A process for the generation of halogens from halide-containing solutions includes the step of conducting electrolysis of the solutions in an electrolytic cell having a platinum based amorphous metal alloy anode.
New lithium ion composite electrolyte, LiI?Li2S?La2O2Sm (m=1, 2) was synthesized from the binary Li2S?LaOI system through solid state reaction. The lithium ion conductive property was investigated by AC impedance spectroscopy. And the highest conductivity of the obtained electrolyte at room temperature was found to be 3.0?10?6?S cm?1. The notable ionic conduction was attributed to the in situ formed amorphous LiI.
This paper describes inorganic solid electrolytes from a viewpoint of electrolytes for lithium batteries. Lithium ion conductive inorganic solid electrolytes are largely divided into crystalline and amorphous substances. Crystalline substances are known as LiI and Li3N, and also oxygen acid salt. However, when considering application to a battery, its large grain boundary resistance and electrochemical instability would be a problem. Lithium ion conductive amorphous solid electrolytes are divided into an oxide system and a sulfide system. Since most of them do not contain transition metal elements, they are stable against electrochemical reduction, and ions move isotropically in electrolyte. Therefore, ion conduction paths across the grain boundaries may be connected more easily, forming an electrolyte with low grain ...
A body-centered cubic (bcc) Mg-12Li-9Al-1Zn (wt.%) alloy was fabricated in air by electrolysis from LiCl-KCl molten salt at 500 deg. C. Electrolytic deposition of Li atoms on cathode (Mg-Al-Zn alloy) and diffusion of the Li atoms formed the bcc Mg-Li-Al-Zn alloy with 12 wt.% Li and only 0.264 wt.% K. Low K concentration in the bcc Mg alloy strip after the electrolysis process resulted from 47% atomic size misfit between K and Mg atoms and low solubility of K in Mg matrix.
A body-centered cubic (bcc) Mg-12Li-9Al-1Zn (wt.%) alloy was fabricated in air by electrolysis from LiCl-KCl molten salt at 500degreeC. Electrolytic deposition of Li atoms on cathode (Mg-Al-Zn alloy) and diffusion of the Li atoms formed the bcc Mg-Li-Al-Zn alloy with 12wt.% Li and only 0.264wt.% K. Low K concentration in the bcc Mg alloy strip after the electrolysis process resulted from 47% atomic size misfit between K and Mg atoms and low solubility of K in Mg matrix.
This invention pertains to passivation-free solid-state rechargeable batteries composed of Li.sub.4 Ti.sub.5 O.sub.12 anode, a solid polymer electrolyte and a high voltage cathode. The solid polymer electrolyte comprises a polymer host, such as polyacrylonitrile, poly(vinyl chloride), poly(vinyl sulfone), and poly(vinylidene fluoride), plasticized by a solution of a Li salt in an organic solvent. The high voltage cathode includes LiMn.sub.2 O.sub.4, LiCoO.sub.2, LiNiO.sub.2 and LiV.sub.2 O.sub.5 and their derivatives.
This invention pertains to passivation-free solid-state rechargeable batteries composed of Li{sub 4}Ti{sub 5}O{sub 12} anode, a solid polymer electrolyte and a high voltage cathode. The solid polymer electrolyte comprises a polymer host, such as polyacrylonitrile, poly(vinyl chloride), poly(vinyl sulfone), and poly(vinylidene fluoride), plasticized by a solution of a Li salt in an organic solvent. The high voltage cathode includes LiMn{sub 2}O{sub 4}, LiCoO{sub 2}, LiNiO{sub 2} and LiV{sub 2}O{sub 5} and their derivatives. 5 figs.
Research investigating applicability of lithium salts for solid electrolyte batteries was described. The studies included determinations of lithium ion conductivities in solid electrolyte systems based on Li4SiO4, LiTi2(PO4)3, and ceramic materials. Research on all solid state lithium cells utilizing TiS2 NiPS3 electrodes was also reported.
The deformation characteristics of pellets of electrolyte-binder (EB) mixes based on MgO were measured under simulated, thermal-battery conditions. Measurements (using a statistically designed experimental strategy) were made as a function of applied pressure, temperature, and percentage of theoretical density for four molten-salt electrolytes at two levels of MgO. The EB mixes are used as separators in Li-alloy thermal batteries. The electrolytes included LiCl-KCI eutectic, LiCl-LiBr-KBr eutectic, LiBr-KBr-LiF eutectic, and a LiCl-LiBr-LiF electrolyte with a minimum-melting composition. The melting points ranged from 313 C to 436 C. The experimental data were used to develop statistical models that approximate the deformation behavior of pellets of the various EB mixes over the range of experimental ...
Using a new simulative technique developed by us, we systematically investigated new ternary or quaternary molten salt systems, which are based on LiF-LiCl, LiF-LiBr, and LiCl-LiBr binary systems, for use as electrolytes in thermal batteries, and evaluated their ionic conductivities and melting points experimentally. It was confirmed experimentally that LiF-LiBr-KF (melting point: 425^oC, ionic conductivity at 500^oC: 2.52Scm^-^1), LiCl-LiBr-KF (405^oC, 2.56Scm^-^1), LiCl-LiBr-NaF-KF (425^oC, 3.11Scm^-^1), LiCl-LiBr-NaCl-KCl (420^oC, 2.73Scm^-^1), and LiCl-LiBr-NaBr-KBr (420^oC, 2.76Scm^-^1) meet our targets for both melting point (350-430^oC) and ionic conductivity (2.0Scm^-^1 and higher at 500^oC). A single cell using the newly developed LiCl-LiBr-NaCl-KCl molten salt as an ...
Basic properties and battery performances of the novel high temperature stable lithium salt (Li{sub 2}B{sub 12}F{sub 12}, Dilithium Dodecafluorododecaborate; Li{sub 2}DFB) were studied using a Mn-based cathode and anode composed of a hard carbon and graphite mixture. The effect of co-solvents (mainly linear carbonate in electrolyte formulation of PC/EC/co-solvent (5/30/65 vol% mixture)) on conductivity, viscosity, charge-discharge capacities, rate performance, temperature performance, cycle life and storage life at 60 C was investigated. Conductivity of Li{sub 2}DFB electrolyte increased with reducing its viscosity by changing co-solvent and increasing the volume of the higher dielectric solvent. Li{sub 2}DFB electrolytes showed comparable discharge capacity and columbic efficiency against LiPF{sub 6} ...
The results of X-ray and neutron diffraction experiments on molten alkali halides in which some data of our experiments by X-ray diffraction such as those of molten LiCl, NaCl, KCl, LiBr and KBr are included were summarized. The first peak positions in the radial distribution function in molten alkali halides by X-ray or neutron diffraction experiments are always longer than those by computer simulations and the differences of 0.1 -- 0.3 A exceed the experimental error. It seems to be due to the deformation of the electron shell. In the computer simulation, the shell model which has the spherical deformation was expected to have a closer value of the first peak position to the experimental one than the rigid ion model by taking the polarization of ions. However, no change in the first peak position was found. Therefore, the non-spherical deformation of electron shell at the point where ions are in ...
The results of X-ray and neutron diffraction experiments on molten alkali halides in which some data of our experiments by X-ray diffraction such as those of molten LiCl, NaCl, KCl, LiBr and KBr are included were summarized. The first peak positions in the radial distribution function in molten alkali halides by X-ray or neutron diffraction experiments are always longer than those by computer simulations and the differences of 0.1 -- 0.3 A exceed the experimental error. It seems to be due to the deformation of the electron shell. In the computer simulation, the shell model which has the spherical deformation was expected to have more closer value of the first peak position to the experimental one than the rigid ion model by taking the polarization of ions. However, no change in the first peak position was found. Therefore, the non-spherical deformation of electron shell at the point where ions are in ...
Micron-sized Li{sub 4}Ti{sub 5}O{sub 12} was prepared in a single-step solid-state reaction involving TiO{sub 2} and Li{sub 2}CO{sub 3}, and its electrochemical behavior was evaluated in Li and Li-ion cells containing a polyacrylonitrile (PAN)-based solid polymer electrolyte. The usefulness of Li{sub 4}Ti{sub 5}O{sub 12} was demonstrated for three distinctive applications: (1) cathode of a 1.5 V rechargeable Li battery, (2) auxiliary electrode for investigating the electrochemistry of Li insertion cathode materials, and (3) anode of a Li-ion cell in conjunction with a high voltage cathode, e.g., cubic spinel LiMn{sub 2}O{sub 4}. The micron-sized Li{sub 4}Ti{sub 5}O{sub 12} exhibited a capacity of 160 mAh/g at C/20--C/30 rates which about 7% better than the ...
The lithium carbon batteries studied in this paper use plasticized polymer electrolytes made with passive polymer matrix swollen by a liquid electrolyte with a high ionic conductivity (> 10{sup -3} S/cm at 25 deg. C). The polymers used to prepare the gels are polyacrylonitrile (PAN) and vinylidene poly-fluoride (PVdF). The electrochemical and physical properties of these materials are analyzed according to their composition. The behaviour of solid electrolytes with different materials of lithium ion insertion (graphite and LiNiO{sub 2}) are studied and compared to liquid electrolytes. The parameters taken into account are the reversible and irreversible capacities, the cycling performance and the admissible current densities. Finally, complete lithium ion batteries with gelled electrolytes were manufactured and tested. (J.S.) 2 refs.
A helium-3 proportional detector was equipped with the experiment of Liaw-type electrolytic cell contained eutectic LiCl-KCl molten salt saturated by LiD electrolytic to collect the informations of the rate and the energy distribution of possible neutron produced during the electrolysis processes. For long time monitoring, the significant reproducible neutron bursts appeared at several runs of cells during electrolytic processing. The neutron counting rate increased about a factor of two above the level of the background measurement. The pulse height signals were verified of neutron energy ranging from thermal up to 350 keV. (author).
The in-situ observation of dendritic growth in lithium/polymer electrolyte-LiTFSI/lithium battery cells shows that dendrites grow up with about the same rate as anion migration. Memory effects have been evidenced in cycling experiments and limit the dendrites length. An overall movement of the electrolyte due to variations of electrolyte concentration in the vicinity of the electrodes has been observed too. (J.S.) 13 refs.
A review is given of the state of knowledge of the chemistry of astatine with the oxidation number +1. According to the position in the periodic system, astatine has metalloidal properties. The existence of a singly-charged cation in acid solution and the complex formation reactions with halide ions (Cl"-, Br"-, and I"-), with pseudohalide ions (SCN"-, CN"-, C(CN)_3"-, and N_3"-), and with thioureas and their derivatives underline the metalloidal character of At(I). Optimal preparation conditions, chemical composition of astatine compounds, existence and stability regions of At(I) complexes, and stability constants have been investigated by means of electromigration in free electrolyte solutions.
The confocal Raman micro-spectroscopy has been used for the study of a Lithium/polymer electrolyte-LiTFSI/V{sub 2}O{sub 5} type battery in which the polymer electrolyte thickness is of about 80 {mu}m. The analysis is performed on the side of the battery thanks to a specially designed cell which preserves all the characteristics of the real system. The analysis is performed on 20 points aligned between the anode and the cathode and with a depth of several tenth of {mu}m. The analysis of data obtained during charging/output cycles allows to evaluate the gradients of salt concentration inside the electrolyte, the pollutions of LiOH, Li{sub 2}CO{sub 3}, Li{sub 2}O and Li{sub 3}N -type at the lithium interface, but also the structural modifications of the cathode material. The in-situ study of concentration gradients inside the ...
As a series of experimental determinations of the thermal diffusivity of molten alkali halides, this paper describes measurements on five molten alkali metal chlorides (LiCl, NaCl, KCl, RbCl, and CsCl) in the temperature range up to 1440 K by the forced Rayleigh scattering method. K[sub 2]Cr[sub 2]O[sub 7] is employed as a dye substance to color the transparent molten salts. In comparison with the present results converted into thermal conductivity, most of the previous experimental data obtained by steady-state methods show larger values, up to about five times, which may be due to the systematic error caused by the presence of convection and radiation. It is found that the thermal conductivity of these series of molten alkali metal chlorides decreases with increasing molecular weight, and their temperature coefficients are weakly negative. 24 refs., 9 figs., 6 tabs.
The electrochemical intercalation of non-solvated lithium in different graphited materials has been performed in LiClO{sub 4}-ethylene carbonate (EC) medium. The irreversible capacity observed during the first output is mainly due to the formation of a passivation layer made of electrolyte reduction products. These products have been characterized for different electrode reduction potentials using transmission electron microscopy (image, diffraction) and electron energy loss spectroscopy (EELS). EC reduction on the electrode surface in presence of LiClO{sub 4} leads to the formation of Li{sub 2}CO{sub 3} for potentials close to 0.8 V vs Li{sup +}/Li. For lower potentials, the electrolyte reduction reaction goes on with the formation of different lithium alkyl-carbonates. In LiClO{sub 4}-propylene carbonate (PC) medium, ...
The incorporation of additives designed to sacrificially react on the surface of cathode materials of lithium ion batteries has been investigated. Addition of low concentrations of inorganic additives including lithium bisoxalatoborate (LiBOB), lithium difluorooxalatoborate (LiBF{sub 2}(C{sub 2}O{sub 4})), and tetramethoxy titanium (TMTi) to 1 M LiPF{sub 6} in 1:1:1 EC/DEC/DMC improves the capacity retention of Li/Li{sub 1.17}Mn{sub 0.58}Ni{sub 0.25}O{sub 2} cells cycled to 4.9 V vs. Li. Surface analysis of the cathode materials (XPS and IR) suggests that structure of the cathode surface film is modified by the presence of the additives resulting in a decrease in detrimental electrolyte oxidation reactions on the cathode surface. (author)
An electrolyte for high voltage lithium metal anode cells must simultaneously satisfy at least the following requirements; (i) high cycling efficiency on the lithium metal anode; (ii) higher oxidation potential than the charging voltage, and (iii) high specific conductivity. We have examined various electrolytes for lithium metal anode cells using a high voltage cathode, LiMn{sub 1.9}Co{sub 0.1}O{sub 4}. Of the electrolytes resistant to high voltage that we used, a system containing 60 to 90 vol.% of dimethyl carbonate (DMC) mixed with ethylene carbonate (EC) and 1.0 M lithium hexafluorophosphate (LiPF{sub 6}) provided the best cycling efficiency on a lithium metal anode, as well as a high specific conductivity around 10 mS cm{sup -1} at 20 C. (orig.)
Solid-state lithium batteries with a unique construction are reported in this paper. These batteries contain two kinds of lithium ion-conductive solid electrolytes, LiI-Li{sub 2}S-P{sub 2}S{sub 5} glass contacted with the anode material and Li{sub 3}PO{sub 4}-Li{sub 2}S-SiS{sub 2} glass or Li{sub 2}S-GeS{sub 2}-P{sub 2}S{sub 5} crystalline material contacted with the cathode. The former electrolyte was selected as that stable to electrochemical reduction, and the latter two to oxidation. This construction made it possible to use graphite as the anode and LiCoO{sub 2} as the cathode in the solid-state lithium battery. The energy density of the battery is 390 W h{center_dot}l{sup -1} and 160 W h{center_dot}kg{sup -1} per total volume and weight of the cathode and anode layers, respectively, which are comparable to those of commercialized ...
Lithium (Li) plating-stripping reaction properties at the lithium phosphorus oxynitride glass electrolyte (LiPON)/copper thin film (Cu) interface is improved by the insertion of nano-thickness platinum (Pt) layer at the interface. The LiPON films are formed on mirror-polished lithium-ion conductive solid electrolyte sheets, and current collector thin films of Li, Cu-Pt multi layer, and Cu are formed on the LiPON films. The plating-stripping reactions at the LiPON/current collector films interface are carried out by galvanostatic and potential sweep measurements. Galvanostatic measurements reveal that Pt layer insertion reduces the overvoltage of the reaction and improves its coulomb efficiency. Also, cyclic voltammetry measurement suggests formation of Li-Pt alloys at higher voltages than 0 V (vs. ...
Recently, the lithium ion-conductive solid electrolyte draws attention because there is a possibility of producing the maintenance-free battery which is characterized by having such advantages as high energy density and no possibility of electrolyte leak because of solid state structure. The invented lithium ion-conductive solid electrolyte is formed by sintering the granular electrolyte expressed in the following general formula: Li(1+(4-n)x)MxTi(2-x)(PO4)3 (M = mono- or di-valent cation, x = 0.1 - 0.5). Examples of the monovalent cation are Na[sup +], K[sup +], Rb[sup +], Cs[sup +], and Cu[sup +]. Examples of divalent cation are Mg[sup 2+], Fe[sup 2+], Be[sup 2+], Ca[sup 2+], Sr[sup 2+], Ba[sup 2+], Ra[sup 2+], Mn[sup 2+], Co[sup 2+], Cu[sup 2+], Ni[sup 2+], Zn[sup 2+], and Cd[sup 2+]. The electric conductivity of lithium ion is increased with the increase in the content of ...
Advanced lithium batteries presently under development operate either at the high temperatures associated with the LiCl-KCl molten salt (350-450/degree/C), or at ambient temperatures employing organic solvent based electrolytes. An intermediate temperature lithium battery is proposed as an alternative if it reduces corrosion problems present at high temperatures and improved kinetic performance with respect to ambient temperature cells. 17 refs.
Nano-sized particles of a lithium ion conductive solid electrolyte, LiTi{sub 2}(PO{sub 4}){sub 3}, were prepared by laser ablation. The obtained particles were ca. 10nm in diameter. X-ray powder diffraction and Raman spectroscopy showed that they were amorphous with local structure similar to the crystalline counterpart. They were crystallized by the heating at ca. 630{sup o}C. (author)
The new generation of performing rechargeable lithium-ion batteries (``rocking-chair``-type) are penalized by important self-output phenomena linked with the use of highly oxidizing positive electrodes. In order to limit this problem in LiMn{sub 2}O{sub 4}/C batteries, two different passivation techniques were used in order to limit the surface contact between the positive electrode and the electrolyte. Thanks to these treatments, a significant reduction of the percentage of irreversible capacity losses is effectively observed. (J.S.) 3 refs.
We report synthesis, characterization and ion transport in polyether-based ionic melt electrolytes consisting of Li salts of low-basicity anions covalently attached to polyether oligomers. Purity of the materials was investigated by HPLC analysis and electrospray ionization mass spectrometry. The highest ionic conductivity of 7.1 x 10{sup -6} S/cm at 30 deg. C was obtained for the sample consisting of a lithium salt of an arylfluorosulfonimide anion attached to a polyether oligomer with an ethyleneoxide (EO) to lithium ratio of 12. The conductivity order of various ionic melts having different polyether chain lengths suggests that at higher EO:Li ratios the conductivity of the electrolytes at room temperature is determined in part by the amount of crystallization of the polyether portion of the ionic melt.
We report synthesis, characterization and ion transport in polyether-based ionic melt electrolytes consisting of Li salts of low-basicity anions covalently attached to polyether oligomers. Purity of the materials was investigated by HPLC analysis and electrospray ionization mass spectrometry. The highest ionic conductivity of 7.1 x 10-6 S/cm at 30 deg. C was obtained for the sample consisting of a lithium salt of an arylfluorosulfonimide anion attached to a polyether oligomer with an ethyleneoxide (EO) to lithium ratio of 12. The conductivity order of various ionic melts having different polyether chain lengths suggests that at higher EO:Li ratios the conductivity of the electrolytes at room temperature is determined in part by the amount of crystallization of the polyether portion of the ionic melt.
Lithium phosphorous oxynitride(Lipon) thin films as a lithium ion conductive electrolyte were prepared by radio frequency reactive sputtering in N2 plasma. The properties of the amorphous Lipon solid electrolyte were investigated as a function of N2 pressure during reactive sputtering. The ionic conductivity and the electrochemical stability of Lipon thin films improved drastically as the N2 pressure decreased. The ionic conductivity closed to 10?6 S cm?1 and obtained a stability window of 1.0?5.0 V with an N2 pressure of 5 mTorr, where the number of nitrogen bonds between the phosphate groups were more than those formed at higher pressure. It was possible to fabricate the Li//LiCoO2 complete thin film battery using this Lipon solid electrolyte, which exhibited excellent discharge characte...
This paper presents a prototype of an entirely inorganic lithium ions battery cell. LiCoO{sub 2} thin film cathodes and Li{sub 4/3}Ti{sub 5/3}O{sub 4} thin film anodes have been deposited on Li{sub 3x}La{sub 2/3-x}TiO{sub 3} sintered solid electrolyte pellets and the performances of these battery cells have been tested. (J.S.) 5 refs.
The use of POE solid polymer electrolytes in negative lithium electrode batteries allows to reach energy density values close to 150 Wh/kg. The functioning of Li/POE/V{sub 2}O{sub 5} elements has been studied on small capacity elementary cells (about 26 mAh) and the results obtained were confirmed using coiled elements of 1.4 to 1.8 Ah capacity. This work has been carried out for Bollore Technologies (BT) and Electricite de France (EdF) companies. (J.S.)
The development of an electrolytic reduction technology for spent fuels in the form of oxide is of essence to introduce LWR SFs to a pyroprocessing. In this research, the technology was investigated to scale a reactor up, the electrochemical behaviors of FPs were studied to understand the process and a reaction rate data by using U{sub 3}O{sub 8} was obtained with a bench scale reactor. In a scale of 20 kgHM/batch reactor, U{sub 3}O{sub 8} and Simfuel were successfully reduced into metals. Electrochemical characteristics of LiBr, LiI and Li{sub 2}Se were measured in a bench scale reactor and an electrolytic reduction cell was modeled by a computational tool.
For the development of high ionic conductive solid electrolyte, LiTi2(PO4)3 (LTP), one of the promising inorganic solid electrolyte, was synthesized to investigate an effect of additional lithium salt on the ion conductivity. Lithium salt added LTP composite electrolyte sintered at 900{degree}C exhibited highest conductivity, which was two order magnitude higher than pure LTP. Effects of lithium salt addition are as follows. Conductivity of the composite electrolyte provided larger sintering temperature dependence than the pure LTP. From X-ray diffraction analysis, structures and compositions were resemble between two composite electrolytes. Byproducts except LTP provided rather low conductivity. It was suggested that melted constitution in the composite can affect the sintering improvement by the additional lithium salt at temperatures over 800 {degree}C. From ...
High lithium-ion (Li^+) conductive garnet-structured lanthanum lithium zirconate (LLZ) solid electrolyte is prepared by incorporation of appropriate amounts of silicon (Si) and aluminum (Al). The resultant pelletized LLZ obtains total Li^+ conductivity of 6.8x10^-^4Scm^-^1 at 298K. This improved conductivity is nearly identical with the bulk Li^+ conductivity of the LLZ reported earlier, suggesting that the grain boundary resistance is effectively reduced by the incorporation of Si and Al. Microanalyses by transmission electron microscopy coupled with energy-dispersive X-ray microanalysis and electron energy-loss spectroscopy revealed the presence of amorphous Li-Al-Si-O with nano crystalline LiAlSiO4 at grain boundaries. Fast lithium-ion transport around the amorphous Li-Al-Si-O/LiAlSiO4 ...
We are continuing to study the suitability of modified thermal-battery technology as a potential power source for geothermal borehole applications. Previous work focused on the LiSi/FeS{sub 2} couple over a temperature range of 350 C to 400 C with the LiBr-KBr-LiF eutectic, which melts at 324.5 C. In this work, the discharge processes that take place in LiSi/CsBr-LiBr-KBr eutectic/FeS{sub 2} thermal cells were studied at temperatures between 250 C and 400 C using pelletized cells with immobilized electrolyte. The CsBr-LiBr-KBr eutectic was selected because of its lower melting point (228.5 C). Incorporation of a quasi-reference electrode allowed the determination of the relative contribution of each electrode to the overall cell polarization. The results of single-cell tests and limited battery tests are presented, along with preliminary data for battery stacks tested in a simulated ...
Borohydrides such as LiBH{sub 4} have been studied as candidates for hydrogen storage because of their high hydrogen contents (18.4 wt% for LiBH{sub 4}). Limited success has been made in reducing the dehydrogenation temperature by adding reactants such as metals, metal oxides and metal halides. However, full rehydrogenation has not been realized because of multi-step decomposition processes and the stable intermediate species produced. It is suggested that adding second cation in LiBH{sub 4} may reduce the binding energy of B-H. The second cation may also provide the pathway for full rehydrogenation. In this work, several bimetallic borohydrides were synthesized using wet chemistry, high pressure reactive ball milling and sintering processes. The investigation found that the thermodynamic stability was reduced, but the full rehydrogenation is still a challenge. Although our experiments show the partial ...
The aim of this work was to compare the electrochemical behaviors and safety performance of graphite and the lithium titanate spinel Li1.33Ti1.67O4 with half-cells versus Li metal. Their electrochemical properties in 1 M LiPF6/EC + DEC (1:1 w/w) or 1 M LiPF6/PC + DEC (1:1 w/w) at room and elevated temperatures (30 and 60 deg C) have been studied using galvanostatic cycling. At 30 deg C graphite has higher reversible capacity than Li1.33Ti1.67O4 when using the LiPF6/EC + DEC as electrolyte. At 60 deg C graphite declines in cell capacity yet Li1.33Ti1.67O4 remains almost unchanged. In a propylene carbonate (PC) containing electrolyte, graphite electrode exfoliates and loses its mechanical integrity while Li1.33Ti1.67O4 electrode is very stable. An accelerating rate calorimeter ...
The aim of this work is the comparative study of the properties of the natural graphite/liquid organic electrolyte interface by impedance spectroscopy with respect to different lithium salts (LiX with X = ClO{sub 4}{sup -}, BF{sub 4}{sup -}, CF{sub 3}SO{sub 3}{sup -}, N(CF{sub 3}SO{sub 2}){sub 2}{sup -}, PF{sub 6}{sup -}). The evolution of the interface properties during the first electrochemical reduction suggests different mechanisms of formation of passivation films. A more stable, thin and homogenous film seems to develop when the LiN(CF{sub 3}SO{sub 2}){sub 2} or LiPF{sub 6} lithium salts are used. The chemical diffusion coefficient of lithium in graphite has been determined by impedance spectroscopy. (J.S.) 16 refs.
In this research, new thin freestanding films of poly(methyl methacrylate) (PMMA)/50% epoxidised natural rubber (ENR 50) were doped with lithium triflate, LiCF3SO3 salt was prepared by a solvent casting method. The incorporation of ENR 50 is found to increase the conductivity of PMMA/LiCF3SO3 by two orders of magnitude at room temperature. The highest conductivity achieved was 5.09x10-5Scm-1 at room temperature when 60% of LiCF3SO3 salt was introduced into the PMMA blend containing 10% ENR 50. The formation of excessive hydrogen bonds and interchain crosslinking limit the performance of the blend at higher concentrations of ENR 50. The ionic conduction mechanisms in PMMA/ENR 50/LiCF3SO3 electrolytes obey the Arrhenius rule in which the ion transport in these materials is thermally assisted...
Polyacrylonitrile (PAN)-based polymer electrolytes have obtained considerable attention due to their fascinating characteristics such as appreciable ionic conductivity at ambient temperatures and mechanical stability. This study is based on the system PAN-ethylene carbonate (EC)-propylene carbonate (PC)-lithium trifluoromethanesulfonate (LiCF3SO3). The composition 15 mol% PAN-42 mol% EC-36 mol% PC-7 mol% LiCF3SO3 has shown a maximum room temperature conductivity of 1.2 x 10(-3) stop S cm(-1) stop. Also, it was possible to make a thin, transparent film out of that composition. Cells of the form, Li/PAN-EC-PC-LiCF3SO3/polypyrrole (PPy)-alkylsulfonate (AS) were investigated using cyclic voltammetry and continuous charge-discharge tests. When cycled at low scan rates, a higher capacity could be obtained and well-defined peaks were present. The appearance of peaks elucidates the fact that redox reactions ...
A solid electrolyte for lithium batteries requires several properties: a good ionic conductivity of about 10{sup -3} S/cm at 298 deg. K, a high cationic transport number (greater than 0.5), a redox stability window higher than 4.5 V, a good stability of the interface with the lithium electrode, and a sufficient mechanical stability. The family of gelled or hybrid electrolytes seems to meet all these requirements. Thus, a systematic study of the gelling of an ethylene carbonate and lithium bistrifluorosulfonimide (LiTFSI) based electrolyte has been carried out. The polymers used for gel or pseudo-gel synthesis are POE, PMMA and PAN which represent 3 different cases of interaction with the electrolyte. All the properties mentioned above have been studied according to the nature of the polymer and to the concentration of lithium salt, showing the advantages and drawbacks of each ...
ABO{sub 3} perovskite-type oxides having vacancies in the A-sites of their structure are interesting candidates for solid electrolytes when their A-sites are occupied by Li{sup +} ions having a high mobility. This is the case with the [Li{sub 3x}La{sub 2/3-x}]TiO{sub 3} solid solution compound which has a 10{sup -3} S cm{sup -1} ionic conductivity at ambient temperature. Electrochemical intercalation in this material is possible thanks to the presence of Ti{sup 4+} but the small amount of vacancies (0.33 maximum) leads to a low intercalation rate. In order to solve this problem, the LiLaNb{sub 2}O{sub 7} material which has a greater amount of vacancies has been studied and the results relative to the electrochemical intercalation of lithium in this perovskite are presented. The thermodynamical and kinetics properties of the lithium intercalation reaction have been studied by intermittent galvano-static ...
the development of lithium metal batteries is hindered by the bad reversibility of the Li{sup +}/Li pair, due to dendrites formation which limits the amount of active matter and can generate short-circuits. The chemical and electrochemical phenomena which take place at the electrode/organic electrolyte interface lead to the formation of a complex passivation film which is of prime importance for the functioning of this type of batteries. The in-situ infrared reflection spectroscopy is well adapted to the chemical study of the passivation layer. Two different techniques were used: the substraction normalized interfacial transform infrared spectroscopy (SNIFTIRS) and the electro-chemically modulated infrared reflectance spectroscopy. These methods have shown that the passivation layer that develops on the surface of the lithium electrode in contact with organic solutions (propylene carbonate, ethylene carbonate and ...
Data on the reactions of thiocyanogen and thiocyanogen halides with unsaturated compounds are systematised. The kinetic and stereo- and regiochemical regularities of these reactions are analysed. The bibliography includes 81 references.
The interdependence of thermodynamic parameters, phase equilibria, and electrochemical measurements can be used as a powerful tool in the development of high specific energy cells. These principles were used in the analysis of electrochemical experiments performed on ternary lithium-transition metal-oxide (M = Mn, Fe, and Co) positive electrodes. The free energies of formation of LiMnO/sub 2/, Li/sub 5/FeO/sub 4/, LiFeO/sub 2/, and LiCoO/sub 2/ were found to be -178.21, -399.88, -154.18, and 131.62 kcal/mol at 400/sup 0/C. The electrochemical displacement reactions were found to be reversible in LiCl/KCl molten salt cells over a range of 0.0-3.0 Li equivalents per mol at current densities of 5-15 mA/cm/sup 2/. The equilibrium potential vs. Li was found to be a logarithmic function of the calculated oxygen partial pressure for any tie ...
The partial pressures of the components (ThCl_4, MCl and MThCl_5) in the saturated vapours of ThCl_4 solutions in molten LiCl, NaCl, KCl, RbCl and CsCl are determined as a function of temperature (900 to 1200 K) and ThCl_4 concentration (2 to 50 mol% ThCl_4) by dynamic method. Thorium tetrachloride volatility is shown to exceed that of alkali chloride from the melts containing less than 98 LiCl or NaCl, 83 KCl, 67 RbCl and 48 mol% CsCl. From experimental observations the decomposition potential of the electrolytes under investigation was estimated in temperature and concentration ranges of our measurements. Under otherwise equal conditions, it increases in the series of alkali chlorides from LiCl to CsCl. (author).
The paper describes a lithium battery researched on under the Moonlight Project which is a long life secondary battery with high energy density and high power density. Using as a base a Li4SiO4 system which exhibits stable and high Li[sup +] conductivity as solid electrolyte material, partial Si[sup 4+] is replaced with divalent ions such as B[sup 3+] and Al[sup 3+] or divalent ions such as Ni[sup 2+] and Co[sup 2+], by which Li[sup +] for electric charge compensation can be increased and conductivity is enhanced. As to a LiTi2P3O12 system, Ti[sup 4+] is replaced with Sc[sup 3+] and Y[sup 3+]. In both systems, by replaCing Si[sup 4+] or Ti[sup 4+] with trivalent metal ions and increasing mobile Li[sup +], those with ion conductivity exceeding that at 300[degree]C, 10[sup -3]Scm[sup -1], can be developed. TiS2 and NiPS3 are prepared as cathode material and ...
Three kinds of surface modifications were carried out on LiNi{sub 1/2}Mn{sub 3/2}O{sub 4} thin-films to improve the charge and discharge characteristics of LiNi{sub 1/2}Mn{sub 3/2}O{sub 4} positive electrodes. Among them, Zr(OBu){sub 4}/poly(methyl methacrylate) (PMMA)-treated LiNi{sub 1/2}Mn{sub 3/2}O{sub 4} thin-film electrodes showed charge and discharge efficiency of 80-84% in the first cycle, which was much higher than that for an untreated LiNi{sub 1/2}Mn{sub 3/2}O{sub 4} thin-film electrode (73%). The values of the charge and discharge efficiency were still higher than that for an untreated electrode after the 30th cycle. The charge and discharge curves gave two plateaus at around 4.72 and 4.76 V, which were very similar to those for the untreated electrode. Ac impedance spectroscopy revealed that the surface film resistance should not increase by Zr(OBu){sub 4}/PMMA treatment. XPS measurements ...
Lithium ion conducting glass ceramics composed of the crystalline conductive phase Li{sub 1.4}Al{sub 0.4}(Ge{sub 1-x}Ti{sub x}){sub 1.6}(PO{sub 4}){sub 3}(x=0-1.0) with the Nasicon-type structure have been synthesized and characterized by DTA, X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and complex impedance techniques. The experimental results indicated that the glass ceramics were mainly composed of solid solution Li(Ge{sub 1-x}Ti{sub x}){sub 2}(PO{sub 4}){sub 3} formed by LiGe{sub 2}(PO{sub 4}){sub 3} and LiTi{sub 2}(PO{sub 4}){sub 3} in the whole x range and showed conductivity over 10{sup -4} S/cm at room temperature. The maximum room temperature lithium ion conductivity of 6.21x10{sup -4} S/cm with an activation energy as low as 0.32 eV was obtained for the Li{sub 1.4}Al{sub 0.4}(Ge{sub 0.67}Ti{sub 0.33}){sub 1.6}(PO{sub 4}){sub 3} treated at ...
Powder mold type solid state battery was fabricated, and positive electrode compounding ratio and the battery characteristics were studied. The current density depended greatly on the TiS2 content of positive electrode material, and the current density showed maximum value of 800 {mu}A/cm{sup 2} at a TiS2 content of 40 wt%. This composition is expected to be the best to provide better charge-discharge characteristics. The rate capability of TiS2 is dominated by Li{sup +} ion in positive electrode. Further, the diffusion of lithium ion is greatly dominated by TiS2 in positive electrode, compounding ratio of solid state electrolyte and its particle size. Results of charge-discharge characteristics studied for various charge-discharge current densities revealed that the rate capability of TiS2 was more than 50% for a current density of less than 254 {mu}A/cm{sup 2}, and this battery system proved the possibility of high rate of charge-discharge. ...
The present volume on modeling of batteries and fuel cells discusses the significance of the effectiveness factor for flooded porous electrodes, active pore distribution spectroscopy for characterizing porous battery electrodes, the agglomerate model for porous electrodes, and dynamic-performance measurements of battery cells for electric vehicles and other applications. Attention is given to mathematical modeling of a primary zinc/air battery, mathematical modeling of Grace Li-TiS2 cells, modeling of electrocrystallization processes in battery systems, and rotating disk electrode studies in molten Li/K carbonate eutectic. Topics addressed include the variability of nickel oxide cathode dissolution in molten carbonate fuel cells, water transport properties of fuel cell ionomers, modeling water content effects in polymer electrolyte fuel cells, and computer algebra applied in electrochemistry and fuel cell modeling.
The possibilities to electrodeposit thick coatings composed of nanoparticles of Sb and Sb{sub 2}O{sub 3} for use as high-capacity anode materials in Li-ion batteries have been investigated. It is demonstrated that the stability of the coatings depends on their Sb{sub 2}O{sub 3} concentrations as well as microstructure. The electrodeposition reactions in electrolytes with different pH and buffer capacities were studied using chronopotentiometry and electrochemical quartz crystal microbalance measurements. The obtained deposits, which were characterised with XRD and SEM, were also tested as anode materials in Li-ion batteries. The influence of the pH and buffer capacity of the deposition solution on the composition and particle size of the deposits were studied and it is concluded that depositions from a poorly buffered solution of antimony-tartrate give rise to good anode materials due to the inclusion of precipitated Sb{sub ...
Objective of the project is characterization of electrode reactions in molten salt by using metal oxides and silica-based electrode. The scope of project are characterization of metal oxide properties in molten salt and miniaturization of 3-electrode electrochemical test cell. Electrochemical micro-cell for actinide-LiCl-KCl molten salt was newly designed. Electroless and electrochemical deposition technique was applied to Mo coating on quartz tube. From the design of electrode and 3-electrode electrochemical cell suitable for the tests in molten salt electrolyte, so it is anticipated to get the information on the electrochemical behavior of metallic electrode in molten salt and to secure the information on oxidation/reduction behavior of actinide
Alkyl halides react rapidly with purines and pyrimidines in the presence of fluoride ion. Alkylation of thymidine leads to novel dimeric nucleoside derivatives bridged through N3. Alkylation of thymidine...Full Text Available
Spent oxide fuels are reduced in a molten salt of CaCl[sub 2]-CaF[sub 2] to convert them into metals, then melted in an Fe-U bath disposed in an electrolytic refining vessel and brought into contact with molten Mg, to extract transuranium elements and rare earth elements contained in the Fe-U bath as metals in the molten Mg. Then molten Mg is removed and the residue is brought into contact with KCl-LiCl molten salt and electrolyzed using the Fe-U as an anode. Then, uranium is recovered by deposition on an iron cathode disposed in chloride electrolytes of the electrolytic refining vessel. Uranium and transuranium elements can be thus separated and, for example, depleted uranium for use in blanket fuels can be recovered easily. This can greatly reduce the temporary storage amount of depleted uranium, to eliminate requirement for a large-scaled facility used exclusively for storing uranium and long time ...
Spent oxide fuels are reduced in a molten salt of CaCl_2-CaF_2 to convert them into metals, then melted in an Fe-U bath disposed in an electrolytic refining vessel and brought into contact with molten Mg, to extract transuranium elements and rare earth elements contained in the Fe-U bath as metals in the molten Mg. Then molten Mg is removed and the residue is brought into contact with KCl-LiCl molten salt and electrolyzed using the Fe-U as an anode. Then, uranium is recovered by deposition on an iron cathode disposed in chloride electrolytes of the electrolytic refining vessel. Uranium and transuranium elements can be thus separated and, for example, depleted uranium for use in blanket fuels can be recovered easily. This can greatly reduce the temporary storage amount of depleted uranium, to eliminate requirement for a large-scaled facility used exclusively for storing uranium and long time management ...
The partial pressures of the components (ThCl/sub 4/, MCl and MThCl/sub 5/) in the saturated vapours of ThCl/sub 4/ solutions in molten LiCl, NaCl, KCl, RbCl and CsCl are determined as a function of temperature (900 to 1200 K) and ThCl/sub 4/ concentration (2 to 50 mol% ThCl/sub 4/) by dynamic method. Thorium tetrachloride volatility is shown to exceed that of alkali chloride from the melts containing less than 98 LiCl or NaCl, 83 KCl, 67 RbCl and 48 mol% CsCl. From experimental observations the decomposition potential of the electrolytes under investigation was estimated in temperature and concentration ranges of our measurements. Under otherwise equal conditions, it increases in the series of alkali chlorides from LiCl to CsCl.
A family of mixed LiCo{sub y}Ni{sub (1-y)}VO{sub 4} (y=0.2, 0.5 and 0.8) compounds of potential use as high voltage cathode materials in lithium batteries, has been synthesized and characterized. The X-ray diffraction analysis showed that these compounds adopt an inverse spinel structure where in average 85% of the Ni{sup 2+} and Co{sup 2+} ions occupy octahedral sites and the other 15% occupy tetrahedral sites with the V{sup 5+} ions, although this occupation share is somewhat influenced by the preparation temperature. The annealing temperature plays also a key role in determining the particle size, as demonstrated by scanning electron microscope analysis. Cycling voltammetry tests showed that the lithium insertion-deinsertion process in the LiCo{sub y}Ni{sub (1-y)}VO{sub 4} electrode materials occurs reversibly around 4.3-4.4 V vs. Li, as also confirmed by cycling tests. The cycling capacity is somewhat modest; however, ...
A miniature, high-voltage, thermally activated battery has been developed. This battery weighs 41 grams, occupies a volume of 16.4 cu cm, and contains two separate 500-v channels, each designed to charge a 5.25 microfarad capacitor within 300 milli-seconds and remain operational under a 640-kohm load for a minimum of 28 seconds over the temperature range from +16 to +71 C. The electrochemical system utilizes a calcium anode, LiCl-KCl molten salt electrolyte, a CaCrO4-K2CrO4 mixture as the depolarizer or active cathode material, and an iron cathode. The depolarizer and electrolyte, along with a silica binder, are formed into homogeneous pellets, and these pellets are stacked alternately with calcium-iron bimetal disks in beryllium oxide tubes to form cell stacks. The cells are activated by an iron-potassium perchlorate pyrotechnic heat source external to the BeO tubes.
Anionic complexes of transition metals were stabilized in aqueous solutions containing high concentrations of various short-chain quaternary ammonium salts. Compounds with longer paraffin chains were effective in much less concentrated solution. Complex ions were detected spectrophotometrically. FeCl/sub 4//sup -/, which is usually formed in concentrated HCl, was the predominant Fe(III) complex in 30 m choline chloride containing only 0.12 M HCl. A yellow transitory Tc(VII) chloro-addition intermediate, formed in the reduction of TcO/sub 4//sup -/ by concentrated HCl, was stabilized when the solution also contained 25 m choline chloride. Its spectrum, as well as the isolation of an already known Tc(VII) bipyridyl complex, is reported. Concentrated organic electrolytes also stabilized Tc(V) oxide halides against disproportionation and Tc(IV) hexahalides against hydrolysis. Halochromates of Cr(VI) were formed and stabilized in dilute acid ...
Crystalline {alpha}-Fe{sub 2}O{sub 3} powder was prepared by the mechanical milling of crystalline {alpha}-FeOOH at room temperature in air. This result means that crystalline {alpha}-FeOOH is dehydrated by mechanical milling at room temperature. The obtained {alpha}-Fe{sub 2}O{sub 3} powder worked as a rechargeable electrode material in lithium ion conductive organic electrolytes. The electrodes exhibited high discharge capacities of over 1000mAhg{sup -1} corresponding to 6 Li per {alpha}-Fe{sub 2}O{sub 3} at potentials ranging from the open circuit potential to 0.5V (versus Li{sup +}/Li) in the first discharging (lithium insertion) process. This suggests that the valence deviation from Fe{sup 3+} in {alpha}-Fe{sub 2}O{sub 3} to Fe{sup 0} may be caused by electrochemical reduction. In contrast, after the first discharge, the electrodes exhibited high charge capacities of more than 700mAhg{sup -1} ...
A small-sized inexpensive carbon dioxide gassensor was prepared using LiTi2 (PO4)3 +0.2Li3PO4 as lithium-ion conductive, solid electrolyte and its detectability and the effects of co-existing gases were examined. The above compound was obtained by the method where a powdery mixture of Li2CO3, TiO2, (NH4)H2PO4 and Li3PO3 was molded in the presence of a sintering assistant, subjected to hydrostatic press, and sintered. Measurements were made on the relation between CO2 concentration and the electromotive force of the CO2 sensor made of the compound and the influence of concentration of coexisting NO2, SO2 or CH4 on the electromotive force. The results are summarized as follows. A linear relation exists between the electromotive force and the CO2 concentration in the range from 80ppm to 1% to show a good agreement between theoretical and experimental results. Coexistence of NO2 the ...
A electrochemical cell is described comprising an anode, a cathode, a solid polymer electrolyte; and a redox shuttle additive to protect the cell against overcharging and a redox shuttle additive to protect the cell against overcharging selected from the group consisting of: (a) a substituted anisole having the general formula shown in a figure (in an uncharged state): where R{sub 1} is selected from the group consisting of H, 0CH{sub 3}, OCH{sub 2}CH{sub 3}, and OCH{sub 2}phenyl, and R{sub 2} is selected from the group consisting of OCH{sub 3}, OCH{sub 2}CH{sub 3}, OCH{sub 2} phenyl, and O{sup {minus}}Li{sup +}; and (b) a di-anisole compound having the general formula shown in a second figure (in an uncharged state): where R is selected from the group consisting of -OCH{sup 3} and -CH{sub 3}, m is either 1 or 0, n is either 1 or 0, and X is selected from the group consisting of -OCH{sub 3} (methoxy) or its lithium salt -O{sup ...
Analysis of published NMR relaxation data of /sup 6/Li and /sup 7/Li in Li/sub 3/N leads to a unique model fo Li/sup +/ hopping along the c-axis. It is one in which an ion goes directly from one Li(1) plane to another Li(1) plane by passing through the intermediate Li(2) plane.
{gamma}-Butyrolactone-based electrolytes have been used as the operating electrolytes for aluminum electrolytic capacitors. The chemical stability of these electrolytes at elevated temperatures has been examined by monitoring the decrease in their electrolytic conductivities. The deteriorated electrolytes were analyzed by gas and liquid chromatography and the conductivity decrease was directly correlated with the loss of acid components. In quaternary ammonium hydrogen maleate/{gamma}-butyrolactone electrolytes, the maleate anion decomposed by decarboxylation resulting in a complex polymer containing polyester and polyacrylate structures. Quaternary ammonium benzoate/{gamma}-butyrolactone electrolytes decomposed by SN2 reactions giving alkyl benzoates and trialkylamines. The deterioration of the carboxylate ...
Commercial introduction of new polymer materials for use as the electrolyte in solid tantalum and solid aluminum electrolytic capacitors is underway. ...
During past two decades, the importance of rechargeable lithium cells has been emphasized and a large variety of materials has been discovered and evaluated for use as reversible cathodes and electrolytes. Materials that undergo intercalation or topochemical reactions with lithium have been investigated as candidates for cathodes in nonaqueous secondary lithium cells (1). Recent interest in researching cathode active materials has mainly focussed on crystalline transition metal chalcogenides. On the other hand, electrochemical behaviors of several amorphous materials have been reported, for example MoS/sub 2/,MoS/sub 3/,V/sub 2/S/sub 5/ (2) and LiV/sub 3/O/sub 8/ (3). However, no successful cycling behavior has been obtained except for MoS/sub 2/ in the amorphous state. This paper reports electrochemical data on rechargeable vanadate glasses in the system V/sub 2/O/sub 5/-P/sub 2/O/sub 5/.
This study presents three-dimensional simulation results of multispecies and multi-reaction electrorefining for spent nuclear waste treatment. Fluid-dynamic behavior of electrorefining is analyzed by commercial computational fluid-dynamics code. The results of local fluid dynamics are coupled with one-dimensional electrochemical reaction analysis code in order to predict local current density distribution. The new approach shows current distribution patterns over the cathode surface in LiCl-KCl molten-salt electrolyte. The current density distribution patterns are analyzed for various electrode rotational speeds and diverse applied currents and the results show a good agreement with general principle of mass transfer observations. Spatially periodic and vertically striped pattern of current density is predicted at the cathode side due to mass transfer depression at separation points. These slow mass transfer regions are vulnerable to be ...
Iron oxide thin films were prepared by spray pyrolysis technique onto glass substrates from iron chloride solution. They were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and (UV-vis) spectroscopy. The films deposited at T _s #<=# 450 deg. C were amorphous; while those produced at T _s_u_b = 500 deg. C were polycrystalline #alpha#-Fe_2O_3 with a preferential orientation along the (1 0 4) direction. By observing scanning electron microscopy (SEM), it was seen that iron oxide films were relatively homogeneous uniform and had a good adherence to the glass substrates. The grain size was found (by RX) between 19 and 25 nm. The composition of these films was examined by X-ray photoelectron spectroscopy and electron probe microanalysis (EPMA). These films exhibited also a transmittance value about 80% in the visible and infrared range. The cyclic voltammetry study showed that the films of Fe_2O_3 deposited on ITO ...
The Energy crisis happens to be one of the greatest challenges we are facing today. In this view, much effort has been made in developing new, cost effective, environmentally friendly energy conversion and storage devices. The performance of such devices is fundamentally related to material properties. Hence, innovative materials engineering is important in solving the energy crisis problem. One such innovation in materials engineering is porous materials for energy storage. Porous electrode materials for lithium-ion batteries (LIBs) offer a high degree of electrolyte-electrode wettability, thus enhancing the electrochemical activity within the material. Among the porous materials, mesoporous materials draw special attention, owing to shorter diffusion lengths for Li+ and electronic movement. Nanostructured mesoporous materials also offer better packing density compared to their nanostructured counterparts such as nanopowders, nanowires, ...
A new series of lithium ionic liquids were prepared by introducing of two electron-withdrawing trifluoroacetyl groups in borate salts containing two methoxy-oligo(ethylene oxide) groups in the structures. Successive substitution reactions of oligo-ethylene glycol monomethyl ether and trifluroacetic acid from LiBH_4 yielded the lithium salts, which were clear and colorless liquids at room temperature. The fundamental physicochemical properties, such as density, thermal property, viscosity, ionic conductivity, self-diffusion coefficients, and electrochemical stability, were measured. The lithium ionic liquids had self-dissociation ability and conducted ions even in the absence of organic solvents. New polymer electrolytes, named 'ion gels', were prepared by radical cross-linking reactions of a poly(ethylene oxide-co-propylene oxide)tri-acrylate macromonomer in the presence the lithium ionic liquid. An increase in the glass transition temperatures ...
The electrometallurgical treatment process described in this paper builds on our experience in treating spent fuel from the Experimental Breeder Reactor (EBR-II). The work is also to some degree, a spin-off from applying electrometallurgical treatment to spent fuel from the Hanford single pass reactors (SPRs) and fuel and flush salt from the Molten Salt Reactor Experiment (MSRE) in treating EBR-II fuel, we recover the actinides from a uranium-zirconium fuel by electrorefining the uranium out of the chopped fuel. With SPR fuel, uranium is electrorefined out of the aluminum cladding. Both of these processes are conducted in a LiCl-KCl molten-salt electrolyte. In the case of the MSRE, which used a fluoride salt-based fuel, uranium in this salt is recovered through a series of electrochemical reductions. Recovering high-purity uranium from an aluminum-matrix fuel is more challenging than treating SPR or EBR-II fuel because the aluminum- matrix fuel ...
Since ionic liquids (ILs) possess several attractive properties, including chemical and thermal stability, nonflammability, high ionic conductivity, and negligible vapor pressure, a new electrolyte system based on ILs has been proposed for chip type aluminum electrolytic capacitors. Four ILs based on imidazolium/pyrrolidinium cations and maleate/phthalate anions have been synthesized and their thermal stabilities have been examined. The 25wt.% solutions of the four ILs in gamma-butyrolactone (GBL) solvent were prepared as electrolytes of chip type aluminum electrolytic capacitors. The conductivity, sparking voltage and thermal stability of these electrolytes have been systematically investigated. The results revealed that the four IL-based electrolytes exhibited high conductivity. Furthermore, the conductivity of maleate anion-based ...
The passivity and breakdown of passivity of 1018 carbon steel in propylene carbonate (PC) and 1,2-dimethoxyethane (DME) mixtures with 0.5 molar lithium hexafluoroarsenate supporting electrolyte were examined via several electrochemical and surface analytical methods. The PC-DME/0.5 M LiAsF{sub 6} mixtures ranged from 10 to 90 mol % PC. The results from the PC/DME mixtures were compared to passivating mechanisms found in pure PC and DME solutions. In PC-rich mixtures, the breakdown of passivity occurred near the oxidation potentials of either organic solvent. Premature breakdown of the carbon steel in PC-DME mixtures occurred at sulfide inclusions as was observed earlier in PC/0.5 M LiAsF{sub 6} solutions although passive films attempted to form at these inclusion sites in mixtures containing at least 10 mol % DME. As the DME content increased in the PC-DME mixtures, the passive films formed on bare steel surfaces possessed ...
MnO powder materials are investigated as anode active materials for Li-ion batteries. Lithium is stored reversibly in MnO through conversion reaction and interfacial charging mechanism, according to the results of ex situ XRD, TEM and galvanostatic intermittent titration technique. A layer of the solid electrolyte interphase with a thickness of 20-60 nm is covered on MnO particles after full insertion. MnO powder materials show reversible capacity of 650 mAh g{sup -1} with average charging voltage of 1.2 V. It can deliver 400 mAh g{sup -1} at a rate of 400 mA g{sup -1}. The cyclic performance of MnO is improved significantly after decreasing particle size and coating with a layer of carbon. Among observed transition metal oxides, MnO shows relatively lower voltage hysteresis (<0.7 V) between the discharging and the charging curves at 0.05 C. In addition to its environmental benign feature and high density (5.43 g cm{sup -3}), MnO seems a ...
Many investigations of anode materials for lithium-ion secondary batteries have been carried out in order to obtain batteries of higher capacity and energy density. Recently, SnO-based glasses, which were prepared by the usual melt quenching technique, have been proposed as a new anode for lithium-ion secondary batteries by Idota et al. It has been reported that the capacity per unit weight was higher than 600 mAh g{sup {minus}1} and the capacity per unit volume was higher than 2,200 mAh cm{sup {minus}3}, values which are almost double those for carbon materials used as anodes of commercial lithium-ion batteries at present. Thus SnO-based glasses have attracted much interest as high-capacity anode materials for lithium-ion secondary batteries. Amorphous materials in the system SnO-B{sub 2}O{sub 3}-P{sub 2}O{sub 5}, with or without the addition of Li{sub 2}O, were synthesized by mechanical milling treatment of starting oxides in a dry N{sub 2} atmosphere at room ...
The formation of #alpha#'-sialon using Li as a modifying cation was investigated. The effects of the Li content, firing temperatures and Si/Al ratios on #alpha#'- yield were studied. The results indicated that at lower sintering temperatures the stabilisation of #alpha#'-sialons was obtained but the high weight losses of Li at higher temperatures limited the stabilisation. Increased ''Al'' content in the compositions resulted in an increase in the stability of Li-#alpha#'-sialon at higher temperatures, by the formation of a liquid phase which retains Li in the system. (orig.).
The membrane transport of the two stable lithium isotopes, {sup 6}Li and {sup 7}Li, by erythrocytes has been studied using a dual channel atomic absorption spectroscopic technique. {sup 6}Li appears to be taken up preferentially to {sup 7}Li, in the ratio of 10 to 40%, depending on the concentration of total lithium and on the lithium isotopic ratio in the external medium.
aluminum electrolytic capacitors with Freon, trichloroethylene, carbon tetrachloride, or other chlorine or fluorine solvents. Aluminum electrolytic ...
This article describes in situ heating and observation of a LiNH{sub 2}-2LiH mixture in an environmental scanning electron microscope (ESEM). The LiNH{sub 2}-2LiH mixture showed extensive morphological changes with heating and attendant hydrogen desorption. Static images and real-time movies were obtained during the dehydrogenation process. H{sub 2} evolution commences at {proportional_to}150 C (LiNH{sub 2} + 2LiH {yields} Li{sub 2}NH + H{sub 2} + LiH), and continues until {proportional_to}410 C. Dramatic morphological changes are observed at 220 and 410 C (Li{sub 2}NH + LiH {yields} Li{sub 3}N + H{sub 2}). The material converts to a microcrystalline phase at higher temperatures (>500 C). The observed H{sub 2} desorption and morphological changes occur ...
A new preparation method for LiNiVO{sub 4} has been developed. LiNiVO{sub 4} can be readily obtained from the solid state reaction of LiNiO{sub 2} and V{sub 2}O{sub 3} or V{sub 2}O{sub 5} at 700 C for 2 h in air. The quarternary Li-Ni-V-O reaction is strongly dependent on vanadium starting materials, reaction environment atmosphere, reactant stoichiometry and synthesis temperature. Individual particles of LiNiVO{sub 4} powders are well-formed crystallites shown clearly by scanning electron microscopy results to be in the shape of an octahedron. Powder X-ray diffraction studies of this crystalline material indicate that LiNiVO{sub 4} has an inverse spinel structure different from that of known cathode materials such as LT-LiCoO{sub 2} and LiMn{sub 2}O{sub 4}. The Li/LiNiVO{sub 4} cell can be charged ...
This paper presents ionic conductivity results obtained with polymer electrolytes and also with propylene carbonate solutions. The domain of electrochemical activity of this salt has been determined using cycle volt-amperometry in propylene carbonate. Preliminary experiments on the stability of the polymer electrolyte with respect to the lithium electrode have been carried out for a possible subsequent use in lithium batteries. (J.S.) 4 refs.
Nanoparticles of silver halides have been prepared by mixing silver halide powder with a single liquid phase consisting of an ionic liquid, isooctane, n-decanol and water. Much higher nanoparticle concentrations may be formed with ionic liquids using this new simple method than are found with conventionally applied surfactants. This method also emphasizes the applicability of ionic liquids as versatile components in microemulsions and as solvents for the synthesis of nanomaterials. The effect on the nanoparticles of changing the composition of the liquid mixtures and the nature of the ionic liquid is analysed. High nanoparticle concentrations were only found with chloride based ionic liquids, indicating the importance of the ionic liquid anion in the mechanism of the reaction.
Ozone plays a critical role in both the chemistry and radiation balance of the troposphere. Understanding the factors controlling tropospheric ozone levels is critical to our understanding of a variety of issues in global chemistry and climate change. Chlorine atoms have the potential to contribute significantly to the ozone balance in the free troposphere. They can react directly with ozone or alternately, with organics and may actually lead to the formation of ozone in the presence of sufficient NO. Reactions of alkali halides in sea salt particles are a potential source of atomic chlorine, hence reactions of these alkali halides, especially those producing precursors to atomic chlorine, are of great interest. Finally, the mechanisms, intermediates and products of the Cl-biogenic reactions are unknown; these could serve as unique markers of chlorine atom chemistry in the troposphere, and hence are important to define.
The effects of a maltodextrin (dextrose equivalent 12)-electrolyte solution and a maltodextrin-electrolyte solution with added nutrients on net water and electrolyte transport in the secreting rat intestine was compared with the citrate-World Health Organization oral rehydration solution to determine the need for a clinical trial to evaluate the efficacy of these maltodextrin solutions in acute diarrhoea treatment. Cholera toxin consistently produced net water secretion (-36.5 +/- 9.9 mean +/- SEM microliter/min/g dry weight of intestine). All three solutions reversed the cholera toxin-induced net intestinal water secretion to net absorption. Significantly greater net water absorption occurred from the maltodextrin-electrolyte solution compared to the World Health Organization solution (P < 0.05) but not when compared to the maltodextrin-electrolyte-nutrient solution. Net sodium, ...
A solid electrolytic capacitor having a solid electrolyte comprising manganese dioxide dispersed in an aromatic polyamide capable of further cure to form polyimide linkages, the solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects.
Shell model calculations are reported for the properties of normal parity states of /sup 7/Li, /sup 8/Li and /sup 9/Li. Fits to new experimental data are displayed, some ambiguities resolved, and structure information provided for help in further investigations.
Separation of lithium isotope by NTOE compound was carried out with 0.01M HCl solution. The ion exchange capacity of NTOE was 0.8 meq/g. The separation factor, #alpha#=("7Li/"6Li)_s_o_l_i_d/("7Li/"6Li)_l_i_q_u_i_d was 1.0242 by the elution chromatography. The lighter isotope, "6Li was concentrated in the liquid phase, while the heavior isotope, "7Li was enriched in the solid phase. (author).
Isobaric molar heat capacities of powder and microsphere form of Li2TiO3 (s) and powder form of LiAlO2 (s) and Li2ZrO3 (s) were measured using a heat flux type differential scanning calorimeter in the temperature range 320 - 870 K. Specific heat capacities of LiAlO2 (s) was found to be much larger compared to those of Li2TiO3 (s) and Li2ZrO3 (s). (author)
A high-precision Li isotope analysis was developed for determining the Li"+ ion emitted from lithium phosphate as an ion source material by a Re double-filament ionization method in the thermal ionization mass spectrometry. In this method, Li isotopic fractionation is distinctly less sensitive to the filament temperature than those in the previous methods, and stable and high ion beam intensity of more than 8 x 10"-"1"1 A for "7Li is obtained. These advantages in determining the "7Li/"6Li ratio result in the analytical reproducibility of 0.26 per mille (1#sigma#). Furthermore, the sample preparation is simple and the low temperature (850degC) required by this method ensures the analysis of the isotopic composition of small amounts of Li with less influence of Li contamination to the sample, compared with the previous ...
Halide complexes of astatine cations At"+ and AtO"+ were prepared and their rate of migration was measured. The complexes are of the type AtX_2"- and AtOX_2"- (X = Cl"-, Br"-, I"-). The bromo complexes, AtBr_2"- and AtOBr_2"-, have a higher stability than the chloro complexes. The hydrolysis in weakly alkaline solution of AtX_2"- resulted At"-, and that of AtOX_2"- AtO_2"-. (author).
Unsymmetric diaryl alkynes were synthesized from the palladium-catalyzed decarboxylative coupling of aryl halides and propiolic acid using a continuous flow reaction system. This flow chemistry system continuously gave the desired products in moderate to good yields, and produced less byproduct than was formed in the batch reaction.
It is well known that a protective film is formed on the graphite negative electrode in ethylene carbonate (EC) electrolyte solution. This film is lithium-ion conductive and protects the decomposition of the electrolyte solution. In the present paper, the electrode/electrolyte interfaces in lithium-ion rechargeable batteries were characterized by three-dimensional complex impedance plots, whose axes are real, imaginary parts and time. The film resistance R {sub sei} and charge transfer resistance R {sub ct} were determined for negative electrodes in EC/ethyl methyl carbonate (EMC) electrolyte solution, and the formation mechanisms of the interfacial film were discussed. Furthermore, the contributions of vinylene carbonate and ethylene sulfite, which are added into the electrolyte solution for the film formation, were investigated.
It is well known that a protective film is formed on the graphite negative electrode in ethylene carbonate (EC) electrolyte solution. This film is lithium-ion conductive and protects the decomposition of the electrolyte solution. In the present paper, the electrode/electrolyte interfaces in lithium-ion rechargeable batteries were characterized by three-dimensional complex impedance plots, whose axes are real, imaginary parts and time. The film resistance R _s_e_i and charge transfer resistance R _c_t were determined for negative electrodes in EC/ethyl methyl carbonate (EMC) electrolyte solution, and the formation mechanisms of the interfacial film were discussed. Furthermore, the contributions of vinylene carbonate and ethylene sulfite, which are added into the electrolyte solution for the film formation, were investigated.
In 1998, research began at Idaho National Engineering and Environmental Laboratory to investigate the application of {sup 6}Li and {sup 7}Li isotopes to the measurement of neutron and gamma radiation. Various size pairs of {sup 6}Li and {sup 7}Li based detectors were exposed to mixed neutron and gamma radiation. Experiments demonstrated that these detectors could be used to measure low level neutron radiation in the presence of high level gamma radiation. (author)
In 1998, research began at Idaho National Engineering and Environmental Laboratory to investigate the application of "6Li and "7Li isotopes to the measurement of neutron and gamma radiation. Various size pairs of "6Li and "7Li based detectors were exposed to mixed neutron and gamma radiation. Experiments demonstrated that these detectors could be used to measure low level neutron radiation in the presence of high level gamma radiation. (author)
We have determined the nuclear charge radius of 11Li by high-precision laser spectroscopy. The experiment was performed at the TRIUMF-ISAC facility where the 7Li-11Li isotope shift was measured in the 2s to 3s electronic transition using Doppler-free two-photon spectroscopy with a relative accuracy better than 10 5. The accuracy reached in previous experiments on the other lithium isotopes was improved. Most of the isotope shifts measured in the experiment are due to difference in the mass of the nuclei but small contributions are produced by the change in proton distribution, QED and relativistic effects have to be taken into account as well. By comparing the experimental results with sophisticated atomic calculations of the mass dependent effect the nuclear charge radii of the lithium isotopes are found to decrease monotonically from 6Li to 9Li while the nuclear charge radius of ...
Triethanolamine (TEA) has been evaluated as an additive to a commercial electrolyte to enhance the properties of aluminum electrolytic capacitors. The results showed 1-3wt.% TEA additive can prevent the pH and conductivity of the electrolytes from decreasing for 5000h at 60{sup o}C. The anodic restoration ability of an anode aluminum film in the electrolyte with TEA additive showed more efficient than the electrolyte without TEA additive. Low temperature electric characteristics of capacitors showed that TEA additive can prevent the electrolyte inside capacitors from freezing and losing electric characteristics even at -40{sup o}C. Load life test of capacitors impregnated with electrolytes with or without TEA additive showed remarkable differences. The TEA additive promoted 105{sup o}C load life time from 3019h up to 5624h and form 2144h up ...
Artifacts in two-dimensional electrophoresis (2-DE) caused by the presence of salts in isoelectric focusing (IEF) have been previously described as a result of increasing conductivity and inducing electroosmosis....Full Text Available
Angular distributions of "6Li+"6Li elastic scattering were measured for E_l_a_b=5-40 MeV. An optical model analysis of these data together with older data of "7Li+"7Li elastic scattering taken at E_l_a_b = 8-17 MeV was performed with the aim to search for a ''global'' OM potential which describes elastic scattering in both Li-Li systems in a broad energy range. Both surface and volume absorbing potentials can be found which fulfill this requirement if a linear energy dependence is assumed of the depths of the real as well as the imaginary potential. These depths, if fitted to individual angular distributions, are found to vary in a correlated manner with the beam energy. This is taken as indication of strong coupling between elastic, inelastic, and reaction channels. This is corroborated by the existence of resonances in reaction channels at these energies where the potential depths ...
Aluminum electrolytic capacitors are presently not allowed on NASA missions because they outgas water and organic vapors, as well as H2. As a consequence, much larger and heavier packages of tantalum capacitors are used. A hermetically sealed aluminum capacitor has been developed under NASA-MSFC SBIR contracts. This capacitor contains a nongassing electrolyte that was developed for this application so internal pressure would remain low. Capacitors rated at 250 to 540 V have been operated under full load for thousands of hours at 85 and 105 C with good electrical performance and low internal pressure. Electrolyte chemistry and seal engineering concepts will be discussed.
Aluminum electrolytic capacitors, with 1043 failures, are a good example. Also, categorization by size and voltage reveals such frequencies of occurrence as ...
Aluminum electrolytic capacitors have a long history of reliable operation in unattended field sites. However, their use in the expected space applications ...
A zinc-air battery in a case including a zinc particle bed supported adjacent the current feeder and diaphragm on a porous support plate which holds the particles but passes electrolyte solution. Electrolyte is recycled through a conduit between the support plate and top of the bed by convective forces created by a density of differential caused by a higher concentration of high density discharge products in the interstices of the bed than in the electrolyte recycle conduit.
A zinc-air battery in a case is described including a zinc particle bed supported adjacent the current feeder and diaphragm on a porous support plate which holds the particles but passes electrolyte solution. Electrolyte is recycled through a conduit between the support plate and top of the bed by convective forces created by a density of differential caused by a higher concentration of high density discharge products in the interstices of the bed than in the electrolyte recycle conduit. 7 figures.
A poly(ether urethane) (PEUR)/poly(ethylene oxide) (PEO)/SiO2 based nanocomposite polymer is prepared and employed in the construction of high efficiency all-solid-state dye-sensitized nanocrystalline solar cells. The introduction of low-molecular weight PEUR prepolymer into PEO electrolyte has greatly enhance the electrolyte performance by both improving the interfacial contact properties of electrode/electrolyte and decreasing the PEO crystallization, which were confirmed by XRD and SEM characteristics. The effects of polymer composition, nano SiO2 content on the ionic conductivity and I3- ions diffusion of polymer-blend electrolyte are investigated. The optimized composition yields an energy conversion efficiency of 3.71% under irradiation by white light (100 mW cm-2).
Amorphous materials in the system xLi{sub 2}S{center_dot}(100-x)SiS{sub 2}, where x ranged from 50 to 70 mol %, and (100-y) (0.6Li{sub 2}S{center_dot}0.4SiS{sub 2}){center_dot}yLi{sub 4}SiO{sub 4}, where y ranged from 0 to 10 mol %, were synthesized by mechanical milling of crystalline starting materials, Li{sub 2}S, SiS{sub 2} and Li{sub 4}SiO{sub 4}. At the compositions with large amounts of Li{sup +} ions, a part of crystalline Li{sub 2}S used as a starting material remained in the milled powder samples. It was found that the milled powder samples in both systems obtained by mechanical milling exhibited high conductivities in the order of 10{sup -4}S{center_dot}cm{sup -1} at room temperature in spite of the presence of small amounts of Li{sub 2}S crystals. The conductivity values of the pelletized samples of ...
The e.s.r. spectra of (AsPh/sub 4/)(TcNCl/sub 4/), Cs/sub 2/(TcNCl/sub 5/), (AsPh/sub 4/)(TcNBr/sub 4/), and Cs/sub 2/(TcNBr/sub 5/) have been studied in non-aqueous and concentrated aqueous acid solutions. None of the spectra shows evidence for the co-ordination of a fifth halide ligand in the trans position, even under circumstances such as a 2 000-fold excess of halide ion, which would be expected to favour the formation of the pentahalogenonitridotechnetate ion. The predominant species in solution is the tetrahalogenonitridotechnetate ion, where the trans position may be vacant or occupied by a solvent molecule in the case of the non-aqeuous solvents and by a water molecule in the case of HCl and HBr solutions. This conclusion may be contrasted with the behaviour of a number of tetra- and penta-halogeno-oxometal complexes, where the equilibrium (MOX/sub 4/)sup(n-) + X/sup -/< - - > (MOX/sub 5/)sup(n + 1)/sup -/ is clearly established.
Lanthanum halide (LaBr_3:Ce) scintillators offer significantly better resolution (< 3% at 662 keV) relative to NaI(Tl) and have recently become commercially available in sizes large enough for the handheld, Radio-Isotope Identification Device (RIID) market. Drawbacks to lanthanum halide detectors, however, include internal radioactivity contributing to spectral counts, and a low-energy response which can cause detector resolution to be worse than that of NaI(Tl) below 100 keV. To study the potential of this new material for RIIDs we performed a series of measurements comparing a 1.5 x 1.5-inch LaBr_3:Ce detector with an Exploranium GR-135 RIID, which contains a 1.5 x 2.2-inch NaI(Tl) detector. Measurements were taken for short timeframes, as typifies RIID usage. Measurements included examples of naturally occurring radioactive material (NORM), typically found in cargo, and special nuclear materials. Some measurements were non-contact, ...
The e.s.r. spectra of [AsPh_4][TcNCl_4], Cs_2[TcNCl_5], [AsPh_4][TcNBr_4], and Cs_2[TcNBr_5] have been studied in non-aqueous and concentrated aqueous acid solutions. None of the spectra shows evidence for the co-ordination of a fifth halide ligand in the trans position, even under circumstances such as a 2 000-fold excess of halide ion, which would be expected to favour the formation of the pentahalogenonitridotechnetate ion. The predominant species in solution is the tetrahalogenonitridotechnetate ion, where the trans position may be vacant or occupied by a solvent molecule in the case of the non-aqeuous solvents and by a water molecule in the case of HCl and HBr solutions. This conclusion may be contrasted with the behaviour of a number of tetra- and penta-halogeno-oxometal complexes, where the equilibrium [MOX_4]sup(n-) + X"-< - - > [MOX_5]sup(n + 1)"- is clearly established. (author).
In the past, organic substance is generally deemed as electrical insulator, but in recent years, molecular crystals and polymers showing electroconductivity like metal were synthesized and even those showing superconductivity have appeared. These materials are called organic metals or synthetic metals and have peculiar solid state physical properties. Examples of real application of organic electroconductive materials are becoming available, but in this article, a chip type aluminum solid electrolytic capacitor using polypyrrole is introduced. There are four kinds of capacitors including ceramic capacitors and aluminum electrolytic capacitors, etc. The aluminum electrolytic capacitor is most retarded than any other type of capacitor in introducing its chip type since its use of electrolytic solution becomes an obstacle. Polypyrrole synthesized by electrolytic polymerization through ...
R-matrix analyses of neutron-induced reactions for many of the lightest p-shell nuclei are difficult due to a lack of distinct resonance structure in the reaction cross sections. Initial values for the required R-matrix parameters, E,sub(lambda) and ..gamma..sub(lambdac) for states in the compound system, can be obtained from shell model calculations. In the present work, the results of recent shell model calculations for the lithium isotopes have been used in R-matrix analyses of /sup 6/Li+n and /sup 7/Li+n reactions for E sub(n) < 8 MeV. Consequences of the shell model predictions for the level structure of /sup 7/Li and /sup 8/Li on the /sup 6/Li+n and /sup 7/Li+n reaction mechanisms and cross sections are discussed.
As a continuation of our previous study, further experiments were performed on Li[sub 3]PO[sub 4]-Li[sub 2]S-SiS[sub 2] lithium ion conductive glass. In the present study, we employed a twin roller for quenching process instead of liquid nitrogen. We found that the glass forming region expands by twin roller technique and conductivity up to 1.5x10[sup -3] S/cm was achieved. Structural analysis on the glass revealed that Li[sub 3]PO[sub 4] doping changes the glass structure of Li[sub 2]S-SiS[sub 2], thereby enhancing the electrical conductivity
Observations are reported of the lithium feature (6708 A) in some bright southern stars, most of which are F, G, or K dwarfs. Three of these stars have been suggested as belonging to the Ursa Major Group. Two of these three have the large Li abundance and strong Ca II H and K emission expected of such young stars. The third potential Ursa Major Group member has little Li, but is also not a true kinematic member. No stars were found with abnormal (Li-6)/(Li-7) ratios, in accord with other recent analyses. Thus it appears that all stars have (Li-6)/(Li-7) near the solar/terrestrial value of 0.08. 31 references.
The initiation and inhibition of pitting corrosion on zirconium and hafnium in aqueous solutions have been investigated by potentiodynamic, potentiostatic and galvanostatic measurements at 25/sup 0/C. Effects of Cl/sup -/, Br/sup -/and I/sup -/ have been examined over a range of salt concentrations and pH. All three halide ions cause pitting attack on the two metals, but this may be inhibited by other anions. The results show that hafnium is more easily protected against pitting than is zirconium. The data are treated by the Butler-Volmer equation to yield more information about the mechanisms of the pitting corrosion.
A computerized corrosion measuring system (EG and G model 350 A) was used to study the influence of Cr, Mo, Ti, Nb and W on the pitting corrosion of nickel base alloys in 3% NaCl at 90"0C. The electrochemical parameters under investigation are the corrosion potential E_c_o_r_r, pitting potential E_p and protection potential E_p_p. The corrosion behaviour of nickel base alloys were studied by using pitting scan and potentiostatic techniques. Values of corrosion potential, pitting potential and protection potential were used for a ranking of alloys for corrosion resistance.
Carbalkoxylation of vinyl electrophiles was investigated using platinum complexes. This reaction occurs in two steps: (a) carbonyl insertion of {sigma}-vinyl Pt(II) halides and (b) alcoholysis of vinylic acyl Pt(II) complexes. Alcoholysis of vinylic acyl Pt(II) triflate complexes is investigated kinetically. Vinylic acyl Pt(II) complexes were isolated and characterized. 51 refs., 5 figs., 6 tabs.
A chemically assisted micro-beam etching system for 3D microanalysis was designed. Using chemically assisted ion beam etching (CAIBE) method with FIB shave-off scanning, about several hundred micrometers clean cross-section will be acquired in a few hours. We use focused ion beam (FIB) and electron beam (EB) as micro-beams, halogen or halide mainly as reactive gases. The apparatus was manufactured based on this concept. We found that the FIB, Q-MS and SED worked as expected. The instrumentation has been completed.
Gas evolution in aluminum electrolytic capacitors constitutes one of their main drawbacks in comparison to other types of capacitors lacking a liquid electrolyte. In this respect, one of the most common causes of failure shown by liquid electrolyte capacitors is electrolyte leakage through the seal or even explosions produced by internal pressure buildup. In order to prevent these hazards, some substances, known as depolarizers, are usually added to the capacitor electrolyte with the purpose of absorbing the hydrogen evolved at the cathode (1, 2). Although the gas evolution problem in electrolytic capacitors has been known for a long time, there is a lack of literature on both direct measurements of the gas evolved and assessments of the amount of depolarizer active for the hydrogen absorption process. Aluminum electrolytic capacitors of ...
The high temperature solid-state reaction between LiNiO{sub 2} and V{sub 2}O{sub 3} (or V{sub 2}O{sub 5}) in air used to prepare LiNiVO{sub 4} has been further studied. This quaternary Li-Ni-V-O reaction is strongly dependent on reaction temperature and lithium stoichiometry in Li{sub x}Ni{sub 2-x}O{sub 2} and has produced a highly crystalline LiNiVO{sub 4} material whose structure has been confirmed to be an inverse spinel by Rietveld analysis with a Bragg R-factor of 1.18 in the absence of crystal orientation preference. The cell performance of LiNiVO{sub 4} prepared at various temperatures or by varying x-values in Li{sub x}Ni{sub 2-x}O{sub 2} has been examined in lithium coin cells and indicated that preparation at low temperatures or when x=0.89 provided an electrode material with higher cell capacity. (orig.)
Electrochemical performance and structural properties of the high-voltage cathode material Li{sub 2}CoPO{sub 4}F have been investigated. The cyclic voltammetry and coulometry under potential step mode in the voltage range 3.0-5.1 V vs. Li revealed a structural transformation at potentials above 4.8 V. This transformation occurring upon Li-extraction appears to be irreversible: the subsequent Li-insertion does not result in restoration of the initial structure, but takes place within a new ''modified'' framework. According to the structure refinement this modification involves the mutual rotations of (CoO{sub 4}F{sub 2}) octahedra and (PO{sub 4}) tetrahedra accompanied by the considerable unit cell expansion which is expected to enhance the Li-transport upon subsequent cycling. The new framework demonstrates a reversible ...
Latent inhibition (LI) manifests as poorer conditioning to a CS that has previously been presented without consequence. There is some evidence that LI can be potentiated by reduced mesoaccumbal dopamine...Full Text Available
A series of spinel Li4Ti5O12 samples were synthesized via a composite molten-salt method (CMSM) using the mixtures of LiCl and KCl with different L values (L is defined as the molar ratio of LiCl:KCl) as the reaction media. It is found that the melting point of the composite molten salt can effectively influence the formation of particles, and leads to different electrochemical performances of the as-prepare Li4Ti5O12. The investigations of X-ray diffraction (XRD), particle size distribution (PSD), Brunauer-Emmet-Teller (BET) surface area, and scanning electron microscopy (SEM) indicate that the as-prepared Li4Ti5O12 with L = 1.5 is a pure phase, and has uniform homogeneous octahedral shape particles, rather narrow PSD, and high BET surface area. Electrochemical tests show that the optimized Li4Ti5O12 with L = 1.5 has an initial discharge capacity of 169 mAh g-1 ...
The dependence of the rms radius of the deuteron cluster in /sup 6/Li on the relative d-..cap alpha.. momentum was investigated on the basis of the three-body wave function given by Rai, Lehman, and Ghovanlou.
Differences in the biological disposition and in the effects of the stable lithium isotopes, Li-6 and Li-7, in animals were characterized. A somewhat higher toxicity was associated with WLiCl compared to XLiCl with NLiCl intermediate. All lithium treatments increased water intake and resulted in weight gain. Peak plasma concentration was slightly high for 6Li than 7LiCl suppressed action potential amplitudes during tetanic stimulation more than NaCl when added to Renger solution bathing ganglia.
Kinetics of decomposition of gallium and alkali metal intermetallic compounds in the systems LiGa-LiOH, LiGa-NaOH and LiGa-KON was studied in the temperature range of 40-80 deg C. It was ascertained that increase in temperature gives rise to increase in decomposition rate, whereas increase in hydroxide concentration involves the reaction deceleration. An assumption was made that the decomposition occurs with superimposing of two mechanisms, i.e. chemical and electrochemical decomposition. Basic kinetic characteristics of the process were determined - decomposition rate constant and current density
Lithium tetrachloroaluminate solutions in thionylchloride, methylacetate and their mixtures are studied by "7Li and "2"7Al NMR. It is found that introduction of methylacetate in the LiAlCl_4-SOCl_2 system results in a change of lithium tetrachloroaluminate formation constant. In the ternary system, Li"+ is solvated by methyl-acetate after complete destruction of tetrachloroaluminate anion. Refs. 9, figs. 2.
The electrical resistivity at low temperatures (T = 10 to 90 K) of the lithium isotopes /sup 6/Li and /sup 7/Li and of an isotopic mixture /sup 7 +6/Li has been studied. The specimens contained a small amount of chemical impurities. An appreciable difference was observed in the temperature dependence of the resistivity produced both by deformation of the phonon spectrum, related to the change in isotopic composition, and by the presence of chemical impurities making the nonequilibrium part of the electron distribution function more isotropic.
A computerised curve-fitting method was developed to calculate the trapping parameters in LiF TLD-100 and LiF:Mg, Ti. After irradiation in a "6"0Co field and with X rays emitted at different voltages the TL process is best described by first-order kinetics. A dependence of the trapping parameters on both the concentration of Mg and Ti and photon energy was detected. (author).
Polysaccharides like cellulose and chitosan are known for their filmic properties. This paper concerns the synthesis and the study of chitosan-based polymer electrolytes. A preliminary work concerns the study of glucosamine reactivity. The poly-condensation of chitosan ethers (obtained by reaction with ethylene oxide or propylene oxide) with bifunctional and monofunctional oligo-ethers leads to the formation of thin lattices (10 {mu}m) having excellent mechanical properties. The presence of grafted polyether chains along the polysaccharide skeleton allows to modify the vitreous transition temperature and the molecular disorder of the system. Two type of polymer electrolytes have been synthesized: electrolytes carrying a dissolved alkaline metal salt and ionomers. The analysis of their thermal, dynamical mechanical, nuclear magnetic relaxation, electrical, and electrochemical properties shows that this new class of polymer ...
A research program has been initiated to screen and select electrolyte materials for use in steam electrolyzers in the 300-600/sup 0/C temperature range. Screening of a significant number of acid anhydrides, hydroxides, oxides, and phospates for their electrolytic conductivity properties is underway. Of the binary materials examined to date, only polymerized phosphoric acid, immobilized on an H/sup +/ substituted zeolite, shows promise. A substantial number of ternary compounds remain to be synthesized and evaluated.
The electrolyte was brought into contact with air and potassium carbonate was measured with various contact time in order to check the defect of carbon dioxide in the air on zinc-air cell. The relationship between potassium carbonate concentration in electrolyte and battery capacity was also studied. The potassium carbonate concentration in the electrolyte. The rate of carbon dioxide absorption was mainly affected by the pore size of hydrophobic membrane. Our study showed that adapting the pore of hydrophobic membrane decreased the loss of cell discharge performance due to the presence of carbon dioxide or water vapor in the atmosphere. 7 refs., 12 figs., 1 tab.
The authors investigated the influence of tartaric acid, which possesses complex-forming properties. In order to establish the optimum system of possible refinement of tellurium, the authors study the kinetics of both the cathodic and the anodic processes. The investigation of processes of discharging-ionization of tellurium from nitric acid electrolytes in the presence of tartrate ions showed the possibility of preparing a nitric-tartaric acid electrolyte which can be used for commercial purposes and from which a high-purity raffinate was obtained from technical tellurium.
Systems MEMS sensors C11-20 Lifetime Distributions of Aluminum Electrolytic Capacitors C11-22 Adhesion Strength of Advanced Polymer Films for Flexible and Rigid...
In a double blind test on 40 men and women high performance fencers the influence of a multivitamin-electrolyte-preparation on reaction time, hit-frequency and neuromuscular irritability was determined....Full Text Available
... The effects of these voids were more noticeable for tantalum and aluminum electrolytic capacitors, which usually exhibited severe case deformation ...
A kind of polymer-metal complex gel electrolyte is successfully prepared and is used in dye-sensitized solar cells. Raman and X-ray photoelectron spectroscopy confirm the structure of this complex and is found that the metal ion reacts with nitrogen in the polymer. This novel electrolyte shows apparent diffusion coefficient of iodide of 8.37 x 10-7 cm2 s-1 and the energy conversion efficiency of 6.10% when the amount of ZnI2 is 0.04 M. By studying the dissociation active energy of the inorganic salt in electrolytes, we find that the metal salts can dissociate more easily after reacting with polymer and as a result can provide extra free iodide ion. The cell maintains ca. 93% of its initial efficiency after 20 d without further sealing, which shows good long-time stability.
The deterioration of AA2024, AA6061 and AA7475 anodised in an environmentally-compliant tartaric acid/sulphuric acid electrolyte has been examined as a function of the immersion time in the electrolyte after termination of anodising. By transmission electron microscopy and scanning electron microscopy, degradation of the porous oxide film was qualitatively observed on AA2024. Electrochemical impedance spectroscopy revealed that AA2024 and AA7075 were more sensitive to prolonged immersion in the anodising electrolyte compared with AA6061, due to increased barrier layer thinning rates and increased susceptibility to localized corrosion. Salt spray tests confirmed the previous, indicating decay of anticorrosion performance for AA2024 and AA7075.
... C14 and C15 are special aluminum electrolytic capacitors manufactured by Cornell-Dubilier and designed for high-frequency capability, long life ...
Pulsed atomic beams produced in vacuum by laser induced ablation from a lithium target are analyzed by laser induced fluorescence (LIF). The 1-mixing processes induced in the n = 9, 10 Li Rydberg states by collisions with CO_2 molecules illustrate the application of the method. Resolution is limited by the 1 mm diameter of the probe laser beam. Combining LIF and absorption measurements gives n_L_i as a function of time at various distances from the target surface. The investigation of the Li-C0_2 1-mixing process in a heat pipe oven proved impossible due to the high reactivity of Li with C0_2. This problem was solved by renewing the Li atoms at each laser shot. Values obtained for n = 9, n = 10 are k = 17 x 10"-"8 and 15 x 10"-"8 cc/sec, respectively.
We obtain x-ray absorption near-edge structures (XANES) by solving the equation of motion for the two-particle Green's function for the electron-hole pair, the Bethe-Salpeter equation (BSE), within the all-electron full-potential linearized augmented plane wave method (FPLAPW). The excited states are calculated for the Li K-edge in the insulating solids LiF, Li_2O and Li_2S, and absorption spectra are compared with independent particle results using the random phase approximation (RPA), as well as supercell calculations using the core-hole approximation within density functional theory (DFT). The binding energies of strongly bound excitations are determined in the materials, and core-exciton wavefunctions are demonstrated for LiF.
We have studied the vibrational properties of the filled tetrahedral semiconductor LiMgAs and its binary analog AlAs by using the plane-wave pseudopotential method within density functional theory. The calculated lattice constants for the studied compounds are in good agreement with previous theoretical and experimental results. The phonon dispersion curves and phonon density of states are calculated by using density functional perturbation theory. The sound speeds in different directions are quantitatively similar in LiMgAs and AlAs. The assignment of the zone center modes to the relative motion of the atoms shows that the lower optic modes are due to the Mg-As pair vibrations, while for the upper ones the Li-Mg pair dominates, which is attributed to the smaller Mg atom mass. The longitudinal interatomic force constant of Mg-As is about 66% higher than that of Li-As, showing the relatively high ...
Hexavalent Cr has been identified as one of the toxic metals commonly present in industrial effluents. Among the treatment techniques developed for removing Cr(VI) from waste waters, sorption is most commonly applied, due to its simplicity and efficiency. However, few adsorbents can be recycled and reused cost-effectively. In this study, the removal and recovery of Cr(VI) from water using Li/Al LDH was investigated. The removal of Cr(VI) by Li/Al LDH was evaluated in a batch mode. The results demonstrated that Cr(VI) adsorption onto Li/Al LDH occurs by replacing the Cl{sup -} that originally exists in the interlayer of the adsorbent. The degree of Cr(VI) adsorption observed for Li/Al LDH was relatively high and the process occurred rapidly; however, a portion of adsorbed Cr(VI) was gradually desorbed, due to the Li de-intercalation of Li/Al LDH. Lithium ...
The experiment on the determination of the tensor polarization of the residual nucleus is described for the reaction "6Li (#alpha#, #alpha#') "6Li. It is based on the unique connection of polarization tensors t_l_m of the residual nucleus for the reaction (#alpha#, #alpha#') and the angular correlation function W (#omega#_1, #omega#_2) for #alpha#'-particle and decay product of this nucleus, where #omega#_1, #omega#_2 are motion directions of #alpha#'-particle and decay product. The angular correlations of #alpha#'-particle and deuteron are measured for the "6Li (#alpha#, #alpha#', d)"4He reaction on the 27.2 MeV #alpha#-particle beam. The recording system consists of six silicon detectors and provides the energy resolution about 0.8 MeV and the angular resolution #+-# 3 deg. The polarization tensors of the residual nucleus "6Li (2.185 MeV, 3"+) are determined as the result of measuring the angular ...
Lithium hexa-fluoro-phosphate LiPF{sub 6} is recommended for the replacement of the toxic LiAsF{sub 6} and the explosive perchlorates (like LiClO{sub 4}) in rechargeable lithium electrochemical generators. The aim of this work is to develop a new method of synthesis of this salt and to check its stability with respect to carbonated solvents: ethylene carbonate (EC), propylene carbonate (PC) and dimethyl-carbonate (DMC) in already optimized EC/DMC and PC/DMC binary mixtures. Two methods using HPF{sub 6} are proposed: the first one uses the direct neutralization of this commercial acid by LiOH in aqueous, alcoholic or acetonitrile environment, while in the second one LiPF{sub 6} is obtained from pyridinium hexa-fluoro-phosphate synthesized from HPF{sub 6} using a new and simple protocol. (J.S.) 24 refs.
A series of spinel Li4Ti5O12 samples were synthesized via a composite molten-salt method (CMSM) using the mixtures of LiCl and KCl with different L values (L is defined as the molar ratio of LiCl:KCl) as the reaction media. It is found that the melting point of the composite molten salt can effectively influence the formation of particles, and leads to different electrochemical performances of the as-prepare Li4Ti5O12. The investigations of X-ray diffraction (XRD), particle size distribution (PSD), Brunauer-Emmet-Teller (BET) surface area, and scanning electron microscopy (SEM) indicate that the as-prepared Li4Ti5O12 with L=1.5 is a pure phase, and has uniform homogeneous octahedral shape particles, rather narrow PSD, and high BET surface area. Electrochemical tests show that the optimized...
The fundamental optical absorption of ion crystals characterizes the creation of different free low energetic electronic excitation (the excitons and electron-hole pairs), but their straight registration is not possible because of incommensurable big absorption factor of alkali halide monocrystals. So to registration the spectrums of alkali halide monocrystal very fine layers are necessary. We have received fine films of Nal and KCl in system of KCl-Nal-KCl, KCl-KI-KCl on the base of universal vacuum post VUP-4, VUP-5 by thermal evaporation. A unique spectral unit has been created For this on the basic the SDL-2 complex. Complex consists of radiator, systems of condensers, monochromators MDR-12 and MDR-23, receivers of radiation, controller by unit. Connect and control of monochromators by means of IBM-compatible computer has been created. Kinematics schemes of monochromators provide consequent removing on output slot of monochromatic radiation ...
Since several years we apply the radiation-grafting technique to prepare polymeric membranes for application in polymer electrolyte fuel cells (PEFCs). Our investigations presented here focus on changes in toughness of these materials after the various synthesis steps and the importance of membrane toughness for their application in PEFCs. (author) 2 figs., 4 refs.
The electrochromatographic behavior of 25 metal ions on zirconium tungstate-impregnated papers is described. Six background electrolytes were used. On the basis of the differential mobilities of metal ions which depend on the ion-exchange properties of zirconium tungstate and the nature of complex formation with the electrolytes, some important binary and ternary separations have been achieved.
Analytical expression of the dependence of freezing temperature of electrolyte (CdCl_2, CdSO_4, BeSO_4) aqueous solutions on their composition was found. Three different methods were suggested were suggested for calculation of water activity in multicomponent solution. It was established that sublinear extrapolation of freezing temperature of salt aqueous solutions was possible not up to -5 deg C, but up to -15 deg C, independently of their composition. 6 refs.; 2 figs.
A process for the removal of H/sub 2/S from sour gas streams is disclosed, the process being characterized by the utilization of washing solutions containing oxidizing metal chelates of nitrilotriacetic acid, and by the electrolytic regeneration of the spent solutions.
Hydrogen uptake and embrittlement of tantalum by electrolytically produced hydrogen is investigated on samples of varying composition and type of pretreatment. Of decisive influence on the uptake of hydrogen are the oxide layers present on the tantalum surface. By contact with platinum group metals as alloying constituents, surface coatings or anodic protection, a protection of tantalum can be obtained depending on the experimental conditions.
Hydrogen uptake and embrittlement of tantalum by electrolytically produced hydrogen is investigated on samples of varying composition and type of pretreatment. Of decisive influence on the uptake of hydrogen are the oxide layers present on the tantalum surface. By contact with platinum group metals as alloying constituents, surface coatings or anodic protection, a protection of tantalum can be obtained depending on the experimental conditions. (orig.).
Water transport in the ionomeric membrane, typically Nafion{reg_sign}, has profound influence on the performance of the polymer electrolyte fuel cell, in terms of internal resistance and overall water balance. In this work, high resolution neutron imaging of the Nafion{reg_sign} membrane is presented in order to measure water content and through-plane gradients in situ under disparate temperature and humidification conditions.
A gas diffusion semiconductor electrode and solar cell and a process for gaseous fixation, such as nitrogen photoreduction, CO/sub 2/ photoreduction and fuel gas photo-oxidation are described. The gas diffusion photosensitive electrode has a central electrolyte porous matrix with an activated semiconductor material on one side adapted to be in contact with an electrolyte and a hydrophobic gas diffusion region on the opposite side adapted to be in contact with a supply of molecular gas.
The stability constants of [AtX_2]"- with X = Cl, Br and I in ethanol and methanol as well as their ion mobilities at a temperature of 298 K and an ionic strength of 0.05 were determined by horizontal zone electromigration in homogeneous electrolyte solution. The results are compared with existing data from aqueous electrolyte systems. (author).
Investigations of alternative renewable energy resources continue, with many studies concentrating on hydrogen storage. However, there are a few problems such as storage, transportation, delivery to the user and usage safely, to be addressed to facilitate commercialization and wide usage of the hydrogen. The absorbed form within the metal hydrides seems to be the best solution of this problem. Since Li is the lightest metal, it has the advantage as the stored amount of hydrogen mass ratio. LiBH{sub 4} production process was investigated using elemental Li, B and H{sub 2}. Spex type ball milling with tungsten carbide, stainless steel and zirconia type vessels, was used to mix the different amount of Li and B under argon atmosphere. X-ray diffraction pattern demonstrated that the LiB was obtained. A system was designed to provide a hydrogen atmosphere of 60 bars to force hydrogen into ...
In this paper, we report the electrochemical characteristics of a novel cathode material, Li{sub 2}CoPO{sub 4}F, prepared by solid-state reactions. The solid-state reaction mechanism involved in synthesizing the Li{sub 2}CoPO{sub 4}F also is analyzed in this paper. When cycled between 2.0 V and 5.0 V during cyclic voltammetry measurements, the Li{sub 2}CoPO{sub 4}F samples present one, fully reversible anodic reaction at 4.81 V. When cycled between 2.0 V and 5.5 V, peaks occurring at 4.81 V and 5.12 V in the first anodic scan evolved to one broad oxidative, mound-like pattern in subsequent cycles. Correspondingly, the X-ray diffraction (XRD) pattern of the Li{sub 2}CoPO{sub 4}F electrode discharged from 5.5 V to 2.0 V is slightly different from the patterns exhibited by a fresh sample and the sample discharged from 5.0 V to 2.0 V. This difference may correspond to a structural relaxation that appears ...
Lead is known to enter substitutionally in divalent state when doped in alkali halides. When irradiated at room temperature these lead centers (Pb"+"+) act as traps for electrons knocked off from the halogen ions and become Pb"+ and Pb"0 (for large doses of irradiation). These changes could be followed in the optical absorption studies. These lead-doped crystals after X-ray irradiation yield a thermoluminescence output smaller than that observed in 'pure' crystals. However, two new glow peaks are observed in additions to those due to F-centers. In KCl : Pb and Kbr : Pb crystals part of the F-center glow preceds the new glow peaks. The new peaks are attributed to the Pb"+ and Pb"0 centers. The glow peak temperatures and trap depths for these peaks an obtained by total-curve fitting method are reported. (author).
3-Azido-..beta..-lactams react with the derivatives of trivalent phosphorus acids under mild conditions with the formation of 3-phosphoranediylamino-1,4-diaryl-2-azetidinones, which are readily hydrolyzed with the elimination of alcohol (thiol) to 3-phosphoranylamino-1,4-diaryl-2-azetidinones. The phosphine imide compounds obtained from the aryl alkyl phosphites are hydrolyzed with the elimination of phenols. 3-Phosphoranediylamino-1,4-diaryl-2-azetidinones react readily with alkyl and acyl halides with the formation of 3-(N-alkylphosphoryl-amino)- and 3-(N-acylphosphorylamino)-1,4-diaryl-2-azetidinones, respectively.
3-Azido-#beta#-lactams react with the derivatives of trivalent phosphorus acids under mild conditions with the formation of 3-phosphoranediylamino-1,4-diaryl-2-azetidinones, which are readily hydrolyzed with the elimination of alcohol (thiol) to 3-phosphoranylamino-1,4-diaryl-2-azetidinones. The phosphine imide compounds obtained from the aryl alkyl phosphites are hydrolyzed with the elimination of phenols. 3-Phosphoranediylamino-1,4-diaryl-2-azetidinones react readily with alkyl and acyl halides with the formation of 3-(N-alkylphosphoryl-amino)- and 3-(N-acylphosphorylamino)-1,4-diaryl-2-azetidinones, respectively.
Results of experiments performed utilizing high-power microwave sources for laser-discharge switching and preionization are reported. These results are not definitive, but are promising. Significant preionization using microwaves is possible. Some ability to switch the discharge and operate a laser have been demonstrated. More work needs to be performed to perfect the microwave coupling to the laser mixture. In particular, experiments with the microwaves better concentrated between the electrodes should be performed. The best way to accomplish this appears to be using the side-feed geometry; however, a large expansion of the microwaves should occur (to well below the power able to break down the window), and then a cylindrical lens should be used to focus the microwaves between the electrodes. 2 references.
The pitting resistance of Fe-Cr and Fe-Cr-Mo alloys has been correlated with characteristics of the passive films analyzed by Auger electron spectroscopy (AES). Increased film protectiveness as a result of increased Cr in the alloy can be directly attributed to Cr enrichment of the film and decreased film thickness. Increased Mo in the alloy or passivation at noble potentials promotes passive film resistance to breakdown, but neither does much to change the macrocharacteristics of the film. Rather, it is suggested that the roles of alloying and/or passivation conditions are related to the susceptibility and distribution of weak points of the film. In solutions in which pitting occurs, chloride is generally not incorporated into the film, suggesting that the role of halides is to interact with weak points of the film at the solution/film interface. At 260/sup 0/C, the films are much thicker and likely to be much more defective in structure than those formed at ...
Stainless steels can get pitting corrosion in halide containing solution, which make them a big risk in industrial production. Many investigations were made in the past in order to understand processes involved in pitting corrosion, pit initiation and pit growth. Results about the influence of alloying elements, their contents, the state of the structure, the condition of the surface, the content of chloride, the temperature, the pH-value, the velocity of flow and of the oxidizer on the chloride induced pitting corrosion of passive stainless steels are presented. Electrochemical measurements and the application of surface analytical methods (SEM, SAM, XPS) with high lateral resolution are carried out. A part of the samples received a diffusion annealing in order to obtain reproducible results. Pitting Resistance Equivalents (PRE) - Pitting Index - with different multipliers are given and discussed critical. An electrochemical method for selecting materials without ...
The change in the concentration of hydrogen peroxide in the course of its decomposition was shown, catalyzed by 0.02 M PbI/sub 2/, 0.03 M CuI, 0.02 M KI, 0.02 M FeSo/sub 4/, 6 M HCl, and 1 M HCL + 2 M H/sub 2/SO/sub 4/ at 25 C. It was suggested that in the process of the catalytic decomposition at the initial stage of the reaction, the formation of an intermediate active species containing positively charged halogen occurs; depending on the oxidative power of the counterion, the relative proportions of the hydrogen peroxide decomposing under the action of either the cation or the anion varied.
The cost-effectiveness (CE) analysis presents an evaluation of the technical efficiency of pollutant control options for the proposed effluent limitations guidelines. The proposed BAT and PSES apply to six subcategories: Dissolving Kraft; Dissolving Sulfite; Bleached Papergrade Kraft; Papergrade Sulfite; Unbleached Kraft; and Semichemical. The document compares the total annualized cost incurred for each of the regulatory options within each subcategory to the corresponding effectiveness of that option in reducing the discharge of pollutants. Section Two discusses the cost-effectiveness methodology and identifies the pollutants included in the analysis and their toxic weighting factors. Section Three describes the options evaluated for each subcategory. Section Four presents the results of the CE analysis. Section Five presents a separate analysis of AOX (adsorbable organic halides).
This paper describes stable strontium as composed of four stable isotopes ( Sr 88, Sr 87, Sr 86, and Sr 84), of which Sr 88 contributes more than 82% to its composition. Strontium exists in three crystalline, plymorphic forms; face-centered cubic alpha form, hexagonal beta form and body-centered cubic gamma form. Strontium occupies in many physicochemical aspects an intermediate position between calcium and barium, as does the solubility of strontium salts. As a result of its oxidation potential, strontium readily forms oxides, halides, and sulfide. The author proposes that the slight discrimination against strontium incorporation into bony tissues may be due to the difference in ionic potential (14%) between strontium and calcium. Ionic potential is an indicator of the strength of ionic bonds: strontium has a smaller ratio of ionic charge to ionic radius when compared with calcium.
Single-electrode transient behavior was measured mainly during the discharging process for a model cell of electric double layer capacitor with nano-porous carbon electrodes and reference electrode. Apparent conductivity in the cell, which we call `effective conductivity,` is determined with approximation of current in transient behavior to a one-dimensional electrophoretic model. A comparison of effective conductivity with conductivity of bulk solution suggests an interesting mechanism of transfer of electrolyte ions. The difference in transient behavior between various electrolyte ions was not conspicuous in spite of distinctive differences in conductivity of each bulk solution. The large pore diameter of the carbon electrode results in rapid transient behavior and such an electrode should be suitable for rapid charge and discharge. The effect of origin of carbon electrode is found to be significant to bring considerable differences in ...
The composite of doped lanthanum gallate (La_0_._9Sr_0_._1Ga_0_._8Mg_0_._2O_2_._8_5, LSGM) and doped ceria (Ce_0_._8Sm_0_._2O_1_._9, CSO) was investigated as an electrolyte for solid oxide fuel cell (SOFC). The LSGM-CSO composite was examined by X-ray diffraction (XRD) and impedance spectroscopy. It was found that the sintered LSGM-CSO composite contains mainly fluorite CeO_2 phase and a minority impurity phase, Sm_3Ga_5O_1_2. The LSGM-CSO composite electrolyte shows a small grain boundary response in the impedance spectroscopy as compared to LSGM and CSO pellets. The composite electrolyte exhibits the highest conductivity in the temperature range of 250-600 "oC, compared to LSGM and CSO. The LSGM-CSO composite can be expected to be an attractive intermediate temperature electrolyte material for solid oxide fuel cells.
The nature of the electrolyte strongly influences the electrode kinetics of the oxygen evolution reaction (OER) and electrochemical ozone production (EOP) mainly by affecting the degree of coverage by the intermediates of both processes. The anomalous behaviour of the Tafel coefficient, b, as a function of temperature was attributed to surface adsorption of the electrolyte species, and the competition between them, as well as gas bubble adherence. Comparison of the current efficiencies of the EOP, PHI_E_O_P, determined for different temperatures and supporting electrolyte compositions, showed the presence of fluorinated anions increases PHI_E_O_P. The influence of the anion nature on PHI_E_O_P, when analysed in the light of the proposed electrode mechanism, reveals introduction into the electrolyte of anions having a high electronegativity changes the double layer structure resulting in an increase of ...
LiNiO{sub 2} is one of the most promising material for positive electrodes of lithium-ion batteries. However, its behaviour during cycling and the existence of several phase transitions induced by the lithium ions de-intercalation process has not been explained so far. A transition electron microscopy study of various Li{sub x}NiO{sub 2} (0.25
The "7Be(#alpha#,#gamma#)"1"1C and "7Li(#alpha#,#gamma#)"1"1B reactions are investigated in the three-cluster Generator Coordinate Method. The microscopic wave functions are described from #alpha# and "3He ("3H) clusters, with two coupling modes: #alpha#+"7Be ("7Li) and "3He ("3H)+"8Be. Different internal states of "7Be ("7Li) and "8Be are taken into account. The model is tested on "1"1C and "1"1B spectroscopic properties, which agree fairly well with experiment. We suggest that, in both nuclei, the (3)/(2)"- and (5)/(2)"- states located close to the #alpha#+"7Be ("7Li) threshold, are intruder states. The "7Be(#alpha#,#gamma#)"1"1C and "7Li(#alpha#,#gamma#)"1"1B reaction rates are calculated for temperatures up to 10"9 K. A strong enhancement is found with respect to the reaction rates currently used in astrophysical calculations. ((orig.)).
The LiMnO{sub 2} lamellar oxide, obtained by exchange reaction from its sodium homologue {alpha}-NaMnO{sub 2}, has been used as a positive electrode for lithium batteries. After the first electrochemical cycle, the shape of the potential-composition curve changes and indicates a change in the structure. This modification changes imperceptibly at each cycle and after about 40 cycles, a stationary state is reached. Powder spectra refinement using the Rietvelt method shows a migration of manganese ions from the thin sheets towards the inter-sheet space. After a single cycle, 8% of the manganese ions are already present in the lithium site and this rate reaches 13% after 3 cycles. During long cycling, a redistribution of ions and vacancies inside the cfc oxygenated pile leads to a structure very similar to the LiMn{sub 2}O{sub 4} spinel. This structure evolution is to be compared with the one obtained from the orthorhombic variety of ...
1,2,3-Trisilacyclopenta-1,4-diene 2, featuring three skeletal Si atoms in the five-membered ring, was synthesized by the thermolysis of the 1,2,3-trisilabicyclo[1.1.0]butane derivative 1 at 130 degrees C in the presence of hex-3-yne. Possessing the properties of nonconjugated cyclopentadiene, 2 readily underwent reduction with KC(8), which was followed by treatment with LiBr to form the lithium salt of 1,2,3-trisilacyclopentadienide 3(-)*[Li(+)(thf)], from which the ketone-coordinated derivative 3(-)*[Li(+)(O=C(t)Bu(2))] was prepared. Both 3(-)*[Li(+)(L)] (L = thf, O=C(t)Bu(2)) are classified as novel 6pi-electron aromatic systems based on their characteristic X-ray crystal and NMR spectral data. Addition of 12-crown-4 to 3(-)*[Li(+)(thf)] resulted in the unexpected formation of 4(-)*[Li(+)(12-crown-4)(2)], featuring the unprecedented cyclic disilenide ion 4(-). ...
Lithium-ion batteries are now considered to be the technology of choice for future hybrid electric and full electric vehicles to address global warming. LiCoO2 has been the most widely used cathode material in commercial lithium-ion batteries. Since LiCoO2 has economic and environmental issues, intensive research has been directed towards the development of alternative low cost, environmentally friendly cathode materials as possible replacement of LiCoO2. Among them, spinel LiNi0.5Mn1.5O4 material is one of the promising and attractive cathode materials for next generation lithium-ion batteries because of its high voltage (4.7V), acceptable stability, and good cycling performance. Research advances in high voltage spinel LiNi0.5Mn1.5O4 are reviewed in this paper. Developments in synthesis,...
Crystalline MnMoO{sub 4} was synthesized using a conventional solid reaction method and investigated for its physical and electrochemical properties as an anode material for Li secondary battery. The reversible amount of Li insertion/removal of MnMoO{sub 4} anode during the first cycle was about 800 mA h/g, accompanied by irreversible structural transformation into amorphous material. The amorphization during the first Li insertion was investigated by structural analysis using XRD of electrode. The charge compensation during Li insertion/removal was examined by measurement of X-ray Absorption Near Edge Structure (XANES) spectroscopy. Despite its irreversible structural transformation to amorphous during the first lithiation, subsequent cycles showed a reasonable cyclability. This paper presents the electrochemical properties of MnMoO{sub 4} and discusses the mechanism underlying the ...
Uranium dendrites which were deposited at a solid cathode of an electrorefiner contained a certain amount of salts. These salts should be removed for the recovery of pure metal using a cathode processor. In the uranium deposits from the electrorefining process, there are actinide chlorides and rare earth chlorides in addition to uranium chloride in the LiCl-KCl eutectic salt. The evaporation behaviors of the actinides and rare earth chlorides in the salts should be investigated for the removal of salts in the deposits. Experiments on the salt evaporation of rare earth chlorides in a LiCl-KCl eutectic salt were carried out. Though the vapor pressures of the rare earth chlorides were lower than those of the LiCl and KCl, the rare earth chlorides were co-evaporized with the LiCl-KCl eutectic salt. The Hertz-Langmuir relation was applied for this evaporation, and also the evaporation rates of the salt were ...
The influence of Cr on the structure and electrochemical properties of LiCoVO{sub 4} was studied using X-Ray diffraction, scanning electron microscopy, Raman Spectroscopy and cycle tests. Doping levels up to 10 mol% were achieved, which improved the electrochemical stability of the structure of LiCoVO{sub 4}, resulting in a significant increase in the initial charge and discharge capacity. The Raman spectroscopy data for the Cr-doped LiCoVO{sub 4} is similar as for LiCoVO{sub 4}. The replacement of a dopant for the Co-ion in the inverse spinel structure causes several Raman shifts. The X-ray diffraction patterns show no new phases and combined with the Raman spectroscopy data it is concluded that the Cr dopant will be located at the octahedral site (16d) where they create an electronic pathway that enhances the electronic conductivity. However, the capacity dropped significantly after prolonged cycling, ...
Thermal, electrical, and electrochemical properties were investigated for the (100-x)(0.6Li{sub 2}S{center{underscore}dot}0.4SiS{sub 2}){center{underscore}dot}xLi{sub 4}SiO{sub 4} oxysulfide glasses. The glass with x = 5 exhibited high electrical conductivity of about 10{sup {minus}3} S cm{sup {minus}1} at room temperature, high glass stability against crystallization, and good chemical stability in contact with Li metal. Cyclic voltammetry also suggested that this glass has a wide electrochemical window of more than 10 V. On the other hand, further addition of Li{sub 4}SiO{sub 4} up to 20 mol% lowered the conductivity, glass stability against crystallization, and electrochemical stability for the oxysulfide glasses.
The irradiation behavior of Li{sub 2}TiO{sub 3} under a fusion reactor environment was simulated by simultaneous irradiation of Li{sub 2}TiO{sub 3} by the triple ion beams and the respective single ion beams of O{sup 2+}, He{sup +} and H{sup +}. The microstructural changes in Li{sub 2}TiO{sub 3} caused by the irradiation were measured by FT-IR photoacoustic spectroscopy. The results suggest that the amount of TiO{sub 2} formed is proportional to the dpa and that the method of irradiation does not affect the dependence of formation of TiO{sub 2}. On the other hand, the amount of defects and/or radiolytic products generated by irradiation, which is considered to trap hydrogen near the surface, is found to be affected by the method of irradiation. Such phenomena are believed to affect the tritium release behavior from Li{sub 2}TiO{sub 3}, and durability of Li{sub 2}TiO{sub 3} and ...
The irradiation behavior of Li_2TiO_3 under a fusion reactor environment was simulated by simultaneous irradiation of Li_2TiO_3 by the triple ion beams and the respective single ion beams of O"2"+, He"+ and H"+. The microstructural changes in Li_2TiO_3 caused by the irradiation were measured by FT-IR photoacoustic spectroscopy. The results suggest that the amount of TiO_2 formed is proportional to the dpa and that the method of irradiation does not affect the dependence of formation of TiO_2. On the other hand, the amount of defects and/or radiolytic products generated by irradiation, which is considered to trap hydrogen near the surface, is found to be affected by the method of irradiation. Such phenomena are believed to affect the tritium release behavior from Li_2TiO_3, and durability of Li_2TiO_3 and compatibility of Li_2TiO_3 with other components of the ...
The aim of this work is to combine the MCFC cathode Li{sub x}Ni{sub 1-x}O properties to those of the protective coatings of LiCoO{sub 2}, Li{sub 2}TiO{sub 3} or of CeO{sub 2}, less soluble in the molten carbonates. In the cases of LiCoO{sub 2}, have been carried out by controlled potential coulometry in aqueous solution, a deposition of Co{sub 3}O{sub 4} on dense Ni. The cobalt oxide reacts rapidly in the Li{sub 2}CO{sub 3}-Na{sub 2}CO{sub 3} medium at 650 C to give LiCoO{sub 2}, a spinel cubic phase revealed by Raman spectroscopy. (O.M.)
Effects of dopant and coating carbon nanotube on anodic performance of Si were studied for metallic anode Li ion rechargeable battery with large capacity. Although the large Li intercalation capacity higher than 1500mAhg{sup -1} is exhibited on pure Si, it decreased drastically with increasing cycle number. Increasing the electrical conductivity by doping Cr or B is effective for increasing the initial capacity and the cycle stability of Si for Li intercalation. Coating semiconductive Si with the carbon nanotube by decomposition of hydrocarbon is effective for increasing the cycle stability, though the initial Li intercalation capacity slightly decreased. Conducting binder is also important for increasing the cycle stability and it was found that Li intercalation capacity higher than 1500mAhg{sup -1} can be sustained by using poly vinyliden fruolide. Consequently, reversible ...
An ever first attempt has been made to investigate the possible anode performance characteristics of LiFePO{sub 4}, popularly known so far as an environmentally compatible and economically viable lithium battery cathode material. The compound LiFePO{sub 4} has been synthesized via solid state method and explored for the first time as an anode material against lithium metal through the present study. Surprisingly, an initial capacity of circa 620 mAh/g has been exhibited by LiFePO{sub 4} anode, which is about 4-5 times higher than the capacity of the corresponding LiFePO{sub 4} cathodes. Also an excellent coulombic efficiency value of 99% has been shown by the compound, especially upon extended cycling. The extraordinarily higher specific capacity values of LiFePO{sub 4} anodes may be exploited suitably for practical lithium battery applications.
A weak shift of the isotope concentration ratio Li{sup 6}/Li{sup 7} was measured in the coexisting phases of the miscibility gap of lithium-ammonia solutions. Li{sup 6} is slightly enriched in the concentrated metallic phase (enrichment factor {alpha} = 1.009 {+-} 0.002). This effect can be enhanced in a counter-current column to yield any desired enrichment of the two isotopes. The counter current system and its operation were tested succesfully with a sodium-potassium-ammonia solution.
Angular distributions for the elastic and inelastic scattering of /sup 12/C at 80 MeV by /sup 88/Sr and of /sup 7/Li at 36, 42 and 48 MeV by /sup 54/Fe have been analysed. The optical potentials of /sup 12/C and /sup 7/Li ions are calculated in terms of the alpha-particle and triton optical potentials. Coupled-channels calculations using these potentials are performed. Good fits to the experimental data and the phenomenological calculations are obtained for /sup 12/C projectiles.
Single crystals of Li{sub 1.8}(In{sub 0.55}Zr{sub 0.45}){sub 2}(PO{sub 4}){sub 3} and Li{sub 3}(In{sub 1-x}Sc{sub x}){sub 2}(PO{sub 4}){sub 3} (x=0.67,0.73) were grown by a flux method. The crystal structure of Li{sub 1.8}(In{sub 0.55}Zr{sub 0.45}){sub 2}(PO{sub 4}){sub 3} was found to be similar to that of the high temperature {gamma}-phase of Li{sub 3}Sc{sub 2}(PO{sub 4}){sub 3}. However, Li ions were located on only one site among three available sites. On the other hand, those of Li{sub 3}In{sub 2}(PO{sub 4}){sub 3}-Li{sub 3}Sc{sub 2}(PO{sub 4}){sub 3} solid solutions were found to be similar to that of the low temperature {alpha}-phase of Li{sub 3}Sc{sub 2}(PO{sub 4}){sub 3}. The ionic conductivity of Li{sub 1.8}(In{sub 0.55}Sc{sub 0.45}){sub 2}(PO{sub 4}){sub 3} was measured along with the ...
Neutron yield from the "6","7Li + d reaction has been investigated. The results obtained are compared with the published data with some theoretical models.
The determination of Li and proton-capture element abundances in globular cluster (GC) giants allows us to constrain several key questions on the multiple population scenarios in GCs, from formation and early evolution to pollution and dilution mechanisms. In this Letter, we present our results on Li abundances for a large sample of giants in the intermediate-metallicity GC NGC 6121 (M4), for which Na and O have been already determined by Marino et al. The stars analyzed are both below and above the red giant branch bump luminosity. We found that the first and second generation stars share the same Li content, suggesting that a Li production must have occurred. This provides strong observational evidence supporting the scenario in which asymptotic giant branch stars are GC polluters.
A nonneutral /sup 7/Li/sup +/ ion plasma is described in which ion Langmuir waves are observed for the first time. The properties of these waves near the Brillouin density limit are investigated.
The paper studies the effect of crystal structure of LiNbO_3 monocrystals on NMR spectra of "7 Li and "9"3 Nb. Models of defect structure are analyzed via comparison of NMR experimental spectra and gradients of electrical field predicted on the basis of the calculations on "7 Li and "9"3 Nb nuclei using the relevant model. It is shown that no one of the main models of lithium niobate defect structure explains the peculiarities of NMR spectra. Conclusions are made about the independence of the reasons of occurrence of NMR additions lines "7 Li and "9"3 Nb, as well as, about links of "9"3 Nb NMR weak additional lines with the ranges of a different crystalline phase that may form while growing. 18 refs., 2 figs., 3 tabs.
CeO{sub 2}-coated LiMn{sub 2}O{sub 4} spinel cathode was synthesized using two-step synthesis method. All the samples exhibited a pure cubic spinel structure without any impurities in the XRD patterns. The results of the electrochemical performances on CeO{sub 2}-coated electrode are compared to those of electrodes based on LiMn{sub 2}O{sub 4} spinel without CeO{sub 2} coating. CeO{sub 2}-coated LiMn{sub 2}O{sub 4} cathode improved the cycling stability of the electrode. The capacity retention of 2 wt% CeO{sub 2}-coated LiMn{sub 2}O{sub 4} was more than 82% after 150 cycles between 3.0 and 4.4 V at room temperature and 82% after 40 cycles at elevated temperature of 60 C. The amounts of dissolved manganese-ions in CeO{sub 2}-coated LiMn{sub 2}O{sub 4} significantly are smaller than pristine LiMn{sub 2}O{sub 4} systems especially at elevated temperatures. ...
The last developments in lithium batteries design have demonstrated the advantages of graphite: competitive cost, flat output curve, high capacity thanks to the obtention of a final compound close to LiC{sub 6}, good behaviour during cycling and a high mass energy. However, these advantages are slightly tarnished by parasite secondary reactions during the evolution of the element. Two different cases are encountered: the formation of a passivation layer (loss of Li ions and formation of irreversible bounds) and the formation of a passivation layer with a reaction between graphite and the solvent (partial destruction of the graphite crystal lattice). In the first case, the theoretical graphite insertion capacity remains at 372 mAh/g while in the second case the insertion capacity is greatly reduced. Abstract only. (J.S.)
As a new high-voltage cathode candidate for post 4V cathodes, ordered-olivine LiCoPO{sub 4} and fluoride phosphate, Li{sub 2}CoPO{sub 4}F were synthesized by solid-state reaction. Their structures were identified by neutron diffraction. The 5V discharge profiles were demonstrated using coin-type cells. Two important issues for commercial use, metal dissolution and oxygen release at elevated temperatures, were also tested with an atomic absorption spectrophotometer and differential scanning calorimeter, respectively. (author)
The electrochemical behavior of Sb(III) ions was investigated in LiCl-KCl molten salt at 673K. The reaction mechanism and transport parameters of electroactive species were determined by transient electrochemical techniques (such as cyclic voltammetry, square wave voltammetry, chronopotentiometry and chronoamperometry) at a molybdenum electrode. The results showed that electrochemical reduction of Sb(III) in LiCl-KCl melts occurred in a reaction step with an exchange of three electrons. A voltammogram with a different scan rate in LiCl-KCl containing 1.45x10^-^4molcm^-^3 SbCl3 showed that the deposition/dissolution reaction of Sb(III) ions was not completely reversible. The diffusion coefficient of Sb(III) ions was 1.65(+/-0.01)x10^-^5cm^-^2s^-^1 at 673K. The electroreduction of Sb(III) io...
High-temperature LiCl-KCl molten salt medium provides an efficient way to produce the paramagnetic Eu(II) ion to be magnetically diluted into a diamagnetic host medium. Eu(II) was formed by a dissolution and an auto-reduction processes in a high-temperature LiCl-KCl eutectic melt at 723 K by using Eu{sub 2}O{sub 3} as a starting material. By using EPR and luminescence spectroscopic method, we studied the nature of the magnetically isolated paramagnetic Eu(II) ion diluted in a LiCl-KCl medium. With the aid of these spectroscopic tools, it was found that stable Eu(II) species was formed spontaneously at 723 K under anaerobic conditions. EPR and luminescence spectroscopy provided detailed information regarding the nature of the europium ion in a molten salt.
High-temperature LiCl-KCl molten salt medium provides an efficient way to produce the paramagnetic Eu(II) ion to be magnetically diluted into a diamagnetic host medium. Eu(II) was formed by a dissolution and an auto-reduction processes in a high-temperature LiCl-KCl eutectic melt at 723 K by using Eu_2O_3 as a starting material. By using EPR and luminescence spectroscopic method, we studied the nature of the magnetically isolated paramagnetic Eu(II) ion diluted in a LiCl-KCl medium. With the aid of these spectroscopic tools, it was found that stable Eu(II) species was formed spontaneously at 723 K under anaerobic conditions. EPR and luminescence spectroscopy provided detailed information regarding the nature of the europium ion in a molten salt.
High-temperature LiCl-KCl molten salt medium provides an efficient way to produce the paramagnetic Eu(II) ion to be magnetically diluted into a diamagnetic host medium. Eu(II) was formed by a dissolution and an auto-reduction processes in a high-temperature LiCl-KCl eutectic melt at 723K by using Eu2O3 as a starting material. By using EPR and luminescence spectroscopic method, we studied the nature of the magnetically isolated paramagnetic Eu(II) ion diluted in a LiCl-KCl medium. With the aid of these spectroscopic tools, it was found that stable Eu(II) species was formed spontaneously at 723K under anaerobic conditions. EPR and luminescence spectroscopy provided detailed information regarding the nature of the europium ion in a molten salt.
In the electrorefining step of the pyrochemical process, actinide ions dissolved in the LiCl-KCl eutectic salt are recovered as pure actinide metals at a cathode for a re-use as a nuclear fuel from the aspect of its nonproliferation of the nuclear fuel cycles. The lanthanide species dissolved in the LiCl-KCl eutectic salt play an important role in an effective metal purification during the electrorefining step, so it is necessary to understand the chemical and physical behaviors of lanthanides in molten salt. The in situ spectroscopic measurement system and studies according to temperature changes are essential for better understandable information. To our knowledge, the absorption studies of lanthanides at high temperatures have been reported before, but the fluorescence studies of those at high temperature are not reported yet. We will discuss here the fluorescence behaviors of lanthanides in LiCl-KCl molten salt medium ...
In the electrorefining step of the pyrochemical process, actinide ions dissolved in the LiCl-KCl eutectic salt are recovered as pure actinide metals at a cathode for a re-use as a nuclear fuel from the aspect of its nonproliferation of the nuclear fuel cycles. The lanthanide species dissolved in the LiCl-KCl eutectic salt play an important role in an effective metal purification during the electrorefining step, so it is necessary to understand the chemical and physical behaviors of lanthanides in molten salt. The in situ spectroscopic measurement system and studies according to temperature changes are essential for better understandable information. To our knowledge, the absorption studies of lanthanides at high temperatures have been reported before, but the fluorescence studies of those at high temperature are not reported yet. We will discuss here the fluorescence behaviors of lanthanides in LiCl-KCl molten salt medium ...
Interactions (FCCI) University of Wisconsin, Madison Thermal Properties of LiCl-KCl Molten Salt for Nuclear Waste Separation University of Wisconsin, Madison Next Generation...
Cathode materials for rechargeable rocking chair or lithium-ion batteries, are reviewed. The emphasis is placed on the comparison between specific capacities and rechargeability of lithium-containing high voltage cathode materials such as manganese oxides and LiMO{sub 2} compounds, where M is Co or Ni. It is generally found that the maximum reversible capacities for the most promising materials fall in the range 100-120 mAh/g, and decaying to around 75 mAh/g after several hundred cycles. The rechargeability is similar for the most commonly considered materials: LiMn{sub 2}O{sub 4}, LiCoO{sub 2} and LiNiO{sub 2}. No improvements in capacity or rechargeability, beyond what have been found for these materials, is observed by substitution of other elements into these compounds
... earns money through receiving protection funds from embattled ... relationship between the TTP and LI ... relevant considering that Pakistan's military is ...
The properties of a new commercial thermoluminescent dosimeter, CaSO4:Dy without a LiF binder (TLD-900) was studied for low-exposure measurements in diagnostic radiology. The former TLD-900 had a LiF binder (herein referred to as ''TLD-900/LiF''). The principle features of this dosimeter are its high sensitivity to low-energy radiation and its relatively low fading which permits measurements down to less than 2.6 X 10(-8) C kg (0.1 mR) with an accuracy better than 20%. The characteristics, annealing procedures, light sensitivity, energy response, reproducibility, and fading, of TLD-900 are discussed and compared with TLD-900/LiF. When the precautions presented in this paper are used, the dosimeters can be used for the measurement of x-ray exposures.
Density functional theory (DFT) calculations using plane-wave methods were performed for Li2TMPO4F, LiTMPO4F, and TMPO4F (TM=V, Mn, Fe, Co, Ni) to address their feasibility as high-voltage cathode materials for Li ion batteries. We computed their structures, average open circuit voltages, and thermal stabilities for step-wise lithiation/delithation (discharge/charge) reactions. The calculations suggest that associated unit cell volume changes are sufficiently small on average that they should not be a significant detriment to the mechanical stability of the cathode. In the nickel case, the calculated volume change deviates from the series by increasing during the first delithiation step. Furthermore, the volume increases for all these materials during the second delithiation step. It appears that the relative volume expansion in the series during delithiation is directly correlated to the degree of d-p rehybridization. ...
We present a laser spectroscopic approach for measuring the charge radius of the halo nucleus {sup 11}Li and report on recent progress in the development of the experimental apparatus.
An interest in electronic materials has led me to investigate new synthetic approaches to III-V' type semiconducting (13-15, current IUPAC designation for B and N groups in the Periodic Table) and magnetic (3-15) compounds. It is now possible to prepare binary (GaAs and GdP) and ternary mixed-metal (Al[sub x]Ga[sub 1-x]As) and mixed-pnictide (GaP[sub x]As[sub 1-x]) compounds in seconds from rapid, low-temperature-initiated metathesis reactions between a metal (III) trihalide and a trisodium pnictide, exemplified by MX[sub 3] + Na[sub 3]Pn [yields] MPn + 3 NaX, where M is Al, Ga, In, (Al,Ga), or a lanthanide; X is F, Cl, or I; and Pn is P, As, Sb, or (P,As). The precursors are mixed together in a dry box and ignited by light grinding with a mortar and pestle, or by brief, local heating from a hot filament. These reactions are very exothermic (calculated [Delta]H[sub rxn] (GaAs) = 138 kcal/mol) and typically reach temperatures in excess of 700[degrees]C within seconds of ...
The thermo-chemical treatments of steels with plasma is normally carried out in low-pressure ionized gaseous atmospheres. Among the treatments used most often are: nitruration, carburization and boronized. A plasma can also generate at atmospheric pressure. One way to produce it is with an electrochemical cell that works at a relatively high inter-electrode voltage and under conditions of heavy gas generation. This type of plasma is known as electrolytic plasma. This work studies the feasibility of using electrolytic plasma for the surface processing of steels. Two processes were selected: boronized and nitruration., for the hardening of two types of steel: one with low carbon (1020) and one with low alloy (4140). In the case of the nitruration, the 1020 steel was first aluminized. The electrolytes were aqueous solutions of borax for the boronizing and urea for the nitruration. The electrolytic plasmas ...
In order to get the separation of natural isotopes of lithium by electrolytic amalgamation, an electrolytic cell with a confined mercury cathode was used to obtain data for the design of a separation stage. The initial work was followed by the design of a moving mercury cathode electrolytic cell and three experiments with six batches stages were performed for the determination of the elementary separation factor. The value obtained, 1.053, was ill agreement: with the specialized literature. It was verified in all experiments that the lithium - 6 isotope concentrated in the amalgam phase and that the lithium - 7 isotope concentrated in the aqueous phase. A stainless-steel cathode for the decomposition of the lithium amalgam and the selective desamalgamation were also studied. In view of the results obtained, a five stages continuous scheme was proposed. (author)
Ultra-thin, uniform, pinhole-free solid polymer electrolyte films having a fixed carboxylic ester group of approximately 1 {mu}m thickness were prepared by polymerization of methyl acrylate and tris(2-methoxyethoxy)vinylsilane in a glow discharge plasma. The carboxylic ester group of the plasma polymer were transformed to lithium carboxylate groups by treatment with lithium iodide. This process give a single lithium ion conductive film. These solid polymer electrolyte films showed ionic conductivities of the order of 10{sup -8} S cm{sup -1} (10{sup 4} {omega} cm{sup 2} resistance per unit area) at room temperature. (orig.).
Ultrathin solid polymer electrolyte membranes containing sulfonic ester groups were prepared by polymerization of methyl benzenesulfonate and octamethylcyclotetrasiloxane in a glow discharge plasma. The sulfonic ester groups of the plasma polymer were transformed to lithium sulfonate groups by treatment with lithium iodide. Hybridization of this plasma polymer containing the lithium sulfonate groups with poly(ethylene oxide) (average Mw 300) resulted in the formation of a single lithium ion conductive film. The hybrid polymer electrolyte films were about 1 #mu#m thick, pinhole-free, adherent to various substrates, and showed ionic conductivities at 60 degrees C of the order of 10"- "6 S cm"- "1 (10"2 #OMEGA# cm"2 resistance per unit area of as-prepared solid polymer electrolyte). This material shows promise for electrochemical applications such as all solid-state lithium batteries, sensors, and electrochemical display ...
A sulfonated fluoroalkyl graft polymer (FGP) membrane was prepared as a polymer electrolyte. First, the FGP membrane was grafted with styrene under UV irradiation. The grafted FGP was then sulfonated to functionalize it for proton conductivity. The grafting degree of the membrane increased with increasing grafting time during UV irradiation. The proton conductivity of the membrane increased with increasing grafting degree. The swelling ratio was independent of the grafting time, however, the water uptake increased with increasing grafting degree. Based on these results, it was found that the UV-initiated styrene grafting occurred along the membrane thickness direction. Moreover, the membrane was embedded within the glass fibers of the composite. This composite electrolytic membrane had 1.15 times the proton conductivity of a Nafion 117 membrane.
Manganese dioxide (MnO2) was prepared using the ultrasonic method. Its electrochemical performance was evaluated as the cathode material for a high voltage hybrid capacitor. And the specific capacitance of the MnO2 electrode reached 240 F.g-1. The new hybrid capacitor was constructed, combining Al/Al2O3 as the anode and MnO2 as the cathode with electrolyte for the aluminum electrolytic capacitor to solve the problem of low working voltage of a supercapacitor unit. The results showed that the hybrid capacitor had a high energy density and the ability of quick charging and discharging according to the electrochemical performance test. The capacitance was 84.4 mF, and the volume and mass energy densities were greatly improved compared to those of the traditional aluminum electrolytic capacito...
It has been reported by the present authors that behavior of tritium release from solid breeder grain is consisted of diffusion in grain, tritium transfer at surface layer and surface reactions on grain surface such as adsorption or isotope exchange reactions. Tritium release curves estimated using the tritium release model gave good agreement with observed tritium release curves from Li{sub 4}SiO{sub 4}, Li{sub 2}ZrO{sub 3} or LiAlO{sub 2}. Tritium release behavior from Li{sub 2}TiO{sub 3} under humid purge gas, dry purge gas and dry purge gas with hydrogen conditions is discussed in this study, tritium release curves using the release model that we proposed previously give a good agreements with experimental tritium release curves. Tritium effective diffusivity in the crystal grain of Li{sub 2}TiO{sub 3} is also estimated in this study using a curve-fitting method applied to the ...
It has been reported by the present authors that behavior of tritium release from solid breeder grain is consisted of diffusion in grain, tritium transfer at surface layer and surface reactions on grain surface such as adsorption or isotope exchange reactions. Tritium release curves estimated using the tritium release model gave good agreement with observed tritium release curves from Li_4SiO_4, Li_2ZrO_3 or LiAlO_2. Tritium release behavior from Li_2TiO_3 under humid purge gas, dry purge gas and dry purge gas with hydrogen conditions is discussed in this study, tritium release curves using the release model that we proposed previously give a good agreements with experimental tritium release curves. Tritium effective diffusivity in the crystal grain of Li_2TiO_3 is also estimated in this study using a curve-fitting method applied to the release curves obtained under the humid purge ...
Model phosphate-metal solvation complexes have been studied by ab-initio self-consistent-field techniques. The complexes studied include (RO)2PO2-(R = H or CH3) with Li+, Na+, K+, Be++, Mg++, Ca++,...Full Text Available
Tensor polarization of "6Li(2.18 MeV, 3"+) nucleus at inelastic scattering of #alpha# particles for #THETA#_l_a_b=45 deg angle is measured. The results are described by the calculations in terms of Born approximation of distorted waves with internucleonic interaction realistic potential.
The pace of development and fielding of electric vehicles is briefly described and the principal advanced battery chemistries expected to be used in the EV application are identified as Ni/MH in the near term and Li-ion/Li-polymer in the intermediate to long term. The status of recycling process development is reviewed for each of the two chemistries and future research needs are discussed.
A comparison of nucleation and crystallization of Li{sub 2}O{sm_bullet}2SiO{sub 2} between microwave and conventional heating was investigated. Standard stereological techniques were used to evaluate the results. Nucleation and crystallization behaviors during microwave heating appeared different from conventional heating. Work is in progress to better understand the effects of microwaves on nucleation and crystallization in glass.
Four inorganic hydrogen-bonded crystals with second-order nonlinear properties have been discovered: K_4LiH_3(SO_4)_4, Na_2SeO_4#centre dot#H_2SeO_3#centre dot#H_2O, Cs_1_,_5Li_1_,_5H(SO_4)_2 and NH_4HSeO_4. (author)
When used for tissue-equivalent monitoring, the thermoluminescence material LiF:Mg, Cu, P shows an 'under-response' to low-energy photons. This paper explores a new way to increase its low-energy response effectively, and to make it adjustable to some extent, by adding elements with high Z{sub eff}. At the same time its excellent thermoluminescente (TL) performance is maintained. (author).
A series of spinel Li{sub 4}Ti{sub 5}O{sub 12} samples were synthesized via a composite molten-salt method (CMSM) using the mixtures of LiCl and KCl with different L values (L is defined as the molar ratio of LiCl:KCl) as the reaction media. It is found that the melting point of the composite molten salt can effectively influence the formation of particles, and leads to different electrochemical performances of the as-prepare Li{sub 4}Ti{sub 5}O{sub 12}. The investigations of X-ray diffraction (XRD), particle size distribution (PSD), Brunauer-Emmet-Teller (BET) surface area, and scanning electron microscopy (SEM) indicate that the as-prepared Li{sub 4}Ti{sub 5}O{sub 12} with L = 1.5 is a pure phase, and has uniform homogeneous octahedral shape particles, rather narrow PSD, and high BET surface area. Electrochemical tests show that the optimized Li{sub 4}Ti{sub ...
A simple arrangement of standard horizontal coaxial Ge(Li) detectors with the aim of constructing a Compton linear-polarimeter was tested. High polarization sensitivity and detection efficiency were achieved. The characteristics of the polarimeter and analysis of the observed quantities in terms of the linear-polarization mixing coefficient Hsub(l)(LL') are described.
Experimental results are presented on the quasi-statistic polarization reversal and on the effect of high dc electric field on the behaviour of LiNH_4SO_4 and LiND_4SO_4 monocrystals, namely in the vicinity of the II-III phase transformation.
In the present work, electrochemical measurements and corrosion tests in NaCl solutions were carried out to study the effect of aging treatments on pitting corrosion behavior in a 8090 alloy and its high purity Al-Li binary alloy analogue. The pitting corrosion characteristics and corrosion resistance of the 8090 alloy have been determined in relation to precipitation microstructures. (orig.).
The temperature and concentration dependence of the densities of binary CaBr_2-(Li, Na, K, Rb, Cs)Br, NaBr-(Sr, Ba)Br_2 and KBr-SrBr_2 mixtures have been measured using the method of hydrostatic weighing. With exception of the systems LiBr-CaBr_2 and NaBr-(Sr, Ba)Br_2 the calculated molar excess volumes are positiv in the investigated mixtures. (author).
Effect of hydroxide nature, concentration and temperature on corrosion resistance of domestic steels and alloys to hot NaOH, KOH, LiOH solutions is considered. It is ascertained that by corrosion growth in relation to stainless steels and nickel alloys, the hydroxides are placed in the following sequence: LiOH
A simple arrangement of standard horizontal coaxial Ge(Li) detectors with the aim of constructing a Compton linear-polarimeter was tested. High polarization sensitivity and detection efficiency were achieved. The characteristics of the polarimeter and analysis of the observed quantities in terms of the linear-polarization mixing coefficient Hsub(l)(LL') are described. (orig.).
The Anglo-Danish programme of research on materials for advanced vehicular transport and other storage batteries is about to enter its fifth year. Here, the results of the work to date on solid electrolytes, electrode materials and cell design are reviewed and discussed as a systematic programme of cell testing gets underway.
Analysis of results of an investigation into the structure of lithium salt aqueous solutions is presented. An anomaly in lithium ion behaviour in solutions at the structural level is noted. 40 refs., 3 tabs.
The project has been developing Yttria Stabilized Zirconia (YSZ)-Alumina Composites as an electrolyte of a self-support type planar Solid Oxide Fuel Cell (SOFC) from the following points of view: a path of alumina particles with high thermal conductivity can be designed as an electrolyte sheet; there are some possibilities that the electrolyte can be enhanced in mechanical strength. As previously reported, these composite materials have higher mechanical strength and better thermal shock resistance than those of YSZ. These composites containing 0-30 wt% of Al[sub 2]O[sub 3] were measured by AC impedance method at temperatures of 250-1,000[degree]C. Electrical conductivities of 8YSZ without Al[sub 2]O[sub 3] and a composite consisting of 80 wt% YSZ and 20 wt%Al[sub 2]O[sub 3] as sintered samples were 1.2 x 10[sup -1]S/cm and 1.0 x 10[sup -1]S/cm respectively at 1,000[degree]C. The composite containing 20 wt% of Al[sub ...
This paper describes zinc-air battery for electric vehicle (EV). This battery is composed of air electrode, zinc electrode, and alkali electrolyte. During the discharge, oxygen taken from the air is reduced at the air electrode, and zinc is dissolved at the zinc electrode. The whole reaction is formation of zinc oxide from oxygen and zinc. This is taken out to use as a secondary battery through exchange and regeneration, which is called mechanical charge. For Electric Fuel, discharged products in the zinc electrode from a spent EV are extracted by a vibrating crusher, and are dissolved in KOH to prepare zinc ion electrolyte. Thus, zinc is obtained through the electrolytic refining. Since the regenerated zinc is separated from the electrolytic electrode as a form of dendritic powder, it is recovered, treated by press molding, regenerated, and used as a zinc electrode. The battery developed by Electric ...
The possibility of using lead or lead-bismuth mixed oxides as positive materials in organic electrolyte lithium cells with a working voltage similar to those of conventional systems (1.5 V) has been considered. Performances and main characteristics of this new class of lithium batteries are described.
twenty 350 V, 2.5 mF aluminum electrolytic capacitors with 10.8 mH inductors made of multi-strand wire. The PFN discharge was controlled using an silicon ...
The invention comprises an improved rechargeable zinc-air cell/battery having recirculating alkaline electrolyte and a zinc electrode comprising a porous foam support material which carries the active zinc electrode material. 5 figs.
Protonic ceramic membrane fuel cells (PCMFCs) based on proton-conducting electrolytes have attracted much attention because of many advantages, such as low activation energy and high energy efficiency. A stable, easily sintered perovskite oxide BaCe_0_._5Zr_0_._3Y_0_._1_6Zn_0_._0_4O_3_-_#delta# (BCZYZ) as electrolyte for proton-conducting solid oxide fuel cells (SOFCs) with Sm_0_._5Sr_0_._5CoO_3_-_#delta# (SSC) composite cathode is investigated. By fabricating thin membrane BCZYZ electrolyte (#approx#20 #mu#m) synthesized by a modified Pechini method on NiO-BCZYZ anode support, PCMFCs are assembled and tested by selecting SSC perovskite cathode with high mixed ionic and electronic conductivities. An open-circuit potential of 1.015 V, a maximal power density of 528 mW cm"-"2, and a low polarization resistance of the electrodes of 0.15 #OMEGA# cm"2 is achieved at 700 "oC. The results indicate that BCZYZ proton-conducting ...
the network were assembled of custom 450 volt Aluminum electrolytic capacitors provided by the Mallory Capacitor Company. A comparison between theoretical ...
This article reports of the nickel-metal-hydride battery and its ability to compete with the lead-acid battery in electric-powered vehicles. The topics of the article include development of the battery, the impetus for development in California environmental law, battery performance, packaging for the battery's hazardous materials, and the solid electrolyte battery.
A study has been performed of the initial corrosion of support structure alloys in crevices of various geometries, when galvanically coupled to alloy 600. Corrosion rates were monitored continuously by measuring the galvanic current flowing in each couple, transduced by a zero impedance ammeter. Experiments were performed in a single-pass flowing electrolyte system, with AVT water pumped through alloy 600 tubing past the orifice of each crevice. Fourteen crevices were studied simultaneously in two parallel flow arms containing seven specimens each. The steady state AVT water pH/hydrazine/oxygen concentrations were controlled by microcomputer, allowing the effect of secondary water chemistry on the corrosion rate to be studied easily. Control of the crevice electrolyte composition was achieved by separately pumping electrolyte, at a low rate, directly into the crevices of the seven specimens in the lower flow arm. In ...
A solar water splitting cell composed of WO3, Polymer Electrolyte Membrane (PEM) and Pt was constructed for producing hydrogen from deionized water in sunlight. Spectral responsivity measurements under various temperatures and bias voltages were conducted for the cell using the Incident Photon to Current Efficiency (IPCE) method. For comparison, a known WO3 Photo Electro Chemical (PEC) cell containing H3PO4 electrolyte, WO3/H3PO4/Pt, was tested using the same test method. The WO3/PEM-H2O/Pt cell showed better Quantum Efficiency (QE) performance compared to that obtained from the cell with the chemical electrolyte. For the first time, spectral responsivity of photo water splitting process without bias power was unveiled in the new WO3 cell, demonstrating the self-sustained photo electrolysi...
BackgroundIn mammals, vasopressin (AVP) is released from magnocellular neurons of the hypothalamus when osmotic pressure exceeds a fixed set-point. AVP participates to the hydromineral...Full Text Available
Lithium, with its strong reducing property and very low potential (-3.045 V/ENH), is one of the best material for electrodes. By combining lithium with an oxidizer, one can obtain an energy and electromotive force higher than with any other electrochemical couple. The density of lithium is low (0.534 g/cm{sup 3}) and thus, its specific capacity is higher than other classical anode materials. This article presents the technology of lithium batteries: 1 - presentation; 2 - negative electrodes: metallic lithium based, lithiated carbon based, transition metal compounds based negative electrodes; 3 - positive electrodes: 'low' voltage and 'high' voltage cathode materials; 4 - electrolytes: introduction, organic solvents and lithium salts-based electrolytes (case of the lithium anode battery, case of the lithium-ion battery), polymer electrolytes; 5 - metallic lithium anode and liquid ...
The agglomerate for the element is made from activated charcoal powder, an electrically conducting additive and a neutral electrolyte. The activated charcoal makes up 30 to 50 percent of the weight of the agglomerate. It is a mixture of hydrophobized and unhydrophobized powder in a ratio of 85 to 70 to 15 to 30. The element has high discharge characteristics.
A 300 W fuel cell power pack has been developed for educational purposes in close collaboration with the Fachhochschule Solothurn Nordwestschweiz. The project was initiated and financed by the Swiss Federal Office of Energy. The outlay and the performance of the power pack are described. (author) 3 figs.
Radioactive rare earth chlorides in waste LiCl-KCl molten salts have to be separated as a stable form to minimize waste volume and to achieve stable solidification. In this work, thermal behavior of rare earth chlorides (CeCl3, GdCl3, NdCl3, PrCl3) was investigated in an oxygen condition to recover rare earth oxides from a LiCl-KCl-RECl3 system. The rare earth chlorides in the LiCl-KCl molten salts were smoothly converted to an oxychloride form at a higher temperature than 650degreeC, except for CeCl3. CeCl3 was totally converted to an oxide from at a higher temperature than 450degreeC. The rare earth oxychlorides (GdOCl, NdOCl, PrOCl) were effectively converted to oxide forms at a higher temperature than 1100degreeC. It was confirmed that rare earth oxides can be recovered from a LiCl-KCl...
The structure and vibrational properties of high voltage cathode materials, namely LiNi{sub 1-y}CO{sub y}VO{sub 4} solid solution with (0{<=}y{<=}1), have been studied using X-ray diffraction, Raman scattering and FTIR measurements. Rietveld refinements show that LiNi{sub 1-y}Co{sub y}VO{sub 4} vanadates belong to the inverse spinel structure with Fd3m(O{sup 7}{sub h}) space group. Analysis of Raman spectra has been carried out in the molecular approximation using a local environment model including VO{sub 4} tetrahedra, (Ni, Co)O{sub 6} and LiO{sub 6} octahedra as vibrational local units. (orig.)
In this study a modified solid state synthesis (auto-ignition method) is used to form nanosized spinel type material LiMg{sub 0.05}Ni{sub 0.45}Mn{sub 1.5}O{sub 4}. This material presents a high voltage plateau at 4.75 V vs. Li/Li{sup +}. Structural and electrochemical characterisations have been performed using a wide range of techniques (TEM, neutron diffraction, galvanostatic measurements, and impedance spectroscopy). Besides, in situ XAS has been performed to monitor the evolution of Ni and Mn oxidation state during Li intercalation. The material presents an ordered cubic spinel structure, good capacity retention upon cycling (131 mAh g{sup -1} at C/10 and 117 mAh g{sup -1} at 1C) and good electronic conductivity (10{sup -6} S cm{sup -1} at RT). The simultaneous presence of Mn{sup 3+}/Mn{sup 4+} in the structure has been investigated and explained by inclusion of disordered nanodomains in the structure. (author)
The glasses with the composition of 37.5Li2O?(25?x)Fe2O3?xNb2O5?37.5P2O5 (mol%) (x=5,10,15) are prepared, and it is found that the addition of Nb2O5 is effective for the glass formation in the lithium iron phosphate system. The glass?ceramics consisting of Nasicon-type Li3Fe2(PO4)3 crystals with an orthorhombic structure are developed through conventional crystallization in an electric furnace, showing electrical conductivities of 3?10?6?Scm?1 at room temperature and the activation energies of 0.48?eV (x=5) and 0.51?eV (x=10) for Li+ ion conduction in the temperature range of 30?200??C. A continuous wave Nd:YAG laser (wavelength: 1064?nm) with powers of 0.14?0.30?W and a scanning speed of 10??m/s is irradiated onto the surface of the glasses, and the formation of Li3Fe2(PO4)3 crystals is c...
Previous behavioral and pharmacological studies have implicated endorphins in radiation-induced locomotor hyperactivity of the C57BL/6J mouse. However, the endogenous opiate(s) responsible for this behavioral change have not been identified. The present study measured beta-endorphin-like immunoreactivity (beta-END-LI) in brain, blood, and combined brain and pituitary samples from irradiated and sham-irradiated C57BL/6J mice. After radiation exposure, levels of beta-END-LI decreased significantly in the brain. A similar, but not statistically significant, decline was measured in combined brain and pituitary samples. Concentrations of blood beta-END-LI were not changed by irradiation. These radiogenic changes in beta-END-LI are in some ways similar to those observed after other stresses. However, radiation-induced locomotor hyperactivity may be mediated more by alterations of ...
We studied the effects of co-doping with Li and Al on the energy gaps of MgB2 by performing point-contact Andreev-reflection spectroscopy (PCAR) in polycrystalline Mg1-x(Al?Li1-?)xB2 samples with x?0.4. Even though the lattice parameters and the critical temperature of the compound simply scale with the effective Al content ?x, irrespective of the Li concentration, the energy gaps do not. In particular, for a given effective Al content, the comparison with Mg1-y(Al)yB2 with y = ?x shows that the ? bandgap is practically the same while the ? bandgap is higher. A clear gap merging is observed in the most doped sample (x = 0.4) when Tc<20 K. The results are discussed within the two-band Eliashberg theory and compared to the outcomes of first-principles calculations of the effects of Li and Al co-doping on the electronic structure of magnesium diboride.
The electrochemical behavior of lanthanide oxides in molten alkaline chloride media is of great concern in pyrochemical processes for advanced nuclear fuel cycle. We have studied the solubilities of various lanthanide oxides in LiCl-KCl eutectic melt. In general, lanthanide oxides appeared to be insoluble/sparingly soluble in LiCl-KCl eutectic at 723 K. However, europium oxide exhibited an abnormal behavior in solubility and redox chemistry. The solubility of europium oxide was measured to be 1-2 order of magnitude higher than those of other lanthanide oxides. This abnormal solubility may be attributable to different electrochemical behavior of europium in the same experimental conditions. Most lanthanides ion exists as trivalent oxidation states. However, we observed divalent europium dissolved in LiCl-KCl molten salt by applying electron paramagnetic resonance(EPR) spectroscopy. (Figure 1) With the aid of this ...
Kitchen oils (olive, soybean and butter) are selected for carbon coatings on LiFePO{sub 4}. The surface properties of LiFePO{sub 4} are unknown or vary depending on synthetic methods. The multi-functional groups of fatty acids in the oils can orient properly to cope with the variable surface properties of LiFePO{sub 4}, which can lead to dense carbon coatings. The low price and low toxicity of kitchen oils are other advantages of the coating process. LiFePO{sub 4} (D{sub 50} = 121 nm)combined with the carbon coating enhances the rate capability. Capacities at the 2C rate reach 150 mAh g{sup -1} or higher. The charge retention values of 2.0C/0.2C are between 94.4 and 98.9%. (author)
The atomic masses of the alkali-metal isotopes "6Li,"2"3Na,"3"9","4"1K,"8"5","8"7Rb, and "1"3"3Cs have been obtained from measurements of cyclotron frequency ratios of pairs of ions simultaneously trapped in a Penning trap. The results, with one standard deviation uncertainty, are: M("6Li)=6.015 122 887 4(16)u,M("2"3Na)=22.989769 282 8(26)u,M("3"9K)=38.963 706 485 6(52)u,M("4"1K)=40.961 825 257 4(48)u,M("8"5Rb)=84.911 789739(9)u,M("8"7Rb)=86.909 180 535(10)u, and M("1"3"3Cs)=132.905 451 963(13)u. Our mass of "6Li yields an improved neutron separation energy for "7Li of 7251.1014(45) keV.
The pH of the solution is shown to significantly effect the reflection anisotropy spectroscopy (RAS) profiles of adenine adsorbed at Au(110)/electrolyte interfaces. At pH 12.8 the net adsorption is very weak due the formation of negative adenine ions in solution. The sensitivity of the RAS profiles to the pH of the solution is probably due to a change in the geometry of the adsorbed molecules caused by a disruption of the base stacking configuration that is adopted when adenine is adsorbed from solutions at pH 7.1. (Abstract Copyright [2010], Wiley Periodicals, Inc.)
A solid electrolyte cell comprises an alkali metal anode, e.g. lithium, a halogen-containing organic polymer cathode and a solid elecrolyte between the anode and the cathode. The cathode comprises iodine-containing vacuum-cyclised polyacrylonitrile, and the solid electrolyte is preferably lithium iodide and halogen-free vacuum-cyclised polyacrylonitrile. This patent also discloses the use of isotactic polyacrylonitrile, a method of making a cathode comprising iodine-containing vacuum-cyclised polyacrylonitrile, and novel methods of making the solid elecrolyte cells described.
Several commercially available capacitors were evaluated at the liquid nitrogen temperature (77 K). Our primary interest was their performance under a bias voltage when used as DC link capacitors in cryogenic power electronics. In general, the performance of polymer capacitors and certain ceramic capacitors is almost independent of the temperature, DC bias, and frequency. On the other hand, ceramic capacitors based on high dielectric constant materials showed a strong dependence on the boundary conditions. Aluminum electrolytic capacitors showed a dramatic decrease of capacitance at 77 K, possibly due to the electrolyte being frozen and therefore losing its conductivity.
Fuel cells based on solid oxides ('SOFC') are excellent alternative devices for power generation, when they are operated at high temperature, e.g. above 600 C. Having only fixed parts for the power generating part of the device is only one advantage of the fuel cell. Due to their unique design, these devices offer a maximum of efficiency for energy conversion compared to conventional power generating systems, which are mainly based on turbines. One aim of this thesis is the examination of alternative electrolyte and cathode materials for the SOFC applications at reduced temperatures, which means in the temperature range between 600 C and 750 C. For the first main task, several materials from the oxygen ion conducting electrolytes were selected. Different strontium and magnesium doped lanthanum gallate (LSGM) materials with additional transition metal doping were selected and prepared via two different preparation methods. The ...
Equivalent circuit and electrical parameters for H-doped NH_4UO_2PO_4.3H_2O self supported membranes have been determined by impedance spectroscopy. The measurements were carried out with a dry membrane, at different temperatures, and a wet membrane in contact with different electrolyte solutions. Resistance values for the dry membrane decrease with temperature increase, which agrees with the weak protonic character of the H-doped ammonium uranylphosphate. On the other hand, differences in the electrical parameters, depending on the electrolyte considered were also obtained and are attributed to different conduction mechanisms. (Author).
We investigated the effects of additives to the etching solution of 1 M hydrochloric acid on the electrochemical etching behavior for aluminum electrolytic capacitors, using scanning and transmission electron microscopy, and AC impedance spectroscopy. For the addition of 1 M sulfuric acid or 5% ethylene glycol to the hydrochloric acid solution, the distribution of etch tunnels was more uniform with high density of etch pits compared with that without addition. The highest specific surface area was obtained from the electrolyte with 5% ethylene glycol additive. The correlation of internal morphologies of etched foils with impedance parameters was interpreted by impedance techniques.
In this work, we perform spectroscopic studies to characterize the energy transfer processes occurring in rare-earth doped lithium fluoride systems, aiming the optimization of the population inversion of these media. Yb{sup 3+} ion was used in order to probe the electron-phonon coupling in LiYF{sub 4}, LiGdF{sub 4} and LiLuF{sub 4} matrices. In these systems it was obtained the average phononenergy, the vibronic transition probability and Huang-Rhys coupling constant. These parameters are dependent on the crystal host and the LiLuF{sub 4} system presents excluded correlation effects, an electronic repulsion that weakens the vibronic coupling. The Tm:Ho:LiYF{sub 4} system was studied under diode laser pumping at 796 nm, aiming the 2 {mu}m emission optimization. The ideal conditions of concentration and laser power were determined favouring the latter emission. Upconversion processes ...
Lithium-ion batteries are now considered to be the technology of choice for future hybrid electric and full electric vehicles to address global warming. LiCoO{sub 2} has been the most widely used cathode material in commercial lithium-ion batteries. Since LiCoO{sub 2} has economic and environmental issues, intensive research has been directed towards the development of alternative low cost, environmentally friendly cathode materials as possible replacement of LiCoO{sub 2}. Among them, spinel LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} material is one of the promising and attractive cathode materials for next generation lithium-ion batteries because of its high voltage (4.7 V), acceptable stability, and good cycling performance. Research advances in high voltage spinel LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} are reviewed in this paper. Developments in synthesis, structural characterization, effect of ...
Lithium-ion batteries are now considered to be the technology of choice for future hybrid electric and full electric vehicles to address global warming. LiCoO2 has been the most widely used cathode material in commercial lithium-ion batteries. Since LiCoO2 has economic and environmental issues, intensive research has been directed towards the development of alternative low cost, environmentally friendly cathode materials as possible replacement of LiCoO2. Among them, spinel LiNi0.5Mn1.5O4 material is one of the promising and attractive cathode materials for next generation lithium-ion batteries because of its high voltage (4.7 V), acceptable stability, and good cycling performance. Research advances in high voltage spinel LiNi0.5Mn1.5O4 are reviewed in this paper. Developments in synthesis, structural characterization, effect of doping, and effect of coating are presented. In ...
LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} was prepared through a solid-state reaction using various Ni precursors. The effect of precursors on the electrochemical performance of LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} was investigated. LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} made from Ni(NO{sub 3}){sub 2}.6H{sub 2}O shows the best charge-discharge performance. The reversible capacity of LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} is about 145 mAh g{sup -1} and remained 143 mAh g{sup -1} after 10 cycles at 3.0-5.0 V. The XRD results showed that the precursors and the dispersion methods had significant effect on their phase purity. Pure spinel phase can be obtained with high energy ball-milling method and Ni(NO{sub 3}){sub 2}.6H{sub 2}O as precursor. Trace amount of NiO and Li{sub 2}MnO{sub 3} phase were detected in LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} with manual-mixture method and using Ni(CH{sub ...
The particle surface of Li[Ni{sub 1/3}Co{sub 1/3}Mn{sub 1/3}]O{sub 2} was modified by AlF{sub 3} as a new coating material to improve the electrochemical properties in the high cutoff voltage of 4.5 V. The AlF{sub 3}-coated Li[Ni{sub 1/3}Co{sub 1/3}Mn{sub 1/3}]O{sub 2} showed no difference in the bulk structure compared with the pristine one and the uniform AlF{sub 3} coating layers whose thickness is of about 10 nm covered Li[Ni{sub 1/3}Co{sub 1/3}Mn{sub 1/3}]O{sub 2} particles, as confirmed by a transmission electron microscopy. The AlF{sub 3} coating on Li[Ni{sub 1/3}Co{sub 1/3}Mn{sub 1/3}]O{sub 2} particles improved the overall electrochemical properties such as the cyclability, rate capability and thermal stability compared with those of the pristine Li[Ni{sub 1/3}Co{sub 1/3}Mn{sub 1/3}]O{sub 2}. Such enhancements were attributed to the presence of the stable AlF{sub 3} layer ...
High voltage cathode materials Li-excess layered oxide compounds Li[Ni{sub x}Li{sub 1/3-2x/3}Mn{sub 2/3-x/3}]O{sub 2} (0 < x < 1/2) are investigated in a joint study combining both computational and experimental methods. The bulk and surface structures of pristine and cycled samples of Li[Ni{sub 1/5}Li{sub 1/5}Mn{sub 3/5}]O{sub 2} are characterized by synchrotron X-Ray diffraction together with aberration corrected Scanning Transmission Electron Microscopy (a-S/TEM). Electron Energy Loss Spectroscopy (EELS) is carried out to investigate the surface changes of the samples before/after electrochemical cycling. Combining first principles computational investigation with our experimental observations, a detailed lithium de-intercalation mechanism is proposed for this family of Li-excess layered oxides. The most striking characteristics in these high ...
This paper describes a reactor design to facilitate a room-temperature nuclear fusion/fission reaction to generate heat without generating unwanted neutrons, gamma rays, tritium, or other radioactive products. The room-temperature fusion/fission reaction involves the sequential triggering of billions of single-molecule, "6LiD 'fusion energy pellets' distributed in lattices of a palladium ion accumulator that also acts as a catalyst to produce the molecules of "6LiD from a solution comprising D_2O, "6LiOD with D_2 gas bubbling through it. The D_2 gas is the source of the negative deuterium ions in the "6LiD molecules. The next step is to trigger a first nuclear fusion/fission reaction of some of the "6LiD molecules, according to the well-known nuclear reaction: "6Li + D #-># 2"4He + 22.4 MeV. The highly energetic alpha particles ("4He nuclei) generated by this ...
Lithium Ceramics offer tremendous potential as a source for the production of tritium ("3H) for fusion power reactors. Their successful application will depend to a great extent upon the diffusion properties of the "6Li within the matrix. Consequently knowledge of "6Li concentration gradients in the ceramic matrices is an important requirement in the continued development of the technology. In this investigation, the neutron depth profile (NDP) technique has been applied to the study of concentration profiles of "6Li in lithium aluminate ceramics, doped with 1.8%, 50% and 95% "6Li isotopic concentrations. Specimen for analysis were prepared at Battelle (PNL) as pellet discs. Samples for diffusion studies were arranged as diffusion couples in the following manner: 1.8% "6Li discs/85% "6Li powder. Experiments were performed at the Texas A and M Nuclear Science ...
High-precision laser spectroscopy on lithium isotopes is of fundamental interest, experimentally as well as theoretically. The lithium atom has long served as a test system for the calculation of various atomic properties in few-electron atoms and significant advances have been made in the last decade[1-3]. Recently, calculations of transition energies for the 22S1/2 -> 32S1/2 and the 22S1/2 -> 22P1/2, 3/2 transitions and of the mass-dependant isotope shift (IS) in these transitions have been reported with a relative accuracy of better than 1 X 10-7 and 5 x 10-6, respectively[4, 5]. These calculations are the foundation for experimental efforts, currently underway at GSI Darmstadt, Germany, to determine the root-mean-square (rms) charge radius of the unstable lithium isotopes[6, 7]. The basic principle is that if all mass-dependent contributions to the IS can be calculated with sufficient accuracy, the residual discrepancy between the experimentally observed shift and the ...
Cerium is known to enter substitutionally in trivalent state when doped in alkali halides. Cerium doped NaCl crystals exhibit greatly enhanced thermoluminescence output upon X-irradiation at RT, the intensity of emission being about 10 times that in undoped crystals for similar dosage of irradiation. The cerium doped crystals give upon X-irradiation a very intense glow peak at 145degC with shoulders at 120degC and 210degC. Upon partially bleaching the crystal with F-light, the peak at 120degC becomes prominent probably due to faster bleaching of the glow at 145degC. From further optical bleaching studies, it is concluded that the glow peak at around 120degC is due to cerium centres in the irradiated crystal and the 145degC peak due to F centres. This F centre emission occurs at lower temperature, compared to that in the undoped crystals where it occurs at around 180degC. The spectral emission in the Ce doped crystals is in the blue-green region as compared to the ...
New five complexes of the type of [RuL sub(3-x)(dmby) sub(x)]X sub(2)(x = 1,2,3, L = 2,2'-bipyridyl or 1,10-phenanthroline, dmby = 3,3'-dimethy1-2,2'-bipyridyl, X = halide ion) have been synthesized in order to investigate the effects of two methyl groups of dmby on the absorption and emission spectra, luminescence quantum yields, and lifetimes. Values of the radiative and nonradiative rate constants have been calculated from these data at 77K. Although the absorption and emission maxima and the lifetimes are not much affected by the dmby ligand substitution, the molar extinction coefficients and emission quantum yields are decreased compared with trischelated complexes of the parent bipyridyl or phenanthroline ligands. At 25"0C the emission yields of the complexes containing dmby decrease by 3 - 4 orders of magnitude than at 77K. Possible causes of the decrease in the quantum yields are discussed. (author).
Methyl halide fluxes were measured from fine (nonwoody) litter samples at a temperate deciduous forest site in Scotland on 16 occasions over more than a year and at a coniferous forest site. The resulting mean (+-1 sd) CH3Br and CH3Cl fluxes were 4.1 +- 3.7 ng kg-1 h-1 and 0.98 +- 0.62 mg kg-1 h-1, respectively, for dry mass leaf litter and 5.7 +- 6.3 ng kg-1 h-1 and 0.47 +- 0.14 mg kg-1 h-1 for dry mass needle litter. Temporal variations of net fluxes from leaf litter were significantly greater than spatial variations suggesting seasonality in the fluxes. The mean CH3Cl/CH3Br mass ratio of fluxes was 200 (to 1 sig. fig.), an order of magnitude larger than the ratio of their estimated global turnovers. Temperate forest litter may be a moderate net source of CH3Cl globally but a negligible ...
Chlorine is widely used in drinking water disinfection due to be a powerful and not expense disinfection. Although the benefits of disinfection, the formation of stable disinfection by-products of the health concern, is the result of the interaction of aqueous chlorine with natural organic matter presents in water. Disinfection by-products generated in major concentration are trihalomethane and haloacetic acids. Disinfection by-products generated in minor concentration are haloacetonitriles, haloketones,chloral hydrate and chloropicrin and some new groups such as cyanogen halides and trihaloacetaldydes. In this work two analytical methods.: headspace/gas chromatography/electron capture detector and liquid-liquid microextraction/gas chromatography/electron capture detector are studied and compared to determine the minor by-products and to establish finally, a systematic control of them in the different stages of the Water Treatment Plant of San Joan Despi ...
The exchange charge model of crystal field theory has been used to analyze systematically the ground state absorption spectra of octahedrally coordinated Ni{sup 2+} ion in isostructural nickel halide crystals NiCl{sub 2}, NiBr{sub 2}, and NiI{sub 2}. The parameters of the crystal field acting on the Ni{sup 2+} ion are calculated from the available crystal structure data. The obtained energy level schemes are compared with experimental absorption spectra; a good agreement with experimental data is demonstrated. Dependencies of the crystal field invariants and covalence effects on the type of ligands are considered. It is shown numerically that the overlap effects between Ni{sup 2+} ion and ligands increase with an increase of the ligands' atomic number resulting in the following order of the degree of covalence: NiI{sub 2}>NiBr{sub 2}>NiCl{sub 2}.
The exchange charge model of crystal field theory has been used to analyze systematically the ground state absorption spectra of octahedrally coordinated Ni"2"+ ion in isostructural nickel halide crystals NiCl_2, NiBr_2, and NiI_2. The parameters of the crystal field acting on the Ni"2"+ ion are calculated from the available crystal structure data. The obtained energy level schemes are compared with experimental absorption spectra; a good agreement with experimental data is demonstrated. Dependencies of the crystal field invariants and covalence effects on the type of ligands are considered. It is shown numerically that the overlap effects between Ni"2"+ ion and ligands increase with an increase of the ligands' atomic number resulting in the following order of the degree of covalence: NiI_2>NiBr_2>NiCl_2.
This report is a compilation of the groundwater sampling results from the Area 5 Radioactive Waste Management Site (RWMS) including calendar year 2008 results. Each of the three Pilot Wells was sampled on March 11, 2008, and September 10, 2008. These wells were sampled for the following indicators of contamination: pH, specific conductance, total organic carbon, total organic halides, and tritium. Indicators of general water chemistry (cations and anions) were also monitored. Results from all samples collected in 2008 were within the limits established by agreement with the Nevada Division of Environmental Protection for each analyte. These data indicate that there has been no measurable impact to the uppermost aquifer from the Area 5 RWMS. There were no significant changes in measured groundwater parameters compared to previous years. Other information in the report includes an updated Cumulative Chronology for the Area 5 RWMS Groundwater Monitoring Program and ...
This report is a compilation of the groundwater sampling results from the Area 5 Radioactive Waste Management Site (RWMS) for calendar year 2006. Pilot wells UE5PW-1, UE5PW-2, and UE5PW-3 were sampled in April and October 2006 for the following indicators of contamination: pH, specific conductance, total organic carbon, total organic halides, and tritium. Indicators of general water chemistry (cations and anions) were also monitored. Results from all samples collected in 2006 were within the limits established by agreement with the Nevada Division of Environmental Protection for each analyte. These data indicate that there has been no measurable impact to the uppermost aquifer from the Area 5 RWMS. There were no significant changes in measured groundwater parameters compared to previous years. Other information in the report includes an updated Cumulative Chronology for the Area 5 RWMS Groundwater Monitoring Program and a brief description of the site hydrogeology.
LiNi{sub 0.8}Co{sub 0.2}O{sub 2} particles from high-power lithium-ion cells were examined to determine material changes that result from accelerated aging tests. X-ray absorption spectroscopy (XAS) and transmission electron microscope (TEM) data indicated a Li{sub x}Ni{sub 1-x}O-type layer on the particle surfaces. The greater thickness on particles from high-power fade cells indicate that these surface layers are a significant contributor to cathode impedance rise observed during cell tests.
The irradiation behavior of Li{sub 2}TiO{sub 3} under a fusion reactor environment was simulated by simultaneous irradiation of Li{sub 2}TiO{sub 3} by the triple ion beams and the respective single ion beams of O{sup 2+}, He{sup +} and H{sup +}. The microstructural changes in Li{sub 2}TiO{sub 3} caused by the irradiation were measured by Raman spectroscopy and FT-IR photoacoustic spectroscopy. The results suggest that the formation of TiO{sub 2} due to displacements by irradiation occurs, and the irradiation defects generated by irradiation trap hydrogen and increase the amount of hydroxyl near the surface. Such phenomena are believed to significantly affect the chemical form of the released tritium and the tritium inventory in the breeding materials of a fusion reactor.
The irradiation behavior of Li_2TiO_3 under a fusion reactor environment was simulated by simultaneous irradiation of Li_2TiO_3 by the triple ion beams and the respective single ion beams of O"2"+, He"+ and H"+. The microstructural changes in Li_2TiO_3 caused by the irradiation were measured by Raman spectroscopy and FT-IR photoacoustic spectroscopy. The results suggest that the formation of TiO_2 due to displacements by irradiation occurs, and the irradiation defects generated by irradiation trap hydrogen and increase the amount of hydroxyl near the surface. Such phenomena are believed to significantly affect the chemical form of the released tritium and the tritium inventory in the breeding materials of a fusion reactor.
Single stage separation factors ..cap alpha.. have been determined for /sup 6/Li and /sup 7/Li between lithium ions in methanol and complexed ions with a cryptand (2 sub(B), 2, 1) polymer. The /sup 6/Li was concentrated in the cryptand. The separation factors were compared with the values of other chemical exchange systems. The maximum enrichment factor obtained was epsilon = 0.047 +- 0.002. The figure is one of the greatest in the chemical exchange reactions without valence change and almost 10 times larger than the values of ion exchangers. The variation in ..cap alpha.. depending on the chemical species was small in the non-aqueous system. High enrichment of lithium isotopes was expected to be achievable by means of the chromatographic application of the cryptand (2 sub(B), 2, 1).
Spherical nano-sized YSZ (yttria stabilized ZrO2) powders were successfully synthesized via a reverse microemulsion system. The water droplets in the microemulsion system of yclohexane/water/span85/Triton X-100/hexyl alcohol can act as the nano-reactors which solubilize zirconium oxychloride and ammonia water separately. The minute original reactors are favor to the formation of nano-sized spherical YSZ powders and the dispersibility of the powders can be controlled effectually by adjusting the weight ratio of the LiNO3 molten salt to the precursor. The phase transformation from cubic to monoclinic starts at and 500??C and finally monoclinic and cubic phase with increased crytallinity coexist at 800??C. The effect of LiNO3 molten salt in the formation of YSZ powders was also discussed.
A 15-nm lithium fluoride (LiF) thin film evaporated on glass substrate is shown to enhance the nucleation of microcrystalline Si grown by plasma enhanced chemical vapour deposition at the amorphous/microcrystalline boundary conditions. The effect is more pronounced at low substrate temperatures, nucleation density being 10 times higher at {approx} 80 {sup o}C. The effect is ascribed to the ionic chemical nature of LiF, the low work function material used in organic electronic devices, and we propose its use for micro patterning crystalline Si regions in otherwise amorphous Si film.
One measured fission and fusion cross sections of "4","6He+"2"0"9Bi and "7Li+"2"0"8Pb reactions within the range from the Coulomb barrier up to 200 MeV. The measured functions of fission and fusion for the mentioned reactions are shown to have close values within the excitation energy wide range. One analyzed the excitation functions of fusion and fission for "4He+"2"0"9Bi, "6He+"2"0"9Bi and "7Li+"2"0"8Pb reactions resulting in formation of "2"1"3","2"1"5At compound systems
The proton and neutron densities, root-mean-square (rms) radii of proton density and neutron density, and neutron skin thickness of "4"-"1"0He, "6"-"1"1Li, and "7"-"1"2Be isotopes are calculated using Skyrme-Hartree-Fock method with SLy4, SLy5, SLy6, and SLy7 force parameters. The evaluated results are compared with experimental data. Also, the results of halo nuclei ("6","8He, "1"1Li, and "1"1Be) are compared with the results of other isotopes for selected nuclei having the same neutron configuration.
The electrochemical performances of orthorhombic LiMnO{sub 2} compounds are analyzed in order to find a structural and/or morphological origin to the differences of electrochemical behaviours observed in compounds with different size of crystallites and different amounts of lattice defects. Energy capacity performances of 200 Ah/kg are reached for materials with crystallites of about 10{sup 7} Angstrom{sup 3} and with about 7% of defects, while energy capacities of only 80 Ah/kg are obtained for materials with ten times bigger crystallites. (J.S.) 3 refs.
The molten salt reactor (MSR), which is one of the generation IV reactors, can meet the demand of transmutation and breeding. The thermodynamic properties of the molten salt system like LiF-NaF-BeF2 influence the design and construction of the fuel salt and coolant in the MSR for the new generation. In this paper, the equation of state of the ternary system 15%LiF-58%NaF-27%BeF2, over the temperature range from 873.15 to 1 073.15 K at one atmosphere pressure, is described using a modified Peng-Robinson (PR) equation. The densities of the ternary system and its components are estimated by this equation directly, and compared with the experimental data. Based on the equation of state, the other thermodynamic properties such as the enthalpy, entropy and heat capacity at constant pressure are ...
Recent developments in rechargeable Li-ion battery technology include the use of lithium-carbon compounds instead of metallic anodes. Non-graphitizable carbons offer high capacity as the anode material but it's large irreversible capacity must be solved. The ultimate goals of the present work are to understand the origin of the high capacity and large irreversible capacity in conjunction with the structural change due to Li intercalation and thus to establish a scientific basis for optimizing their performance in real batteries. 'House of cards' model is considered and emphasis is given to find out the size of the pores present in the carbon fibers prepared from an isotropic petroleum pitch and heat treated at 1200degC. Small angle neutron scattering and wide angle neutron scattering results provide enlargement of pores and d-spacing of grapheme layers after Li intercalation. (author)
Pyrochemical processing of nuclear fuels using molten salts has attracted much attention because of its potential to be applied for a future spent nuclear fuel management. In the pyrochemical processing, there are a number of steps to electro-refine and electro-win each element of lanthanides and actinides, commonly called trans-uranic elements (TRU). In order to materialize the pyrochemical processing in the nuclear power plant environments, qualitatively and quantitatively monitoring of each elements is necessary. Thus, we have undertaken to develop an on-line observing system of the TRU in LiCl-KCl molten salt media by using electrochemical and spectroscopic methods. In this work, the electrochemical and spectroscopic behaviors of europium as a proxy material for TRU were investigated simultaneously in the LiCl-KCl molten salt.
Pyrochemical processing of nuclear fuels using molten salts has attracted much attention because of its potential to be applied for a future spent nuclear fuel management. In the pyrochemical processing, there are a number of steps to electro-refine and electro-win each element of lanthanides and actinides, commonly called trans-uranic elements (TRU). In order to materialize the pyrochemical processing in the nuclear power plant environments, qualitatively and quantitatively monitoring of each elements is necessary. Thus, we have undertaken to develop an on-line observing system of the TRU in LiCl-KCl molten salt media by using electrochemical and spectroscopic methods. In this work, the electrochemical and spectroscopic behaviors of europium as a proxy material for TRU were investigated simultaneously in the LiCl-KCl molten salt
Hyperspherical-harmonics method to investigate the lightest nuclei having three-cluster structure is discussed together with recent experiments. Properties of bound states and methods to explore three-body continuum are presented. The challenges created by large neutron excess and halo phenomena are highlighted. Astrophysical aspects of the "7Li + n "#-># "8Li + #gamma# reaction and the solar-boron-neutrinos problem are analyzed. Three-cluster structure of highly excited states in "8Be is shown to be responsible for extreme isospin mixing. Progress in studies of "6He- and "1"1Li-induced inclusive and exclusive nuclear reactions is demonstrated, providing information on the nature of continuum structures of Borromean nuclei.
As a contribution to the US/Japan cooperative program in fusion neutronics, we have prepared a library of multigroup neutron cross sections, scattering matrices, and covariances (uncertainties and their correlations). This 74-group library, called COVFILS-2, is being used at Los Alamos and at the University of California at Los Angeles in the sensitivity and uncertainty analysis of the Li_2O integral experiment recently performed at the Fast Neutron Source (FNS) in Japan. Another intended use of this library is in the estimation of the uncertainty in key performance parameters (such as breeding ratio) of conceptual fusion reactors. The 14 materials included in the first version of COVFILS-2 are H, "6Li, "7Li, Be, C, N, O, Na, Al, Si, Cr, Fe, Ni, and Pb.
Silicon thin film with thickness in range 1000-5300 A deposited on rough Cu foil by a radio frequency magnetron sputtering is used as anode materials for Li-ion rechargeable batteries. The SEM, XRD and TEM analysis reveals that the Si thin film has a floccular nano-sized multi-crystalline structure. Li ions insertion/extraction evaluation is performed mainly with constant current charge/discharge cycling and cyclic voltammetry (CV) at room temperature. The cycleability and reversible discharge capacity are found to depend on the film thickness, and thinner films give larger accommodation capacity. A 3120 A Si film provides a reversible specific capacity over 3500 mA hg{sup -1} with excellent cycleability under 0.5 C charge/discharge rate.
Effects of ions of Group IA, IIA, IIIB, and VIIB elements on the cathodic deposition of a molybdenum were investigated in a KCl-LiCl (eutectic)-MoCl/sub 3/ molten salt at 773 K (500/degree/C). The results can be summarized as follows: The addition of potassium, rubidium, cesium, and barium cations and fluorine anions to the KCl-LiCl (eutectic)-MoCl/sub 3/ molten salt is effective in depressing the cathodic deposition of the molybdenum subchloride, which hinders the smooth, flat electrodeposition of molybdenum. The addition of lithium, sodium, magnesium, calcium, strontium, and aluminum cations and bromine and iodine anions promotes the undesirable cathodic deposition of the molybdenum subchloride.
The real parts of the optical model potentials for 104 MeV alpha-particle and 156 MeV "6Li ion scattering from "4"0,"4"8Ca are calculated in terms of folding model approaches. The validity of different procedures is tested by comparing the differential cross section predictions with experimental data measured with high angular accuracy. It is found that a refined folding potential accounting for density dependence of an effective nucleon-nucleon interaction is appropriate for alpha particle scattering without any parameter adjustment. However, for "6Li ion scattering renormalization of the depth of the real potentials is necessary. (orig.).
Lithium metal-polymer electrolyte batteries with improved utilisation of the active material at a moderate-low temperature (65degC) were realised. Low molecular weight poly(ethylene glycol) (PEG, MW=2000) was used as the lithium-ion conductive matrix in the composite cathode. The cathode active material was crystalline V{sub 2}O{sub 5}. A blend of poly(ethylene oxide) (PEO, MW=4x10{sup 6}) and PEG was used as a solid polymer electrolyte (SPE). The transport properties of the SPE were evaluated at various temperatures. A specific conductivity as high as 1.0x10{sup -4} S cm{sup -1} was calculated at 45degC. The temperature dependence of the interfacial resistances between lithium/SPE and cathode material/PEG was evaluated. The lithium/SPE interfacial resistance decreases linearly with the temperature. The charge transfer resistance between cathode material and PEG reaches a minimum at 60degC and it does not decrease with a further temperature ...
This paper proposes a model to explain tritium release behavior of an irradiated Li_4SiO_4 sample made by Forschungszentrum Karlsruhe. The release curves were obtained in a series of experiments carried out using out-pile temperature programmed desorption techniques in the Kyoto University Reactor (KUR). Tritium release curves obtained for different purge gas compositions (N_2, N_2 + H_2, N_2 + H_2O) were compared for selection of suitable conditions to determine the apparent diffusivity of tritium in a crystal grain of Li_4SiO_4.In the model formation, some mass transfer steps in the bulk of the crystal grain and those on the surface of the grain were taken into account, which were diffusion of tritium in the grain, adsorption and desorption of water on the surface of the grain, two types of isotope exchange reactions, and water formation reaction by the addition of hydrogen to the purge gas.Diffusivities of tritium in the crystal grain of ...
The structural change of the (100-x)(0.6Li{sub 2}S{center_dot}0.4SiS{sub 2})centre dotxLi{sub 3}PO{sub 4} oxysulfide glassesduring crystallization was analyzed by means of solid-state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS). The unique tetrahedral units of SiO{sub n}S{sub 4-n} (n=1,2,3) and PO{sub n}S{sub 4-n} (n=1,2,3) present in the glass samples vanished and the SiS{sub 4}, PS{sub 4}, SiO{sub 4} units increased with proceeding of the crystallization process. Nonbridging sulfur and oxygen atoms decreased while bridging oxygens and S{sup 2-} increased with proceeding of the crystallization process. Large structural difference between the glass and the corresponding crystallized sample explained the high stability against crystallization found in the oxysulfide glass with the composition of X=5. (author)
The structural change of the (100-x)(0.6Li[sub 2]S[center dot]0.4SiS[sub 2])centre dotxLi[sub 3]PO[sub 4] oxysulfide glassesduring crystallization was analyzed by means of solid-state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS). The unique tetrahedral units of SiO[sub n]S[sub 4-n] (n=1,2,3) and PO[sub n]S[sub 4-n] (n=1,2,3) present in the glass samples vanished and the SiS[sub 4], PS[sub 4], SiO[sub 4] units increased with proceeding of the crystallization process. Nonbridging sulfur and oxygen atoms decreased while bridging oxygens and S[sup 2-] increased with proceeding of the crystallization process. Large structural difference between the glass and the corresponding crystallized sample explained the high stability against crystallization found in the oxysulfide glass with the composition of X=5. (author)
A trans-uranium (TRU) fuel should be manufactured and loaded in transmutation systems in order to transmute the long-lived TRU nuclides into short-lived ones. However, since all of the TRU nuclides are not completely transmuted in one cycle lifetime in transmutation systems, the spent TRU fuel has to be treated to recover the long-lived radionuclides or fuel matrix materials. One concept to manufacture TRU fuel for transmutation is to recover uranium from TRU and molten salt. If this type of fuel is adopted for transmutation, uranium could also be an objective material to be recovered and recycled. Since electrowinning is a promising technology to be employed for the recovery of uranium from fuel materials, some experimental work of electrowinning using anode of Cd-Li alloy was carried out in this study. The basic salt chosen was a mixture of LiCl-KCl which has an eutectic point at 357 .deg. C.
A trans-uranium (TRU) fuel should be manufactured and loaded in transmutation systems in order to transmute the long-lived TRU nuclides into short-lived ones. However, since all of the TRU nuclides are not completely transmuted in one cycle lifetime in transmutation systems, the spent TRU fuel has to be treated to recover the long-lived radionuclides or fuel matrix materials. One concept to manufacture TRU fuel for transmutation is to recover uranium from TRU and molten salt. If this type of fuel is adopted for transmutation, uranium could also be an objective material to be recovered and recycled. Since electrowinning is a promising technology to be employed for the recovery of uranium from fuel materials, some experimental work of electrowinning using anode of Cd-Li alloy was carried out in this study. The basic salt chosen was a mixture of LiCl-KCl which has an eutectic point at 357 .deg. C
NFAT involvement in adipocyte physiological processes was examined by treatment with CsA and/or GSK3{beta} inhibitors (Li{sup +} or TZDZ-8), which prevent or increase NFAT nuclear translocation, respectively. CsA treatment reduced basal and TNF{alpha}-induced rates of lipolysis by 50%. Adipocytes preincubated with Li{sup +} or TZDZ-8 prior to CsA and/or TNF{alpha}, exhibited enhanced basal rates of lipolysis and complete inhibition of CsA-mediated decreased rates of lipolysis. CsA treatment dramatically reduced the mRNA levels of adipocyte-specific genes (aP2, HSL, PPAR{gamma}, ACS and Adn), compared with control or TNF{alpha}-treatment, whereas Li{sup +} pretreatment blocked the inhibitory effects of CsA, and mRNA levels of aP2, HSL, PPAR{gamma}, and ACS were found at or above control levels. NFAT nuclear localization, assessed by EMSA, confirmed that CsA or Li{sup +} treatments inhibited or increased ...
A study was undertaken of the effect of monovalent cations (Li/sup +/, Na/sup +/, K/sup +/) on the dielectric constant (epsilon) of the water-lipid interface of unilamellar phosphatidylcholine (PC) vesicles, i.e., the ester carbonyl oxygen region of the PC molecules or the neighborhood of the oxygen atoms of the phosphorylcholine moiety. epsilon was determined by reacting the free radical 1,1-diphenyl-2-picrylhydrazyl with ..cap alpha..-tocopherol incorporated in the lipid vesicles. The results are consistent with a decrease of epsilon (LiCl: 35.5 to 29.5; NaCl: 34 to 29; KCl: 33 to 29) as the concentration of the salts in the solvent media increases from 0.025 to 0.5 M. These effects can be rationalized in terms of dielectric saturation at the water-lipid interface brought about by ion-induced local electric fields. In the unilamellar PC vesicles the effect of the ions on epsilon follows the sequence K/sup +/ > Na/sup +/ > ...
The gamma spectrum and gamma - gamma coincidences of /sup 177/W were measured with a Ge(Li) detector. A level scheme was proposed for /sup 177/Ta. (tr-auth)
Elevated pH operation to the pH value of 7.3 at 285degC is known to be effective for the reduction of radiation source in the primary water system of PWRs. A research project was started in 1989 and concluded in 1996 to study and verify the optimum pH and/or Li concentration from the viewpoint of radiation source reduction and materials integrity under improved water chemistry. This research project is sponsored by the Ministry of International Trade and Industries (MITI) in Japan and has two programs; high pH and high Li. The high Li program was conducted to establish the optimum Li concentration for the high boron concentration region (1100 - 1800 ppm) of the high burn up operation. In this paper, we shall discuss radiation source behavior under high pH conditions and PWSCC (Primary Water Stress Corrosion Cracking) susceptibility of materials with change of primary water chemistry conditions and the ...
The high-energy reaction cross sections of Li and Be isotopes are calculated using a simplified Glauber model and densities constrained by the empirical binding energies. We find excellent agreement with experiment, reproducing the large increase for the most neutron-rich nuclei.
LiFePO{sub 4} cathode materials with distinct particle sizes were prepared by a planetary ball-milling method. The effects of particle size on the morphology, thermal stability and electrochemical performance of LiFePO{sub 4} cathode materials were investigated. The ball-milling method decreased particle size, thereby reducing the length of diffusion and improving the reversibility of the lithium ion intercalation/deintercalation. It is worth noting that the small particle sample prepared using malonic acid as a carbon source achieved a high capacity of 161 mAh g{sup -1} at a 0.1 C rate and had a very flat capacity curve during the early 50 cycles. However, the big particle samples ({proportional_to}400 nm) decayed more dramatically in capacity than the small particle size samples ({proportional_to}200 nm) at high current densities. The improvement in electrode performance was mainly due to the fine particles, the small size distribution, and ...
We report the experimental and theoretical results on the anisotropies in the magnetic properties and x-ray absorption spectra of single-crystal LiFePO4. A mean-field theory is developed to explain the observed strong anisotropies in Lande g-factor, paramagnetic Curie temperature, and effective moment for LiFePO4 single crystals. The values of the in-plane nearest- and next-nearest-neighbor spin exchange (J1 and J2), interplane spin exchange (J{perpendicular}), and single-ion anisotropy (D), obtained recently from neutron scattering measurements, are used for calculating the Curie temperatures with the formulas derived from the mean-field Hamiltonian. It is found that the calculated Curie temperatures match well with that obtained by fitting the magnetic susceptibility curves to the modified Curie-Weiss law. For the polarized Fe K-edge x-ray absorption spectra of single-crystal LiFePO4, a different feature assignment for ...
An earlier representation of the radial distribution of dose about the path of a heavy ion in liquid water is modified and extended to include silicon, lithium fluoride, and sodium iodide. 6 refs., 5 figs., 1 tab.
Cyclic voltammetry (CV), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) were employed to investigate the electrodeposition of Eu and Al in an LiCl-KCl eutectic melt containing Eu{sup 2+} and Al{sup 3+} at 450 deg. C. In order to deposit a pure Eu and Al alloy, the stoichiometrically lower concentration of Al{sup 3+} than that of Eu{sup 2+} and Al wires as a counter electrode was introduced into the bath of LiCl-KCl melt for the electrodeposition. The electrodeposition takes place at a potential more negative than -1.95 V vs. Ag|Ag{sup +} while the deposit is oxidized at more positive potential than -1.92 V. Two new reduction peaks and an anodic peak on a W working electrode were observed at -2.39 V, -2.42 V, and -2.1 V, vs. Ag|Ag{sup +}, respectively, suggesting that the potential window of the Al system in LiCl-KCl melt can be extended to -2.43 V vs. Ag|Ag{sup +}. The EDS analysis indicated ...
Cyclic voltammetry (CV), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) were employed to investigate the electrodeposition of Eu and Al in an LiCl-KCl eutectic melt containing Eu2+ and Al3+ at 450 deg. C. In order to deposit a pure Eu and Al alloy, the stoichiometrically lower concentration of Al3+ than that of Eu2+ and Al wires as a counter electrode was introduced into the bath of LiCl-KCl melt for the electrodeposition. The electrodeposition takes place at a potential more negative than -1.95 V vs. Ag|Ag+ while the deposit is oxidized at more positive potential than -1.92 V. Two new reduction peaks and an anodic peak on a W working electrode were observed at -2.39 V, -2.42 V, and -2.1 V, vs. Ag|Ag+, respectively, suggesting that the potential window of the Al system in LiCl-KCl melt can be extended to -2.43 V vs. Ag|Ag+. The EDS analysis indicated that AlEu can be deposited at the potential ...
The "2"0 "2"1 "2"2Ne("6Li, d)"2"4 "2"5 "2"6Mg reactions have been studied at a bombarding energy of 32 MeV. Alpha particle spectroscopic strengths have been extracted for several low-lying levels by a finite-range distorted wave analysis. These are compared with theoretical predictions. The agreement is good both for relative strengths to different levels within a nucleus and for ground-state strengths relative to the "1"6O("6Li, d) result. Strengths calculated using eigenfunctions determined in large shell-model computations agree well with pure symmetry SU(3) predictions. The "2"1Ne("6Li, d) angular distributions for transitions to the ground-state band of "2"5Mg are characterized by the lower of the two L-transfers allowed for populating each level. For the 3"+(5.24 MeV) unnatural parity level in "2"4Mg, a two-step calculation gives a better account of the data than does a compound nuclear calculation. (Auth.).
Neutron-rich He-, Li-, and Be-isotopes in the vicinity of the drip-line have been studied by "1"2C- and "1"4C-induced multi-nucleon transfer reactions on "1"0Be and "1"3","1"4C-targets. This study revealed unknown excited states in "8","1"0He, "1"0","1"1Li and in "1"3","1"4Be. Both excitation energies and widths have been measured. In some cases most probable spins and parities could be assigned to the particle-unstable states observed. (orig.).
The response of a real time neutron dosemeter using a thin LiF target sandwiched between tow parallel surface barrier semiconductor detectors is studied for different neutron distributions and different angles of incidence. Calculations of the response function defined for a simultaneous detection by the two detectors of the particles emitted when the reaction "6Li(n,t)#alpha# occurs in the target are fulfilled by geometrical considerations of the reaction kinematics and the differential cross section variations. Finally, the efficiency of the studied detection systems is analyzed for dosimetric uses. (author).
A method and apparatus for nuclear borehole logging, and in particular, neutron porosity logging, uses a neutron source, and a pair of spaced lithium detectors, preferably Li"6I crystal or Li"6 doped glass, to detect neutrons emitted from a borehole formation being logged. The spectrum developed by the lithium detectors is processed to remove the gamma ray background radiation and the hydrogen absorption peak, thus allowing a more accurate neutron count. A Gaussian curve is fitted to the neutron peak of the spectrum, the curve eliminating the hydrogen absorption peak. The area under this Gaussian curve represents the neutron count. (author).
Direct determination of "2"3"2U and its decay products in animal tissues appears to be feasible using an intrinsic Ge(Li) diode detector (for energies of 5-100 keV) and a NaI(Tl) anticoincidence-shielded Ge(Li) diode for higher-energy gamma photons. The detection sensitivity for "2"3"2U and "2"2"8Th is 0.03 and 0.01 nCi, respectively, using a 300-min counting time.
A simple method for preparing LiCaAlF6:Eu2+ phosphor is reported. Photoluminescence (PL) and thermoluminescence (TL) studies were carried out. The TL sensitivity of the phosphor is nearly twice that of CaSO4:Dy TLD phosphor. Several other properties required for TL dosimetry are superior as well. It is suggested that the phosphor can be a suitable replacement for CaSO4:Dy. (Copyright 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)
The following questions, concerning the application of the harmonic oscillator representation (HOR) in the theory of scattering and reactions, are discussed: the formulation of the scattering theory in HOR; exact solutions of the free motion Schroedinger equation in HOR; separable expansion of the short range potentials and the calculation of the phase shifts; `isolated states` as generalization of the Wigner-von Neumann bound states embedded in continuum; a nuclear coupled channel problem in HOR; and the description of true three body scattering in HOR. As an illustration the soft dipole mode in the (11)Li nucleus is considered in a frame of the (9)Li+n+n cluster model taking into account three body continuum effects.
The fusion excitation function for the radioactive projectile "8 Li on a "2"0"8 Pb target has been measured at energies near the Coulomb barrier. The results show that in the considered energy interval, the evaporation of four neutrons is the most relevant mechanism. However, at the highest energies used in the experiment, the Sn channel begins to appear. The preliminary experimental cross sections show a good agreement with the predictions of a simple evaporation calculation using the code PACE. (Author) 16 refs., 1 tab., 4 figs.
In order to understand the physical processes concerned with the selective heating by ion cyclotron resonance and with the subsequent collection of heated particles, experiments were carried out with the extraction of lithium samples, enriched with "6Li isotopes. Probe and integral extractors allow to collect enriched Li at the end of the selective heating region. Surface density distribution on the collector and local isotopic content of lithium are measured, as a function of the screen height and the retarding potential. Dependence of the collected amount of lithium and of its isotopic content on the value of the magnetic field is also measured. 4 figs., 2 tabs., 5 refs.
Full text of publication follows: Li{sub 2}TiO{sub 3} is regarded as one of the most suitable candidates for the solid tritium breeder material of D-T fusion reactors. It is known that, in an operating fusion reactor, the radiation damage in Li{sub 2}TiO{sub 3} will be caused by fast neutrons, energetic tritons and helium ions generated in {sup 6}Li(n,{alpha}){sup 3}H reaction. The irradiation damage caused by such radiation may result in the microstructural changes, and the changes may affect the characteristics of Li{sub 2}TiO{sub 3} such as tritium release behavior. Thus the study of irradiation defects and microstructural changes caused by irradiation in Li{sub 2}TiO{sub 3} is essential to evaluate its irradiation performance. Simulation of the fusion reactor environment and hence the study of a synergistic effect of atomic displacement damage in Li{sub ...
Excitation transfer between the 3S[sub 1/2] states of the lithium isotopes [sup 6]Li and [sup 7]Li is measured in a thermionic diode. The 3S level is excited by off-resonant two-photon transitions with a single mode cw laser. The relative densities of the directly excited and collisionally populated levels are probed by further laser excitation to the 12P levels. An energy transfer cross section of 585 A[sup 2] [+-] 160 A[sup 2] is found at the experimental temperature of about 850 K. A simple semiclassical calculation yields a cross section of 450 A[sup 2]. (orig.)
Separation of lithium isotopes was investigated by chemical ion exchange with a hydrous manganese(IV) oxide ion exchanger using an elution chromatography. The capacity of manganese(IV) oxide ion exchanger was 0.5 meq/g. The heavier lithium isotope was enriched in the solution phase, while the lighter isotope was enriched in the ion exchanger phase. The separation factor was determined according to the method of Glueckauf from the elution curve and isotopic assays. The separation factor of {sup 6}Li{sup +} -{sup 7}Li{sup +} isotope pair fractionation was 1.018.
The physical foundations are described of radionuclide X-ray fluorescence analysis (RXFA) and the table shows the values of K- and L-absorption thresholds and the K- and L-line energies of elements. The calculation of the intensity of characteristic radiation during RXFA proceeds from relations derived for conventional X-ray fluorescence analysis. The choice of the radionuclide source is ruled by the nature of the analysed substance and the used detection technique. The diagram shows the areas of radionuclide sources and the energy of the fluorescence radiation of elements. The table shows the spectra of radionuclide sources suitable for the purposes of RXFA measured by semiconductor Si(Li) and Ge(Li) detectors. (ES).
In order to discuss effects of lithium iodide (LiI) doping on condensation structure of brown coals during heating, spectral changes were measured by using an in-situ FT-IR. It was found that the LiI doping accelerates weight reduction due to heating, and the doping effect is affected by coal structure. Both of Loy Yang (LY) coal and its LiI doped coal (DLY) had absorption intensity of the FT-IR spectra decreased with rising temperature, and the absorption center belonging to an OH group shows different shifts between the LY and DLY coals. This indicates that the LiI doping has affected the change in hydrogen bonding patterns associated with heating. Both of South Banko (SB) and LY coals had the absorption spectral intensity in the OH group decreased as the weight reduction (conversion) rate increased. Reduction in the OH groups associated with heating is caused by volatilization and condensation ...
This report summarizes the results of research conducted during the sixteen month continuation of a program to develop rechargeable zinc-air batteries for electric vehicles. The zinc-air technology under development incorporates a metal foam substrate for the zinc electrode, with flow of electrolyte through the foam during battery operation. In this ``soluble`` zinc electrode the zincate discharge product dissolves completely in the electrolyte stream. Cycle testing at Lawrence Berkeley Laboratory, where the electrode was invented, and at MATSI showed that this approach avoids the zinc electrode shape change phenomenon. Further, electrolyte flow has been shown to be necessary to achieve significant cycle life (> 25 cycles) in this open system. Without it, water loss through the oxygen electrode results in high-resistance failure of the cell. The Phase I program, which focused entirely on the zinc electrode, elucidated ...
This report summarizes the results of research conducted during the sixteen month continuation of a program to develop rechargeable zinc-air batteries for electric vehicles. The zinc-air technology under development incorporates a metal foam substrate for the zinc electrode, with flow of electrolyte through the foam during battery operation. In this soluble'' zinc electrode the zincate discharge product dissolves completely in the electrolyte stream. Cycle testing at Lawrence Berkeley Laboratory, where the electrode was invented, and at MATSI showed that this approach avoids the zinc electrode shape change phenomenon. Further, electrolyte flow has been shown to be necessary to achieve significant cycle life (> 25 cycles) in this open system. Without it, water loss through the oxygen electrode results in high-resistance failure of the cell. The Phase I program, which focused entirely on the zinc ...
The kinetics of calcium sulfate crystal growth is of importance in various fields, such as geochemistry, desalination technology, petroleum industry, and water and wastewater treatment. The seeded crystal growth rate of calcium sulfate dihydrate was measured as a function of supersaturation in NaCl electrolyte solutions from 0 to 6 m at temperatures of 25, 50, 70, and 90 C. The growth followed a second-order parabolic rate law with activation energies greater than 53 kJ/mol which suggested the surface reaction as the rate-limiting step. It was observed that the rate constant and the activation energy are solution composition dependent. The rate constant increases with NaCl concentration up to 3 molal and then begins to fall slightly. The activation energy dropped from 61 kJ/mol in the pure Ca-SO[sub 4]H[sub 2]O system to 53 kJ/mol in 3.0 m NaCl solutions. The electrolyte effect was similar to the crystal solubility behavior in aqueous ...
The single-electrode capacitance of a nano-porous carbon electrode used as an electric double layer capacitor was measured. The charged state of the electrolyte ion was discussed from the results. Single-electrode capacitance was not proportional to the specific surface area of the electrode. This implies that the whole surface of the electrode is not effective for the formation of an electric double layer. It is considered that edge orientation of the carbon structure would give a dominant contribution to capacitance. For measurements with aqueous solutions of various electrolytes, capacitance was about the same value for each salt compound. For aqueous acid solution, on the other hand, capacitance was twice to three times as large as that for salt compounds. This difference, however, became negligibly small if the concentration of electrolyte solution was lowered. Taking account of the hydrated ionic radius of each ion, ...
The publication is an economic evaluation of the Bureau of Mines electrolytic process for recovering lead from scrap lead-acid batteries. In this process, scrap batteries are crushed and separated into metal and sludge fractions. The metal fraction is cast as anodes and electro-refined. Lead in the sludge fraction is converted to lead carbonate by reaction with an ammonium carbonate-ammonium bisulfite solution. The lead carbonate is then dissolved in a fluosilicic acid electrolyte from which pure lead metal is electrowon. A cost estimate is presented for a plant capable of processing 10,000 scrap batteries per day. The fixed capital cost for the plant is estimated to be $14 million on a fourth quarter 1984 basis. Operating costs are estimated to be $0.15/lb Pb recovered. Assuming a lead selling price of $0.17/lb, the interest rate of return on investment after taxes is 11 pct. A lead selling price of about $0.21/lb is needed to obtain a ...
This project will determine whether electrolytic dialysis has promise in the separation of charged particles in an aqueous solution. The ability to selectively move ions from one aqueous solution to another through a semipermeable membrane will be studied as a function of emf, amperage, and particle electrical charge. The ions selected for the study are Cl{sup -} and SO{sub 4}{sup 2-}. These ions are of particular interest because of their electrical conduction properties in aqueous solution resulting with their association with the corrosive action of metals. The studies will be performed with commercial membranes on solutions prepared in the laboratory from reagent salts. pH adjustments will be made with dilute reagent acid and base. Specific objectives of the project include testing a selected membrane currently available for electrolytic dialysis, membrane resistance to extreme pH conditions, the effectiveness of separating a mixture of two ...
Na/S battery can have the higher energy density and higher power density than that of existing high performance secondary battery. This battery is expected to use for electric load leveling and electric vehicle. Ni/MH battery was developed in advanced countries, but it is one of the advanced technologies which are preserved in their own country. In the study on Na/S battery, properties of B{sup -}alumina electrolyte was investigated. Also the construction technologies of this test cell was established by combining tube type of B{sup -}alumina solid electrolyte with Na-, S- electrode etc. Especially of this cell, charge/discharge performance and open circuit voltage was examined. Mi/MH battery sample were tested with SBT500 system for self-discharge rate at room temp, was measured. It was found that the electrolyte and separator can be optimized to minimize the self-discharge rate. (author). refs., figs., tabs.
The spontaneous ionic polymerization of 4-vinyl-pyridine in presence of mono-tosylated or bromated short chains of poly(ethylene oxide)-(PEO) is used to prepare amorphous comb-like poly-cations with low Tg. The polymer electrolyte properties of these new structures have been studied without any addition of salts. The ionic conductivity of these fixed cation poly-electrolytes depends on the length of the grafted PEO and varies from 10{sup -7} to 10{sup -4} S/cm between 25 and 80 deg. C. It is only weakly dependent on the nature of the cation but it is controlled by the movements of the pyridinium cation which are facilitated by the plastifying effect of the POE chains which do not directly participate to the ionic transport. (J.S.) 17 refs.
The preparation, crystal structure, and the electrical properties of the compound (ET)/sub 3/Ag/sub x/I/sub 8/ where x = approx. 6.4 and ET is bis(ethylenedithio)tetrathiafulvalene, C/sub 10/S/sub 8/H/sub 8/, are described. The compound possesses a truly two-dimensional polymeric anion, one which combines the structural features of both an organic electronic conductor and an inorganic solid electrolyte. The crystal structure consists of alternating anion and cation donor layers. The compound exhibits high electronic conductivity dominated by the electronic contribution, at least near room temperature.
A series of modifications which increased the capacity of Canadian Electrolytic Zinc's Valleyfield plant from 220,000 MT/year to 260,000 MT/year during the last decade is discussed, combined with an an overview of the plant's operations. The modifications included modernisation of the waste disposal methods and facilities, such as a new high-density sludge wastewater treatment process, a new process to remove selenium from weak acid solutions and the jarofix process. Roasting capacity also has been improved by recent investments in new cooling coils, rebricking, oxygen enrichment and process automation. In addition to increases in refining capacity, the improvements also enabled the company to minimize its impact on the environment and the community.
A numerical model is developed to study electrolyte dependent kinetics in fuel cells. The model is based on the Poisson-Nernst-Planck (PNP) and generalized-Frumkin-Butler-Volmer (gFBV) equations, and is used to understand how the diffuse layer and ionic transport play a role in the performance difference between acidic and alkaline systems. The laminar flow fuel cell (LFFC) is used as the model fuel cell architecture to allow for the appropriate comparison of equivalent acidic and alkaline systems. We study the overall cell performance and individual electrode polarizations of acidic and alkaline fuel cells for both balanced and unbalanced electrode kinetics as well as in the presence of transport limitations. The results predict cell behavior based on electrolyte composition that strongly...
Production engineering measures for improving production techniques to increase the reliability of high voltage, high temperature aluminum electrolytic capacitors have been completed. The required number of capacitors for each contract item were life tested at 85C for 10,000 hours. There were 9,400 capacitors on the extended life test. Reliability for CU13 and CU17 capacitors and contract item 2AG rated 1.5 mfd - 400 V are shown. The verification testing, which was performed at 125 C on 40 capacitors for each contract item, met the requirements of MIL-C-39018A. It further demonstrated that in addition to CU13 styles which are designed to operate at 125 C, the CU17 manufactured for this contract are capable of operating at 125C with derated voltage. Process specifications and Quality Control Manual are included.
This document reproduces the final project of David San Fabian Ayuso, presented on May 26, 2005, for the obtention of the engineer degree of the Carlos III University of Madrid. A single-phase, isothermal model, including both electron and proton transport, is introduced for the simulation of polymer electrolyte fuel cells (PEM). The model is implemented in the commercial code Fluent 6.0, through the use of UDFs (User Defined Functions). In order to validate the model, a single canal of a PEM monocell is simulated in three dimensions. The obtained result are qualitatively satisfactory. It is observed that it is not essential to solve the current collectors when a monocell is considered (and not a stack). in the present study, the number of nodes is the computational grid appears to be too low in the membrane zone in order to make a complete validation of the model. (Author) 20 refs.
Yttria stabilized zirconia (YSZ) with 8 mol% Y was deposited by reactive magnetron sputtering onto oxidized (100) silicon substrates. It was possible to switch film texture from (111) to (200) by applying a strong RF substrate bias. Transmission electron microscopy showed that the film deposited under bias is porous and exhibits nanoscaled grains, whereas the film deposited without bias is dense and columnar. The ionic conductivity as a function of temperature revealed an activation energy of 1.04 eV. The mechanical stress could be tuned to low values by thermal post-annealing. Using the dense (111) film as electrolyte layer, and the porous (200) film as an interlayer to a porous Pt anode, an open circuit voltage of 0.85 V was obtained in a micro machined fuel cell structure.
In Polymer Electrolyte Fuel Cell (PEFC) technology the reducing of volume and mass of the fuel cell stack and the improvement of catalyst utilization are of great interest. These parameters affect applicability and system cost. In this work we present an alternative way for reducing the stack volume by combining gas distribution and catalytic active area in one plate. Micro machined glassy carbon electrodes serve as support material for the platinum catalyst, as well as gas distributor at the same time. A comparison of these electrodes with conventional platinum-black gas diffusion electrodes under fuel cell conditions shows that the new system is a promising electrode type for enhanced power density and catalyst utilization. (author) 3 figs., 5 refs.
The measurement of local heat transfer coefficients is necessary to record the basic phenomena of heat transfer in thin-film apparatuses. For this reason the so-called electrochemical analogy method was developed and used for this application. The electrochemical method implies a specifically composed electrolyte which substitutes the fluid to be evaporated in the thin-film apparatus. Using the redox electrolyte (0,025 kmol/m/sup 3/ K/sub 4/Fe(CN)/sub 6/ resp. k/sub 4/Fe(CN)/sub 6/ and 2nNaOH) the viscosity was, for the first time, thickened until 0.4 Pa s by the help of hydroxyethyl-cellulose.
An effective method of enhancing charge injection and electroluminescence efficiency of polymer-based light emitting diode is introduced. Spin-coated films of poly (N-vinylcarbazole) blended with electron-transport material (Bu-PBD), laser dye (Coumarin6), and the typical supporting electrolyte (tetraethylammonium perchlorate; TEAP) were examined and it was found that the injection current and luminance of the light emitting diode doped with TEAP were enhanced dramatically after heat-treatment at 80 deg. C and appropriate biasing in an external electric field of 1.5x10"8 V/m at this temperature. The thermally stimulated current (TSC) was also measured to investigate the relaxation process of ionic space charges in the films. The relaxation times of ionic polarization were found to be related to the cation size of the electrolyte. And the relaxation time becomes long enough by the use of TEAP doping.
Ceramic coatings with high emission were fabricated on Ti6Al4V alloy by microarc oxidation (MAO) with additive FeSO4 into the electrolyte. The microstructure, chemical composition and chemical state of the coatings were determined by SEM, XRD, EDS and XPS, respectively. The bonding strength between the coating and substrate was studied by tensile strength test, together with the thermal shock resistance of the coating. The results showed that Fe content in the coating layer significantly affect its thermal emissivity. The relative content of Fe in the coatings surface increased at first and then decreased with increasing the concentration of FeSO4 in electrolytes, so does the emissivity of the coatings. The bonding strength became weaker with increasing the concentration of FeSO4. In addit...
In situ composite coating of hydroxyapatite (HA)/TiO2 were produced on titanium (Ti) substrate by micro-arc oxidation coupled with electrophoretic deposition (MAO&EPD) technique with different concentrations of HA particles in the 0.2M NaOH electrolyte solution. The surface morphology and chemical composition of the hybrid coating were effected by HA concentration. The amount of HA particles incorporated into coating layer increased with increasing HA concentration used in the electrolyte solution. The corrosion behavior of the coating layer in simulated body fluids (SBF) was evaluated using a potentiodynamic polarization test. The corrosion resistance of the coated sample was increased compared to the untreated Ti sample. The in vitro bioactivity assessment showed that the MAO&EPD treated...
Equivalent circuit and electrical parameters for H-doped NH{sub 4}UO{sub 2}PO{sub 4}.3H{sub 2}O self supported membranes have been determined by impedance spectroscopy. The measurements were carried out with a dry membrane, at different temperatures, and a wet membrane in contact with different electrolyte solutions. Resistance values for the dry membrane decrease with temperature increase, which agrees with the weak protonic character of the H-doped ammonium uranylphosphate. On the other hand, differences in the electrical parameters, depending on the electrolyte considered were also obtained and are attributed to different conduction mechanisms. (Author).
Brookhaven National Laboratory is involved in a conceptual design study of a commercial nuclear power system which utilizes high-temperature electrolysis to produce synthetic fuels. The system is called HYFIRE. It includes a tokamak fusion power reactor supplying electrical and thermal energy to an array of electrolytes. The electrolytes produce hydrogen which can be used either directly as a fuel or in the production of hydrocarbons. The purpose of the study is to provide a mechanism for DOE to further assess the commercial potential of fusion using a tokamak reactor to produce synthetic fuel. The HYFIRE design is based on the tokamak commercial power reactor, STARFIRE. STARFIRE uses the deuterium/tritium/lithium fuel cycle. The HYFIRE study assumes the plasma shape and characteristics of STARFIRE study but uses a different blanket design. This study is particularly interested in the possibility of using the STARFIRE tokamak in the production ...
This paper explores the through-/in-plane characteristics of water transport in the cathode gas diffusion layer (GDL) of a polymer electrolyte fuel cell (PEFC). Theoretical analysis is performed on the non-isothermal two-phase flow under flow channels. A dimensionless group Da (Damkohler number for PEFC operation), defined as the ratio of water generation rate to water vapor-phase removal rate, is formulated to characterize the flow regimes in a PEFC. This group, lumping geometrical parameters and physical properties, compares the water vapor-phase removal capability (via water diffusion and holding capacity) with the rate of water production by the oxygen reduction reaction. We find that this dimensionless group can be used to characterize the non-isothermal, two-phase phenomena: when Da&...
Hydrogen has the potential to serve as both an energy storage means and an energy carrier in renewable energy systems. When renewable energy sources such as solar or wind power are used to produce electrical power, the output can vary depending on weather conditions. By using renewable sources to produce hydrogen, a fuel which can be stored and transported, a reliable and continuously available energy supply with a predictable long-term average output is created. Electrolysis is one method of converting renewable energy into hydrogen fuel. In this experiment we examine the use of an electrolyzer based on polymer-electrolyte membrane technology to separate water into hydrogen and oxygen. The oxygen is vented to the atmosphere and the hydrogen is stored in a small pressure vessel.
High temperature proton conductor (HTPC) oxides are attracting extensive attention as electrolyte materials alternative to oxygen-ion conductors for use in solid oxide fuel cells (SOFCs) operating at intermediate temperatures (400-700 "0C). The need to lower the operating temperature is dictated by cost reduction for SOFC pervasive use. The major stake for the deployment of this technology is the availability of electrodes able to limit polarization losses at the reduced operation temperature. This review aims to comprehensively describe the state-of-the-art anode and cathode materials that have so far been tested with HTPC oxide electrolytes, offering guidelines and possible strategies to speed up the development of protonic SOFCs. (topical review)
This study compares two series of solvents for application in aluminum electrolytic capacitors: ethylene glycol (EG) and water mixtures, and ethylene glycol and 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMI.BF4) ionic liquid (IL) mixtures. Electrochemical impedance spectroscopy and cyclic voltammetry were carried out with a previously anodized aluminum disk electrode. Comparative measurements of solution resistance, polarization resistance, AC capacitance, and passive current were made. The results show that EG?IL mixtures with low amounts of IL (10% IL?90% EG v/v) have a low solution resistance. Low values of solution resistance, high values of polarization resistance, small passive current, and uniform capacitance of anodized aluminum in EG?IL mixtures are favorable properties of ...
For the development of a rechargeable zinc/air battery, La[sub 0.6]Ca[sub 0.4]CoO[sub 3]-catalyzed (perovskite) bifunctional oxygen electrodes and pasted zinc electrodes were prepared and tested in monopolar zinc/air cells. In addition, a bipolar Zn/air stack was tested using reticulated copper foam as substrate for the zinc deposit. The cells were cycled in moderately alkaline ZnO-saturated electrolyte with KF as an electrolyte additive. The maximum power as well as the cycle life of the cells was investigated. The differences in porosity of the zinc electrode before and after the long-term test were analyzed using mercury porosimetry. (author) 8 figs., 13 refs.
A Brownian dynamics simulation has been used to investigate the aggregation kinetics of bimodal colloidal mixtures with similar surface chemistries but different sizes, driven by the DLVO interaction potential. The time evolution of structural formation is examined by the mean number of neighbors under fast and slow aggregation regions. It was found that the electrolyte ionic strength affects the kinetic pattern of colloidal aggregation. Under the high electrolyte ionic strength conditions (fast aggregation), the selective aggregation of the least stable single component can take place in the early stage, while the other component is enriched in this least stable component in the later stage. With the ionic strength decreasing (towards the slow aggregation), the hybrid aggregation (selecti...
Effects of some experimental parameters (supporting electrolyte, initial pH and current density) on the performance of electrocoagulation process using iron electrodes were investigated. Results of experiments showed that dissolution of iron is purely electrochemical and fits well with Faraday's law and leads to Fe^2^+ which are chemically oxidized into Fe^3^+ in aerated conditions. In neutral and alkaline conditions, the reaction between hydroxyl ions generated at the cathode and dissolved iron ions forms insoluble hydroxo-iron species. Potentiodynamic polarization tests showed that the formation of passive film on iron anode limits the continuous electrochemical dissolution of iron. Corrosion and pitting potentials largely depend on the nature of supporting electrolyte. The dissolution o...
This patent describes an improved zinc electrode for a rechargeable zinc-air battery comprising an outer frame and a porous foam electrode support within the frame which is treated prior to the deposition of zinc thereon to inhibit the formation of zinc dendrites on the external surface thereof. The outer frame is provided with passageways for circulating an alkaline electrolyte through the treated zinc-coated porous foam. A novel rechargeable zinc-air battery system is also disclosed.
A hydrous oxide film for the application as dielectric film is synthesized by immersion of pure aluminum in hot water. From a Rutherford backscattering analysis, the ratio of aluminum to oxygen atoms was found to be 3:2 in the anodized aluminum oxide film, and 2:1 in the hydrous oxide layer. Anodization of the hydrous oxide layer was more effective for the transition of amorphous anodic oxides to the crystalline aluminum oxides.
The state of lithium electrode surface after contact with triethylamine-modified propylene carbonate solutions of lithium perchlorate was studied using the pulse galvanostatic technique as well as methods of SIMS and electron microscopy. It was shown that amine added into the solutions stabilizes the state of lithium and prevents the formation of a secondary porous passive film on the lithium surface. Chemical composition of the primary film remains unchanged. Certain properties of passive films formed in electrolyte solutions studied were evaluated.
The study presented in this thesis is a contribution about the analysis of failures modes of electrolytic capacitors and thyristors. The studied components are main elements of the protection system of the superconductive magnets of the LHC. The study of the ageing of the electrolytic capacitors has shown that their reliability is strongly related to their technological characteristic. Evolution of their principal indicator of ageing (ESR) can be modeled according to different laws chosen according to their running mode. It appears that the prediction of failure of these components other than that due to wear can be only statistical taking into account the many causes of failure involving various modes of failure. In order to be able to evaluate influence of the ageing of the electrolytic capacitors on a system, simple models taking into account this parameters as well as the effective temperature of the component are ...
In a redox battery using a titanium redox system or chromium redox system as an active material for the negative electrode or a manganese redox system as an active material for the positive electrode, the electromotive force of the battery and the stability of electrolyte solutions are enhanced by addition of a chelating agent such as citric acid or a complexing agent such as phosphoric acid to the redox system used therein.
A cathode of improved discharge characteristics for a zinc-air battery is prepared from mixtures containing gamma-MnO/sub 2/ 33-67 wt%, C 12-40 wt% and KOH 20-28 wt%.
The objective of this research is to gain a better understanding of the corrosion of the aluminized type 316 stainless steel employed in the seal areas of the molten carbonate fuel cell. The seals are formed between the aluminized Type 316 SS surface and the electrolyte (generally a mixture of molten alkali carbonates and lithium aluminate).
Pitting corrosion is a kind of electrolytic corrosion by which the surface of a material is locally affected owing to inhomogeneities on the part of the material or medium. The paper deals briefly with questions relating to the importance, to parameters medium or materialwise, influence on production and construction, as well as the general conditions for pitting corrosion. In particular oxygen corrosion in unalloyed and low-alloy steel, and pitting corrosion in ferritic chromium-steel and austenitic chromium-nickel (molybdenum) steel is described. (DG).
This report forms part of a joint study on a PEFC propulsion system for surface ships, summarized in a presentation to this Seminar, entitled {open_quotes}Study on a Polymer Electrolyte Fuel Cell (PEFC) Propulsion System for Surface Ships{close_quotes}, and which envisages application to a 1,500 DWT cargo vessel. The aspect treated here concerns an experiment in reducing by methanation to a level below 10 ppm the CO that is contained to around 1% in reformate gas.
Several Mg-Y binary ribbons with Y content up to {approx}17.9 at.% were fabricated by melt-spinning. X-ray diffraction (XRD) revealed that the phase structure changes with increasing Y content from extended solid solution to partially amorphous, and then fully intermetallic Mg{sub 24}Y{sub 5}. Anodic potentiodynamic polarization performed in 0.01 M NaCl electrolyte (pH=12) revealed improved anodic passivity behavior compared to pure Mg for all the Mg-Y alloys. X-ray photoelectron spectroscopy (XPS) revealed that the improved passivity of Mg-Y was more related to the elemental oxidation state rather than the concentration of the surface components. To study the effect of Cl{sup -} ion on the passivity behavior, anodic potentiodynamic and potentiostatic polarization were performed on Mg-17.9 at.% Y in alkaline (pH=12) NaCl electrolytes containing Cl{sup -} ion in the concentration range from 0.00 to 0.50 M. The passive films formed in 0.01 M NaCl ...
Several Mg-Y binary ribbons with Y content up to #approx#17.9 at.% were fabricated by melt-spinning. X-ray diffraction (XRD) revealed that the phase structure changes with increasing Y content from extended solid solution to partially amorphous, and then fully intermetallic Mg_2_4Y_5. Anodic potentiodynamic polarization performed in 0.01 M NaCl electrolyte (pH=12) revealed improved anodic passivity behavior compared to pure Mg for all the Mg-Y alloys. X-ray photoelectron spectroscopy (XPS) revealed that the improved passivity of Mg-Y was more related to the elemental oxidation state rather than the concentration of the surface components. To study the effect of Cl"- ion on the passivity behavior, anodic potentiodynamic and potentiostatic polarization were performed on Mg-17.9 at.% Y in alkaline (pH=12) NaCl electrolytes containing Cl"- ion in the concentration range from 0.00 to 0.50 M. The passive films formed in 0.01 M NaCl ...
A flexible battery is printed on paper by screen-printing a zinc/carbon/polymer composite anode on one side of the sheet, polymerising a poly(3,4-ethylenedioxythiophene) (PEDOT) cathode on the other side of the sheet, and applying a lithium chloride electrolyte between the two electrodes. The PEDOT cathode is prepared by inkjet printing a pattern of iron(III)p-toluenesulfonate as a solution in butan-1-ol onto paper, followed by vapour phase polymerisation of the monomer. The electrolyte is prepared as a solution of lithium chloride and lithium hydroxide and also applied by inkjet printing on to paper, where it is absorbed into the sheet cross-section. Measurements on a zinc/carbon-PEDOT/air battery in a similar configuration on a polyethylene naphthalate substrate shows a discharge capacity of up to 1.4 mAh cm{sup -2} for an initial load of 2.5 mg zinc, equivalent to almost 70% of the zinc content of the anode, which generates 0.8 V at a ...
In the area of seasonally thawing soil, porous or broken coatings cannot significantly retard the process of pile metal destruction, since it will occur through electroosmotic penetration of the base electrolyte to the metal surface. Such processes can be prevented by electrochemical protective methods. Systems based on grid cathode stations with power control and distribution units are recommended for use for cathode protection of steel pile foundations.
Goal was developing optical methods for study of dynamic processes at the electrode/electrolyte interface. In the past year, optical second harmonic generation was used for time-resolved measurements of thallium deposition on Cu(111). The studies of carrier dynamics in photo-excited materials have involved both steady-state and picosecond time-resolved luminescence measurements following photoexcitation of the semiconductor material.
Interpenetrated lattices (IPL) are combinations of reticulated polymers linked together by permanent crisscross. This structure is well-adapted to combined highly incompatible pairs of polymers. The in-situ sequential method has been applied successfully to the synthesis of ethylene poly-oxides / poly-siloxanes IPLs. The results concerning the preparation of such lattices and their behaviour as solid polymer electrolytes are presented in this paper. (J.S.) 24 refs.
Oxide ionic conductivities of (CeO_2)_x(Sc_2O_3)_(_0_._1_1_-_x_)(ZrO_2)_0_._8_9 (x = 0.01-0.10) electrolytes were optimized for the application in intermediate-temperature solid oxide fuel cell (IT-SOFC). Powders with different contents of CeO_2 and Sc_2O_3 were prepared via a co-precipitation method. The obtained powders and pellets were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and impedance spectroscopy. Among all the compositions, (CeO_2)_0_._0_4(Sc_2O_3)_0_._0_7(ZrO_2)_0_._8_9(4Ce7ScZr) gives the highest ionic conductivity of 0.065 S cm"-"1 at 800 "oC. The effects on densification and electrical properties of different sintering additives, such as SiO_2, MgO, Co_3O_4, MoO_3 and Bi_2O_3, were studied and different conducting behavior with these additives were observed. The densification temperatures of CeO_2 and Sc_2O_3 co-doped electrolytes can be reduced by around ...
The need for cost effective, high performance, long life capacitors with improved reliability is discussed. It is shown that a low cost, miniature aluminum capacitor, with improved reliability and proven life, can be produced with existing technology. It is further shown that the capacitor can be specified for 125 C life and shelf test requirements, and meet established standards for their parametric performance.
Sodium-ion-conducting glasses are considered a promising alternative to the ceramic electrolytes. The glass upon which the most development work has been done is a sodium borate glass, which has an ionic resistivity of about 2 x 10/sup 4/ #OMEGA#-cm at 300"0C. Because of its high resistivity, cells using this borate glass require thousands of hollow glass fibers, each about 80 micrometers outer diameter (15 micrometer wall). In spite of its greater complexity, the cell with the glass electrolyte is of interest because of its potential for lower cost and higher power than the cell with ceramic electrolyte. Recently, silicate glasses of lower resistivity have been proposed for this application. These include: a soda-alumina-silica glass (900 #OMEGA#-cm at 300"0C), a soda-zirconia-magnesia-silica glass (700 #OMEGA#-cm at 300"0C), and a soda-zirconia-silica glass (600 #OMEGA#-cm at 300"0C). These lower resistivity glasses would ...
Apparent molar heat capacities for KI[sub 3](aq) were determined from flow-microcalorimetric measurements of KI(aq) solutions containing dissolved iodine. From these, the conventional partial molar heat capacity C[sub p,2][sup [infinity
According to the invention, a zinc foil is arranged between the negative electrode of a zinc/air battery (round cell) and the expansion space compensating for the reactive increase in volume of the zinc powder. This zinc foil functioning as a stop diaphragm particularly ensures, from the very onset, that the zinc filling has a density and compactness necessary for good electronic conductance.
A synergistic effect exists when benzotriazole (BTAH) and iodide ions are used together to prevent the corrosion of copper in sulfuric acid. The nature of this effect has been studied systematically by using electrochemical techniques and X-ray photoelectron spectroscopy. The synergistic effect is due largely to the formation of a film of Cu(IBTA) complex and is probably polymeric in nature. This new complex film greatly depresses copper dissolution.
One of several methods to build YSZ electrolyte of SOFC is plasma spraying. This system heats particle to a melting point and then pushing them into target and forming a deposition. This paper presents heating studies of YSZ particle in plasma jet. By simple model it is shown that the required time such those YSZ particle with grain size of 50 ?m to be melt is around 12 x 10-4 second. (author)
Aluminum, due to its low density and low cost, is a key material for future lightweight applications. However, like other structural materials, aluminum is subject to various forms of corrosion damage that annually costs the United States approximately 5% of its GNP [1]. The main goal is to investigate the effects of various solution anions on aluminum surfaces, and specifically probe pit initiation and inhibition. Using surface analysis techniques including X-ray photoelectron spectroscopy, Auger electron spectroscopy, and scanning electron microscopy, results have been correlated with those obtained from electrochemical methods and a radiolabeling technique developed in the Wieckowski laboratory. Analysis of data has indicated that important variables include type of anion, solution pH, and applied electrode potential. While aggressive anions such as chloride are usually studied to elucidate corrosion processes to work ultimately toward inhibition, its corrosive properties can be ...
The complex formation of astatine(I) cation with diethylene triamine pentaacetic acid (DTPA) and characterization of the complexes were investigated by electromigration in free electrolytes and by gel-chromatography on Sephadex G 25. The conjugation procedure for the production of At-DTPA conjugated polyclonal antibodies is described. (author) 15 refs.; 2 figs.
Porous nanostructured LiFePO{sub 4} powder with a narrow particle size distribution (100-300nm) for high rate lithium-ion battery cathode application was obtained using an ethanol based sol-gel route employing lauric acid as a surfactant. The synthesized LiFePO{sub 4} powders comprised of agglomerates of crystallites <65nm in diameter exhibiting a specific surface area ranging from 8m{sup 2}g{sup -1} to 36m{sup 2}g{sup -1} depending on the absence or presence of the surfactant. The LiFePO{sub 4} obtained using lauric acid resulted in a specific capacity of 123mAhg{sup -1} and 157mAhg{sup -1} at discharge rates of 10C and 1C with less than 0.08% fade per cycle, respectively. Structural and microstructural characterization were performed using X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) with energy dispersive X-ray (EDX) analysis while ...
Little clinical evidence has been provided to show the minimization of radiation resistance of tumors using high linear energy transfer radiation. We therefore investigated the radiobiological and molecular pathological aspects of carbon beam therapy. A total of 27 patients with squamous cell carcinoma (SCC) of the cervix were treated using a carbon beam and 50 control patients with SCC of the cervix using a photon beam. The expression of Ki-67, p53, and p27 proteins before radiotherapy and 5 and 15 days after therapy initiation were investigated using immunohistochemistry. Similar changes were observed in Ki-67 labeling index (LI) and p53 LI during carbon and photon beam therapies. However, for carbon beam therapy, the mean p27 LI significantly decreased from 25.2% before treatment to 18.6% on the 5th day after treatment initiation, followed by a significant increase to 36.1% on the 15th day. In contrast, for photon beam ...
Chemical phase identifications of complex, multilayered corrosion products formed on Fe-Ni-Cr alloys immersed in molten NaNO/sub 3/-KNO/sub 3/ and LiNO/sub 3/-NaNO/sub 3/-KNO/sub 3/ were obtained by X-ray diffraction analysis. Diffraction analyses performed after successive material removal steps provided depth profiles of corrosion products and identified the dominant phases as NaFeO/sub 2/, Fe/sub 3/O/sub 4/, and Cr/sub 2/O/sub 3/ for Alloy 800 and 316SS after immersion in NaNO/sub 3/-KNO/sub 3/. In LiNO/sub 3/-NaNO/sub 3/-KNO/sub 3/, the major corrosion products identified on Alloy 800 were LiFeO/sub 2/, Fe/sub 3/O/sub 4/, and Cr/sub 2/O/sub 3/. X-ray diffraction results were supplemented by electron microprobe analyses that revealed the solid solution nature of several of the oxide phases.
A surplus USN 40 mm ammunition can was subjected to a variety of tests. Pressure tests were carried out with nitrogen gas, followed by the venting of actual Li/SO/sub 2/ cells and batteries inside the can. A fire test was also conducted on a can packed with 10 each 10-cell batteries surrounded by vermiculite. Test results indicate the US Navy (USN) 40-mm ammunition can is suitable as a shipping container for Li/SO/sub 2/ batteries on passenger aircraft. To provide a further measure of safety, a sulfur dioxide getter was incorporated into the can. Studies indicated a commercial material, ASC carbon, is suitable for this purpose. The granular material was packaged in porous paper desiccant bags and placed in the can with the batteries and vermiculite. The batteries were vented inside the sealed can and the internal pressure monitored. Pressure returned to normal within several minutes, indicating that this arrangement should prevent sulfur ...
For the first time, rheological phase method, a simple and effective route, is applied to synthesize novel cathode material LiCoPO{sub 4}. X-ray diffraction spectrometer (XRD), X-ray photoelectron spectrometer (XPS), transmission electron microscope (TEM) and electrochemical impedance spectroscopy (EIS) are taken to investigate this material, respectively. XRD figure shows that the rheological sample is better crystallized than the solid-state one. XPS result of the rheological sample exhibits that the valence of Co is 2+. TEM images show that better dispersed particles with smaller size can be formed by rheological method comparing to the solid-state route. Charge-discharge test is carried out in the range of 3.0-5.0 V at 0.2 mA cm{sup -2}. The initial discharge capacity for rheological phase and solid-state powder is 71.5 and 30.9 mAh g{sup -1}, respectively. The better electrochemical property should be ascribed to the better crystallized rheological phase ...
For the first time, rheological phase method, a simple and effective route, is applied to synthesize novel cathode material LiCoPO4. X-ray diffraction spectrometer (XRD), X-ray photoelectron spectrometer (XPS), transmission electron microscope (TEM) and electrochemical impedance spectroscopy (EIS) are taken to investigate this material, respectively. XRD figure shows that the rheological sample is better crystallized than the solid-state one. XPS result of the rheological sample exhibits that the valence of Co is 2+. TEM images show that better dispersed particles with smaller size can be formed by rheological method comparing to the solid-state route. Charge-discharge test is carried out in the range of 3.0-5.0 V at 0.2 mA cm-2. The initial discharge capacity for rheological phase and solid-state powder is 71.5 and 30.9 mAh g-1, respectively. The better electrochemical property should be ascribed to the better crystallized rheological phase production with better ...
The effect of neutralizing cations on the secondary reactions of the primary products from CO hydrogenation over ion-exchanged zeolite-supported Ru catalysts was investigated using zeolites with different alkali cations (Li/sup +/, Na/sup +/, K/sup +/, Rb/sup +/, Cs/sup +/). The transformation of olefins (propylene and butene) on the zeolites without the metal, under conditions similar to those used for CO hydrogenation, was also studied in order to understand the effect of the various constituents of the support, i.e., the Broensted acid sites generated during catalyst preparation and the alkali cations, on possible secondary reactions of the primary olefinic products. It was established that secondary acid-catalyzed reactions of these primary products can play a major role in shaping product selectivity during CO hydrogenation over zeolite-supported catalysts. Depending on the concentration and the strength of the acid sites, various competitive reaction paths ...
We examined whether proton magnetic resonance spectroscopy (MRS) could provide accurate information on histological grade and cell proliferation in astrocytomas. We studied 23 patients with astrocytomas: five grade II, 10 grade III and eight with grade IV (glioblastoma multiforme). We performed proton MRS and determined the Ki-67 labeling index (LI), a tumour proliferation marker, in the same areas of the astrocytomas, and examined the statistical relationship between proton MRS and Ki-67 LI. The N-acetylaspartate (NAA)/creatine-phosphocreatine (Cr) and NAA/choline (Cho)-containing compound ratios were always significantly lower and the Cho/Cr ratios significantly higher than those for normal brain. The Cho/Cr ratio correlated positively and the NAA/Cho ratio inversely with Ki-67 LI. These findings suggest that the Cho signal in proton MRS reflects cellular proliferation. In Kaplan-Meier survival analysis, there was no ...
Li{sub 1.3}Al{sub 0.3}Ti{sub 1.7}(PO{sub 4}){sub 3} thin films were successfully prepared by the solution deposition using lithium acetate, aluminum nitrate, ammonium dihydrogen phosphate and titanium butoxide as starting materials. The structure, surface morphology, electrochemical window, and ionic conductivity of the films were studied by X-ray diffraction, scanning electron microscopy, cyclic voltammetry and AC impedance. The results showed that Li{sub 1.3}Al{sub 0.3}Ti{sub 1.7}(PO{sub 4}){sub 3} thin films annealed between 750 deg. C and 900 deg. C prepared by this method were well crystallized, homogenous and crack-free. The electrochemical window was beyond 2.4 V and the ionic conductivity was approximately 1.57x10{sup -5} S/cm at room temperature for the film annealed at 800 deg. C for 30 min.
Li_1_._3Al_0_._3Ti_1_._7(PO_4)_3 thin films were successfully prepared by the solution deposition using lithium acetate, aluminum nitrate, ammonium dihydrogen phosphate and titanium butoxide as starting materials. The structure, surface morphology, electrochemical window, and ionic conductivity of the films were studied by X-ray diffraction, scanning electron microscopy, cyclic voltammetry and AC impedance. The results showed that Li_1_._3Al_0_._3Ti_1_._7(PO_4)_3 thin films annealed between 750 deg. C and 900 deg. C prepared by this method were well crystallized, homogenous and crack-free. The electrochemical window was beyond 2.4 V and the ionic conductivity was approximately 1.57x10"-"5 S/cm at room temperature for the film annealed at 800 deg. C for 30 min.
Panel cooling of buildings offers energy savings over conventional space-cooling systems. We present a procedure for calculating the performance of H[sub 2]O-LiBr absorption-panel cooling systems, in which the evaporator is the panel itself. Nomographs have been developed for this approach. Under the conditions examined, the H[sub 2]O-LiBr absorption unit operates with a theoretical performance coefficient of about 90% and with a practically constant specific cooling capacity of 2394 kJ/kg H[sub 2]O. For common values of the parameters involved, the panel cooling power varies from 25 to 175 W/m[sup 2] and the cooling water mass-flow through the panel is 40-260 g/m[sup 2]h. The thermal power needed to drive the system varies from 27 to 200 W/m[sup 2] and the associated temperatures from 70 to 100[sup o]C; thus, the system may be operated on solar energy. (Author).
Large area, single-element Si(Li) detectors have been fabricated using a novel geometry which yields detectors with reduced capacitance and hence reduced noise at short amplifier pulse-processing times. A typical device employing the new geometry with a thickness of 6 mm and an active area of 175 mm 2 has a capacitance of only 0.5 pf, compared to 2.9 pf for a conventional planar device with equivalent dimensions. These new low capacitance detectors, used in conjunction with low capacitance field effect transistors, will result in x-ray spectrometers capable of operating at very high count rates while still maintaining excellent energy resolution. The spectral response of the low capacitance detectors to a wide range of x-ray energies at 80 K is comparable to typical state-of-the-art conventional Si(Li) devices. In addition to their low capacitance, the new devices offer other advantages over conventional detectors. Detector fabrication ...
We report $^{7}$Li pulsed NMR measurements in polycrystalline and single crystal samples of the quasi one-dimensional S=1 antiferromagnet LiVGe$_2$O$_6$, whose AF transition temperature is $T_{\\text{N}}\\simeq 24.5$ K. The field ($B_0$) and temperature ($T$) ranges covered were 9-44.5 T and 1.7-300 K respectively. The measurements included NMR spectra, the spin-lattice relaxation rate ($T_1^{-1}$), and the spin-phase relaxation rate ($T_2^{-1}$), often as a function of the orientation of the field relative to the crystal axes. The spectra indicate an AF magnetic structure consistent with that obtained from neutron diffraction measurements, but with the moments aligned parallel to the c-axis. The spectra also provide the $T$-dependence of the AF order parameter and show that the transition is either second order or weakly first order. Both the spectra and the $T_1^{-1}$ data show that $B_0$ has at most a small effect on the alignment of the AF ...
Liquid-liquid extractive separation of lithium isotopes was carried out in order to investigate the fluctuation of separation factors (a) as a function of salt concentrations in an aqueous phase. Two equations for separation factor (a_o_b_s) as a function of the concentration were introduced; one for the diluted region, and another for the concentrated region. In the former solution where hydrated lithium ions are predominant, 1n a_o_b_s = Ac + B, and in the latter where ion-pairs with anions are predominant, 1n a_o_b_s = Dc + E(c - F)"1"/"3 + G. Some guidelines are derived from the salt-specific constants A, B, D, E, F and G. The heavier isotopes are inclined to be in the more hydrated state in the diluted solution, while the lighter isotopes tend to be in a less hydrated state. In the concentrated solution, heavier isotopes are more likely to be in ion-pair form. Ionic association occurs from the lower concentration in the order of LiI < ...
The static thermophysical properties of the molten salt system like LiF-NaF-BeF_2 influence the design and construction of the fuel salt and coolant in the Molten Salt Reactor for the new generation. In this paper, the equation of state of the ternary system 0.15LiF-0.58NaF-0.27BeF_2, over the temperature range from 873.15K to 1073.15K at one atmosphere pressure, is described by using modified Peng-Robinson equation. The density of the ternary system is evaluated by this equation directly, and compared with the experimental data. Base on the equation of state, the other static thermophysical properties such as the enthalpy, entropy and heat capacity at constant pressure are evaluated by the fugacity coefficient and residual function methods respectively. The density calculated by Peng-Robinson equation is in highly agreement with the experimental data, and the enthalpy, entropy and heat capacity evaluated by such two different methods are ...
The static thermodynamic properties of the molten salt system like LiF-NaF-BeF_2 influence the design and construction of the fuel salt and coolant in the Molten Salt Reactor for the new generation. In this paper, the equation of state of the ternary system 15%LiF-58%NaF-27%BeF_2, over the temperature range of 873.15K to 1073.15K at one atmosphere pressure, is described using Peng-Robinson equation modified by us. And the density of the ternary system is evaluated by this equation directly, and compared with the experimental data. Base on the equation of state, the other static thermodynamic properties such as the enthalpy, entropy and heat capacity at constant pressure are estimated by the residual function method and the fugacity coefficient method respectively. The density calculated by Peng-Robinson equation is in highly agreement with the experimental data, and the enthalpy, entropy and heat capacity evaluated by such two different methods ...
The static thermophysical properties of the molten salt system like LiF-NaF-BeF2 influence the design and construction of the fuel salt and coolant in the Molten Salt Reactor for the new generation. In this paper, the equation of state of the ternary system 0.15LiF-0.58NaF-0.27BeF2, over the temperature range from 873.15K to 1073.15K at one atmosphere pressure, is described by using modified Peng-Robinson equation. The density of the ternary system is evaluated by this equation directly, and compared with the experimental data. Base on the equation of state, the other static thermophysical properties such as the enthalpy, entropy and heat capacity at constant pressure are evaluated by the fugacity coefficient and residual function methods respectively. The density calculated by Peng-Robinson equation is in highly agreement with the experimental data, and the enthalpy, entropy and heat capacity evaluated by such two different methods are ...
The electrode reaction of Pu{sup 3+}/Pu couple at the interface between LiCl-KCl eutectic melt containing PuCl{sub 3} and liquid Bi phase was investigated by cyclic voltammetry at 723, 773 and 823 K. For comparison, the system was also studied using a solid Mo electrode in place of the liquid Bi electrode. It was found that the electrode reaction of Pu{sup 3+}/Pu couple at the Bi electrode was almost reversible. The redox potentials of Pu{sup 3+}/Pu couple at the liquid Bi electrode in the LiCl-KCl eutectic melt containing 0.87 wt% PuCl{sub 3} (0.0014 mole fraction) at 723, 773 and 823 K were observed to be more positive by 0.575, 0.572 and 0.566 V, respectively, than those at the Mo electrode. These differences in potential were thermodynamically analyzed by assuming a lowering of the activity of Pu in Bi phase according to the alloy formation of PuBi{sub 2}. (author)
The author have prepared a new, fusion-oriented library of multigroup neutron cross sections, scattering matrices, and covariances (uncertainties and correlations). The 74-group library, called COVFILS-2, has been used, or will be used, by neutronics groups at Los Alamos National Lab. (LANL) at the University of California at Los Angeles, and at the Swiss Federal Institute for Reactor Research in the sensitivity and uncertainty analysis of fusion-relevant integral experiments such as the Li/sub 2/O experiment performed at the Fast Neutron Source Facility in Japan and the Lithium breeding module experiment planned at the LOTUS facility in Lausanne, Switzerland. Another intended use of this library is in the estimation of the uncertainty in key performance parameters (such as the breeding ratio) of conceptual fusion reactors. The 14 materials included in the first version of COVFILS-2 are hydrogen, /sup 6/Li, /sup 7/Li, ...
The author have prepared a new, fusion-oriented library of multigroup neutron cross sections, scattering matrices, and covariances (uncertainties and correlations). The 74-group library, called COVFILS-2, has been used, or will be used, by neutronics groups at Los Alamos National Lab. (LANL) at the University of California at Los Angeles, and at the Swiss Federal Institute for Reactor Research in the sensitivity and uncertainty analysis of fusion-relevant integral experiments such as the Li_2O experiment performed at the Fast Neutron Source Facility in Japan and the Lithium breeding module experiment planned at the LOTUS facility in Lausanne, Switzerland. Another intended use of this library is in the estimation of the uncertainty in key performance parameters (such as the breeding ratio) of conceptual fusion reactors. The 14 materials included in the first version of COVFILS-2 are hydrogen, "6Li, "7Li, beryllium, carbon, ...
An energy analyzer has been constructed and operated in UHV for the purpose of analyzing the energy of neutral atoms scattered from solid surfaces. The analyzer consists of a LiF single crystal located at an angle close to the normal to the sample crystal so that the diffraction pattern obtained by scanning the LiF crystal yields the energy of the scattered atoms. Two designs which have been used are described. The temperature of both sample and analyzer crystal is near 20 K and once cleaned they can be maintained in the state of initial preparation for many weeks. The sample was a (001) Cu surface in this case. Such an energy analyzer can only be used, in most cases, for He atom scattering although Ne atoms could be used if the scattered intensities were adequate. The detector developed in this study is able to detect about 2 x 10"5 atoms/s. The resolution of the spectrometer depends on the incident energy of the atom and is about 1 meV at an ...
A new two-step solid-state process was developed for synthesis of a pure phase 4.7 V LiMn{sub 1.5}Ni{sub 0.5}O{sub 4-{delta}} (LMNO) spinel of good electrochemical properties. This process which was based on formation of stable Ni{sub 1-x}Mn{sub 2}O{sub 4-{delta}} (x {<=} 0.33) spinel followed by subsequent lithiation, demonstrated the emerging of LiMn{sub 1.5}Ni{sub 0.5}O{sub 4-{delta}} frame work at temperatures of as low as 350 C. During this lithiation process, migration of metal ions (Ni/Mn) from partially occupied tetrahedral 8a sites (in Ni{sub 0.67}Mn{sub 2}O{sub 4-{delta}}) toward octahedral 16d site occurred. The resultant spinel material displayed low irreversible loss, a 97% columbic efficiency and 6% loss in discharge capacity after 100 cycles at 60 C. (author)
An oxidative precipitation reaction of rare-earth chlorides in a LiCl-KCl molten salt was successfully carried out by a lab-scale apparatus. The conversion efficiency of the used rare earth chlorides into the insoluble precipitates was increased with the sparging time and temperature and was affected on oxygen sparger type. In the conditions of 700 .deg. C molten salt temperature and above 540min sparging time, the final conversion efficiencies were over 99% for all the experimented rare-earth chlorides. The hydrodynamic characteristics of an oxygen-molten salt two phase flow system are very important for a co-oxidative precipitation of rare earth elements.
An oxidative precipitation reaction of rare-earth chlorides in a LiCl-KCl molten salt was successfully carried out by a lab-scale apparatus. The conversion efficiency of the used rare earth chlorides into the insoluble precipitates was increased with the sparging time and temperature and was affected on oxygen sparger type. In the conditions of 700 .deg. C molten salt temperature and above 540min sparging time, the final conversion efficiencies were over 99% for all the experimented rare-earth chlorides. The hydrodynamic characteristics of an oxygen-molten salt two phase flow system are very important for a co-oxidative precipitation of rare earth elements
The dosimetry for radiotherapy involving neutrons is very complicated, owing to the complexity of secondary radiation components, whose contributions to the total absorbed dose have to be discriminated, owing to the different radiobiological effects. In order to separate thermal neutrons and photons, LiF dosimeters are mostly utilized. containing different percentage of Li, like as TLD-700, TLD-100 and TLD-600, but many problems arise. In the response of TLD-700 exposed to neutron-gamma mixed fields with high neutron flux, the contribution of thermal neutrons to the Tl emission is high. Moreover. TLD-100 and TLD-600 may undergo radiation damage, and great care has to be taken in order to obtain reliable results. Other TLDs showing lower sensitivity to neutrons are proposed and experimented for such high-flux neutron fields. The faced problems and various proposed solutions are here described. (Author)
We performed hybrid-DFT calculations for La2/3?xLi3xTiO3 (LLT) with lithium ion conductivity, in order to investigate the detailed lithium ion conductive mechanism from the viewpoint of molecular orbital (MO) method. It was concluded that the very ionic lithium ion in bottleneck accelerates the lithium ion conduction. The calculated MO shows no chemical bonding between lithium ion and other ions. In comparison with the perovskite-type trivalent titanium oxide of LaTiO3, the effect of the titanium's reduction was also investigated. We showed the possibility of the high lithium conductivity in LaTiO3.
Hydrostatic weighing was used to measure the pre-melt density of crystalline eutectic mixtures of alkaline metal chlorides of the compositions (mole fractions): 0.605 LiCl + 0.395 CsCl, 0.585 LiCl + 0.415 KCl, 0.297 NaCl + 0.246 KCl + 0.457 CsCl, and 0.348 NaCl + 0.652 CsCl with melting points 598, 628, 753, 763 K, respectively, as a function of temperature. In the same temperature ranges, the compressibility and molar volume of eutectics as well as their sudden change upon melting were estimated. Unusual variations of these properties were revealed near the crystal/liquid phase transition, which were related to local disordering of particle configuration
A technique has been developed which enables the direct sputter generation of atomic negative ion beams of all members of the Group IA elements (Li, Na, K, Rb and Cs). The method is based on the use of sputter samples formed by pressing mixtures of the carbonates of the Group IA elements and 10% (atomic) Cu, Ag or other metal powders. The following intensities are typical of those observed from carbonate samples subjected to approx. = 3 keV cesium ion bombardment: Li/sup -/: greater than or equal to 0.5 ..mu..A; Na/sup -/: greater than or equal to 0.5 ..mu..A; K/sup -/: greater than or equal to 0.5 ..mu..A; Rb/sup -/: greater than or equal to 0.5 ..mu..A; Cs/sup -/: greater than or equal to 0.2 ..mu..A.
All stable even-A molybdenum isotopes and sup(90,92)Zr have been investigated with the (d, "6Li) reaction at Esub(d) = 45 MeV to study proton- and neutron-pair correlations. Differential cross sections were measured for states up to Esub(x) = 3 MeV in "8"6Sr, sup(88,92,94,96)Zr and up to 6 MeV in "8"8Sr and "9"0Zr. Particular attention was paid to the comparison of #alpha#-pickup data with two-nucleon pickup data. The population of low-lying 0"+ and 5"- states for two-neutron and four-nucleon pickup reactions was calculated using simple phenomenological wave functions for the initial and final states. The results of these calculations are in satisfactory agreement with the data. (orig.).
Based on the corrected phase diagrams proper growth conditions for Li2Zn2(MoO4)3 crystals are selected. Large crystals (up to 100 mm), both impurity-free and activated by transition metal ions (Cu, Cr), are grown by the low-gradient Czochralski method. By the EPR method the charge state and structural position of copper and chromium ions are determined. The performed studies of luminescent properties show that for impurity-free crystals luminescence with ? = 388 nm with a two-exponential luminescence decay with ?1 = 2 ns and ?2 = 6 ns is observed at room temperature. At 77 K for both impurity-free crystals and those activated with transition metal ions luminescence with ? = 560 nm and the luminescence lifetime ? = 100 ns is observed, the intensity of luminescence with ? = 560 nm depending ...
A study was made on extraction of a series of lithium and calcium salts by monopodands L with common formula R-C_6H_4-O-(CH_2CH_2O)_n-C_6H_4-R, where R - CH_2P(O)Ph_2, n 1-3. Extraction-chromatographic separation of lithium and calcium isotopes in systems of metal aquacomplex-solvatocomplex with L in organic phase was conducted. It was established that separation coefficients of "6Li/"7Li isotopes ranged between 1.003 #+-#0.001 and 1.017 #+-#0.002 at the maximal separation degree equal to 1.60. Separation of "4"0Ca/"4"4Ca isotopes was not fixed. 12 refs., 4 figs., 1 tab.
Over 100 candidates were examined, including commercial materials and many that were synthesized in house. The mixed oxides were based on Ti, V, Nb, Cr, Mo, W, Mn, Fe, Co, Ni, and Cu doped with other transition metals. A number of individual (single-metal) oxides were included for comparison. The candidates were tested in single cells with Li(Si) anodes and separators based on LiCl-KCl eutectic. Screening was done under constant-current conditions at current densities of 125 me/cm{sup 2} and, to a lesser extent, 50 me/cm{sup 2} at 500 C. Relative performance and limitations of the oxide cathodes are discussed.
Wood-plastic composite (WPC) formation has been studied with simul + styrene system at various compositions of styrene with methanol as the swelling solvent. Effect of additives, e.g. multifunctional monomers (MFM)and oligomers used in very low quantity (1% v/v) on the polymer loading (PL) and tensile strength (TS) of the WPC has been elaborately investigated. Enhanced PL and TS values are observed. Inorganic co-additives like Lithium (Li"+), Copper (Cu"2"+) and acid (H"+) and urea (U) used in combinations with additives (MFM or oligomers) have influenced the results of PL and TS in these systems. Li"+ ion has been a good replacement for H"+ ion; U has substantially enhanced the PL values with retention of the TS values of WPC. Co-additive Cu"2"+ used in these systems can act as a preservative and protective agent for WPC. (Author).
Wood-plastic composites from Syrian tree species (white poplar, cypress tree, and white willow) were prepared using gamma-ray irradiation. Dry wood was impregnated with acrylamide or butylmethacrylate at various methanol compositions as the swelling solvent. Effect of inorganic additives and co-additives such as lithium nitrate (LiNO_3), copper sulfate (CuSO_4) and sulfuric acid (H_2SO_4), used at a very low concentration (1%), on the polymer loading (PL) and the compression strength (CS) was also investigated. It has been found that all the additives and co-additives, except Cu"2"+, increase the PL values and only Li"+ has a positive effect on CS. (Author)
To our knowledge, the fluorescence studies of lanthanides in LiCl-KCl eutectic molten salt at a high temperature are not reported yet. The fluorescence of the lanthanide-ions was generally decreased when the temperature was increased. Moreover, the fluorescence of the lanthanides was strong when the sample was solidified to or from the melt. The temperature, where the fluorescence was decreased, was identified to be different depending on the species of the lanthanides and the substrates was considered to possibly be from quenching of the fluorescence due to either the collisions of melted samples induced by high temperature media or the re-absorption of fluorescence by the samples. Several comparison experiments were performed to explain and understand this phenomenon and improve the fluorescence. In this way, an on-line monitoring of chemical species and the concentration for lanthanides elements in molten salt media of pyrochemical process can be accomplished, ...
The paper presents a procedure for the calculation of an absorption-refrigeration plant that uses an LiBr/ZnBr{sub 2}/CH{sub 3}OH solution and is driven throughout the year by heat received from a solar pond. The calculations for the solar pond are based on a finite-difference solution of the transient heat conduction differential equation during the year, and the operation of the refrigeration unit is simulated by the use of functions describing the thermodynamic behaviour of the working medium. On the basis of the procedure devised, correlations and nomographs are developed that describe the seasonally optimum operation of the proposed composite system. The nomographs may be employed for a first estimation in the design of such systems. (Author).
Modifications of the structure and mechanical properties in LiF crystals irradiated with MeV-energy Au ions have been studied using nanoindentation, atomic force microscopy and optical spectroscopy. The nanostructuring of crystals under a high-fluence irradiation (above 1013 ions/cm2)?was?observed. Nanoindentation tests show a strong ion-induced increase of hardness (up?to 150?200%), which is related to the high volume concentration of complex color centers, defect aggregates, dislocation loops and grain boundaries acting as strong barriers for dislocations. From the?depth profiling of the hardness and energy loss it follows that both nuclear and electronic stopping mechanisms of MeV Au ions contribute to the creation of damage and hardening. Whereas the electronic stopping is dominating i...
To gain in efficiency, lightness and volume, the hybrid and electric-powered cars will certainly follow the cellular phone path. The key of success of todays hybrid cars is the Ni-MH battery developed by Matsushita (87.5% of the market in 2004). The lithium-ion batteries will be the next step and would allow to supply 80 to 100% of the energy of the vehicle, the thermal engine becoming just an auxiliary system for additional power, autonomy and air-conditioning. Prototypes can reach today 200 to 450 km of autonomy and 130 km/h speeds with batteries of about 200 kg. If most of the safety problems linked with the Li technology have been solved, the main drawback remains the cost of the Li-ion technology. Short paper. (J.S.)
Abstract Nanocomposites based on SnO2 with carbon scaffold were used as highly porous anode films on Ni substrates. The films were obtained by in situ deposition of the particles without any binder or excess carbon black avoiding any secondary treatment. Compared to similarly prepared uncoated SnO2 nanoparticles as well as conventionally prepared powder samples the capacity loss of the in situ deposited nanocomposite films is significantly reduced. Thus, this newly developed anode material combined with in situ film formation is a promising approach for high capacity anodes in Li-ion batteries. SEM-micrograph of a SnO2/C nanoparticle film.
Digital topographic models are the foundation of more advanced modeling applications and ultimately inform planning and decision making in many fields. Despite this, the error associated with these models and derived attributes is commonly overlooked. Little attention has been given in the scientific literature to the benefits gained from having less error in a model or to the corresponding cost associated with reducing model error by choosing one product over another. To address these gaps in knowledge we evaluated the error associated with five digital elevation models (DEMs) and derived attributes of slope and aspect relative to the same attributes derived from LiDAR data. We also estimated the acquisition and processing costs per square kilometer of the five test models and the LiDAR m...
It is planned to bulk-heat a unit cell of a fusion reactor solid-breeder blanket in a fission reactor to study thermo-mechanical and thermal-hydraulic properties of fusion blankets. This study investigates the neutronic feasibility of using the Power Burst Facility (PBF) for this purpose. Heating rates were calculated for a Li/sub 2/O experiment placed in the PBF test space. The ANISN code and a 56-group coupled neutron-gamma library based on FLUNG and VITAMIN C were used to compute the heating rates. The results show that an average heating rate level of 1-3 W/cc can be produced in PBF with a local power profile that should be typical of a fusion blanket unit cell.
The study of SO{sub 2} reduction in non-aqueous solvent can help to understand the functioning of Li/SO{sub 2} batteries and to find a simpler way for the synthesis of Li{sub 2}S{sub 2}O{sub 4} dithionite. This paper presents the results of electrochemical studies (cycle volt-amperometry in semi-infinite and thin film diffusion conditions, visible spectro-electrochemistry) and spectroscopic studies (UV, visible and RPE) performed on SO{sub 2} solutions. A mechanism of SO{sub 2} reduction is proposed and discussed. (J.S.) 18 refs.
A model is described for simulating thermal hydraulic and chemical conditions within fuel crud deposits. Heat transfer takes place by wick boiling in which water flows through the porous deposit and evaporates into steam at the surface of chimneys. The transport and chemistry of dissolved species within the deposit is also modelled. This chemistry includes the equilibrium chemistry of Li/boric acid species, the equilibrium chemistry of Fe/Ni species and the radiolysis chemistry of water. The unique feature of this model is that the chemistry is coupled to the thermal hydraulics via the increase in the saturation temperature with the concentration of dissolved species. This has a profound effect on evaporative heat transfer within thick deposits, leading to conditions that explain the precipitation of LiBO{sub 2} and the possible formation of bonaccordite. The model helps understand several crud scrape observations, including why AOA is observed ...
Calcium-activated chloride channels (CaCCs) are widely expressed in mammalian tissues, including intestinal epithelia, where they facilitate fluid secretion. Potent, selective CaCC inhibitors have not been available. We established a high-throughput screen for identification of inhibitors of a human intestinal CaCC based on inhibition of ATP/carbachol-stimulated iodide influx in HT-29 cells after lentiviral infection with the yellow fluorescent halide-sensing protein YFP-H148Q/I152L. Screening of 50,000 diverse, drug-like compounds yielded six classes of putative CaCC inhibitors, two of which, 3-acyl-2-aminothiophenes and 5-aryl-2-aminothiazoles, inhibited by >95% iodide influx in HT-29 cells in response to multiple calcium-elevating agonists, including thapsigargin, without inhibition of calcium elevation, calcium-calmodulin kinase II activation, or cystic fibrosis transmembrane conductance regulator chloride channels. These compounds also inhibited ...
For several decades most of the efforts to develop new scintillator materials have concentrated on high-light-yield inorganic single-crystals while polycrystalline ceramic scintillators, since their inception in the early 1980 s, have received relatively little attention. Nevertheless, transparent ceramics offer a promising approach to the fabrication of relatively inexpensive scintillators via a simple mechanical compaction and annealing process that eliminates single-crystal growth. Until recently, commonly accepted concepts restricted the polycrystalline ceramic approach to materials exhibiting a cubic crystal structure. Here, we report our results on the development of two novel ceramic scintillators based on the non-cubic crystalline materials: Lu SiO:Ce (LSO:Ce) and LaBr:Ce. While no evidence for texturing has been found in their ceramic microstructures, our LSO:Ce ceramics exhibit a surprisingly high level of transparency/ translucency and very good scintillation ...
This report is a compilation of the calendar year 2003 groundwater sampling results from the Area 5 Radioactive Waste Management Site, Nevada Test Site. Wells Ue5PW-1, Ue5PW-2, and Ue5PW-3 were sampled semi-annually for the required analytes: pH, specific conductance, total organic carbon (TOC), total organic halides (TOX), tritium, and major cations/anions. Results from all samples collected in 2003 were within established criteria. These data indicate that there has been no measurable impact to the uppermost aquifer from the Resource Conservation and Recovery Act (RCRA) regulated unit within the Area 5 Radioactive Waste Management Site and confirm that any previous detections of TOC and TOX were false positives. Contamination indicator data are presented in control chart and tabular form with investigation levels indicated. Gross water chemistry data are presented in graphical and tabular form. There were no major changes noted in the monitored groundwater ...
The purpose of this work was to establish a new binary data base by compiling the activity coefficients of plutonium and uranium at oxidation state +IV to better account for media effects in the liquid-liquid extraction operations implemented to reprocess spent nuclear fuel. Chapter 1: first reviews the basic thermodynamic concepts before describing the issues involved in acquiring binary data for the tetravalent actinides. The difficulties arise from two characteristics of this type of electrolyte: its radioactive properties (high specific activity requiring nuclearization of the experimental instrumentation) and its physicochemical properties (strong hydrolysis). After defining the notion of fictive binary data, an approach based on the thermodynamic concept of simple solutions is described in which the activity coefficient of an aqueous phase constituent is dependent on two parameters: the water activity of the system and the total concentration of dissolved ...
The project is devoted to the development of novel insoluble anodes for copper electrowinning and electrolytic manganese dioxide (EMD) production. The anodes are made of titanium-lead composite material produced by techniques of powder metallurgy, compaction of titanium powder, sintering and subsequent lead infiltration. The titanium-lead anode combines beneficial electrochemical behavior of a lead anode with high mechanical properties and corrosion resistance of a titanium anode. In the titanium-lead anode, the titanium stabilizes the lead, preventing it from spalling, and the lead sheathes the titanium, protecting it from passivation. Interconnections between manufacturing process, structure, composition and properties of the titanium-lead composite material were investigated. The material containing 20-30 vol.% of lead had optimal combination of mechanical and electrochemical properties. Optimal process parameters to manufacture the anodes were identified. ...
The K alpha / K beta ratio of Mn KX-rays scattered by metallic samples changed remarkably with the geometry between the sample and the (55)Fe source-Si(Li) detector system. On the contrary, this intensity ratio changed little in the cases of non-metallic scatterer samples such as lucite or mylar. This difference is interpreted as due to the occurrence of strong or weak interference in the coherent scattering photons. PMID:7280291
The detection efficiency of a lithium glass detector was calculated using MCNP code, and the calculation was compared with the published results in Pulsed Sphere Plan. A lithium glass detector of our own was made, and its neutron efficiency was calculated. The calculated neutron efficiency was verified with both pulsed and steady DD neutrons. Characteristics of Neutron response of "6Li detector was discussed. (authors)
An investigation of the Ll x-#gamma# angular correlations following the decay of "2"0"7Bi is done by using a Si(Li) semiconductor counter as L x-ray detector. Coincidence measurements at five different angles were made between the 570-keV #gamma# ray (gated in the movable counter) and the Ll x spectrum (displayed in a multichannel analyzer).
A number of high voltage cathode materials are now being considered for their ability to increase the energy density of lithium-ion batteries. In this study, a lithium-nickel composite alloy (LiNiVO{sub 4}) was synthesized using a rheological phase reduction method that incorporated mixtures of LiOH-H{sub 2}O, Ni(CH{sub 3}COO){sub 2}, 4H{sub 2}O, NH{sub 4}VO{sub 3} and C{sub 2}H{sub 2}O{sub 4}-2H{sub 2}O. The rheological phase method was used to prepare the compounds from a solid-liquid rheological mixture. Solid reactants were first mixed in a proper molar ratio, and water or solvents were added to the solid-liquid rheological body. X-ray powder diffraction (XRD) and Fourier Transform (FT) analyses were conducted to characterize the powders. Scanning electron microscopy (SEM) was used to characterize the morphological features and particle sizes of the powders. Results of the analyses indicated that the single-phase ...
Determination of Cr, Fe, Cu, Zn and Pb in drinking water preconcentrated on a chelating ion exchanger of Czechoslovak production is described. The analytical system consisted of a radionuclide source "2"3"8Pu, a Si/Li semiconductor detector and a multichannel analyzer. Results are compared with trehshold limit values recommended for drinking water. (author) 9 refs.; 2 figs.
Low-lying nuclear energy levels in "1"1"0In and "1"1"2In were determined from de-excitation #gamma#-rays produced with "1"0"7Ag(#alpha#,n#gamma#)-"1"1"0In, "1"0"8Pd("6Li,4n#gamma#)"1"1"0In, "1"0"9Ag(#alpha#,n#gamma#)"1"1"2In and "1"1"0Pd("6Li,4n#gamma#)"1"1"2In reactions. In addition, the "1"1"4In energy level structure was investigated with the "1"1"0Pd("7Li,3n#gamma#)"1"1"4In reaction. Properties of de-excitation #gamma#-rays were determined from #gamma#-#gamma# coincidence, excitation, and angular distribution measurements conducted with Ge(Li) and Ge(intr.) #gamma#-ray detectors. A sequence of intraconnected levels in each of "1"1"0,"1"1"2,"1"1"4In were assigned to the (#pi#g"-"1/sub 9/2/, #nu#h/sub 11/2/) configuration. For the "1"1"0,"1"1"2,"1"1"4In energy level schemes a model calculation has been performed using the pairing-plus-quadrupole model, which reproduced states of the (#pi#g"-"1/sub ...
An experimental study was performed in order to study the nuclear structure in odd--odd In isotopes. Low lying nuclear energy levels in "1"1"0In and "1"1"2In were determined from de-excitation #gamma#-rays produced with "1"0"7AG(#alpha#,n#gamma#)"1"1"0In, "1"0"8Pd("6Li,4n#gamma#)"1"1"0In, "1"0"9Ag(#alpha#,n#gamma#)"1"1"2In and "1"1"0Pd("6Li,4n#gamma#)"1"1"2In reactions. In addition, the "1"1"4In energy level structure was investigated with the "1"1"0Pd("7Li,3n#gamma#)"1"1"4In reaction. Properties of de-excitation #gamma#-rays were determined from #gamma#--#gamma# coincidence excitation and angular distribution measurements conducted with Ge(Li) and Ge(intr.) #gamma#-ray detectors. A sequence of intraconnected levels in each of "1"1"0 "1"1"2 "1"1"4In were assigned to the (#pi#"-"1/sub 9/2/, #nu#h/sub 11/2) configuration. For the "1"1"0 "1"1"2"1"1"4In energy level schemes a model calculation was performed ...
Lithium-ion batteries are becoming more and more important not only for portable electronic devices, but also in prevision of high power electric vehicles. In such an optic, deep studies regarding all the components of a secondary battery are in development. In this study, high voltage cathode materials have been selected. Crystals with spinel structure have a 3D vacancy pathway suitable for Li-ions transport. The material under study was LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} doped with magnesium replacing the nickel. Various samples were synthesized via three different routes: a solid-state method, a modified sol-gel method and a xerogel method. The structure and morphology of the powders were analyzed with HRTEM and XRD. Electrochemical tests were also performed. A wide range of particle sizes (from micro to nanosize) was the result of the different synthesis routes. Unfortunately pure materials were not always obtained. The electrochemical tests ...
An integrated mirrorless bistable optical device based on the Mach-Zehnder interferometric optical switch has been proposed and demonstrated experimentally using a Ti:LiNbO3 waveguide. The resulting device is capable of combining more than two of them to realize multifunctional optical devices such as optical multivibrators.
Cigarette smoking is the major environmental risk factor for bladder cancer in humans. Aromatic amines, potent DNA-reactive bladder carcinogens present in cigarette smoke, contribute significantly. However, increased cell proliferation, caused by direct mitogenesis or in response to cytotoxicity, may also play a role since urothelial hyperplasia has been observed in human cigarette smokers. We examined the urothelial effects of cigarette smoke (whole body inhalation exposure (Teague) system) in female C57BL/6 mice at various times in two studies, including reversibility evaluations. In both studies, no urothelial hyperplasia was observed by light microscopy in any group. However, in study 1, the Ki-67 labeling index (LI) of the urothelium was significantly increased in the smoke exposed group compared to controls through 3 months, but was not present at 6, 9 or 12 months even with continued exposures. In the groups that discontinued smoke exposure, it returned to ...
Fe, Mn, Ni, V, Ti and Mo were determined in aerosols from manual arc welding. Samples of welding aerosols were trapped on a Synpor 4 filter. The amount of determined elements in aerosols was detected using the method of radionuclide X-ray fluorescence analysis. A /sup 241/Am annular source was used as the source of excitation radiation and radiation was processed using a Si(Li) spectrometer.
Fe, Mn, Ni, V, Ti and Mo were determined in aerosols from manual arc welding. Samples of welding aerosols were trapped on a Synpor 4 filter. The amount of determined elements in aerosols was detected using the method of radionuclide X-ray fluorescence analysis. A "2"4"1Am annular source was used as the source of excitation radiation and radiation was processed using a Si(Li) spectrometer. (E.S.).
The gamma-ray spectrum following neutron capture on /sup 87/Sr was measured at 3 neutron energies: E/sub n/ = thermal, 2 keV, and 24 keV. Gamma rays were detected in a three-crystal Ge(Li)-NaI-NaI pair spectrometer. Gamma-ray intensities deduced from these spectra by spectral unfolding are presented.
Li shell-model calculation has been made in the isospin formalism in the complete (0 + n)#Planck constant##omega# model space with the assumption of a closed core "4He. The calculation could probably be improved by use of a better effective interaction and increasing shell model space. With the use of faster computer with large memories, the authors are in hope of calculation in spsd shell-model space
The dynamic behavior of electrooptic bistable devices with delayed feedback is investigated theoretically and experimentally. The operation principle of the system is analyzed by the method of iterated maps. Stable, bistable, periodic, higher periodic, and chaotic solutions are discussed and realized experimentally by using an integrated Mach-Zehnder interferometer on LiNbO3 as a basic nonlinear element. Taking into account the periodic modulator characteristic, the application of this device as a simple and fast bistable and monostable multivibrator is demonstrated. In addition, the synchronization properties of the astable multivibrator are investigated.
Radionuclide X-ray fluorescence method with a Si/Li semiconductor detector and "2"3"8Pu exciting source was used in the determination of Cr, Fe, Ni, Cu, and Zn content in industrial wastewaters. Simultaneously, the effects of the wastewaters on activated sludge biocenose were evaluated. (author) 6 refs.; 1 fig.; 1 tab.
Radionuclide X-ray fluorescence method was used for the determination of Fe and Zn in healing plants (Sage, Peppermint, Stinging, Common Agrimony, Milfoil, Ribwort, Tansy, White Dead-Nettle). "2"3"8Pu exciting source and Si/Li semiconductor detector were used for the determination. (author)
Radionuclide X-ray fluorescence method with Si/Li semiconductor detector and "2"3"8Pu exciting source was used for the determination of Cu, Ni, Zn and Pb in plant samples (Taraxacum officinale) from various localities near the highway D-61 Bratislava-Trnava (SR). (author) 2 refs.; 1 fig.; 1 tab.
Radionuclide X-ray fluorescence method with Si/Li semiconductor detector and "2"3"8Pu exciting source was used for the determination of Cu, Ni, Pb, and Zn in soil samples from various localities near the D-61 Bratislava-Trnava highway (CSFR). (author) 1 ref.; 1 tab.
Several examples of the 14-membered, para-bridged ring system of the cyclopeptide alkaloids have been synthesized via an active ester cyclization. The yield of monomeric cyclopeptide varied from 1 to 33% and was affected by the amino acid substitution pattern and amide conformation of the linear peptide precursors. Both the synthetic models and a naturally occurring cyclopeptide alkaloid, ceanothine B, bind monovalent (Li"+) and divalent (Ca"2"+, Mg"2"+) cations. 4 figures, 1 table.
In a cold fusion method by electrolysis, a hydrogen occluding material mainly comprising vanadium is used as a material for a negative electrode, and lithium isotopes are incorporated in the material by more than 93%. That is, the ratio of lithium 7 ("7Li) isotope is increased to higher than the natural existent ratio, so that tritium ("3H) concentration in the hydrogen occluding material can be increased, to attain energy at high efficiency. (T.M.).
An energy sensitive Si(Li) detector XRF analyzer built by ATOMKI, Hungary, has been applied for various analytical purposes in alumina production at the Almasfuezitoe Alumina Company, Hungary. Specifically, the CaO content in red mud was determined by the new XRF technique using isotope excitation sources. The analysis of other components is under way. (R.P.).
A new, magnetically insulated negative ion source has recently been discovered which can produce pulsed negative ion beams (H/sup -/, Li/sup -/, and C/sup -/) with intensities of 100-300 A/cm/sup 2/ at 1-4 MeV. This source may provide the basis for a high energy neutral beam system for heating large tokamaks.
Carbon stable isotope trichloroethylene ("1"3C TCE) was used to investigate the formation of chloromethane (CM) during the electrolytic dechlorination of trichloroethylene (TCE) at a granular-graphite packed cathode. A method was developed to use a conventional GC/MS to analyze and quantify regular and "1"3C TCE and their dechlorination products. The concentration of a "1"3C compound can be calculated, based on the concentration of its regular counterpart, from the response ratio of two fragments of different mass per charge values from the compounds in a sample and two characteristic MS spectrum ratios: one is the response ratio of the two fragments of the regular compound, and the other is the response ratio of the corresponding fragments of the regular and "1"3C compounds at the same concentrations. The method was used to analyze the regular and "1"3C compounds observed in an experiment of dechlorination in an ammonium acetate solution that contained both ...
The crystallization of calcium sulfate from aqueous solutions with NaCl is both geological and industrial interest because NaCl is the dominant solute in natural brines and many industrial fluids. Induction periods for the nucleation of calcium sulfate dihydrate were experimentally determined as a function of supersaturation in NaCl solutions from 0 to 6 m at 25 C and in 3.0-m NaCl solutions at temperatures from 25 to 90 C. Using classic nucleation theory, the interfacial tension between gypsum and 3.0-m NaCl solution was estimated to be about 39 mJ/m[sup 2] at 25 C and increases with increasing temperature (to 63 mJ/m[sup 2] at 90 C). It was observed that the induction period decreases with increasing NaCl concentrations up to 3 m and then starts to increase slightly at a given temperature and saturation state. The electrolyte effect on nucleation was proportional to the enhanced solubility of calcium sulfate dihydrate in NaCl solutions. This phenomenon may result ...
Sm"1"."8Ce"0"."2CuO"4-xCe"0"."9Gd"0"."1O"1"."9"5 (SCC-xCGO, x=0-12vol.%) composite cathodes supported on Ce"0"."9Gd"0"."1O"1"."9"5 (CGO) electrolyte are studied for applications in IT-SOFCs. Results show that Sm"1"."8Ce"0"."2CuO"4 material is chemically compatible with Ce"0"."9Gd"0"."1O"1"."9"5 at 1000^oC. The composite electrode exhibits optimum microstructure and forms good contact with the electrolyte after sintering at 1000^oC for 4h. The polarization resistance (R"p) reduces to the minimum value of 0.17@Wcm^2 at 750^oC in air for SCC-CGO06 composite cathode. The relationship between R"p and oxygen partial pressure indicates that the reaction rate-limiting step is the surface diffusion of the dissociative adsorbed oxygen on the composite cathode.
The initiation and characteristics of mossy zinc electrodeposits have been investigated. Batteries with zinc electrodes are candidates for electric vehicle applications; however, this electrode is prone to form non-compact deposits that contribute to capacity loss and battery failure. Moss is deposited when the current density is far from the limiting current. This morphology first appears only after the bulk deposit is approximately 1 {mu}m thick. In this investigation, the effects of flow rate (Re=0--4000), current density (0--50 mA/cm{sup 2}), concentration of the electroactive species (0.25 and 0.5 M), and the concentration of supporting electrolyte (3, 6, and 12 M) on the initiation of moss were examined. The rotating concentric cylinder electrode was employed for most of the experiments; and a flow channel was used to study the development of morphology. After the experiment, the deposit was characterized using microscopic, x-ray diffraction, and ...
A commercial CFD code, Fluent, has been used to analyse the design of a filter-press reactor operating with characteristic linear flow velocities between 0.024 and 0.192 m s-1. Electrolyte flow through the reactor channel was numerically calculated using a finite volume approach to solve the Navier-Stokes equations. The length of the channel was divided into 7 sections corresponding to distances of 0, 0.01, 0.04, 0.08, 0.12, 0.14 and 0.15 m from the electrode edge nearest to the inlet. The depth of the channel was divided into three planes parallel to the channel bottom. For each channel section, a velocity profile was obtained at each depth together with the average velocity in each plane. The flow predictions show that the flow development, as the electrolyte passes through the cell, is strongly affected by the manifold causing strong vortex structures at the entrance and exit of the channel. Although the flow disturbances are a function of ...
An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M.sub.x Z.sub.y Mn.sub.(1-y) O.sub.2, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. ...
The deposition of platinum on various carbon blacks was carried out by forming active functional groups on the surface of the carbon support, and exchanging these active groups with different platinum complexes. Using H{sub 2}PtCl{sub 6} solution, an impregnation rather than an exchange takes place. However, using divalent platinum complexes [Pt(NH{sub 3}){sub 4}]{sup 2+}, a fast exchange takes place which leads to extremely small platinum particles highly dispersed on the surface of carbon black. A comparison of the catalytic activities of platinum supported on various carbon blacks was also carried out. The performances of PEFC (Polymer Electrolyte Fuel Cell) based on the process of the ion exchange are reported. (authors) 3 refs.
The effects of gas diffusion layer's (GDL's) anisotropic bending stiffness on the degradation behavior of polymer electrolyte membrane fuel cells have been investigated under freezing conditions. We have prepared GDL sheet samples such that the higher stiffness direction of GDL roll is aligned with the major flow field direction of a metallic bipolar plate at angles of 0^o (parallel: '0^o GDL') and 90^o (perpendicular: '90^o GDL'). The I-V performances before and after 1000 temperature cycles between -10 and 1 ^oC of 90^o GDL stack are higher than those of 0^o GDL stack, and the voltages of 90^o GDL stack are decreased slower than those of 0^o GDL stack, indicating a higher durability of 90^o GDL stack. Furthermore, the values and increasing rates of high-frequency resistance of 90^o GDL s...
A comparison between the concepts of the hybrid electric vehicle (HEV) and the ultra low emission vehicle (ULEV) was presented. The ULEV uses a much larger engine compared to the HEV, but it uses a lower Kw generator/motor and inverter/charger to use the latest engine and battery technology. The underlying goal of the ULEV is to supply auxiliary power under start-up and heavy load conditions and to remove indirect systems such as steering, starting and blower control from the engine via small electric drives. The challenge is to build a ULEV that is robust enough to withstand any environmental conditions. Since the ULEV engine is larger, it can experience compartment temperatures greater than 125 degrees C, which limits the use of conventional filter capacitors. Nippon Chemi-Con has recently developed U787D, the world's first continuous 150 degrees C rated aluminum electrolytic capacitor designed to meet the ambient, ripple currents and vibration ...
Proof-of-principle experiments are reported for a new concept in electrically rechargeable zinc-air battery. The zinc electrode is a porous flow-thru type using a copper foam metal substrate with zinc deposition onto the foam metal from concentrated zincate electrolyte (as used in zinc-slurry type batteries). The bifunctional air electrode employs low-cost materials, being fabricated entirely from carbon-based precursors and small amounts of nickel and/or cobalt oxide. Corrosion measurements on the graphite materials in the air electrode indicate sufficient corrosion resistance for 8000 h life on charge. A prototype single cell was constructed having 1.5 Ah capacity producing 1.2 V discharge -2.0 charge at the three hour rate and has produced stable voltages for more than 150 cycles. Based on the 1.5 Ah prototype characteristics, design calculations for a 32 kWh battery project an energy density of about 110 Wh/kg, peak power density of 140 W/kg, electrical ...
Measurements of PEM fuel cell device performance were made with different gas inlet temperatures and relative humidity using a newly-designed test fixture. Significant improvement in device performance was observed when the fuel inlet temperature was increased above the operating temperature of the cell. These measurements were then correlated to a model to describe energy and mass transport processes. Proton exchange membrane (PEM), fuel cells--the focus of this study--use an ion conducting polymer, especially polyperfluorosulfonic acid materials. These polymer materials, when imbibed with water, exhibit solution-like properties, but because the anions are chemically bound to the polymeric structure, the electrolyte is contained. Importantly, product water removal is simplified, as electrolyte dilution is not a concern. However, the proton transport rate is a function of the polymer geometry, which is set, in part, by the polymer water ...
Apparatus and methods are described for generating heat and electricity from the consumption of a variety of aluminum products. The method consists of (A) a reaction chamber containing an aqueous electrolyte solution and adapted for introduction therein of aluminum pieces of various shapes and sizes up to a certain maximum predetermined size and for effecting a chemical reaction between said aqueous electrolyte and said aluminum pieces yielding aluminum hydroxide and an intermediate reactant; (B) means for feeding said aluminum pieces into said reaction chamber in small quantities upon demand; (C) means for removing the heat generated in said chamber as a result of said reaction; (D) means for removing said aluminum hydroxide reaction product; and (E) means for oxidizing said intermediate reactant in an electrochemical cell, thereby generating electrical energy. The intermediate reactant is preferably hydrogen or zinc. The latter may be used in ...
Apparatus and methods for generating heat and electricity from the consumption of a variety of aluminum products comprise: (A) a reaction chamber containing an aqueous electrolyte solution and adapted for introduction therein of aluminum pieces of various shapes and sizes up to a certain maximum predetermined size and for effecting a chemical reaction between said aqueous electrolyte and said aluminum pieces yielding aluminum hydroxide and an intermediate reactant; (B) means for feeding said aluminum pieces into said reaction chamber in small quantities upon demand; (C) means for removing the heat generated in said chamber as a result of said reaction; (D) means for removing said aluminum hydroxide reaction product; and (E) means for oxidizing said intermediate reactant in an electrochemical cell, thereby generating electrical energy. The intermediate reactant is preferably hydrogen or zinc. The latter may be used in a slurry type zinc/air ...
Degradation reactions of a nylon 6 battery separator material have been studied in 4-34% aqueous KOH electrolytes at 35/sup 0/-110/sup 0/C. In a Ni/Cd cell, this degradation involves a slow hydrolysis reaction followed by fast electrochemical oxidations of the hydrolysis reaction products. Arrhenius activation energy of the hydrolysis reaction in 34% KOH was 20.0 +- 0.3 kcal/mole. A plot of the hydrolysis rate at 100/sup 0/C vs. hydroxyl ion concentration gave a rate maximum at about 16% KOH, and the mechanism for this effect is discussed. Electrochemical oxidations of the hydrolysis product, 6-aminocaproate ion, appear to proceed rapidly in several sequential steps at a nickel oxide electrode. In a Ni/Cd cell, the combination of nylon separator hydrolysis followed by electrochemical oxidation of the products can seriously degrade the battery lifetime. The rate of the hydrolysis of nylon 66 separator material was approximately one half of that of the nylon 6 ...
The AP-0 Target Hall Collection Lens is a pulsed device which focuses anti-protons just downstream of the Target. Since the angles at which the anti-protons depart the Target can be quite large, a very high focusing strength is required to maximize anti-proton capture into the downstream Debuncher Ring. The current design of the Collection Lens was designed to operate with a focusing gradient of 1,000 T/m. However, multiple failures of early devices resulted in lowering the normal operating gradient to about 750 T/m. At this gradient, the Lens design fares much better, lasting several million pulses, but ultimately still fails. A Finite Element Analysis (FEA) has been performed on this Collection Lens design to help determine the cause and/or nature of the failures. The Collection Lens magnetic field is created by passing high current through a central conductor cylinder. A uniform current distribution through the cylinder will create a tangential or azimuthal magnetic field that ...
Separations of metal ions on the basis of Donnan dialysis across anion-exchange membranes should be possible if the receiver electrolyte composition favors the formation of selected anionic complexes of the sample metal ions. Moreover, such a separation has the possibility of being better suited from some applications than batch or column experiments with anion-exchange resins. The above hypothesis are tested on the platinum-group metal ions, Pt(IV), Rh(III), Pd(II), Ir(III), and Ir(IV). 13 references, 4 tables.
Polymer electrolyte membrane fuel cells (PEMFCs) are energy conversion devices that produce electricity from a supply of fuel, such as hydrogen. One of the major challenges in achieving efficient energy conversion is the development of cost-effective materials that can act as electrocatalysts for PEMFCs. In this letter, we demonstrate that, instead of conventional noble metals, such as platinum, chromium nitride nanocrystals of fcc structure exhibit attractive catalytic activity for PEMFCs. Device testing indicates good stability of nitride nanocrystals in low temperature fuel cell operational environment.
Crystallization points of aqueous solution of the systems M(ClO_4)_2-H_2O (M"2 = Mg"2"+, Ca"2"+, Sr"2"+, Ba"2"+), depending on the salt concentration, were identified by visual-polythermal method. Relying on model notions on the structure of the electrolyte solutions, specific features of strontium perchlorate solubility polytherm and concentration dependence of the relative dynamic viscosity of the salt aqueous solutions are discussed
Cement-based composites are widely used in applications which demand long-term service life. One important example is in immobilization matrices for low-level radioactive and other hazardous wastes, which demands long-term retention and durability. The authors describe conductivity measurements of grouts flooded with water and in contact with a sink that consists of pure water. The conductivity measurements were designed and carried out in parallel with present quality verification methods and standard leach tests of the nuclear waste management industry. For the first time, the authors show that the method of replacing intrusive chemical analysis with conductivity measurements of the leaching samples yields equivalent results.
The addition of carbon to samples, during imaging, presents a barrier to accurate TEM analysis, the controlled deposition of hydrocarbons by a focused electron beam can be a useful technique for local nanometer-scale sculpting of material. Here we use hydrocarbon deposition to form nanopores from larger focused ion beam (FIB) holes in silicon nitride membranes. Using this method, we close 100-200nm diameter holes to diameters of 10nm and below, with deposition rates of 0.6nm per minute. I-V characteristics of electrolytic flow through these nanopores agree quantitatively with a one dimensional model at all examined salt concentrations.