (compared to pure Pt and to the Pt₃Os alloy) because the 0.37 eV barrier decreases to 0.23 eV. To understand what aspects of the core shell structure lead to this improved performance, we considered the effect on ORR of compressing the alloy slab to the dimensions of pure Pt. However this had little effect, with the same RDS barrier 0.37 eV. This shows that the ligand effect (the electronic structure modification resulting from the Os substrate) plays a more important role than the strain effect, and is responsible for the improved activity of the core- shell catalyst. Experimental materials characterization proves the core-shell feature of our catalyst. The electrochemical experiment for Pt_2ML/Os/C showed 3.5 to 5 times better ORR activity at 0.9V (vs. NHE) in 0.1M HClO₄ solution at 25 degrees C as compared to those of commercially available Pt/C. The excellent correlation between experimental half potential and the OH binding energies and RDS barriers validate the feasibility of predicting catalyst activity using QM calculation and a simple Langmuir–Hinshelwood model.

In part II, we used QM calculations to study methane stream reforming on a Ni-alloy catalyst surfaces for solid oxide fuel cell (SOFC) application. SOFC has wide fuel adaptability but the coking and sulfur poisoning will reduce its stability. Experimental results suggested that the Ni4Fe alloy improves both its activity and stability compared to pure Ni. To understand the atomistic origin of this, we carried out QM calculations on surface segregation and found that the most stable configuration for Ni₄Fe has a Fe atom distribution of (0%, 50%, 25%, 25%, 0%) starting at the bottom layer. We calculated that the binding of C atoms on the Ni4Fe surface is 142.9 Kcal/mol, which is about 10 Kcal/mol weaker compared to the pure Ni surface. This weaker C binding energy is expected to make coke formation less favorable, explaining why Ni₄Fe has better coking resistance. This result confirms the experimental observation. The reaction energy barriers for CHx decomposition and C binding on various alloy surface, Ni₄X (X=Fe, Co, Mn, and Mo), showed Ni₄Fe, Ni₄Co, and Fe₄Mn all have better coking resistance than pure Ni, but that only Ni₄Fe and Fe₄Mn have (slightly) improved activity compared to pure Ni.

In part III, we used QM to examine the proton transport in doped perovskite-ceramics. Here we used a 2x2x2 supercell of perovskite with composition Ba₈X₇M₁(OH)₁O₂₃ where X=Ce or Zr and M=Y, Gd, or Dy. Thus in each case a 4⁺ X is replace by a 3⁺ M plus a proton on one O. Here we predicted the barriers for proton diffusion allowing both includes intra-octahedron and inter-octahedra proton transfer. Without any restriction, we only observed the inter-octahedra proton transfer with similar energy barrier as previous computational work but 0.2 eV higher than experimental result for Y doped zirconate. For one restriction in our calculations is that the O_donor-O_acceptor atoms were kept at fixed distances, we found that the barrier difference between cerates/zirconates with various dopants are only 0.02~0.03 eV. To fully address performance one would need to examine proton transfer at grain boundaries, which will require larger scale ReaxFF reactive dynamics for systems with millions of atoms. The QM calculations used here will be used to train the ReaxFF force field.

Geology of the Pacoima Area, Los Angeles County, California

The Pacoima area is located on an isolated hill in the northeast section of the San Fernando, the northeast portion of the Pacoima Quadrangle, Los Angeles County, California. Within it are exposed more than 2300 feet of Tertiary rocks, which comprise three units of Middle Miocene (?) age, and approximately 950 feet of Jurassic (?) granite basement. The formations are characterized by their mode of occurrence, marine and terrestial origin, diverse lithology, and structural features.

The basement complex is composed of intrusive granite, small masses of granodiorite and a granodiorite gneiss with the development of schistosity in sections. During the long period of erosion of the metamorphics, the granitic rocks were exposed and may have provided clastic constituents for the overlying formations.

As a result of rapid sedimentation in a transitional environment, the Middle Miocene Twin Peaks formation was laid down unconformably on the granite. This formation is essentially a large thinning bed of gray to buff pebble and cobble conglomerate grading to coarse yellow sandstone. The contact of conglomerate and granite is characterized by its faulted and depositional nature.

Beds of extrusive andesite, basalt porphyry, compact vesicular amygdaloidal basalts, andesite breccia, interbedded feldspathic sands and clays of terrestial origin, and mudflow breccia comprise the Pacoima formation which overlies the Twin Peaks formation unconformably. A transgressing shallow sea accompanied settling of the region and initiated deposition of fine clastic sediments.

The marine Topanga (?) formation is composed of brown to gray coarse sandstone grading into interbedded buff sandstones and gray shales. Intrusions of rhyolitedacite and ash beds mark continued but sporatic volcanism during this period.

The area mapped represents an arch in the Tertiary sediments. Forces that produced the uplift of the granite structural high created stresses that were relieved by jointing and faulting. Vertical and horizontal movement along these faults has displaced beds, offset contacts and complicated their structure. Uplift and erosion have exposed the present sequence of beds which dip gently to the northeast. The isolated hill is believed to be in an early stage of maturity.

A control of gas-vacuolate cyanobacteria

The cyanobacteria that cause problems in water supply are principally the colonial forms that are buoyed up by gas vesicles. The success of these organisms is due, in part, to their gas vesicles, which enable them to perform vertical migrations or to maintain themselves in the euphotic zone. The gas vesicles are also the root cause of the problems. In calm periods they cause the cyanobacteria to float to the water surface forming noxious scums, and they may prevent the colonies from sedimenting in water treatment plants. Gas vesicles are hollow, gas-filled structures; they are rigid but can be collapsed by the application of pressure. Their critical collapse pressure is influenced by their dimensions, which vary in different organisms. Gas vesicles are formed by the assembly of two types of protein, which determine their mechanical and physical properties. Methods for collapsing gas vesicles in natural populations of cyanobacteria will be considered. They may have application to the control of cyanobacteria in water supply.

Electromagnetic fields and transmission properties in tapered hollow metallic waveguides

We analyze the electromagnetic spatital distributions and address an important issue of the transmission properties of spherical transverse-electric (TE) and transverse-magnetic (TM) eigenmodes within a tapered hollow metallic waveguide in detail. Explicit analytical expressions for the spatital distributions of electromagnetic field components, attenuation constant, phase constant and wave impedance are derived. Accurate eigenvalues obtained numerically are used to study the dependences of the transmission properties on the taper angle, the mode as well as the length of the waveguide. It is shown that all modes run continuously from a propagating through a transition to an evanescent region and the value of the attenuation increases as the distance from the cone vertex and the cone angle decrease. A strict distinction between pure propagating and pure evanescent modes cannot be achieved. One mode after the other reaches cutoff in the tapered hollow metallic waveguide as the distance from the cone vertex desreases. (C) 2008 Optical Society of America

Focusing properties of concentric piecewise cylindrical vector beam

The focusing properties of a concentric piecewise cylindrical vector beam is investigated theoretically in this paper. The beam consists of three portions with different and changeable phase retardation and polarization. Numerical simulations show that the evolution of the focal shape is very considerable by changing the radius and polarization rotation angle of each portion of the vector beam. And some interesting focal spots may occur, such as two- or three-peak focus, dark hollow focus, ring focus, and two-ring-peak focus. Corresponding gradient force patterns are also computed, and novel trap patterns, including cup shell shape trap with one trap at its each side along axis, rectangle shell shape trap with one trap at its each side, dumbbell optical trap, spherical shell optical trap, may occur, which shows that the concentric piecewise cylindrical vector beam can be used to construct controllable optical tweezers. (c) 2006 Elsevier GmbH. All rights reserved.