Electrically Conductive Anodized Aluminum Surfaces

NASA Technical Reports Server (NTRS)

Nguyen, Trung Hung

2006-01-01

Anodized aluminum components can be treated to make them sufficiently electrically conductive to suppress discharges of static electricity. The treatment was conceived as a means of preventing static electric discharges on exterior satin-anodized aluminum (SAA) surfaces of spacecraft without adversely affecting the thermal-control/optical properties of the SAA and without need to apply electrically conductive paints, which eventually peel off in the harsh environment of outer space. The treatment can also be used to impart electrical conductivity to anodized housings of computers, medical electronic instruments, telephoneexchange equipment, and other terrestrial electronic equipment vulnerable to electrostatic discharge. The electrical resistivity of a typical anodized aluminum surface layer lies between 10(exp 11) and 10(exp 13) Omega-cm. To suppress electrostatic discharge, it is necessary to reduce the electrical resistivity significantly - preferably to < or = 10(exp 9) Omega-cm. The present treatment does this. The treatment is a direct electrodeposition process in which the outer anodized surface becomes covered and the pores in the surface filled with a transparent, electrically conductive metal oxide nanocomposite. Filling the pores with the nanocomposite reduces the transverse electrical resistivity and, in the original intended outer-space application, the exterior covering portion of the nanocomposite would afford the requisite electrical contact with the outer-space plasma. The electrical resistivity of the nanocomposite can be tailored to a value between 10(exp 7) and 10(exp 12) Omega-cm. Unlike electrically conductive paint, the nanocomposite becomes an integral part of the anodized aluminum substrate, without need for adhesive bonding material and without risk of subsequent peeling. The electrodeposition process is compatible with commercial anodizing production lines. At present, the electronics industry uses expensive, exotic, electrostaticdischarge- suppressing finishes: examples include silver impregnated anodized, black electroless nickel, black chrome, and black copper. In comparison with these competing finishes, the present nanocomposite finishes are expected to cost 50 to 20 percent less and to last longer.

The influence of electrolyte additives on the anodic dissolution of aluminum in alkaline solutions

NASA Astrophysics Data System (ADS)

Boehnstedt, W.

1980-09-01

The paper describes the effect of electrolyte additives on the anodic dissolution of aluminum in alkaline solutions. The dissolution is accelerated by the addition of small quantities of gallium or indium ions to the electrolyte indicated by the shift of the zero current potential by about 250 mV on the current-potential curve. Scanning electron microscope studies showed that gallium ions produce many small cracks in the aluminum electrode and collect at the grain boundary areas, increasing the electrode surface; this enlargement, in combination with increased electrolyte agitation due to greater hydrogen evolution, provides higher current densities at the same potential. It is concluded that this process will widen the possibilities of using aluminum and its alloys in high-rate batteries.

Anodic Dissolution of Al Current Collectors in Unconventional Solvents for High Voltage Electrochemical Double-Layer Capacitors.

PubMed

Krummacher, Jakob; Heß, Lars-Henning; Balducci, Andrea

2017-09-04

This study investigated the anodic dissolution of Al current collectors in unconventional electrolytes for high voltage electrochemical double-layer capacitors (EDLCs) containing adiponitrile (ADN), 3-cyanopropionic acid methyl ester (CPAME), 2-methyl-glutaronitrile (2-MGN) as solvent, and tetraethylammonium tetrafluoroborate (Et 4 NBF 4 ) and tetraethylammonium bis(trifluoromethanesulfonyl)imide (Et 4 NTFSI) as conductive salts. To have a comparison with the state-of-the-art electrolytes, the same salts were also used in combination with acetonitrile (ACN). The chemical-physical properties of the electrolytes were investigated. Furthermore, their impact on the anodic dissolution of Al was analyzed in detail as well as the influence of this process on the performance of high voltage EDLCs. The results of this study indicated that in the case of Et 4 NBF 4 -based electrolytes, the use of an alternative solvent is very beneficial for the realization of stable devices. When Et 4 NTFSI is used, the reduced solubility of the complex Al(TFSI) 3 appears to be the key for the realization of advanced electrolytes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High resolution electrolyte for thinning InP by anodic dissolution and its applications to EC-V profiling, defect revealing and surface passivation

NASA Technical Reports Server (NTRS)

Faur, Maria; Faur, Mircea; Weinberg, Irving; Goradia, Manju; Vargas, Carlos

1991-01-01

An extensive experimental study was conducted using various electrolytes in an effort to find an appropriate electrolyte for anodic dissolution of InP. From the analysis of electrochemical characteristics in the dark and under different illumination levels, x ray photoelectron spectroscopy and SEM/Nomarski inspection of the surfaces, it was determined that the anodic dissolution of InP front surface layers by FAP electrolyte is a very good choice for rendering smooth surfaces, free of oxides and contaminants and with good electrical characteristics. The FAP electrolyte, based on HF, CH3COOH, and H2O2 appears to be inherently superior to previously reported electrolytes for performing accurate EC-V profiling of InP at current densities of up to 0.3 mA/sq cm. It can also be used for accurate electrochemical revealing of either precipitates or dislocation density with application to EPD mapping as a function of depth, and for defect revealing of multilayer InP structures at any depth and/or at the interfaces.

Accelerated corrosion of stainless steel in thiocyanate-containing solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pistorius, P Chris; Li, Wen

2012-09-19

It is known that reduced sulfur compounds (such as thiocyanate and thiosulfate) can accelerate active corrosion of austenitic stainless steel in acid solutions, but before we started this project the mechanism of acceleration was largely unclear. This work combined electrochemical measurements and analysis using scanning electron microscopy (SEM) and X-ray photo-electron spectroscopy (XPS), which provided a comprehensive understanding of the catalytic effect of reduced sulfur species on the active corrosion of stainless steel. Both the behavior of the pure elements and the steel were studied and the work focused on the interaction between the pure elements of the steel, whichmore » is the least understood area. Upon completion of this work, several aspects are now much clearer. The main results from this work can be summarized as follows: The presence of low concentrations (around 0.1 mM) of thiocyanate or tetrathionate in dilute sulfuric acid greatly accelerates the anodic dissolution of chromium and nickel, but has an even stronger effect on stainless steels (iron-chromium-nickel alloys). Electrochemical measurements and surface analyses are in agreement with the suggestion that accelerated dissolution really results from suppressed passivation. Even well below the passivation potential, the electrochemical signature of passivation is evident in the electrode impedance; the electrode impedance shows clearly that this pre-passivation is suppressed in the presence of thiocyanate. For the stainless steels, remarkable changes in the morphology of the corroded metal surface and in the surface concentration of chromium support the suggestion that pre-passivation of stainless steels is suppressed because dissolution of chromium is accelerated. Surface analysis confirmed that adsorbed sulfur / sulfide forms on the metal surfaces upon exposure to solutions containing thiocyanate or thiosulfate. For pure nickel, and steels containing nickel (and residual copper), bulk sulfide (visible as a black corrosion product) forms during anodic dissolution. The sulfide is electronically conductive, and gives an increase of several orders of magnitude in the electrode capacitance; the sulfide also causes anodic activation to persist after the pure metals and steels were removed from the thiocyanate-containing electrolyte and transferred to a thiocyanate-free electrolyte. The main practical implications of this work are that low concentrations of reduced sulfur compounds strongly affect anodic dissolution of stainless steels, and that selecting steels with elevated concentrations of chromium, nickel or molybdenum would serve to limit the anodic dissolution rate in the presence of reduced sulfur compounds.« less

Liquid permeation and chemical stability of anodic alumina membranes

PubMed Central

Buldakov, Dmitrii A; Tishkin, Alexey A; Lukashin, Alexey V; Eliseev, Andrei A

2017-01-01

A study on the chemical stability of anodic alumina membranes and their performance in long-term water and organic solvent permeation experiments is reported. Anodic alumina possesses high stability for both protonic and aprotonic organic solvents. However, serious degradation of the membrane occurs in pure water, leading to a drastic decrease of permeance (over 20% of the initial value after the passing of 0.250 m3/m2 of pure water). The drying of the membrane induces further permeance drop-off. The rate of membrane degradation strongly depends on the pH of the penetrant solution and increases in basic media. According to 27Al NMR and thermogravimetry results, the degradation of the membranes is associated with the dissolution of water-soluble [Al13O4(OH)24(H2O)12]7+ polyhydroxocomplexes and their further redeposition in the form of [Al(OH)4]−, resulting in channels blocking. This process intensifies in basic pH due to the high positive charge of the anodic alumina surface. An approach for improving anodic aluminum oxide stability towards dissolution in water by carbon CVD coating of the membrane walls is suggested. PMID:28382245

In situ fabrication of electrochemically grown mesoporous metallic thin films by anodic dissolution in deep eutectic solvents.

PubMed

Renjith, Anu; Roy, Arun; Lakshminarayanan, V

2014-07-15

We describe here a simple electrodeposition process of forming thin films of noble metallic nanoparticles such as Au, Ag and Pd in deep eutectic solvents (DES). The method consists of anodic dissolution of the corresponding metal in DES followed by the deposition on the cathodic surface. The anodic dissolution process in DES overcomes the problems associated with copious hydrogen and oxygen evolution on the electrode surface when carried out in aqueous medium. The proposed method utilizes the inherent abilities of DES to act as a reducing medium while simultaneously stabilizing the nanoparticles that are formed. The mesoporous metal films were characterized by SEM, XRD and electrochemical techniques. Potential applications of these substrates in surface enhanced Raman spectroscopy and electrocatalysis have been investigated. A large enhancement of Raman signal of analyte was achieved on the mesoporous silver substrate after removing all the stabilizer molecules from the surface by calcination. The highly porous texture of the electrodeposited film provides superior electro catalytic performance for hydrogen evolution reaction (HER). The mechanisms of HER on the fabricated substrates were studied by Tafel analysis and electrochemical impedance spectroscopy (EIS). Copyright © 2014 Elsevier Inc. All rights reserved.

Process and apparatus for recovery of fissionable materials from spent reactor fuel by anodic dissolution

DOEpatents

Tomczuk, Zygmunt; Miller, William E.; Wolson, Raymond D.; Gay, Eddie C.

1991-01-01

An electrochemical process and apparatus for the recovery of uranium and plutonium from spent metal clad fuel pins is disclosed. The process uses secondary reactions between U.sup.+4 cations and elemental uranium at the anode to increase reaction rates and improve anodic efficiency compared to prior art processes. In another embodiment of the process, secondary reactions between Cd.sup.+2 cations and elemental uranium to form uranium cations and elemental cadmium also assists in oxidizing the uranium at the anode.

Anode shroud for off-gas capture and removal from electrolytic oxide reduction system

DOEpatents

Bailey, James L.; Barnes, Laurel A.; Wiedmeyer, Stanley G.; Williamson, Mark A.; Willit, James L.

2014-07-08

An electrolytic oxide reduction system according to a non-limiting embodiment of the present invention may include a plurality of anode assemblies and an anode shroud for each of the anode assemblies. The anode shroud may be used to dilute, cool, and/or remove off-gas from the electrolytic oxide reduction system. The anode shroud may include a body portion having a tapered upper section that includes an apex. The body portion may have an inner wall that defines an off-gas collection cavity. A chimney structure may extend from the apex of the upper section and be connected to the off-gas collection cavity of the body portion. The chimney structure may include an inner tube within an outer tube. Accordingly, a sweep gas/cooling gas may be supplied down the annular space between the inner and outer tubes, while the off-gas may be removed through an exit path defined by the inner tube.

What Happens during Natural Protein Fibre Dissolution in Ionic Liquids.

PubMed

Chen, Jingyu; Vongsanga, Kylie; Wang, Xungai; Byrne, Nolene

2014-08-28

Here, we monitor the dissolution of several natural protein fibres such as wool, human hair and silk, in various ionic liquids (ILs). The dissolution of protein-based materials using ILs is an emerging area exploring the production of new materials from waste products. Wool is a keratin fibre, which is extensively used in the textiles industry and as a result has considerable amounts of waste produced each year. Wool, along with human hair, has a unique morphology whereby the outer layer, the cuticle, is heavily cross linked with disulphide bonds, whereas silk does not have this outer layer. Here we show how ILs dissolve natural protein fibres and how the mechanism of dissolution is directly related to the structure and morphology of the wool fibre.

Electrochemical Deburring

NASA Technical Reports Server (NTRS)

Burley, R. K.

1983-01-01

Electrochemical deburring removes burrs from assembled injector tubes. Since process uses liquid anodic dissolution in liquid electrolyte to proide deburring action, smoothes surfaces and edges in otherwise inaccessible areas. Tool consists of sleeve that contains metallic ring cathode. Sleeve is placed over tube, and electrolytic solution is forced to flow between tube and sleeve. The workpiece serves an anode.

X-ray reflectivity study of formation of multilayer porous anodic oxides of silicon.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chu, Y.; Fenollosa, R.; Parkhutik, V.

1999-07-21

The paper reports data on the kinetics of anodic oxide films growth on silicon in aqueous solutions of phosphoric acids as well as a study of the morphology of the oxides grown in a special regime of the oscillating anodic potential. X-ray reflectivity measurements were performed on the samples of anodic oxides using an intense synchrotron radiation source. They have a multilayer structure as revealed by theoretical fitting of the reflectivity data. The oscillations of the anodic potential are explained in terms of synchronized oxidation/dissolution reactions at the silicon surface and accumulation of mechanic stress in the oxide film.

Investigation of Oral Preparation That Is Expected to Improve Medication Administration: Preparation and Evaluation of Oral Gelling Tablet Using Sodium Alginate.

PubMed

Ito, Ikumi; Ito, Akihiko; Unezaki, Sakae

2017-01-01

We investigated the preparation of a gelling tablet that swells and forms a gel upon absorbing water, and hence would be easy for patients to swallow. We prepared naked tablets and compressed coated tablets by the direct tableting or wet granule-compression methods, using the commonly prescribed drug acetaminophen (AA) and sodium alginate (AG) as a thickening agent. The tablets quickly absorbed water, had favorable gelling properties, low adhesiveness, appropriate drug dissolution profile, and at the same time, were easy to swallow. In the case of naked tablets, water absorption increased upon granulation, but gelling of AG interfere when AA and AG were present together. There was no change in the adhesiveness, and more than 30 min were required to achieve a 25% dissolution ratio. Compressed coated tablets that were made with AA in the inner layer and granulated AG in the outer layer showed improved dissolution behavior, it was about 90% dissolution ratio in 30 min, owing to the water absorption property of AG, and decreased adhesiveness. In this case, there was a difference in the outer layer thickness. As the outer layer amount increased, dissolution slowed, but it did not depend on the compression pressure. Our gelling tablet can be prepared by using AA (main drug) in the inner layer and an appropriate thickness of granulated AG in the outer layer of compressed coated tablets.

Anode current density distribution in a cusped field thruster

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Huan, E-mail: wuhuan58@qq.com; Liu, Hui, E-mail: hlying@gmail.com; Meng, Yingchao

2015-12-15

The cusped field thruster is a new electric propulsion device that is expected to have a non-uniform radial current density at the anode. To further study the anode current density distribution, a multi-annulus anode is designed to directly measure the anode current density for the first time. The anode current density decreases sharply at larger radii; the magnitude of collected current density at the center is far higher compared with the outer annuli. The anode current density non-uniformity does not demonstrate a significant change with varying working conditions.

Superhydrophilicity of novel anodic alumina nanofibers films and their formation mechanism

NASA Astrophysics Data System (ADS)

Peng, Rong; Yang, Wulin; Fu, Licai; Zhu, Jiajun; Li, Deyi; Zhou, Lingping

2017-06-01

A novel anodic alumina nanofibers structure, which is different from the traditional porous anodic structure, has been quickly fabricated via anodizing in a new electrolyte, pyrophosphoric acid. The effects of the solution concentration and the anodizing time on the formation of the anodic alumina nanofibers were analyzed. The results show that the nanostructure of anodic alumina can change to the nanofiber oxide from the porous oxide by increasing the solution concentration. Prolonging the anodizing time is beneficial to obtain alumina nanofibers at high solution concentration. Growth behavior of the alumina nanofibers was also discussed by scanning electron microscopy observations. Owing to the unique hexagonal structure of anodic alumina as well as the preferential chemical dissolution between the porous anodic alumina and the anodic alumina nanotips, the slightly soluble anodic alumina nanotips could form novel alumina nanofibers during anodizing. The results show that the nanofibers-covered aluminum surface exhibits superhydrophilic property, with a near-zero water contact angle. Such alumina nanofibers with superhydrophilic property could be used for various potential applications.

Integral edge seals for phosphoric acid fuel cells

DOEpatents

Granata, Jr., Samuel J.; Woodle, Boyd M.; Dunyak, Thomas J.

1992-01-01

A phosphoric acid fuel cell having integral edge seals formed by an elastomer permeating an outer peripheral band contiguous with the outer peripheral edges of the cathode and anode assemblies and the matrix to form an integral edge seal which is reliable, easy to manufacture and has creep characteristics similar to the anode, cathode and matrix assemblies inboard of the seals to assure good electrical contact throughout the life of the fuel cell.

What Happens during Natural Protein Fibre Dissolution in Ionic Liquids

PubMed Central

Chen, Jingyu; Vongsanga, Kylie; Wang, Xungai; Byrne, Nolene

2014-01-01

Here, we monitor the dissolution of several natural protein fibres such as wool, human hair and silk, in various ionic liquids (ILs). The dissolution of protein-based materials using ILs is an emerging area exploring the production of new materials from waste products. Wool is a keratin fibre, which is extensively used in the textiles industry and as a result has considerable amounts of waste produced each year. Wool, along with human hair, has a unique morphology whereby the outer layer, the cuticle, is heavily cross linked with disulphide bonds, whereas silk does not have this outer layer. Here we show how ILs dissolve natural protein fibres and how the mechanism of dissolution is directly related to the structure and morphology of the wool fibre. PMID:28788183

Direct electrochemical reduction of metal-oxides

DOEpatents

Redey, Laszlo I.; Gourishankar, Karthick

2003-01-01

A method of controlling the direct electrolytic reduction of a metal oxide or mixtures of metal oxides to the corresponding metal or metals. A non-consumable anode and a cathode and a salt electrolyte with a first reference electrode near the non-consumable anode and a second reference electrode near the cathode are used. Oxygen gas is produced and removed from the cell. The anode potential is compared to the first reference electrode to prevent anode dissolution and gas evolution other than oxygen, and the cathode potential is compared to the second reference electrode to prevent production of reductant metal from ions in the electrolyte.

Powerful glow discharge excilamp

DOEpatents

Tarasenko, Victor F.; Panchenko, Aleksey N.; Skakun, Victor S.; Sosnin, Edward A.; Wang, Francis T.; Myers, Booth R.; Adamson, Martyn G.

2002-01-01

A powerful glow discharge lamp comprising two coaxial tubes, the outer tube being optically transparent, with a cathode and anode placed at opposite ends of the tubes, the space between the tubes being filled with working gas. The electrodes are made as cylindrical tumblers placed in line to one other in such a way that one end of the cathode is inserted into the inner tube, one end of the anode coaxially covers the end of the outer tube, the inner tube penetrating and extending through the anode. The increased electrodes' surface area increases glow discharge electron current and, correspondingly, average radiation power of discharge plasma. The inner tube contains at least one cooling liquid tube placed along the axis of the inner tube along the entire lamp length to provide cathode cooling. The anode has a circumferential heat extracting radiator which removes heat from the anode. The invention is related to lighting engineering and can be applied for realization of photostimulated processes under the action of powerful radiation in required spectral range.

Engineering of highly ordered TiO2 nanopore arrays by anodization

NASA Astrophysics Data System (ADS)

Wang, Huijie; Huang, Zhennan; Zhang, Li; Ding, Jie; Ma, Zhaoxia; Liu, Yong; Kou, Shengzhong; Yang, Hangsheng

2016-07-01

Finite element analysis was used to simulate the current density distributions in the TiO2 barrier layer formed at the initial stage of Ti anodization. The morphology modification of the barrier layer was found to induce current density distribution change. By starting the anodization with proper TiO2 barrier layer morphology, the current density distribution can be adjusted to favor the formation of either nanotube arrays or nanopore arrays of anodic TiO2. We also found that the addition of sodium acetate into the electrolyte suppressed both the field-assisted chemical dissolution of TiO2 and the TiF62- hydrolysis induced TiO2 deposition during anodization, and thus further favored the nanopore formation. Accordingly, highly ordered anodic TiO2 nanopore arrays, similar to anodic aluminum oxide nanopore arrays, were successfully prepared.

First-Principles Modeling of Mn(II) Migration above and Dissolution from Li x Mn 2 O 4 (001) Surfaces

DOE PAGES

Leung, Kevin

2016-12-10

The density functional theory and ab initio molecular dynamics simulations are applied to investigate the migration of Mn(II) ions to above-surface sites on spinel Li xMn 2O 4 (001) surfaces, the subsequent Mn dissolution into the organic liquid electrolyte, and the detrimental effects on graphite anode solid electrolyte interphase (SEI) passivating films after Mn(II) ions diffuse through the separator. The dissolution mechanism proves complex; the much-quoted Hunter disproportionation of Mn(III) to form Mn(II) is far from sufficient. Key steps that facilitate Mn(II) loss include concerted liquid/solid-state motions; proton-induced weakening of Mn–O bonds forming mobile OH – surface groups; and chemicalmore » reactions of adsorbed decomposed organic fragments. Mn(II) lodged between the inorganic Li 2CO 3 and organic lithium ethylene dicarbonate (LEDC) anode SEI components facilitate electrochemical reduction and decomposition of LEDC. Our findings help inform future design of protective coatings, electrolytes, additives, and interfaces.« less

Mechanisms of boron removal from hydraulic fracturing wastewater by aluminum electrocoagulation.

PubMed

Sari, Mutiara Ayu; Chellam, Shankararaman

2015-11-15

Boron uptake from highly saline hydraulic fracturing wastewater by freshly precipitated amorphous Al(OH)3 precipitates is due to ligand exchange and complexation with surface hydroxyl groups. Consequently, aluminum electrocoagulation can be a feasible approach to remove boron from flowback/produced water. Actual hydraulic fracturing wastewater containing ∼120mg/L boron from the Eagle Ford shale play was employed. Electrocoagulation was performed over a range of aluminum dosages (0-1350mg/L), pH 6.4 and 8, and high current densities (20-80mA/cm(2)) using a cylindrical aluminum anode encompassed by a porous cylindrical 316-stainless steel cathode. Direct measurements of boron uptake along with its chemical state and coordination were made using Attenuated Total Reflection-Fourier Transform Infrared spectroscopy (ATR-FTIR) and X-Ray Photoelectron Spectroscopy. Boron removal increased monotonically with aluminum dosage and was higher at pH 8, but remained relatively constant at ⩾20mA/cm(2). Chloride ions induced anodic pitting and super-Faradaic (131% efficiency) aluminum dissolution and their electrooxidation produced free chlorine. ATR-FTIR suggested outer-sphere and inner-sphere complexation of trigonal B(OH)3 with Al(OH)3, which was confirmed by the BO bond shifting toward lower binding energies in XPS. Severe AlO interferences precluded evidence for tetrahedral B(OH)4(-) complexation. No evidence for co-precipitation was obtained. Copyright © 2015 Elsevier Inc. All rights reserved.

Temporal patterning of the potential induced by localized corrosion of iron passivity in acid media. Growth and breakdown of the oxide film described in terms of a point defect model.

PubMed

Sazou, Dimitra; Pavlidou, Maria; Pagitsas, Michael

2009-10-21

This work analyses the nature of temporal patterning of the anodic potential induced by chlorides during polarization of iron under current-controlled conditions in acid solutions. It is shown that potential oscillations emerged as a result of the local chloride attack of a thin oxide layer, which covers the iron surface in its passive state. The mechanism by which both the local oxide breakdown and the subsequent localized active dissolution (pitting) occur is explained by considering a point defect model (PDM) developed to describe the oxide growth and breakdown. According to the PDM, chlorides occupy oxygen vacancies resulting in the inhibition of oxide growth and autocatalytic generation of cation vacancies that destabilize the oxide layer. Simultaneous transformation of the outer surface of the inner oxide layer to non-adherent ferrous chloride or oxo-chloride species leads to a further thinning of the oxide layer and its lifting-on from the iron surface. The process repeats again yielding sustained oscillations of the anodic potential. Analysis of the oscillatory response obtained under current-controlled conditions as a function of either the current or the time allows the suggestion of a set of alternate diagnostic criteria, which might be used to characterize localized corrosion of iron in acid solutions.

ANODIC TREATMENT OF URANIUM

DOEpatents

Kolodney, M.

1959-02-01

A method is presented for effecting eloctrolytic dissolution of a metallic uranium article at a uniform rate. The uranium is made the anode in an aqueous phosphoric acid solution containing nitrate ions furnished by either ammonium nitrate, lithium nitrate, sodium nitrate, or potassium nitrate. A stainless steel cathode is employed and electrolysls carried out at a current density of about 0.1 to 1 ampere per square inch.

Dissolution of Platinum in the Operational Range of Fuel Cells

PubMed Central

Keeley, Gareth P.; Geiger, Simon; Zeradjanin, Aleksandar R.; Hodnik, Nejc; Kulyk, Nadiia

2015-01-01

Abstract One of the most important practical issues in low‐temperature fuel‐cell catalyst degradation is platinum dissolution. According to the literature, it initiates at 0.6–0.9 VRHE, whereas previous time‐ and potential‐resolved inductively coupled plasma mass spectrometry (ICP–MS) experiments, however, revealed dissolution onset at only 1.05 VRHE. In this manuscript, the apparent discrepancy is addressed by investigating bulk and nanoparticulated catalysts. It is shown that, given enough time for accumulation, traces of platinum can be detected at potentials as low as 0.85 VRHE. At these low potentials, anodic dissolution is the dominant process, whereas, at more positive potentials, more platinum dissolves during the oxide reduction after accumulation. Interestingly, the potential and time dissolution dependence is similar for both types of electrode. Dissolution processes are discussed with relevance to fuel‐cell operation and plausible dissolution mechanisms are considered. PMID:27525206

Electrochemical polishing of thread fastener test specimens of nickel-chromium iron alloys

DOEpatents

Kephart, Alan R.

1991-01-01

An electrochemical polishing device and method for selective anodic dissolution of the surface of test specimens comprised, for example, of nickel-chromium-iron alloys, which provides for uniform dissolution at the localized sites to remove metal through the use of a coiled wire electrode (cathode) placed in the immediate proximity of the working, surface resulting in a polished and uniform grain boundary.

Electrolyte with Low Polysulfide Solubility for Li-S Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Ke; Wu, Qin; Tong, Xiao

Here, Li-S battery is one of the most promising next generation rechargeable battery technologies due to its high theoretical energy density and low material cost. While its success is impeded by the low energy efficiency and fast capacity fade primarily caused by the discharge intermediates, Li-polysulfides (PS), dissolution in the electrolyte. Mitigation of PS dissolution in electrolyte involves the search of new electrolyte solvent system that exhibits poor solvation to the PS while still have good solvation ability to the electrolyte salt for high ionic conductivity. Applying co-solvents with reduced solvating power but compatible with the state of art Li-Smore » battery’s ether-based electrolyte is one of the most promising concepts. This route is also advantageous of having a low scale-up cost. With the aids of Quantum Chemical Calculation, we have identified high carbon-to-oxygen (C/O) ratio ethers as co-solvent in the new electrolytes that effectively impede PS dissolution while still maintaining high ionic conductivity. Significantly improved cycle life and cycling Coulombic efficiency are observed for Li-S cells using the new composite electrolytes. Anode analysis with different methods also demonstrate that reducing electrolyte’s PS solubility results in less sulfur total amount on the lithium anode surface and lower ratio of the longer-chain PS, which is probably a sign of suppressed side reactions between the anode and PS in the electrolyte.« less

Electrolyte with Low Polysulfide Solubility for Li-S Batteries

DOE PAGES

Sun, Ke; Wu, Qin; Tong, Xiao; ...

2018-05-23

Here, Li-S battery is one of the most promising next generation rechargeable battery technologies due to its high theoretical energy density and low material cost. While its success is impeded by the low energy efficiency and fast capacity fade primarily caused by the discharge intermediates, Li-polysulfides (PS), dissolution in the electrolyte. Mitigation of PS dissolution in electrolyte involves the search of new electrolyte solvent system that exhibits poor solvation to the PS while still have good solvation ability to the electrolyte salt for high ionic conductivity. Applying co-solvents with reduced solvating power but compatible with the state of art Li-Smore » battery’s ether-based electrolyte is one of the most promising concepts. This route is also advantageous of having a low scale-up cost. With the aids of Quantum Chemical Calculation, we have identified high carbon-to-oxygen (C/O) ratio ethers as co-solvent in the new electrolytes that effectively impede PS dissolution while still maintaining high ionic conductivity. Significantly improved cycle life and cycling Coulombic efficiency are observed for Li-S cells using the new composite electrolytes. Anode analysis with different methods also demonstrate that reducing electrolyte’s PS solubility results in less sulfur total amount on the lithium anode surface and lower ratio of the longer-chain PS, which is probably a sign of suppressed side reactions between the anode and PS in the electrolyte.« less

Ellipsometry of anodic film growth

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, C.G.

1978-08-01

An automated computer interpretation of ellisometer measurements of anodic film growth was developed. Continuous mass and charge balances were used to utilize more fully the time dependence of the ellipsometer data and the current and potential measurements. A multiple-film model was used to characterize the growth of films which proceeds via a dissolution--precipitation mechanism; the model also applies to film growth by adsorption and nucleation mechanisms. The characteristic parameters for film growth describe homogeneous and heterogeneous crystallization rates, film porosities and degree of hydration, and the supersaturation of ionic species in the electrolyte. Additional descriptions which may be chosen aremore » patchwise film formation, nonstoichiometry of the anodic film, and statistical variations in the size and orientation of secondary crystals. Theories were developed to describe the optical effects of these processes. An automatic, self-compensating ellipsometer was used to study the growth in alkaline solution of anodic films on silver, cadmium, and zinc. Mass-transport conditions included stagnant electrolyte and forced convection in a flow channel. Multiple films were needed to characterize the optical properties of these films. Anodic films grew from an electrolyte supersatuated in the solution-phase dissolution product. The degree of supersaturation depended on transport conditions and had a major effect on the structure of the film. Anodic reaction rates were limited by the transport of charge carriers through a primary surface layer. The primary layers on silver, zinc, and cadmium all appeared to be nonstoichiometric, containing excess metal. Diffusion coefficients, transference numbers, and the free energy of adsorption of zinc oxide were derived from ellipsometer measurements. 97 figures, 13 tables, 198 references.« less

Characterization of Localized Filament Corrosion Products at the Anodic Head on a Model Mg-Zn-Zr Alloy Surface

DOE PAGES

Rossouw, David; Fu, Dong; Leonard, Donovan N.; ...

2017-02-15

In this study, localized filament corrosion products at the anodic head on a model Mg-1%Zn-0.4%Zr alloy surface were characterized by electron microscopy techniques of site-specific lamella prepared by focused ion beam milling. It is revealed that the anodic head propagates underneath a largely intact thin and dense MgO surface film and comprises dense aggregates of nano-crystalline MgO within a nano-porous Mg(OH) 2 network. In conclusion, the findings contribute new supportive direct imaging insight into the source of the enhanced H 2 evolution that accompanies anodic dissolution of Mg and its alloys.

Characterization of Localized Filament Corrosion Products at the Anodic Head on a Model Mg-Zn-Zr Alloy Surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rossouw, David; Fu, Dong; Leonard, Donovan N.

In this study, localized filament corrosion products at the anodic head on a model Mg-1%Zn-0.4%Zr alloy surface were characterized by electron microscopy techniques of site-specific lamella prepared by focused ion beam milling. It is revealed that the anodic head propagates underneath a largely intact thin and dense MgO surface film and comprises dense aggregates of nano-crystalline MgO within a nano-porous Mg(OH) 2 network. In conclusion, the findings contribute new supportive direct imaging insight into the source of the enhanced H 2 evolution that accompanies anodic dissolution of Mg and its alloys.

ELECTROCHEMICAL DECONTAMINATION AND RECOVERY OF URANIUM VALUES

DOEpatents

McLaren, J.A.; Goode, J.H.

1958-05-13

An electrochemical process is described for separating uranium from fission products. The method comprises subjecting the mass of uranium to anodic dissolution in an electrolytic cell containing aqueous alkali bicarbonate solution as its electrolyte, thereby promoting a settling from the solution of a solid sludge from about the electrodes and separating the resulting electrolyte solution containing the anodically dissolved uranium from the sludge which contains the rare earth fission products.

Combined Effect of Alternating Current Interference and Cathodic Protection on Pitting Corrosion and Stress Corrosion Cracking Behavior of X70 Pipeline Steel in Near-Neutral pH Environment.

PubMed

Wang, Liwei; Cheng, Lianjun; Li, Junru; Zhu, Zhifu; Bai, Shuowei; Cui, Zhongyu

2018-03-22

Influence of alternating current (AC) on pitting corrosion and stress corrosion cracking (SCC) behavior of X70 pipeline steel in the near-neutral pH environment under cathodic protection (CP) was investigated. Both corrosion and SCC are inhibited by -0.775 V SCE CP without AC interference. With the superimposition of AC current (1-10 mA/cm²), the direct current (DC) potential shifts negatively under the CP of -0.775 V SCE and the cathodic DC current decreases and shifts to the anodic direction. Under the CP potential of -0.95 V SCE and -1.2 V SCE , the applied AC current promotes the cathodic reaction and leads to the positive shift of DC potential and increase of cathodic current. Local anodic dissolution occurs attributing to the generated anodic current transients in the positive half-cycle of the AC current, resulting in the initiation of corrosion pits (0.6-2 μm in diameter). AC enhances the SCC susceptibility of X70 steel under -0.775 V SCE CP, attributing to the promotion of anodic dissolution and hydrogen evolution. Even an AC current as low as 1 mA/cm² can enhance the SCC susceptibility.

A Kinetics and Equilibrium Study of Vanadium Dissolution from Vanadium Oxides and Phosphates in Battery Electrolytes: Possible Impacts on ICD Battery Performance.

PubMed

Bock, David C; Marschilok, Amy C; Takeuchi, Kenneth J; Takeuchi, Esther S

2013-06-01

Silver vanadium oxide (Ag 2 V 4 O 11 , SVO) has enjoyed widespread commercial success over the past 30 years as a cathode material for implantable cardiac defibrillator (ICD) batteries. Recently, silver vanadium phosphorous oxide (Ag 2 VO 2 PO 4 , SVPO) has been studied as possibly combining the desirable thermal stability aspects of LiFePO 4 with the electrical conductivity of SVO. Further, due to the noted insoluble nature of most phosphate salts, a lower material solubility of SVPO relative to SVO is anticipated. Thus, the first vanadium dissolution studies of SVPO in battery electrolyte solutions are described herein. The equilibrium solubility of SVPO was ~5 times less than SVO, with a rate constant of dissolution ~3.5 times less than that of SVO. The vanadium dissolution in SVO and SVPO can be adequately described with a diffusion layer model, as supported by the Noyes-Whitney equation. Cells prepared with vanadium-treated anodes displayed higher AC impedance and DC resistance relative to control anodes. These data support the premise that SVPO cells are likely to exhibit reduced cathode solubility and thus less affected by increased cell resistance due to cathode solubility compared to SVO based cells.

The study of aluminium anodes for high power density Al/air batteries with brine electrolytes

NASA Astrophysics Data System (ADS)

Nestoridi, Maria; Pletcher, Derek; Wood, Robert J. K.; Wang, Shuncai; Jones, Richard L.; Stokes, Keith R.; Wilcock, Ian

Aluminium alloys containing small additions of both tin (∼0.1 wt%) and gallium (∼0.05 wt%) are shown to dissolve anodically at high rates in sodium chloride media at room temperatures; current densities >0.2 A cm -2 can be obtained at potentials close to the open circuit potential, ∼-1500 mV versus SCE. The tin exists in the alloys as a second phase, typically as ∼1 μm inclusions (precipitates) distributed throughout the aluminium structure, and anodic dissolution occurs to form pits around the tin inclusions. Although the distribution of the gallium in the alloy could not be established, it is also shown to be critical in the formation of these pits as well as maintaining their activity. The stability of the alloys to open circuit corrosion and the overpotential for high rate dissolution, both critical to battery performance, are shown to depend on factors in addition to elemental composition; both heat treatment and mechanical working influence the performance of the alloy. The correlation between alloy performance and their microstructure has been investigated.

Effect of the Crevice Former on the Corrosion Behavior of 316L Stainless Steel in Chloride-Containing Synthetic Tap Water

NASA Astrophysics Data System (ADS)

Kim, Seon-Hong; Lee, Ji-Hoon; Kim, Jung-Gu; Kim, Woo-Cheol

2018-05-01

To restrain the failure of the plate heat exchanger (PHE) in customer boiler working fluid, the effect of crevice former type on the corrosion behavior of the 316L stainless steel plate was investigated using electrochemical methods and surface analyses in chloride-containing synthetic tap water (60 °C). The localized corrosion under metal-metal crevice condition was initiated more easily than that under the metal-gasket crevice condition due to the restricted mass transport at the gasket crevice mouth. However, the anodic current under the metal-metal crevice condition was lower than that under metal-gasket crevice condition at a higher anodic potential, indicating that that the metal dissolution under EPDM crevice would be higher than that under metal crevice under the accelerated corrosion condition. Because narrow crevice gap that was formed under gasket accelerated the anodic dissolution at the crevice mouth, the perforation tendency under metal-gasket crevice condition is much higher than that under metal-metal crevice condition. As a result, the crevice geometry, especially the crevice gap, mainly affected the corrosion behavior of PHE material.

Effect of the Crevice Former on the Corrosion Behavior of 316L Stainless Steel in Chloride-Containing Synthetic Tap Water

NASA Astrophysics Data System (ADS)

Kim, Seon-Hong; Lee, Ji-Hoon; Kim, Jung-Gu; Kim, Woo-Cheol

2018-03-01

To restrain the failure of the plate heat exchanger (PHE) in customer boiler working fluid, the effect of crevice former type on the corrosion behavior of the 316L stainless steel plate was investigated using electrochemical methods and surface analyses in chloride-containing synthetic tap water (60 °C). The localized corrosion under metal-metal crevice condition was initiated more easily than that under the metal-gasket crevice condition due to the restricted mass transport at the gasket crevice mouth. However, the anodic current under the metal-metal crevice condition was lower than that under metal-gasket crevice condition at a higher anodic potential, indicating that that the metal dissolution under EPDM crevice would be higher than that under metal crevice under the accelerated corrosion condition. Because narrow crevice gap that was formed under gasket accelerated the anodic dissolution at the crevice mouth, the perforation tendency under metal-gasket crevice condition is much higher than that under metal-metal crevice condition. As a result, the crevice geometry, especially the crevice gap, mainly affected the corrosion behavior of PHE material.

Interconnection of bundled solid oxide fuel cells

DOEpatents

Brown, Michael; Bessette, II, Norman F; Litka, Anthony F; Schmidt, Douglas S

2014-01-14

A system and method for electrically interconnecting a plurality of fuel cells to provide dense packing of the fuel cells. Each one of the plurality of fuel cells has a plurality of discrete electrical connection points along an outer surface. Electrical connections are made directly between the discrete electrical connection points of adjacent fuel cells so that the fuel cells can be packed more densely. Fuel cells have at least one outer electrode and at least one discrete interconnection to an inner electrode, wherein the outer electrode is one of a cathode and and anode and wherein the inner electrode is the other of the cathode and the anode. In tubular solid oxide fuel cells the discrete electrical connection points are spaced along the length of the fuel cell.

Passivation dynamics in the anisotropic deposition and stripping of bulk magnesium electrodes during electrochemical cycling

DOE PAGES

Wetzel, David J.; Malone, Marvin A.; Haasch, Richard T.; ...

2015-08-10

Rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, though little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pitmore » densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. Finally, the passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.« less

Passivation dynamics in the anisotropic deposition and stripping of bulk magnesium electrodes during electrochemical cycling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wetzel, David J.; Malone, Marvin A.; Haasch, Richard T.

Rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, though little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pitmore » densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. Finally, the passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.« less

Passivation Dynamics in the Anisotropic Deposition and Stripping of Bulk Magnesium Electrodes During Electrochemical Cycling.

PubMed

Wetzel, David J; Malone, Marvin A; Haasch, Richard T; Meng, Yifei; Vieker, Henning; Hahn, Nathan T; Gölzhäuser, Armin; Zuo, Jian-Min; Zavadil, Kevin R; Gewirth, Andrew A; Nuzzo, Ralph G

2015-08-26

Although rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pit densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. The passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.

Tandem dissolution of UO 3 in amide-based acidic ionic liquid and in situ electrodeposition of UO 2 with regeneration of the ionic liquid: a closed cycle

DOE PAGES

Wanigasekara, Eranda; Freiderich, John W.; Sun, Xiao-Guang; ...

2016-05-19

A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO 3 to UO 2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid N,N-dimethylacetimidium bis(trifluoromethanesulfonimide) in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonimide) serving as the diluent. Bulk electrolysis performed at 1.0 V vs. Ag reference yields a dark brown-black uranium deposit (UO 2) on the cathode. Anodic oxidation of water in the presence of dimethylacetamide regenerates the acidic ionic liquid. We have demonstrated the individual steps in the cycle together with a sequential dissolution, electroreduction, and regeneration cycle.

Tandem dissolution of UO 3 in amide-based acidic ionic liquid and in situ electrodeposition of UO 2 with regeneration of the ionic liquid: a closed cycle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wanigasekara, Eranda; Freiderich, John W.; Sun, Xiao-Guang

A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO 3 to UO 2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid N,N-dimethylacetimidium bis(trifluoromethanesulfonimide) in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonimide) serving as the diluent. Bulk electrolysis performed at 1.0 V vs. Ag reference yields a dark brown-black uranium deposit (UO 2) on the cathode. Anodic oxidation of water in the presence of dimethylacetamide regenerates the acidic ionic liquid. We have demonstrated the individual steps in the cycle together with a sequential dissolution, electroreduction, and regeneration cycle.

Anodic Behavior of the Aluminum Current Collector in Imide-Based Electrolytes: Influence of Solvent, Operating Temperature, and Native Oxide-Layer Thickness.

PubMed

Meister, Paul; Qi, Xin; Kloepsch, Richard; Krämer, Elisabeth; Streipert, Benjamin; Winter, Martin; Placke, Tobias

2017-02-22

The inability of imide salts to form a sufficiently effective passivation layer on aluminum current collectors is one of the main obstacles that limit their broad application in electrochemical energy-storage systems. However, under certain circumstances, the use of electrolytes with imide electrolyte salts in combination with the aluminum current collector is possible. In this contribution, the stability of the aluminum current collector in electrolytes containing either lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) or lithium fluorosulfonyl-(trifluoromethanesulfonyl) imide (LiFTFSI) as conductive salt was investigated by electrochemical techniques, that is, cyclic voltammetry (CV) and chronocoulometry (CC) in either room-temperature ionic liquids or in ethyl methyl sulfone. In particular, the influence of the solvent, operating temperature, and thickness of the native oxide layer of aluminum on the pit formation at the aluminum current collector surface was studied by means of scanning electron microscopy. In general, a more pronounced aluminum dissolution and pit formation was found at elevated temperatures as well as in solvents with a high dielectric constant. An enhanced thickness of the native aluminum oxide layer increases the oxidative stability versus dissolution. Furthermore, we found a different reaction rate depending on dwell time at the upper cut-off potential for aluminum dissolution in TFSI- and FTFSI-based electrolytes during the CC measurements; the use of LiFTFSI facilitated the dissolution of aluminum compared to LiTFSI. Overall, the mechanism of anodic aluminum dissolution is based on: i) the attack of the Al 2 O 3 surface by acidic species and ii) the dissolution of bare aluminum into the electrolyte, which, in turn, is influenced by the electrolyte's dielectric constant. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hybrid pulse anodization for the fabrication of porous anodic alumina films from commercial purity (99%) aluminum at room temperature.

PubMed

Chung, C K; Zhou, R X; Liu, T Y; Chang, W T

2009-02-04

Most porous anodic alumina (PAA) or anodic aluminum oxide (AAO) films are fabricated using the potentiostatic method from high-purity (99.999%) aluminum films at a low temperature of approximately 0-10 degrees C to avoid dissolution effects at room temperature (RT). In this study, we have demonstrated the fabrication of PAA film from commercial purity (99%) aluminum at RT using a hybrid pulse technique which combines pulse reverse and pulse voltages for the two-step anodization. The reaction mechanism is investigated by the real-time monitoring of current. A possible mechanism of hybrid pulse anodization is proposed for the formation of pronounced nanoporous film at RT. The structure and morphology of the anodic films were greatly influenced by the duration of anodization and the type of voltage. The best result was obtained by first applying pulse reverse voltage and then pulse voltage. The first pulse reverse anodization step was used to form new small cells and pre-texture concave aluminum as a self-assembled mask while the second pulse anodization step was for the resulting PAA film. The diameter of the nanopores in the arrays could reach 30-60 nm.

Performance Enhancement and Side Reactions in Rechargeable Nickel-Iron Batteries with Nanostructured Electrodes.

PubMed

Lei, Danni; Lee, Dong-Chan; Magasinski, Alexandre; Zhao, Enbo; Steingart, Daniel; Yushin, Gleb

2016-01-27

We report for the first time a solution-based synthesis of strongly coupled nanoFe/multiwalled carbon nanotube (MWCNT) and nanoNiO/MWCNT nanocomposite materials for use as anodes and cathodes in rechargeable alkaline Ni-Fe batteries. The produced aqueous batteries demonstrate very high discharge capacities (800 mAh gFe(-1) at 200 mA g(-1) current density), which exceed that of commercial Ni-Fe cells by nearly 1 order of magnitude at comparable current densities. These cells also showed the lack of any "activation", typical in commercial batteries, where low initial capacity slowly increases during the initial 20-50 cycles. The use of a highly conductive MWCNT network allows for high-capacity utilization because of rapid and efficient electron transport to active metal nanoparticles in oxidized [such as Fe(OH)2 or Fe3O4] states. The flexible nature of MWCNTs accommodates significant volume changes taking place during phase transformation accompanying reduction-oxidation reactions in metal electrodes. At the same time, we report and discuss that high surface areas of active nanoparticles lead to multiple side reactions. Dissolution of Fe anodes leads to reprecipitation of significantly larger anode particles. Dissolution of Ni cathodes leads to precipitation of Ni metal on the anode, thus blocking transport of OH(-) anions. The electrolyte molarity and composition have a significant impact on the capacity utilization and cycling stability.

Synthesis and characterization of nanoporous anodic oxide film on aluminum in H3PO4 + KMnO4 electrolyte mixture at different anodization conditions

NASA Astrophysics Data System (ADS)

Verma, Naveen; Jindal, Jitender; Singh, Krishan Chander; Mari, Bernabe

2016-04-01

The micro structural properties of nanoporous anodic oxide film formed in H3PO4 were highly influenced by addition of a low concentration of KMnO4 (0.0005 M) in 1 M H3PO4 solution. The KMnO4 as additive enhanced the growth rate of oxide film formation as well as thickness of pore walls. Furthermore the growth rate was found increased with increase in applied current density. The increase in temperature and lack of stirring during anodization causes the thinness of pore wall which leads to increase in pore volume. With the decrease in concentration of H3PO4 in anodizing electrolyte from 1M to 0.3 M, keeping all other conditions constant, the decrease in porosity was observed. This might be due to the dissolution of aluminium oxide film in highly concentrated acidic solution.

Passive films on magnesium anodes in primary batteries

NASA Technical Reports Server (NTRS)

Ratnakumar, B. V.

1988-01-01

The characteristics of the passive films over Mg anodes, which essentially govern the voltage delay of the latter, have been determined nondestructively from an analysis of the transient and steady-state response of the electrode potential to low amplitude galvanostatic polarization under various experimental conditions viz., with different corrosion inhibitor coatings on Mg, after various periods of ageing of anode in solutions containing corrosion inhibitors, at various low temperatures etc. Using these parameters, the kinetics of film build-up or dissolution under these conditions have been monitored. The morphology of the anode film has been verified with scanning electron microscopy. Similar transients at low temperatures point out a steep rise in the film resistivity which is essentially responsible for the severe voltage delay. Finally, possible application of this technique in secondary Li batteries to improve cycling characteristics of the Li anode has been pointed out.

Evaluating the Passivation of Corrosion of API-X100 Steel with Cyclic Voltammetry

NASA Astrophysics Data System (ADS)

Eliyan, Faysal Fayez; Alfantazi, Akram

2017-10-01

In this research, cyclic voltammetry, in oxygen-free low bicarbonate-carbonate solutions, was used to study the corrosion reactions of a high-strength steel, API-X100. With cycles of different scan ranges, the effects of cycling, transpassivation, and cathodic reduction on the electrochemistry of the passive films were analyzed. It was found that carbonate in higher concentrations reduces the anodic activity and the cathodic reactions of the surface. Bicarbonate in small concentrations in solutions that contained low carbonate concentrations catalyzed dissolution and disrupted the formation of the passive films, in reference to the measured anodic currents. From the experiments, there was electrochemical evidence that with more cycles, the passive films were growing thicker, the transpassivation deteriorated the passive films, and during the cathodic reduction, the dissolution was occurring at lower potentials to facilitate later the passivation at higher potentials.

Effect of Hydrogen Charging on the Stress Corrosion Behavior of 2205 Duplex Stainless Steel Under 3.5 wt.% NaCl Thin Electrolyte Layer

NASA Astrophysics Data System (ADS)

Zhao, Tianliang; Liu, Zhiyong; Hu, Shanshan; Du, Cuiwei; Li, Xiaogang

2017-05-01

The effect of hydrogen charging on the stress corrosion cracking (SCC) behavior of 2205 duplex stainless steel (DSS) under 3.5 wt.% NaCl thin electrolyte layer was investigated on precharged samples through hydrogen determination, electrochemical measurement, and slow strain rate tensile test. Results show that hydrogen charging weakens the passive film without inducing any obvious trace of localized anodic dissolution. Therefore, hydrogen charging increases the SCC susceptibility of 2205 DSS mainly through mechanism of hydrogen embrittlement rather than mechanism of localized anodic dissolution. 2205 DSS shows a more susceptibility to hydrogen under the TEL when hydrogen charging current density (HCCD) is between 20 and 50 mA cm-2. The increasing trend is remarkable when hydrogen charging current density increases from 20 to 50 mA cm-2 and fades after 50 mA cm-2.

Analyzing the anodic reactions for iron surface with a porous Al2O3 cluster with the scanning vibrating electrode

NASA Astrophysics Data System (ADS)

Eliyan, Faysal Fayez

2017-09-01

The Scanning Vibrating Electrode Technique (SVET) was used to analyze the anodic reactions inside and around a porous Al2O3 cluster embedded onto an iron foil. The tests were carried out at -0.7 V vs. Saturated Calomel Electrode, in naturally aerated solutions of 0.1, 0.2, 0.35, and 0.5 M bicarbonate concentration. During 10 h of testing, the SVET showed evidence for a formation of a passive film in and around the cluster, in the scanning area shown in the graphical abstract. In the dilute 0.1 and 0.2 M solutions, the passive films formed slower than those in 0.35 and 0.5 M solutions. In the SVET maps, the passive films showed that they could suppress dissolution to currents comparable to those of slower dissolution under the porous Al2O3 cluster.

Fabrication of complete titania nanoporous structures via electrochemical anodization of Ti

PubMed Central

2011-01-01

We present a novel method to fabricate complete and highly oriented anodic titanium oxide (ATO) nano-porous structures with uniform and parallel nanochannels. ATO nano-porous structures are fabricated by anodizing a Ti-foil in two different organic viscous electrolytes at room temperature using a two-step anodizing method. TiO2 nanotubes covered with a few nanometer thin nano-porous layer is produced when the first and the second anodization are carried out in the same electrolyte. However, a complete titania nano-porous (TNP) structures are obtained when the second anodization is conducted in a viscous electrolyte when compared to the first one. TNP structure was attributed to the suppression of F-rich layer dissolution between the cell boundaries in the viscous electrolyte. The structural morphologies were examined by field emission scanning electron microscope. The average pore diameter is approximately 70 nm, while the average inter-pore distance is approximately 130 nm. These TNP structures are useful to fabricate other nanostructure materials and nanodevices. PMID:21711844

Double layer, diluent and anode effects upon the electrodeposition of aluminium from chloroaluminate based ionic liquids.

PubMed

Abbott, Andrew P; Qiu, Fulian; Abood, Hadi M A; Ali, M Rostom; Ryder, Karl S

2010-02-28

The deposition of aluminium from a chloroaluminate based ionic liquid was studied to elucidate the effect of a diluent (toluene) and electrolyte (LiCl) on the deposit morphology. A wide variety of analytical techniques was applied to this system to determine the speciation and mechanism of material growth. These included: (27)Al NMR, FAB-MS, cyclic voltammetry, chronocoulometry, chronopotentiometry, scanning electron microscopy and atomic force microscopy. It was found that under-potential deposition (upd) causes a change in the way in which metal grows on the electrode surface. Metal grows in two regimes which are believed to be nano-material and bulk material. The addition of toluene causes a change in speciation and a decrease in upd which in turn changes the morphology of the deposit obtained and can lead to mirror finish aluminium. The addition of LiCl has the opposite effect encouraging upd and leading to larger crystallites and a dark grey deposit. It is also shown for the first time that under many conditions the rate of the anodic dissolution process is overall rate controlling and one effect of the addition of toluene is to increase the rate of anodic dissolution.

First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li xMn 2O 4 (100) Surfaces [First principles modeling of Mn(II) migration to and dissolution from Li xMn 2O 4 (100) surfaces

DOE PAGES

Leung, Kevin

2012-04-13

Density functional theory and ab initio molecular dynamics simulations are applied to investigate the migration of Mn(II) ions to above-surface sites on spinel Li xMn 2O 4 (100) surfaces, the subsequent Mn dissolution into the organic liquid electrolyte, and the detrimental effects on anode solid electrolyte interphase (SEI) passivating films after Mn(II) ions diffuse through the separator. The dissolution mechanism proves complex; the much-quoted Hunter disproportionation of Mn(III) to form Mn(II) is necessary but far from sufficient. Key steps that facilitate Mn(II) ion migration include concerted liquid/solid-state motions, proton-induced weakening of Mn-O bonds forming mobile OH - surface groups; andmore » chemical reactions of adsorbed decomposed organic fragments. Mn(II) lodged between the inorganic Li 2CO 3 and organic lithium ethylene dicarbonate (LEDC) anode SEI component facilitates electrochemical reduction and decomposition of LEDC. These findings help inform future design of protective coatings, electrolytes, additives, and interfaces.« less

A Study on Sealing Process of Anodized Al Alloy Film

NASA Astrophysics Data System (ADS)

Tsujita, Takeshi; Sato, Hiroshi; Tsukahara, Sonoko; Ishikawa, Yuuichi

Since sealing is an important process to improve the corrosion resistance in practical application of anodized aluminum, we prepared anodic oxide films on A5052 alloy in an oxalic acid bath and a sulfuric acid bath, sealed them at various conditions, and analyzed them by scanning electron microscopy, acid-dissolution examination, admittance measurements and infrared spectroscopy. The pore radius of the oxalic acid anodized film was about 5 times larger than that of sulfuric acid anodized film, while the corrosion resistance of the former showed about 2 times higher value than the latter with the same sealed state and amount of hydroxide formed by sealing process of the former was 6 times larger than the latter, respectively. Steam sealing formed dense hydroxide and boiling water sealing formed big coral-like hydroxide, whereas the corrosion resistance of the film sealed by the former showed about 1.5 times higher value than that sealed by the latter, respectively. Thus microstructure of anodic oxide films and their surface morphology after sealing process clearly depended on their anodizing solution and the sealing condition and showed obvious relation to electric and corrosive properties.

Electrostatic lens to focus an ion beam to uniform density

DOEpatents

Johnson, Cleland H.

1977-01-11

A focusing lens for an ion beam having a gaussian or similar density profile is provided. The lens is constructed to provide an inner zero electrostatic field, and an outer electrostatic field such that ions entering this outer field are deflected by an amount that is a function of their distance from the edge of the inner field. The result is a beam that focuses to a uniform density in a manner analogous to that of an optical ring lens. In one embodiment, a conically-shaped network of fine wires is enclosed within a cylindrical anode. The wire net together with the anode produces a voltage field that re-directs the outer particles of the beam while the axial particles pass undeflected through a zero field inside the wire net. The result is a focused beam having a uniform intensity over a given target area and at a given distance from the lens.

Method for providing uranium articles with a corrosion resistant anodized coating

DOEpatents

Waldrop, Forrest B.; Washington, Charles A.

1982-01-01

Uranium articles are provided with anodized oxide coatings in an aqueous solution of an electrolyte selected from the group consisting of potassium phosphate, potassium hydroxide, ammonium hydroxide, and a mixture of potassium tetraborate and boric acid. The uranium articles are anodized at a temperature greater than about 75.degree. C. with a current flow of less than about 0.036 A/cm.sup.2 of surface area while the pH of the solution is maintained in a range of about 2 to 11.5. The pH values of the aqueous solution and the low current density utilized during the electrolysis prevent excessive dissolution of the uranium and porosity in the film or watering. The relatively high temperature of the electrolyte bath inhibits hydration and the attendant deleterious pitting so as to enhance corrosion resistance of the anodized coating.

2D MoS2 as an efficient protective layer for lithium metal anodes in high-performance Li-S batteries.

PubMed

Cha, Eunho; Patel, Mumukshu D; Park, Juhong; Hwang, Jeongwoon; Prasad, Vish; Cho, Kyeongjae; Choi, Wonbong

2018-04-01

Among the candidates to replace Li-ion batteries, Li-S cells are an attractive option as their energy density is about five times higher (~2,600 Wh kg -1 ). The success of Li-S cells depends in large part on the utilization of metallic Li as anode material. Metallic lithium, however, is prone to grow parasitic dendrites and is highly reactive to several electrolytes; moreover, Li-S cells with metallic Li are also susceptible to polysulfides dissolution. Here, we show that ~10-nm-thick two-dimensional (2D) MoS 2 can act as a protective layer for Li-metal anodes, greatly improving the performances of Li-S batteries. In particular, we observe stable Li electrodeposition and the suppression of dendrite nucleation sites. The deposition and dissolution process of a symmetric MoS 2 -coated Li-metal cell operates at a current density of 10 mA cm -2 with low voltage hysteresis and a threefold improvement in cycle life compared with using bare Li-metal. In a Li-S full-cell configuration, using the MoS 2 -coated Li as anode and a 3D carbon nanotube-sulfur cathode, we obtain a specific energy density of ~589 Wh kg -1 and a Coulombic efficiency of ~98% for over 1,200 cycles at 0.5 C. Our approach could lead to the realization of high energy density and safe Li-metal-based batteries.

The rapid growth of 3 µm long titania nanotubes by anodization of titanium in a neutral electrochemical bath

NASA Astrophysics Data System (ADS)

Lockman, Zainovia; Ismail, Syahriza; Sreekantan, Srimala; Schmidt-Mende, L.; MacManus-Driscoll, J. L.

2010-02-01

The length of titania nanotubes formed by anodization of 0.1 mm thick titanium foil was found to be a strong function of the pH of the electrolyte. The longest nanotubes were formed by using an electrolyte consisting of 1 M Na2SO4 plus 5 wt% NH4F with pH 7. At this pH, after 30 min of anodization, 3 µm length nanotubular titania arrays with top diameters of ~50 nm and bottom diameters of 100 nm were produced. No acid was added to this electrolyte. The formation of titania nanotubes in neutral pH systems was therefore successful due to the excess NH4F in the electrolyte which increases the chemical dissolution process at the metal/oxide interface. Since the pH of the electrolyte at the top part of the nanotubes is kept very high, the dissolution of the nanotubes at the surface is minimal. However, the amount is adequate to remove the initial barrier layer, forming a rather well-defined nanoporous structure. All anodized foils were weakly crystalline and the transformation to anatase phase was achieved by heat treatment at temperatures from 200 to 500 °C for 1 h in air. Annealing at temperatures above 500 °C induce rutile phase formation and annealing at higher temperatures accelerates the diffusion of Ti4+ leading to excessive growth and the nanotubular structure diminishes.

2D MoS2 as an efficient protective layer for lithium metal anodes in high-performance Li-S batteries

NASA Astrophysics Data System (ADS)

Cha, Eunho; Patel, Mumukshu D.; Park, Juhong; Hwang, Jeongwoon; Prasad, Vish; Cho, Kyeongjae; Choi, Wonbong

2018-04-01

Among the candidates to replace Li-ion batteries, Li-S cells are an attractive option as their energy density is about five times higher ( 2,600 Wh kg-1). The success of Li-S cells depends in large part on the utilization of metallic Li as anode material. Metallic lithium, however, is prone to grow parasitic dendrites and is highly reactive to several electrolytes; moreover, Li-S cells with metallic Li are also susceptible to polysulfides dissolution. Here, we show that 10-nm-thick two-dimensional (2D) MoS2 can act as a protective layer for Li-metal anodes, greatly improving the performances of Li-S batteries. In particular, we observe stable Li electrodeposition and the suppression of dendrite nucleation sites. The deposition and dissolution process of a symmetric MoS2-coated Li-metal cell operates at a current density of 10 mA cm-2 with low voltage hysteresis and a threefold improvement in cycle life compared with using bare Li-metal. In a Li-S full-cell configuration, using the MoS2-coated Li as anode and a 3D carbon nanotube-sulfur cathode, we obtain a specific energy density of 589 Wh kg-1 and a Coulombic efficiency of 98% for over 1,200 cycles at 0.5 C. Our approach could lead to the realization of high energy density and safe Li-metal-based batteries.

The application of electrolytic photoetching and photopolishing to AISI 304 stainless steel and the electrolytic photoetching of amorphous cobalt alloy

NASA Astrophysics Data System (ADS)

Thomaz, Marita Duarte Canhao da Silva Pereira Fernandes

The results presented cover broad aspects of a quantitative investigation into the elecrolytic etching and polishing of metals and alloys through photographically produced dielectric stencils (Photoresists). A study of the potential field generated between a cathode and relatively smaller anode sites as those defined by a dielectric stencil was carried out. Numerical, analytical and graphical methods yielded answers to the factors determining lateral dissolution (undercut) at the anode/stencil interface. A quasi steady state numerical model simulating the transient behavior of the partially masked electrodes undergoing dissolution was obtained. AISI 304 stainless steel was electrolytically photoetched in 10% w/w HCl electrolyte. The optimised process parameters were utilised for quantifying the effects of galvanostatic etching of the anode as that defined by a relatively narrow adherent resist stencil. Stainless steel was also utilised in investigating electrolytic photopolishing. A polishing electrolyte (orthophosphoric acid-glycerol) was modified by the addition of a surfactant which yielded surface texture values of 70nm (Ra) and high levels of specular reflectance. These results were used in the production of features upon the metal surface through photographically produced precision stencils. The process was applied to the production of edge filters requiring high quality surface textures in precision recesses. Some of the new amorphous material exhibited high resistance to dissolution in commercially used spray etching formulations. One of these materials is a cobalt based alloy produced by chill block spinning. This material was also investigated and electro etched in 10% w/w HCl solution. Although passivity was not overcome, by selecting suitable operating parameters the successful electro photoetching of precision magnetic recording head laminations was achieved. Similarly, a polycrystalline nickel based alloy also exhibiting passivity in commercially used etchants was successfully etched in the above electrolyte.

Self-Formed Hybrid Interphase Layer on Lithium Metal for High-Performance Lithium-Sulfur Batteries.

PubMed

Li, Guoxing; Huang, Qingquan; He, Xin; Gao, Yue; Wang, Daiwei; Kim, Seong H; Wang, Donghai

2018-02-27

Lithium-sulfur (Li-S) batteries are promising candidates for high-energy storage devices due to high theoretical capacities of both the sulfur cathode and lithium (Li) metal anode. Considerable efforts have been devoted to improving sulfur cathodes. However, issues associated with Li anodes, such as low Coulombic efficiency (CE) and growth of Li dendrites, remain unsolved due to unstable solid-electrolyte interphase (SEI) and lead to poor capacity retention and a short cycling life of Li-S batteries. In this work, we demonstrate a facile and effective approach to fabricate a flexible and robust hybrid SEI layer through co-deposition of aromatic-based organosulfides and inorganic Li salts using poly(sulfur-random-1,3-diisopropenylbenzene) as an additive in an electrolyte. The aromatic-based organic components with planar backbone conformation and π-π interaction in the SEI layers can improve the toughness and flexibility to promote stable and high efficient Li deposition/dissolution. The as-formed durable SEI layer can inhibit dendritic Li growth, enhance Li deposition/dissolution CE (99.1% over 420 cycles), and in turn enable Li-S batteries with good cycling stability (1000 cycles) and slow capacity decay. This work demonstrates a route to address the issues associated with Li metal anodes and promote the development of high-energy rechargeable Li metal batteries.

High-capacity aqueous zinc batteries using sustainable quinone electrodes

PubMed Central

Zhao, Qing; Huang, Weiwei; Luo, Zhiqiang; Liu, Luojia; Lu, Yong; Li, Yixin; Li, Lin; Hu, Jinyan; Ma, Hua; Chen, Jun

2018-01-01

Quinones, which are ubiquitous in nature, can act as sustainable and green electrode materials but face dissolution in organic electrolytes, resulting in fast fading of capacity and short cycle life. We report that quinone electrodes, especially calix[4]quinone (C4Q) in rechargeable metal zinc batteries coupled with a cation-selective membrane using an aqueous electrolyte, exhibit a high capacity of 335 mA h g−1 with an energy efficiency of 93% at 20 mA g−1 and a long life of 1000 cycles with a capacity retention of 87% at 500 mA g−1. The pouch zinc batteries with a respective depth of discharge of 89% (C4Q) and 49% (zinc anode) can deliver an energy density of 220 Wh kg−1 by mass of both a C4Q cathode and a theoretical Zn anode. We also develop an electrostatic potential computing method to demonstrate that carbonyl groups are active centers of electrochemistry. Moreover, the structural evolution and dissolution behavior of active materials during discharge and charge processes are investigated by operando spectral techniques such as IR, Raman, and ultraviolet-visible spectroscopies. Our results show that batteries using quinone cathodes and metal anodes in aqueous electrolyte are reliable approaches for mass energy storage. PMID:29511734

High-capacity aqueous zinc batteries using sustainable quinone electrodes.

PubMed

Zhao, Qing; Huang, Weiwei; Luo, Zhiqiang; Liu, Luojia; Lu, Yong; Li, Yixin; Li, Lin; Hu, Jinyan; Ma, Hua; Chen, Jun

2018-03-01

Quinones, which are ubiquitous in nature, can act as sustainable and green electrode materials but face dissolution in organic electrolytes, resulting in fast fading of capacity and short cycle life. We report that quinone electrodes, especially calix[4]quinone (C4Q) in rechargeable metal zinc batteries coupled with a cation-selective membrane using an aqueous electrolyte, exhibit a high capacity of 335 mA h g -1 with an energy efficiency of 93% at 20 mA g -1 and a long life of 1000 cycles with a capacity retention of 87% at 500 mA g -1 . The pouch zinc batteries with a respective depth of discharge of 89% (C4Q) and 49% (zinc anode) can deliver an energy density of 220 Wh kg -1 by mass of both a C4Q cathode and a theoretical Zn anode. We also develop an electrostatic potential computing method to demonstrate that carbonyl groups are active centers of electrochemistry. Moreover, the structural evolution and dissolution behavior of active materials during discharge and charge processes are investigated by operando spectral techniques such as IR, Raman, and ultraviolet-visible spectroscopies. Our results show that batteries using quinone cathodes and metal anodes in aqueous electrolyte are reliable approaches for mass energy storage.

Elimination of Lifetime Limiting Mechanism of Hall Thrusters

NASA Technical Reports Server (NTRS)

Jacobson, David T. (Inventor); Manzella, David H. (Inventor)

2009-01-01

A Hall thruster includes inner and outer electromagnets, with the outer electromagnet circumferentially surrounding the inner electromagnet along a centerline axis and separated therefrom, inner and outer poles, in physical connection with their respective inner and outer electromagnets, with the inner pole having a mostly circular shape and the outer pole having a mostly annular shape, a discharge chamber separating the inner and outer poles, a combined anode electrode/gaseous propellant distributor, located at an upstream portion of the discharge chamber and supplying propellant gas and an actuator, in contact with a sleeve portion of the discharge chamber. The actuator is configured to extend the sleeve portion or portions of the discharge chamber along the centerline axis with respect to the inner and outer poles.

The anodizing behavior of aluminum in malonic acid solution and morphology of the anodic films

NASA Astrophysics Data System (ADS)

Ren, Jianjun; Zuo, Yu

2012-11-01

The anodizing behavior of aluminum in malonic acid solution and morphology of the anodic films were studied. The voltage-time response for galvanostatic anodization of aluminum in malonic acid solution exhibits a conventional three-stage feature but the formation voltage is much higher. With the increase of electrolyte concentration, the electrolyte viscosity increases simultaneously and the high viscosity decreases the film growth rate. With the concentration increase of the malonic acid electrolyte, the critical current density that initiates local "burning" on the sample surface decreases. For malonic acid anodization, the field-assisted dissolution on the oxide surface is relatively weak and the nucleation of pores is more difficult, which results in greater barrier layer thickness and larger cell dimension. The embryo of the porous structure of anodic film has been created within the linear region of the first transient stage, and the definite porous structure has been established before the end of the first transient stage. The self-ordering behavior of the porous film is influenced by the electrolyte concentration, film thickness and the applied current density. Great current density not only improves the cell arrangement order but also brings about larger cell dimension.

Method for providing uranium articles with a corrosion-resistant anodized coating

DOEpatents

Waldrop, F.B.; Washington, C.A.

1981-01-07

Uranium articles are provided with anodized oxide coatings in an aqueous solution of an electrolyte selected from the group consisting of potassium phosphate, potassium hydroxide, ammonium hydroxide, and a mixture of potassium tetraborate and boric acid. The uranium articles are anodized at a temperature greater than about 75/sup 0/C with a current flow of less than about 0.036 A/cm/sup 2/ of surface area while the pH of the solution is maintained in a range of about 2 to 11.5. The pH values of the aqueous solution and the low current density utilized during the electrolysis prevent excessive dissolution of the uranium and porosity in the film or watering. The relatively high temperature of the electrolyte bath inhibits hydration and the attendant deleterious pitting so as to enhance corrosion resistance of the anodized coating.

Double-walled structure of anodic TiO2 nanotubes in H3PO4/NH4F mixed electrolyte

NASA Astrophysics Data System (ADS)

Chen, Siyu; Chen, Ying; Li, Chengyuan; Ouyang, Huijun; Qin, Shuai; Song, Ye

2018-04-01

Normally, the well-ordered anodic TiO2 nanotubes (ATNTs) are obtained in NH4F electrolyte, after annealing, the double-walled structure of nanotubes will appear. Here, after adding H3PO4 into NHF4 electrolyte, we got the double-walled structure of nanotubes by anodizing without annealing, which means the direct existence of anion-contaminated layer in ATNTs. Influence of H3PO4 content on anodizing voltage and morphology of ATNTs were compared in detail. The XRD pattern illustrated that the crystallinity decreases with increasing H3PO4 concentration, and the anion-contaminated layer thickens with the increase of H3PO4 concentration. Meanwhile, the existence of the anion-contaminated layer also proved the limitations of the filed-assisted dissolution theory, while the double-walled structure can be explained by oxygen bubble model and plastic flow model.

Phenomenological Transition of an Aluminum Surface in an Ionic Liquid and Its Beneficial Implementation in Batteries.

PubMed

Shvartsev, B; Gelman, D; Amram, D; Ein-Eli, Y

2015-12-29

Aluminum (Al) electrochemical dissolution in organic nonaqueous media and room temperature ionic liquids (RTILs) is partially hampered by the presence of a native oxide. In this work, Al activation in EMIm(HF)2.3F RTIL is reported. It was confirmed that as a result of the interaction of Al with the RTIL, a new film is formed instead of the pristine oxide layer. Aluminum surface modifications result in a transformation from a passive state to the active behavior of the metal. This was confirmed via the employment of electrochemical methods and characterization by XPS, AFM, and TEM. It was shown that the pristine oxide surface film dissolves in EMIm(HF)2.3F, allowing an Al-O-F layer to be formed instead. This newly built up layer dramatically restricts Al corrosion while enabling high rates of Al anodic dissolution. These beneficial features allow the implementation of Al as an anode in advanced portable power sources, such as aluminum-air batteries.

Cell and method for electrolysis of water and anode

NASA Technical Reports Server (NTRS)

Aylward, J. R. (Inventor)

1981-01-01

An electrolytic cell for converting water vapor to oxygen and hydrogen include an anode comprising a foraminous conductive metal substrate with a 65-85 weight percent iridium oxide coating and 15-35 weight percent of a high temperature resin binder. A matrix member contains an electrolyte to which a cathode substantially inert. The foraminous metal member is most desirably expanded tantalum mesh, and the cell desirably includes reservoir elements of porous sintered metal in contact with the anode to receive and discharge electrolyte to the matrix member as required. Upon entry of a water vapor containing airstream into contact with the outer surface of the anode and thence into contact with iridium oxide coating, the water vapor is electrolytically converted to hydrogen ions and oxygen with the hydrogen ions migrating through the matrix to the cathode and the oxygen gas produced at the anode to enrich the air stream passing by the anode.

Effects of natural organic matter properties on the dissolution kinetics of zinc oxide nanoparticles

USGS Publications Warehouse

Jiang, Chuanjia; Aiken, George R.; Hsu-Kim, Heileen

2015-01-01

The dissolution of zinc oxide (ZnO) nanoparticles (NPs) is a key step of controlling their environmental fate, bioavailability, and toxicity. Rates of dissolution often depend upon factors such as interactions of NPs with natural organic matter (NOM). We examined the effects of 16 different NOM isolates on the dissolution kinetics of ZnO NPs in buffered potassium chloride solution using anodic stripping voltammetry to directly measure dissolved zinc concentrations. The observed dissolution rate constants (kobs) and dissolved zinc concentrations at equilibrium increased linearly with NOM concentration (from 0 to 40 mg C L–1) for Suwannee River humic and fulvic acids and Pony Lake fulvic acid. When dissolution rates were compared for the 16 NOM isolates, kobs was positively correlated with certain properties of NOM, including specific ultraviolet absorbance (SUVA), aromatic and carbonyl carbon contents, and molecular weight. Dissolution rate constants were negatively correlated to hydrogen/carbon ratio and aliphatic carbon content. The observed correlations indicate that aromatic carbon content is a key factor in determining the rate of NOM-promoted dissolution of ZnO NPs. The findings of this study facilitate a better understanding of the fate of ZnO NPs in organic-rich aquatic environments and highlight SUVA as a facile and useful indicator of NOM interactions with metal-based nanoparticles.

Visualizing elemental deposition patterns on carbonaceous anodes from lithium ion batteries: A laser ablation-inductively coupled plasma-mass spectrometry study on factors influencing the deposition of lithium, nickel, manganese and cobalt after dissolution and migration from the Li1[Ni1/3Mn1/3Co1/3]O2 and LiMn1.5 Ni0.5O4 cathode

NASA Astrophysics Data System (ADS)

Schwieters, Timo; Evertz, Marco; Fengler, Alexander; Börner, Markus; Dagger, Tim; Stenzel, Yannick; Harte, Patrick; Winter, Martin; Nowak, Sascha

2018-03-01

In this study, laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is applied to previously aged carbonaceous anodes from lithium ion batteries (LIBs). These electrodes are treated by cyclic aging in a lithium ion cell set-up against Li1[Ni1/3Mn 1/3Co1/3]O2 = NMC111 to elucidate factors that influence transition metal dissolution (TMD) of the cathode and subsequent deposition on the anode. The investigations are carried out by qualitatively visualizing the 7Li and TM patterns (60Ni, 55Mn and 59Co) of whole coin and pouch-bag electrodes. The lithium, as well as the TM amount, found on the anode, is directly correlated to the applied upper cut-off voltage (4.6, 4.7, 4.8 and 4.9 V) showing more deposition of Li and TMs at elevated voltages. While 7Li shows a more homogeneous pattern, the TM distribution is inhomogeneous but showing a similar pattern for all TMs of the same sample. An unequal pressure distribution, resulting in a nonparallel electrode alignment, on the electrode stack is identified to be responsible for the inhomogeneous TM deposition pattern. This uneven electrode orientation results in different diffusion pathways for the TM migration with regard to the spatial distances.

Magnetic circuit for hall effect plasma accelerator

NASA Technical Reports Server (NTRS)

Manzella, David H. (Inventor); Jacobson, David T. (Inventor); Hofer, Richard (Inventor); Peterson, Peter (Inventor); Jankovsky, Robert S. (Inventor)

2009-01-01

A Hall effect plasma accelerator includes inner and outer electromagnets, circumferentially surrounding the inner electromagnet along a thruster centerline axis and separated therefrom, inner and outer magnetic conductors, in physical connection with their respective inner and outer electromagnets, with the inner magnetic conductor having a mostly circular shape and the outer magnetic conductor having a mostly annular shape, a discharge chamber, located between the inner and outer magnetic conductors, a magnetically conducting back plate, in magnetic contact with the inner and outer magnetic conductors, and a combined anode electrode/gaseous propellant distributor, located at a bottom portion of the discharge chamber. The inner and outer electromagnets, the inner and outer magnetic conductors and the magnetically conducting back plate form a magnetic circuit that produces a magnetic field that is largely axial and radially symmetric with respect to the thruster centerline.

Molten salt bath circulation design for an electrolytic cell

DOEpatents

Dawless, Robert K.; LaCamera, Alfred F.; Troup, R. Lee; Ray, Siba P.; Hosler, Robert B.

1999-01-01

An electrolytic cell for reduction of a metal oxide to a metal and oxygen has an inert anode and an upwardly angled roof covering the inert mode. The angled roof diverts oxygen bubbles into an upcomer channel, thereby agitating a molten salt bath in the upcomer channel and improving dissolution of a metal oxide in the molten salt bath. The molten salt bath has a lower velocity adjacent the inert anode in order to minimize corrosion by substances in the bath. A particularly preferred cell produces aluminum by electrolysis of alumina in a molten salt bath containing aluminum fluoride and sodium fluoride.

Hydrogen-facilitated corrosion and stress corrosion cracking of austenitic stainless steel of type 310

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiao Lijie; Chu Wuyang; Miao Huijun

1993-04-01

The effects of hydrogen precharge and stress on anodic dissolution for Type 310 austenitic stainless steel (ASS) have been investigated. An experiment determining the effect of hydrogen on stress corrosion cracking (SCC) was carried out in a boiling 42% MgCl[sub 2] solution and in a 2.5 mol/l H[sub 2]SO[sub 4] + 1 mol/l HCl solution. The results showed that both hydrogen and stress would increase the dissolution rate, and the effects of hydrogen and stress on the dissolution rate were synergistic rather than simply additive. Hydrogen lowered the threshold stress and the shortened fracture time of SCC in a boilingmore » MgCl[sub 2] solution by a factor of 1/5 and 10, respectively.« less

Asymmetrical interfacial reactions of Ni/SAC101(NiIn)/Ni solder joint induced by current stressing

NASA Astrophysics Data System (ADS)

Lin, Chen-Yi; Chiu, Tsung-Chieh; Lin, Kwang-Lung

2018-03-01

An electric current can asymmetrically trigger either atomic migration or interfacial reactions between a cathode and an anode. The present study investigated the dissolution of metallization and formation of an interfacial intermetallic compound (IMC) in the Cu/Ni/Sn1.0Ag0.1Cu0.02Ni0.05In/Ni/Cu solder joint at various current densities in the order of 103 A/cm2 at temperatures ranging from 100 °C to 150 °C. The polarization behavior of Ni dissolution and IMC formation under current stressing were systematically investigated. The asymmetrical interfacial reactions of the solder joint were found to be greatly influenced by ambient temperature. The dissolution of Ni and its effect on interfacial IMC formation were also discussed.

Transient desorption of water vapor - A potential source of error in upper atmosphere rocket experiments

NASA Technical Reports Server (NTRS)

Kendall, B. R. F.; Weeks, J. O.

1974-01-01

Results of measurements of the outgassing rates of samples of materials and surface finishes used on the outer skins of rocket-borne experiment packages in simulated rocket ascents. The results showed outgassing rates for anodized aluminum in the second minute of flight which are two to three orders of magnitude higher than those given in typical tables of outgassing rates. The measured rates for aluminum with chromate conversion surface coatings were also abnormally high. These abnormally high initial rates fell quickly after about five to ten minutes to values comparable with those in the published literature. It is concluded that anodized and chromate conversion coatings on the aluminum outer surfaces of a sounding rocket experiment package will cause gross distortion of the true water vapor environment.

Self-Formed Hybrid Interphase Layer on Lithium Metal for High-Performance Lithium–Sulfur Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Guoxing; Huang, Qingquan; He, Xin

Lithium–sulfur (Li–S) batteries are promising candidates for high-energy storage devices due to high theoretical capacities of both the sulfur cathode and lithium (Li) metal anode. Considerable efforts have been devoted to improving sulfur cathodes. However, issues associated with Li anodes, such as low Coulombic efficiency (CE) and growth of Li dendrites, remain unsolved due to unstable solid-electrolyte interphase (SEI) and lead to poor capacity retention and a short cycling life of Li–S batteries. In this paper, we demonstrate a facile and effective approach to fabricate a flexible and robust hybrid SEI layer through co-deposition of aromatic-based organosulfides and inorganic Limore » salts using poly(sulfur-random-1,3-diisopropenylbenzene) as an additive in an electrolyte. The aromatic-based organic components with planar backbone conformation and π–π interaction in the SEI layers can improve the toughness and flexibility to promote stable and high efficient Li deposition/dissolution. The as-formed durable SEI layer can inhibit dendritic Li growth, enhance Li deposition/dissolution CE (99.1% over 420 cycles), and in turn enable Li–S batteries with good cycling stability (1000 cycles) and slow capacity decay. Finally, this work demonstrates a route to address the issues associated with Li metal anodes and promote the development of high-energy rechargeable Li metal batteries.« less

Self-Formed Hybrid Interphase Layer on Lithium Metal for High-Performance Lithium–Sulfur Batteries

DOE PAGES

Li, Guoxing; Huang, Qingquan; He, Xin; ...

2018-01-29

Lithium–sulfur (Li–S) batteries are promising candidates for high-energy storage devices due to high theoretical capacities of both the sulfur cathode and lithium (Li) metal anode. Considerable efforts have been devoted to improving sulfur cathodes. However, issues associated with Li anodes, such as low Coulombic efficiency (CE) and growth of Li dendrites, remain unsolved due to unstable solid-electrolyte interphase (SEI) and lead to poor capacity retention and a short cycling life of Li–S batteries. In this paper, we demonstrate a facile and effective approach to fabricate a flexible and robust hybrid SEI layer through co-deposition of aromatic-based organosulfides and inorganic Limore » salts using poly(sulfur-random-1,3-diisopropenylbenzene) as an additive in an electrolyte. The aromatic-based organic components with planar backbone conformation and π–π interaction in the SEI layers can improve the toughness and flexibility to promote stable and high efficient Li deposition/dissolution. The as-formed durable SEI layer can inhibit dendritic Li growth, enhance Li deposition/dissolution CE (99.1% over 420 cycles), and in turn enable Li–S batteries with good cycling stability (1000 cycles) and slow capacity decay. Finally, this work demonstrates a route to address the issues associated with Li metal anodes and promote the development of high-energy rechargeable Li metal batteries.« less

Corrosion of Cu-xZn alloys in slightly alkaline chloride solutions studied by stripping voltammetry and microanalysis.

PubMed

Milosev, I; Minović, A

2001-01-01

The mechanism of corrosion of Cu-xZn alloys (x = 10-40 wt %) in slightly alkaline chloride solutions was investigated by analysing solid reaction products by energy dispersive X-ray analysis (EDS) and dissolved reaction products by differential anodic pulse stripping (DAPS) voltammetry. The corrosion process was studied under open circuit and under potentiostatic conditions at selected potentials. Pure metals were studied comparatively so that an interacting effect of particular metal components in the alloy could be determined. All four Cu-xZn alloys show an improved behaviour compared to pure metals. Under open-circuit condition both components dissolve simultaneously in the solution. With increasing immersion time the preferential, dissolution of zinc in the solution becomes pronounced. It is the highest for Cu-10Zn and the lowest for Cu-30Zn alloy. Under potentiostatic control the dissolution mechanism depends on the electrode potential and changes from exclusive dissolution of zinc to simultaneous dissolution of both components with preferential dissolution of zinc. The latter decreases, as the electrode potential becomes more positive.

Dissolution and characterization of HEV NiMH batteries.

PubMed

Larsson, Kristian; Ekberg, Christian; Ødegaard-Jensen, Arvid

2013-03-01

Metal recovery is an essential part of the recycling of hybrid electric vehicle battery waste and the first step in a hydrometallurgical treatment is dissolution of the solid material. The properties of separated battery electrode materials were investigated. Focus was put on both the solid waste and then the dissolution behaviour. The cathode contains metallic nickel that remains undissolved when utilizing non-oxidizing conditions such as hydrochloric or sulphuric acid in combination with a low oxygen atmosphere. In these conditions the cathode active electrode material is fully dissolved. Not dissolving the nickel metal saves up to 37% of the acid consumption for the cathode electrode material. In the commonly used case of oxidizing conditions the nickel metal dissolves and a cobalt-rich phase remains undissolved from the cathode active material. For the anode material a complete and rapid dissolution can be achieved at mild conditions with hydrochloric, nitric or sulphuric acid. Optimal parameters for all cases of dissolution was pH 1 with a reaction time of approximately ≥ 20,000 s. Copyright © 2012 Elsevier Ltd. All rights reserved.

Corrosion fatigue studies on a bulk glassy Zr-based alloy under three-point bending

NASA Astrophysics Data System (ADS)

Grell, Daniel; Wilkin, Yannic; Gostin, Petre F.; Gebert, Annett; Kerscher, Eberhard

2016-12-01

Corrosion fatigue (CF) tests were carried out on bulk glassy Zr52.5Cu17.9Al10Ni14.6Ti5 (Vitreloy 105) samples under load-controlled three-point bending conditions with a load ratio of R = 0.1 in 0.01 M Na2SO4 + 0.01 M NaCl electrolyte. During cyclic testing, the bar-shaped specimens were polarized in situ at constant potentials and the current was monitored. Three different anodic potentials within the interval between the pitting potential EP and the repassivation potential ER, and three different load amplitudes were applied. In some cases, in situ microscopic observations revealed the formation of black corrosion products in the vicinity of the crack tip during anodic polarization. Fractographic analysis revealed a clear distinction between two modes of crack growth characterized by smooth dissolution induced regions on the one hand and slim fast fracture areas on the other hand. Both alternating features contributed to a broad striated corrosion fatigue fracture surface. Moreover, further fatigue tests were carried out under free corrosion conditions yielding additional information on crack initiation and crack propagation period by means of the open circuit potential (OCP) changes. Thereby, a slight increase in OCP was detected after rupture of the passive layer due to bare metal exposed to the electrolyte. The electrochemical response increased continuously according to stable crack propagation until fracture occurred. Finally, the fracture surfaces of the corrosion fatigue samples were investigated by energy dispersive X-ray with the objective of analyzing the elemental distribution after anodic dissolution. Interestingly, anodic polarization at a near repassivation potential of -50 mV vs. SCE (Saturated Calomel Electrode, E = 0.241 V vs. SHE, Standard Hydrogen Electrode) led to favorable effects on the fatigue lifetime. In conclusion, all results are conflated to a corrosion fatigue model for bulk glassy Vitreloy 105 under anodic polarization in chloride-containing electrolyte and compared to the previously proposed stress corrosion mechanisms under similar conditions.

Radiation detector

DOEpatents

Fultz, B.T.

1980-12-05

Apparatus is provided for detecting radiation such as gamma rays and x-rays generated in backscatter Moessbauer effect spectroscopy and x-ray spectrometry, which has a large window for detecting radiation emanating over a wide solid angle from a specimen and which generates substantially the same output pulse height for monoenergetic radiation that passes through any portion of the detection chamber. The apparatus includes a substantially toroidal chamber with conductive walls forming a cathode, and a wire anode extending in a circle within the chamber with the anode lying closer to the inner side of the toroid which has the least diameter than to the outer side. The placement of the anode produces an electric field, in a region close to the anode, which has substantially the same gradient in all directions extending radially from the anode, so that the number of avalanche electrons generated by ionizing radiation is independent of the path of the radiation through the chamber.

Radiation detector

DOEpatents

Fultz, Brent T.

1983-01-01

Apparatus is provided for detecting radiation such as gamma rays and X-rays generated in backscatter Mossbauer effect spectroscopy and X-ray spectrometry, which has a large "window" for detecting radiation emanating over a wide solid angle from a specimen and which generates substantially the same output pulse height for monoenergetic radiation that passes through any portion of the detection chamber. The apparatus includes a substantially toroidal chamber with conductive walls forming a cathode, and a wire anode extending in a circle within the chamber with the anode lying closer to the inner side of the toroid which has the least diameter than to the outer side. The placement of the anode produces an electric field, in a region close to the anode, which has substantially the same gradient in all directions extending radially from the anode, so that the number of avalanche electrons generated by ionizing radiation is independent of the path of the radiation through the chamber.

Enhancing long-term photostability of BiVO4 photoanodes for solar water splitting by tuning electrolyte composition

NASA Astrophysics Data System (ADS)

Lee, Dong Ki; Choi, Kyoung-Shin

2018-01-01

As the performance of photoelectrodes used for solar water splitting continues to improve, enhancing the long-term stability of the photoelectrodes becomes an increasingly crucial issue. In this study, we report that tuning the composition of the electrolyte can be used as a strategy to suppress photocorrosion during solar water splitting. Anodic photocorrosion of BiVO4 photoanodes involves the loss of V5+ from the BiVO4 lattice by dissolution. We demonstrate that the use of a V5+-saturated electrolyte, which inhibits the photooxidation-coupled dissolution of BiVO4, can serve as a simple yet effective method to suppress anodic photocorrosion of BiVO4. The V5+ species in the solution can also incorporate into the FeOOH/NiOOH oxygen-evolution catalyst layer present on the BiVO4 surface during water oxidation, further enhancing water-oxidation kinetics. The effect of the V5+ species in the electrolyte on both the long-term photostability of BiVO4 and the performance of the FeOOH/NiOOH oxygen-evolution catalyst layer is systematically elucidated.

Electrical characterization of TiO2 nanotubes synthesized through electrochemical anodizing method

NASA Astrophysics Data System (ADS)

Manescu Paltanea, Veronica; Paltanea, Gheorghe; Popovici, Dorina; Jiga, Gabriel

2016-05-01

In the present paper, the electrochemical anodizing method was used for the obtaining of TiO2 nanotube layers, developed on titanium surface. Self-organized titanium nanotubes were obtained when an aqueous solution of 49.5 wt % H2O - 49.5 wt % glycerol - 1 wt % HF was used as electrolyte, the anodizing time being equal to 8 hours and the applied voltage to 25 V. Scanning electron microscopy shows that the one-dimensional nanostructure has a tubular configuration with an inner diameter of approximately 60 nm and an outer diameter of approximately 100 nm. The electrical properties of these materials were analyzed through dielectric spectroscopy method.

The anodic surface film and hydrogen evolution on Mg

DOE PAGES

Song, Guang -Ling; Unocic, Kinga A.

2015-06-04

This paper clarifies that the inner and outer layers of the anodic film consist of a nano/micro-porous MgO+Mg(OH) 2 mixture. The film becomes thicker and more porous with increasing potential. It can rupture when potential is too positive in a non-corrosive Mg(OH) 2 solution. Hydrogen evolution becomes more intensive as polarization potential increases, particularly when the potential at the film-covered Mg surface is close to or more positive than the hydrogen equilibrium potential, suggesting that an “anodic hydrogen evolution” (AHE) reaction occurs on the substrate Mg in film pores, and the significantly intensified AHE causes film rupture at high potential.

AGARD Corrosion Handbook. Volume 1. Aircraft Corrosion: Causes and Case Histories

DTIC Science & Technology

1985-07-01

Anodic coatings can be formed in chromic acid, sulphuric acid, phosphoric acid or oxalic acid solutions. Chromic acid anodizing is widely used with...and consists of a thin non-porous barrier layer next to the metal with a porous outer layer that can be sealed by hydrothermal treatment in steam...anaerobic) or an oxidative (aerobic) mechanism. Various organic acids such as citric acid, oxalic acid, gluconic acid, dodecanoic acid, etc., which may be

Molten salt bath circulation design for an electrolytic cell

DOEpatents

Dawless, R.K.; LaCamera, A.F.; Troup, R.L.; Ray, S.P.; Hosler, R.B.

1999-08-17

An electrolytic cell for reduction of a metal oxide to a metal and oxygen has an inert anode and an upwardly angled roof covering the inert mode. The angled roof diverts oxygen bubbles into an upcomer channel, thereby agitating a molten salt bath in the upcomer channel and improving dissolution of a metal oxide in the molten salt bath. The molten salt bath has a lower velocity adjacent the inert anode in order to minimize corrosion by substances in the bath. A particularly preferred cell produces aluminum by electrolysis of alumina in a molten salt bath containing aluminum fluoride and sodium fluoride. 4 figs.

Framework of barrier reefs threatened by ocean acidification.

PubMed

Comeau, Steeve; Lantz, Coulson A; Edmunds, Peter J; Carpenter, Robert C

2016-03-01

To date, studies of ocean acidification (OA) on coral reefs have focused on organisms rather than communities, and the few community effects that have been addressed have focused on shallow back reef habitats. The effects of OA on outer barrier reefs, which are the most striking of coral reef habitats and are functionally and physically different from back reefs, are unknown. Using 5-m long outdoor flumes to create treatment conditions, we constructed coral reef communities comprised of calcified algae, corals, and reef pavement that were assembled to match the community structure at 17 m depth on the outer barrier reef of Moorea, French Polynesia. Communities were maintained under ambient and 1200 μatm pCO2 for 7 weeks, and net calcification rates were measured at different flow speeds. Community net calcification was significantly affected by OA, especially at night when net calcification was depressed ~78% compared to ambient pCO2 . Flow speed (2-14 cm s(-1) ) enhanced net calcification only at night under elevated pCO2 . Reef pavement also was affected by OA, with dissolution ~86% higher under elevated pCO2 compared to ambient pCO2 . These results suggest that net accretion of outer barrier reef communities will decline under OA conditions predicted within the next 100 years, largely because of increased dissolution of reef pavement. Such extensive dissolution poses a threat to the carbonate foundation of barrier reef communities. © 2015 John Wiley & Sons Ltd.

An investigation of passivity and breakdown of amorphous chromium-bromine thin films for surface modification of metallic biomaterials

NASA Astrophysics Data System (ADS)

Cormier, Lyne Mercedes

1998-12-01

The objectives of this investigation of amorphous Cr-B thin films as prospective coatings for biomaterials applications were to (i) produce and characterize an amorphous Cr-B thin film coating by magnetron sputtering, (ii) evaluate its corrosion resistance in physiologically relevant electrolytes, and (iii) propose a mechanism for the formation/dissolution of the passive film formed on amorphous Cr-B in chloride-containing near-neutral salt electrolytes. Dense (zone T) amorphous Cr75B25 thin films produced by DC magnetron sputtering were found to be better corrosion barriers than nanoczystalline or porous (zone 1) amorphous Cr75B25 thin films. The growth morphology and microstructure were a function of the sputtering pressure and substrate temperature, in agreement with the structure zone model of Thornton. The passivity/loss of passivity of amorphous Cr 75B25 in near-neutral salt solutions was explained using a modified bipolar layer model. The chromate ions identified by X-Ray Photoelectron Spectroscopy (XPS) in the outer layer of the passive film were found to play a determinant role in the passive behaviour of amorphous Cr75B 25 thin films in salt solutions. In near-neutral salt solutions of pH = 5 to 7, a decrease in pH combined with an increase in chloride concentration resulted in less dissolution of the Cr75B25 thin films. The apparent breakdown potential at 240 mV (SCE) obtained by Cyclic Potentiodynamic Anodic Polarization (CPAP) was associated with oxidation of species within the passive film, but not to dissolution leading to immediate loss of passivity. Pit Propagation Rate (PPR) testing evaluated the stable pitting potential to be between 600 and 650 mV. Amorphous Cr75B25 thin films ranked the best among other Cr-based materials such as 316L stainless steel, CrB2 and Cr investigated in this study for general corrosion behaviour in NaCl and Hanks solutions by CPAP testing. In terms of corrosion resistance, amorphous Cr75B25 thin films were recognized as a promising material for surface modification of biomaterials.

A novel rotating electrochemically anodizing process to fabricate titanium oxide surface nanostructures enhancing the bioactivity of osteoblastic cells.

PubMed

Chang, Chih-Hung; Lee, Hsin-Chun; Chen, Chia-Chun; Wu, Yi-Hau; Hsu, Yuan-Ming; Chang, Yin-Pen; Yang, Ta-I; Fang, Hsu-Wei

2012-07-01

Titanium oxide (TiO(2) ) surface layers with various surface nanostructures (nanotubes and nanowires) have been developed using an anodizing technique. The pore size and length of TiO(2) nanotubes can be tailored by changing the anodizing time and applied voltage. We developed a novel method to transform the upper part of the formed TiO(2) nanotubes into a nanowire-like structure by rotating the titanium anode during anodizing process. The transformation of nanotubes contributed to the preferential chemical dissolution of TiO(2) on the areas with intense interface tension stress. Furthermore, we further compared the effect of various TiO(2) surface nanostructures including flat, nanotubes, and nanowires on bioactive applications. The MG-63 osteoblastic cells cultured on the TiO(2) nanowires exhibited a polygonal shape with extending filopodia and showed highest levels of cell viability and alkaline phosphatase activity (ALP). The TiO(2) nanowire structure formed by our novel method can provide beneficial effects for MG-63 osteoblastic cells in attachment, proliferation, and secretion of ALP on the TiO(2) surface layer. Copyright © 2012 Wiley Periodicals, Inc.

Enhancing Near Zero Volt Storage Tolerance of Lithium-ion Batteries

NASA Astrophysics Data System (ADS)

Crompton, Kyle R.

There are inherent safety risks associated with inactive lithium ion batteries leading to greater restrictions and regulations on shipping and storage. Maintaining all cells of a lithium ion battery at near zero voltage with an applied fixed resistive load is one promising approach which can lessen (and potentially eliminate) the risk of a lithium ion battery entering thermal runaway when in an inactive state. However, in a conventional lithium ion cell, a near zero cell voltage can be damaging if the anode electrochemical potential increases to greater than the potential where dissolution of the standard copper current collector occurs (i.e. 3.1 V vs. Li/Li+ at room temperature). Past approaches to yield lithium ion cells that are resilient to a near zero volt state of charge involve use of secondary active materials or alternative current collectors which have anticipated tradeoffs in terms of cell performance and cost. In the the present dissertation work the approach of managing the amount of reversible lithium in a cell during construction to prevent the anode potential from increasing to greater than 3.1 V vs. Li/Li+ during near zero volt storage is introduced. Anode pre-lithiation was used in LiCoO 2/MCMB pouch cells to appropriately manage the amount of reversible lithium so that there is excess reversible lithium compared to the cathodes intercalation capacity (reversible lithium excess cell or RLE cell). RLE LiCoO 2/MCMB cells maintained 99% of their original capacity after three, 3-day and three, 7-day storage periods at near zero volts under fixed load. A LiCoO2/MCMB pouch cell fabricated with a pre-lithiated anode also maintained its original discharge performance after three, 3-day storage periods under fixed load at 45°C. The strong recharge performance after near zero volt storage is attributed to the anode potential remaining below the copper dissolution potential during near zero volt storage as informed by reference electrode measurements. Pulse discharge measurements were performed and show that double layer capacitance likely plays a major role in determining the behavior of electrode potentials during near zero volt storage. To further the viability of the anode pre-lithiation method in LiCoO2/MCMB cells, stabilization coatings on the cathode materials are being investigated to increase the tolerance of the cathode to the low potentials it may experience during near zero volt storage of an RLE lithium ion cell. Results show that an AlPO4 coating prevents cation exhange in the cathode crystal structure and substantially increases the cathode's resilience to low electrochemical potentials. Investigations into applying anode pre-lithiation to cells utilizing LiNiCoAlO2 (NCA) cathodes have also been initiated and found to maintain the anode potential below the copper dissolution potential during near zero volt storage. RLE NCA/MCMB cells showed strong recharge performance and improved rate capability retention over a conventional NCA/MCMB cell after ten, 3-day near zero volt storage periods. Scale up of reversible lithium management to NCA/MCMB x3450 pouch cells was achieved using bath lithium addition and rendered a cell that retained 100% of its discharge performance after a 14 day period at near zero volts under fixed load. The near zero volt storage tolerance of lithium ion cells utilizing an advanced, high energy density lithium rich cathode material (0.49Li2MnO3˙0.51LiNi 0.37Co0.24Mn0.39O2 or HE5050) has also been studied and found to be high at room temperature without the need for anode pre-lithiation. HE5050/MCMB cells maintained 100% of their discharge capacity after five, 3-day and five, 7-day near zero volt storage periods at room temperature. HE5050/MCMB also maintained 99% of their discharge capacity after two, 3-day near zero volt storage periods at 40°C. The high first cycle loss and lower intercalation potential of the HE5050 cathode lead to the anode potential remaining <2.8 V vs. Li/Li+ during near zero volt storage and as such, no copper dissolution is expected to be occurring. Finally, Carbon Nanotube (CNT) papers have been shown to be stable up to high potentials vs. Li/Li+ and thus, using them as an anode current collector in place of standard copper can generate lithium ion cells that can tolerate near zero volt storage. However, CNT papers suffer from significant irreversible loss due to their high surface area. An Al2O3 coating deposited by atomic layer deposition is investigated for its effect in reducing the irreversible losses of a CNT paper. The Al2O3 coating was found to reduce irreversible loss by 55% over 50 cycles and still serve as an effective current collector for a graphitic anode composite.

Enhancement of Combustion and Flame Stabilization Using Transient Non-Equilibrium Plasma

DTIC Science & Technology

2007-03-31

cathode spot D = diameter of MGA device D= diffusivity of i’h species d = diameter of arc dcoected= diametrically corrected diameter of arc d.rwwd... cathode and anode, stabilization (4) respectively (Fig. 1). A wire was attached to the cathode , which was separated from the outer anode by 2 mm at the...smallest gap (point (1) in Fig. 1). The wire spiraled progressively closer to the cathode , where it was attached at the largest gap between the two

Outer organic layer and internal repair mechanism protects pteropod Limacina helicina from ocean acidification

NASA Astrophysics Data System (ADS)

Peck, Victoria L.; Tarling, Geraint A.; Manno, Clara; Harper, Elizabeth M.; Tynan, Eithne

2016-05-01

Scarred shells of polar pteropod Limacina helicina collected from the Greenland Sea in June 2012 reveal a history of damage, most likely failed predation, in earlier life stages. Evidence of shell fracture and subsequent re-growth is commonly observed in specimens recovered from the sub-Arctic and further afield. However, at one site within sea-ice on the Greenland shelf, shells that had been subject to mechanical damage were also found to exhibit considerable dissolution. It was evident that shell dissolution was localised to areas where the organic, periostracal sheet that covers the outer shell had been damaged at some earlier stage during the animal's life. Where the periostracum remained intact, the shell appeared pristine with no sign of dissolution. Specimens which appeared to be pristine following collection were incubated for four days. Scarring of shells that received periostracal damage during collection only became evident in specimens that were incubated in waters undersaturated with respect to aragonite, ΩAr≤1. While the waters from which the damaged specimens were collected at the Greenland Sea sea-ice margin were not ΩAr≤1, the water column did exhibit the lowest ΩAr values observed in the Greenland and Barents Seas, and was likely to have approached ΩAr≤1 during the winter months. We demonstrate that L. helicina shells are only susceptible to dissolution where both the periostracum has been breached and the aragonite beneath the breach is exposed to waters of ΩAr≤1. Exposure of multiple layers of aragonite in areas of deep dissolution indicate that, as with many molluscs, L. helicina is able to patch up dissolution damage to the shell by secreting additional aragonite internally and maintain their shell. We conclude that, unless breached, the periostracum provides an effective shield for pteropod shells against dissolution in waters ΩAr≤1, and when dissolution does occur the animal has an effective means of self-repair. We suggest that future studies of pteropod shell condition are undertaken on specimens from which the periostracum has not been removed in preparation.

Transpassive Dissolution of Copper and Rapid Formation of Brilliant Colored Copper Oxide Films

NASA Astrophysics Data System (ADS)

Fredj, Narjes; Burleigh, T. David; New Mexico Tech Team

2014-03-01

This investigation describes an electrochemical technique for growing adhesive copper oxide films on copper with attractive colors ranging from gold-brown to pearl with intermediate colors from red violet to gold green. The technique consists of anodically dissolving copper at transpassive potentials in hot sodium hydroxide, and then depositing brilliant color films of Cu2O onto the surface of copper after the anodic potential has been turned off. The color of the copper oxide film depends on the temperature, the anodic potential, the time t1 of polarization, and the time t2, which is the time of immersion after potential has been turned off. The brilliant colored films were characterized using glancing angle x-ray diffraction, and the film was found to be primarily Cu2O. Cyclic voltammetry, chronopotentiometry, scanning electron microscopy, and x-ray photoelectron spectroscopy were also used to characterize these films.

Zirconium behaviour during electrorefining of actinide-zirconium alloy in molten LiCl-KCl on aluminium cathodes

NASA Astrophysics Data System (ADS)

Meier, R.; Souček, P.; Malmbeck, R.; Krachler, M.; Rodrigues, A.; Claux, B.; Glatz, J.-P.; Fanghänel, Th.

2016-04-01

A pyrochemical electrorefining process for the recovery of actinides from metallic nuclear fuel based on actinide-zirconium alloys (An-Zr) in a molten salt is being investigated. In this process actinides are group-selectively recovered on solid aluminium cathodes as An-Al alloys using a LiCl-KCl eutectic melt at a temperature of 450 °C. In the present study the electrochemical behaviour of zirconium during electrorefining was investigated. The maximum amount of actinides that can be oxidised without anodic co-dissolution of zirconium was determined at a selected constant cathodic current density. The experiment consisted of three steps to assess the different stages of the electrorefining process, each of which employing a fresh aluminium cathode. The results indicate that almost a complete dissolution of the actinides without co-dissolution of zirconium is possible under the applied experimental conditions.

Effects of pretreatment processes for Zr electrorefining of oxidized Zircaloy-4 cladding tubes

NASA Astrophysics Data System (ADS)

Hwa Lee, Chang; Lee, Yoo Lee; Jeon, Min Ku; Choi, Yong Taek; Kang, Kweon Ho; Park, Geun Il

2014-06-01

The effect of pretreatment processes for the Zr electrorefining of oxidized Zircaloy-4 cladding tubes is examined in LiCl-KCl-ZrCl4 molten salts at 500 °C. The cyclic voltammetries reveal that the Zr dissolution kinetics is highly dependent on the thickness of a Zr oxide layer formed at 500 °C under air atmosphere. For the Zircaloy-4 tube covered with a 1 μm thick oxide layer, the Zr dissolution process is initiated from a non-stoichiometric Zr oxide surface through salt treatment at an open circuit potential in the molten salt electrolyte. The Zr dissolution of the samples in the middle range of oxide layer thickness appears to be more effectively derived by the salt treatment coupled with an anodic potential application at an oxidation potential of Zr. A modification of the process scheme offers an applicability of Zr electrorefining for the treatment of oxidized cladding hull wastes.

Electrical neurostimulation with imbalanced waveform mitigates dissolution of platinum electrodes

PubMed Central

Kumsa, Doe; Hudak, Eric M; Montague, Fred W; Kelley, Shawn C; Untereker, Darrel F; Hahn, Benjamin P; Condit, Chris; Cholette, Martin; Lee, Hyowon; Bardot, Dawn; Takmakov, Pavel

2017-01-01

Objective Electrical neurostimulation has traditionally been limited to the use of charge-balanced waveforms. Charge-imbalanced and monophasic waveforms are not used to deliver clinical therapy, because it is believed that these stimulation paradigms may generate noxious electrochemical species that cause tissue damage. Approach In this study, we investigated the dissolution of platinum as one of such irreversible reactions over a range of charge densities up to 160 µC cm−2 with current-controlled first phase, capacitive discharge second phase waveforms of both cathodic-first and anodic-first polarity. We monitored the concentration of platinum in solution under different stimulation delivery conditions including charge-balanced, charge-imbalanced, and monophasic pulses. Main results We observed that platinum dissolution decreased during charge-imbalanced and monophasic stimulation when compared to charge-balanced waveforms. Significance This observation provides an opportunity to re-evaluate the charge-balanced waveform as the primary option for sustainable neural stimulation. PMID:27650936

Effect of protein adsorption on the corrosion behavior of 70Cu-30Ni alloy in artificial seawater.

PubMed

Torres Bautista, Blanca E; Carvalho, Maria L; Seyeux, Antoine; Zanna, Sandrine; Cristiani, Pierangela; Tribollet, Bernard; Marcus, Philippe; Frateur, Isabelle

2014-06-01

Copper alloys often used in cooling circuits of industrial plants can be affected by biocorrosion induced by biofilm formation. The objective of this work was to study the influence of protein adsorption, which is the first step in biofilm formation, on the electrochemical behavior of 70Cu-30Ni (wt.%) alloy in static artificial seawater and on the chemical composition of oxide layers. For that purpose, electrochemical measurements performed after 1h of immersion were combined to surface analyses. A model is proposed to analyze impedance data. In the presence of bovine serum albumin (BSA, model protein), the anodic charge transfer resistance deduced from EIS data at Ecorr is slightly higher, corresponding to lower corrosion current. Without BSA, two oxidized layers are shown by XPS and ToF-SIMS: an outer layer mainly composed of copper oxide (Cu2O redeposited layer) and an inner layer mainly composed of oxidized nickel, with a global thickness of ~30nm. The presence of BSA leads to a mixed oxide layer (CuO, Cu2O, Ni(OH)2) with a lower thickness (~10nm). Thus, the protein induces a decrease of the dissolution rate at Ecorr and hence a decrease of the amount of redeposited Cu2O and of the oxide layer thickness. © 2013.

Modeling the degradation mechanisms of C6/LiFePO4 batteries

NASA Astrophysics Data System (ADS)

Li, Dongjiang; Danilov, Dmitri L.; Zwikirsch, Barbara; Fichtner, Maximilian; Yang, Yong; Eichel, Rüdiger-A.; Notten, Peter H. L.

2018-01-01

A fundamental electrochemical model is developed, describing the capacity fade of C6/LiFePO4 batteries as a function of calendar time and cycling conditions. At moderate temperatures the capacity losses are mainly attributed to Li immobilization in Solid-Electrolyte-Interface (SEI) layers at the anode surface. The SEI formation model presumes the availability of an outer and inner SEI layers. Electron tunneling through the inner SEI layer is regarded as the rate-determining step. The model also includes high temperature degradation. At elevated temperatures, iron dissolution from the positive electrode and the subsequent metal sedimentation on the negative electrode influence the capacity loss. The SEI formation on the metal-covered graphite surface is faster than the conventional SEI formation. The model predicts that capacity fade during storage is lower than during cycling due to the generation of SEI cracks induced by the volumetric changes during (dis)charging. The model has been validated by cycling and calendar aging experiments and shows that the capacity loss during storage depends on the storage time, the State-of-Charge (SoC), and temperature. The capacity losses during cycling depend on the cycling current, cycling time, temperature and cycle number. All these dependencies can be explained by the single model presented in this paper.

Polymer nanoimprinting using an anodized aluminum mold for structural coloration

NASA Astrophysics Data System (ADS)

Kikuchi, Tatsuya; Nishinaga, Osamu; Natsui, Shungo; Suzuki, Ryosuke O.

2015-06-01

Polymer nanoimprinting of submicrometer-scale dimple arrays with structural coloration was demonstrated. Highly ordered aluminum dimple arrays measuring 530-670 nm in diameter were formed on an aluminum substrate via etidronic acid anodizing at 210-270 V and subsequent anodic oxide dissolution. The nanostructured aluminum surface led to bright structural coloration with a rainbow spectrum, and the reflected wavelength strongly depends on the angle of the specimen and the period of the dimple array. The reflection peak shifts gradually with the dimple diameter toward longer wavelength, reaching 800 nm in wavelength at 670 nm in diameter. The shape of the aluminum dimple arrays were successfully transferred to a mercapto-ester ultra-violet curable polymer via self-assembled monolayer coating and polymer replications using a nanoimprinting technique. The nanostructured polymer surfaces with positively and negatively shaped dimple arrays also exhibited structural coloration based on the periodic nanostructure, and reflected light mostly in the visible region, 400-800 nm. This nanostructuring with structural coloration can be easily realized by simple techniques such as anodizing, SAM coating, and nanoimprinting.

Effect of Low-Temperature Environment on Stress Corrosion Cracking Behavior of X80 Pipeline Steel in Simulated Alkaline Soil Solution

NASA Astrophysics Data System (ADS)

Xie, Fei; Wang, Dan; Wu, Ming; Yu, Chengxiang; Sun, Dongxu; Yang, Xu; Xu, Changhao

2018-04-01

The stress corrosion cracking (SCC) of X80 pipeline steel in simulated alkaline soil solution under different temperatures was investigated by slow-strain-rate testing, scanning electron microscopy and energy-dispersive spectroscopy. Results showed that the fracture was transgranular and brittle at 273 K to 278 K (0 °C to 5 °C), and the metal surface was dissolved by a large number of chloride ions. Furthermore, hydrogen embrittlement was caused by the hydrogen atom extended to the high-stress region. The fracture process was controlled by hydrogen-induced cracking, and SCC was highly sensitive at this stage. At 288 K to 298 K (15 °C to 25 °C), the fracture morphology was attributed to the mixed mode of ductile and brittle fractures, the fracture process was controlled by the mechanism of hydrogen-induced cracking and anodic dissolution, and the susceptibility to SCC decreased. When the temperature reached 308 K to 318 K (35 °C to 45 °C), the fracture was mainly intergranular and ductile, the fracture process was controlled by anodic dissolution, and SCC sensitivity was the smallest in this temperature range.

Comment on Peck et al: Vulnerability of pteropod (Limacina helicina) to ocean acidification: shell dissolution occurs despite an intact organic layer

NASA Astrophysics Data System (ADS)

Bednaršek, N.; Johnson, J.; Feely, R. A.

2016-05-01

Pteropods have been recognized as one of the most sensitive marine organisms to ocean acidification (OA). Their susceptibility is mostly related to rapid shell dissolution, which is correlated with exposure to waters undersaturated with respect to aragonite (Ωar≤ 1) (e.g., Lischka et al., 2011; Bednaršek et al., 2012a,b, 2014a,b; Busch et al., 2014). Increased dissolution weakens the shell, increases vulnerability to predation and infection, and imposes an energetic cost. The rapidity of shell dissolution is attributed to the combination of metastable aragonitic crystal structure of shells that are among the thinnest known for calcifying organisms, and an extremely thin outer organic layer (i.e. periostracum <1 μm thick), suggesting insufficient protection against shell dissolution at Ωar≤1 (Bednaršek et al., 2014b). The periostracum generally consists of polysaccharide and proteinaceous components (Gaffey and Bronnimann, 1993) but varies significantly in its structure and composition amongst taxa.

Synthesis and electrochemical performances of amorphous carbon-coated Sn Sb particles as anode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wang, Zhong; Tian, Wenhuai; Liu, Xiaohe; Yang, Rong; Li, Xingguo

2007-12-01

The amorphous carbon coating on the Sn-Sb particles was prepared from aqueous glucose solutions using a hydrothermal method. Because the outer layer carbon of composite materials is loose cotton-like and porous-like, it can accommodate the expansion and contraction of active materials to maintain the stability of the structure, and hinder effectively the aggregation of nano-sized alloy particles. The as-prepared composite materials show much improved electrochemical performances as anode materials for lithium-ion batteries compared with Sn-Sb alloy and carbon alone. This amorphous carbon-coated Sn-Sb particle is extremely promising anode materials for lithium secondary batteries and has a high potentiality in the future use.

Significance of a Shelf-wide Dissolution Event during the Paleocene-Eocene Thermal Maximum, Maryland and New Jersey, USA

NASA Astrophysics Data System (ADS)

Bralower, T. J.; Kump, L. R.; Robinson, M. M.; Self-Trail, J. M.; Zachos, J. C.

2016-12-01

Continental-shelf sediments of the US Atlantic margin experienced a brief episode of carbonate dissolution during the onset of the Paleocene-Eocene Thermal Maximum (PETM). Dissolution is represented by reduced percentages of carbonate, and calcareous microfossil distribution and preservation trends, in cores from Maryland and New Jersey. The base and the top of the dissolution zone are abrupt compared to the gradual nature of the onset of the carbon isotope excursion (CIE). The thickness of the dissolution zone varies from 9 cm in the Bass River core (outer paleoshelf) to 1.6 m in the CamDor core (middle paleoshelf). The decrease in %CaCO3 suggests dissolution locally removed 83 to 100% of the initial biogenic carbonate. Shelf-wide dissolution during the onset of the PETM may be a regional event, associated, for example, with eutrophication. Samples from across the paleoshelf contain abundant fine-grained framboidal pyrite, which suggests photic-zone euxinia occurred before, during, and after the dissolution event. Dissolution may also be associated with oxidation of this pyrite during later exposure to oxidizing groundwaters, although the restricted duration of the dissolution interval argues against this. Alternatively, the dissolution event may have global significance related to surface ocean-water acidification or shoaling of the calcite compensation depth (CCD) to shelf depths. The event began near the onset of the CIE on the shelf, whereas dissolution in deep-sea sections began later. Earlier shelf dissolution is consistent with surface ocean acidification while later deep-sea dissolution is thought to be associated with shoaling of the CCD. In our presentation, we weigh evidence for each of these possibilities and test them using the global dataset.

The effect of current reversal on coated titanium electrodes

NASA Astrophysics Data System (ADS)

Elnathan, Francis

Coated titanium electrodes have applications in the electrochemical industry, including water treatment and swimming pool chlorination. Current/polarity reverse electrolysis is a technique used for "self-cleaning" of the coated titanium anodes employed in water disinfection and treatment. However, the literature holds very little information about the effects of polarity reversal on these anodes. The present work appears to be the first to investigate coated titanium anodes in polarity reversal in a systematic method. Two commercial titanium electrodes (RuTi and IrTa) were studied. Polarity reversal was the main electrochemical technique employing a current density of 1200 A/m 2, except when current density was studied. The effects of NO 3-, SO42-, ClO4 -, HPO42-, CO32-, Mg2+ and Ca2+ on electrode lifetime were examined. Analysis of the electrochemical results showed that plateau time (tau p), for gas evolution, is highly important to the lifetime of the coated titanium anodes. The effects of three electrolysis variables on the coated titanium anode life were examined. Current density was observed to have an inverse relationship with anode life while reversal cycle time had a direct relation with lifetime. NaCl concentration had no discernible effect. In general, the RuTi electrode exhibited longer lifetimes than IrTa except for a few specific conditions. The influence of the concentration of five anions (NO3-, SO42-, ClO 4-, HPO42-, and CO3 2-) was determined. Changing the composition and concentration of anions affected the lifetimes of the two electrodes, especially nitrate, hydrogen phosphate and carbonate. The lifetime of IrTa was highest in nitrate, and increased as a function of nitrate concentration. The service life of RuTi was highest in hydrogen phosphate, and increased with increasing hydrogen phosphate concentration. Lifetime of both anodes decreased with increasing carbonate ions. The effects of Mg2+ and Ca2+ on electrode lifetime were examined with three anions (NO3-, HPO42-, ClO4-) electrolytes. While there were numerous effects and interactions between Mg2+ or Ca2+ and anions on lifetime, these effects were found to mainly affect the amount of time the electrodes spent in the charging and discharging reactions. The times related to gas evolution (which is the plateau time, tau p) were found to be strikingly similar. The charging times (tau C) which are related to adsorption and desorption of species were not also any significantly different. Coating dissolution, substrate and/or coating passivation mechanisms were identified as being responsible for coated titanium anode failure in current reverse and hard water electrolysis. IrTa is believed to have failed predominantly by the dissolution mechanism in nitrate, hydrogen phosphate and perchlorate. RuTi failed predominantly by substrate and/or coating passivation in hydrogen phosphate, nitrate and carbonate. Anode failure is believed to be the result of plateau (taup) and charging (tauC)reactions occurring at the coating/electrolyte and/or substrate/coating interface. The tau p and tauC are useful determinants for the process of anode failure.

Electrolysis of plutonium nitride in LiCl-KCl eutectic melts

NASA Astrophysics Data System (ADS)

Shirai, O.; Iwai, T.; Shiozawa, K.; Suzuki, Y.; Sakamura, Y.; Inoue, T.

2000-01-01

The electrolysis of plutonium nitride, PuN, was investigated in the LiCl-KCl eutectic salt with 0.54 wt% PuCl 3 at 773 K in order to understand the dissolution of PuN at the anode and the deposition of metal at the cathode from the viewpoint of the application of a pyrochemical process to nitride fuel cycle. It was found from cyclic voltammetry that the electrochemical dissolution of PuN began nearly at the theoretically evaluated potential and this reaction was irreversible. Several grams of plutonium metal were successfully recovered at the molybdenum electrode as a deposit with a current efficiency of about 90%, although some fractions of the deposited plutonium often fell from the molybdenum electrode.

Research progress in formation mechanism of anodizing aluminum oxide

NASA Astrophysics Data System (ADS)

Lv, Yudong

2017-12-01

The self-ordering porous anodizing aluminum oxide (AAO) has attracted much attention because of its potential value of application. Valve metals (Al, Ti, Zr etc.) anodic studies have been conducted for more than 80 years, but the mechanism of the formation of hexagonal prismatic cell structure has so far been different. In this paper, the research results of AAO film formation mechanism are reviewed, and the growth models of several AAO films are summarized, including the field-assisted dissolution (FAD), the viscous flow model, the critical current density effect model, the bulk expansion stress model and the steady-state pore growth model and so on. It analyzed the principle of each model and its rationality. This paper will be of great help to reveal the nature of pore formation and self-ordering, and with the hope that through the study of AAO film formation mechanism, the specific effects of various oxidation parameters on AAO film morphology can be obtained.

Formation of TiO2 nanotube arrays in KOH added fluoride-ethylene glycol (EG) electrolyte and its photoelectrochemical response

NASA Astrophysics Data System (ADS)

Nyein, Nyein; Lockman, Zainovia; Matsuda, Astunori; Kawamura, Go; Tan, Wai Kian; Oo, Than Zaw

2016-07-01

In this study, highly ordered TiO2 nanotube arrays were prepared by anodic oxidation of titanium foil in fluoride -EG electrolyte containing a small amount of potassium hydroxide, KOH at 60 V for 30 min. This electrolyte resulted in the formation of long nanotubes with an average length of 10 µm and diameter of 170 nm. For comparison, TiO2 nanotubes anodized in H2O added EG electrolyte which produces short nanotubes with an average tube length of 5 µm and diameter of 170 nm. It appears that the addition of KOH into the fluoride EG electrolyte accelerated the formation of the TiO2 nanotubes as it is believed that the chemical dissolution at the tips of the nanotubes is suppressed. Highly ordered TiO2 nanotubes anodized in KOH added EG electrolyte exhibited the photocurrent density of 2 mA/cm2, which is significantly higher than H2O added sample (1.5 mA/cm2).

Visible light to electrical energy conversion using photoelectrochemical cells

NASA Technical Reports Server (NTRS)

Wrighton, Mark S. (Inventor); Ellis, Arthur B. (Inventor); Kaiser, Steven W. (Inventor)

1983-01-01

Sustained conversion of low energy visible or near i.r. light (>1.25 eV) to electrical energy has been obtained using wet photoelectrochemical cells where there are no net chemical changes in the system. Stabilization of n-type semi-conductor anodes of CdS, CdSe, CdTe, GaP, GaAs and InP to photoanodic dissolution is achieved by employing selected alkaline solutions of Na.sub.2 S, Na.sub.2 S/S, Na.sub.2 Se, Na.sub.2 Se/Se, Na.sub.2 Te and Na.sub.2 Te/Te as the electrolyte. The oxidation of (poly) sulfide, (poly)selenide or (poly)telluride species occurs at the irradiated anode, and reduction of polysulfide, polyselenide or polytelluride species occurs at the dark Pt cathode of the photoelectrochemical cell. Optical to electrical energy conversion efficiencies approaching 15% at selected frequencies have been observed in some cells. The wavelength for the onset of photocurrent corresponds to the band gap of the particular anode material used in the cell.

Simulation of Corrosion Process for Structure with the Cellular Automata Method

NASA Astrophysics Data System (ADS)

Chen, M. C.; Wen, Q. Q.

2017-06-01

In this paper, from the mesoscopic point of view, under the assumption of metal corrosion damage evolution being a diffusive process, the cellular automata (CA) method was proposed to simulate numerically the uniform corrosion damage evolution of outer steel tube of concrete filled steel tubular columns subjected to corrosive environment, and the effects of corrosive agent concentration, dissolution probability and elapsed etching time on the corrosion damage evolution were also investigated. It was shown that corrosion damage increases nonlinearly with increasing elapsed etching time, and the longer the etching time, the more serious the corrosion damage; different concentration of corrosive agents had different impacts on the corrosion damage degree of the outer steel tube, but the difference between the impacts was very small; the heavier the concentration, the more serious the influence. The greater the dissolution probability, the more serious the corrosion damage of the outer steel tube, but with the increase of dissolution probability, the difference between its impacts on the corrosion damage became smaller and smaller. To validate present method, corrosion damage measurements for concrete filled square steel tubular columns (CFSSTCs) sealed at both their ends and immersed fully in a simulating acid rain solution were conducted, and Faraday’s law was used to predict their theoretical values. Meanwhile, the proposed CA mode was applied for the simulation of corrosion damage evolution of the CFSSTCs. It was shown by the comparisons of results from the three methods aforementioned that they were in good agreement, implying that the proposed method used for the simulation of corrosion damage evolution of concrete filled steel tubular columns is feasible and effective. It will open a new approach to study and evaluate further the corrosion damage, loading capacity and lifetime prediction of concrete filled steel tubular structures.

Electrical power production from low-grade waste heat using a thermally regenerative ethylenediamine battery

NASA Astrophysics Data System (ADS)

Rahimi, Mohammad; D'Angelo, Adriana; Gorski, Christopher A.; Scialdone, Onofrio; Logan, Bruce E.

2017-05-01

Thermally regenerative ammonia-based batteries (TRABs) have been developed to harvest low-grade waste heat as electricity. To improve the power production and anodic coulombic efficiency, the use of ethylenediamine as an alternative ligand to ammonia was explored here. The power density of the ethylenediamine-based battery (TRENB) was 85 ± 3 W m-2-electrode area with 2 M ethylenediamine, and 119 ± 4 W m-2 with 3 M ethylenediamine. This power density was 68% higher than that of TRAB. The energy density was 478 Wh m-3-anolyte, which was ∼50% higher than that produced by TRAB. The anodic coulombic efficiency of the TRENB was 77 ± 2%, which was more than twice that obtained using ammonia in a TRAB (35%). The higher anodic efficiency reduced the difference between the anode dissolution and cathode deposition rates, resulting in a process more suitable for closed loop operation. The thermal-electric efficiency based on ethylenediamine separation using waste heat was estimated to be 0.52%, which was lower than that of TRAB (0.86%), mainly due to the more complex separation process. However, this energy recovery could likely be improved through optimization of the ethylenediamine separation process.

Length-dependent corrosion behavior, Ni2+ release, cytocompatibility, and antibacterial ability of Ni-Ti-O nanopores anodically grown on biomedical NiTi alloy.

PubMed

Hang, Ruiqiang; Liu, Yanlian; Bai, Long; Zhang, Xiangyu; Huang, Xiaobo; Jia, Husheng; Tang, Bin

2018-08-01

In the present work, nickel-titanium-oxygen nanopores with different length (0.55-114 μm) were anodically grown on nearly equiatomic nickel-titanium (NiTi) alloy. Length-dependent corrosion behavior, nickel ion (Ni 2+ ) release, cytocompatibility, and antibacterial ability were investigated by electrochemical, analytical chemistry, and biological methods. The results show constructing nanoporous structure on the NiTi alloy improve its corrosion resistance. However, the anodized samples release more Ni 2+ than that of the bare NiTi alloy, suggesting chemical dissolution of the nanopores rather than electrochemical corrosion governs the Ni 2+ release. In addition, the Ni 2+ release amount increases with nanopore length. The anodized samples show good cytocompatibility when the nanopore length is <11 μm. Encouragingly, the length scale covers the one (1-11 μm) that the nanopores showing favorable antibacterial ability. Consequently, the nanopores with length in the range of 1-11 μm are promising as coatings of biomedical NiTi alloy for anti-infection, drug delivery, and other desirable applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Heterogeneous WS x/WO 3 thorn-bush nanofiber electrodes for sodium-ion batteries

DOE PAGES

Ryu, Won -Hee; Wilson, Hope; Sohn, Sungwoo; ...

2016-01-25

Heterogeneous electrode materials with hierarchical architectures promise to enable considerable improvement in future energy storage devices. In this study, we report on a tailored synthetic strategy used to create heterogeneous tungsten sulfide/oxide core–shell nanofiber materials with vertically and randomly aligned thorn-bush features, and we evaluate them as potential anode materials for high-performance Na-ion batteries. The WS x (2 ≤ x ≤ 3, amorphous WS 3 and crystalline WS 2) nanofiber is successfully prepared by electrospinning and subsequent calcination in a reducing atmosphere. To prevent capacity degradation of the WS x anodes originating from sulfur dissolution, a facile post-thermal treatment inmore » air is applied to form an oxide passivation surface. Interestingly, WO 3 thorn bundles are randomly grown on the nanofiber stem, resulting from the surface conversion. We elucidate the evolving morphological and structural features of the nanofibers during post-thermal treatment. The heterogeneous thorn-bush nanofiber electrodes deliver a high second discharge capacity of 791 mAh g –1 and improved cycle performance for 100 cycles compared to the pristine WS x nanofiber. Lastly, we show that this hierarchical design is effective in reducing sulfur dissolution, as shown by cycling analysis with counter Na electrodes.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shkrob, Ilya A.; Pupek, Krzysztof Z.; Gilbert, James A.

Lithium hexafluorophosphate (LiPF 6) is ubiquitous in commercial lithium-ion batteries, but it is hydrolytically unstable and corrosive on electrode surfaces. Using a more stable salt would confer multiple benefits for high-voltage operation, but many such electrolyte systems facilitate anodic dissolution and pitting corrosion of aluminum current collectors that negate their advantages. Lithium 2-trifluoromethyl-4,5-dicyanoimidazolide (LiTDI) is a new salt that was designed specifically for high-voltage cells. In this study we demonstrate that in carbonate electrolytes, LiTDI prevents anodic dissolution of Al current collectors, which places it into a select group of corrosion inhibitors. However, we also demonstrate that LiTDI becomes reducedmore » on lithiated graphite, undergoing sequential defluorination and yielding a thick and resistive solid-electrolyte interphase (SEI), which increases impedance and lowers electrode capacity. The mechanistic causes for this behavior are examined using computational chemistry methods in the light of recent spectroscopic studies. Here, we demonstrate that LiTDI reduction can be prevented by certain electrolyte additives, which include fluoroethylene carbonate, vinylene carbonate and lithium bis(oxalato)borate. This beneficial action is due to preferential reduction of these additives over LiTDI at a higher potential vs. Li/Li +, so the resulting SEI can prevent the direct reduction of LiTDI at lower potentials on the graphite electrode.« less

Electrolytic cell with reference electrode

DOEpatents

Kessie, Robert W.

1989-01-01

A reference electrode device is provided for a high temperature electrolytic cell used to electrolytically recover uranium from spent reactor fuel dissolved in an anode pool, the device having a glass tube to enclose the electrode and electrolyte and serve as a conductive membrane with the cell electrolyte, and an outer metal tube about the glass tube to serve as a shield and basket for any glass sections broken by handling of the tube to prevent their contact with the anode pool, the metal tube having perforations to provide access between the bulk of the cell electrolyte and glass membrane.

Reference electrode for electrolytic cell

DOEpatents

Kessie, R.W.

1988-07-28

A reference electrode device is provided for a high temperature electrolytic cell used to electrolytically recover uranium from spent reactor fuel dissolved in an anode pool, the device having a glass tube to enclose the electrode and electrolyte and serve as a conductive membrane with the cell electrolyte, and an outer metal tube about the glass tube to serve as a shield and basket for any glass sections broken by handling of the tube to prevent their contact with the anode pool, the metal tube having perforations to provide access between the bulk of the cell electrolyte and glass membrane. 4 figs.

Recycling rice husks for high-capacity lithium battery anodes

PubMed Central

Jung, Dae Soo; Ryou, Myung-Hyun; Sung, Yong Joo; Park, Seung Bin; Choi, Jang Wook

2013-01-01

The rice husk is the outer covering of a rice kernel and protects the inner ingredients from external attack by insects and bacteria. To perform this function while ventilating air and moisture, rice plants have developed unique nanoporous silica layers in their husks through years of natural evolution. Despite the massive amount of annual production near 108 tons worldwide, so far rice husks have been recycled only for low-value agricultural items. In an effort to recycle rice husks for high-value applications, we convert the silica to silicon and use it for high-capacity lithium battery anodes. Taking advantage of the interconnected nanoporous structure naturally existing in rice husks, the converted silicon exhibits excellent electrochemical performance as a lithium battery anode, suggesting that rice husks can be a massive resource for use in high-capacity lithium battery negative electrodes. PMID:23836636

Recycling rice husks for high-capacity lithium battery anodes.

PubMed

Jung, Dae Soo; Ryou, Myung-Hyun; Sung, Yong Joo; Park, Seung Bin; Choi, Jang Wook

2013-07-23

The rice husk is the outer covering of a rice kernel and protects the inner ingredients from external attack by insects and bacteria. To perform this function while ventilating air and moisture, rice plants have developed unique nanoporous silica layers in their husks through years of natural evolution. Despite the massive amount of annual production near 10(8) tons worldwide, so far rice husks have been recycled only for low-value agricultural items. In an effort to recycle rice husks for high-value applications, we convert the silica to silicon and use it for high-capacity lithium battery anodes. Taking advantage of the interconnected nanoporous structure naturally existing in rice husks, the converted silicon exhibits excellent electrochemical performance as a lithium battery anode, suggesting that rice husks can be a massive resource for use in high-capacity lithium battery negative electrodes.

Carbon Disulfide Cosolvent Electrolytes for High-Performance Lithium Sulfur Batteries.

PubMed

Gu, Sui; Wen, Zhaoyin; Qian, Rong; Jin, Jun; Wang, Qingsong; Wu, Meifen; Zhuo, Shangjun

2016-12-21

Development of lithium sulfur (Li-S) batteries with high Coulombic efficiency and long cycle stability remains challenging due to the dissolution and shuttle of polysulfides in electrolyte. Here, a novel additive, carbon disulfide (CS 2 ), to the organic electrolyte is reported to improve the cycling performance of Li-S batteries. The cells with the CS 2 -additive electrolyte exhibit high Coulombic efficiency and long cycle stability, showing average Coulombic efficiency >99% and a capacity retention of 88% over the entire 300 cycles. The function of the CS 2 additive is 2-fold: (1) it inhibits the migration of long-chain polysulfides to the anode by forming complexes with polysulfides and (2) it passivates electrode surfaces by inducing the protective coatings on both the anode and the cathode.

Nuclear fuel electrorefiner

DOEpatents

Ahluwalia, Rajesh K.; Hua, Thanh Q.

2004-02-10

The present invention relates to a nuclear fuel electrorefiner having a vessel containing a molten electrolyte pool floating on top of a cadmium pool. An anodic fuel dissolution basket and a high-efficiency cathode are suspended in the molten electrolyte pool. A shroud surrounds the fuel dissolution basket and the shroud is positioned so as to separate the electrolyte pool into an isolated electrolyte pool within the shroud and a bulk electrolyte pool outside the shroud. In operation, unwanted noble-metal fission products migrate downward into the cadmium pool and form precipitates where they are removed by a filter and separator assembly. Uranium values are transported by the cadmium pool from the isolated electrolyte pool to the bulk electrolyte pool, and then pass to the high-efficiency cathode where they are electrolytically deposited thereto.

Research on rechargeable oxygen electrodes

NASA Technical Reports Server (NTRS)

Giner, J.; Malachesky, P. A.; Holleck, G.

1971-01-01

Studies were carried out on a number of factors which may influence the behavior of the platinum electrocatalyst of oxygen electrodes for use in rechargeable metal-oxygen batteries or hydrogen-oxygen fuel cells. The effects of pretreatments for various potentials and added ionic species, which could be present in such systems, were studied with reguard to: (1) the state of surface oxidation, (2) platinum dissolution, (3) the kinetics of oxygen evolution and reduction (including the role of hydrogen peroxide), and (4) changes in porous electrode structure. These studies were carried out on smooth platinum, platinized platinum, and Teflon-bonded platinum black electrodes in carefully purified electrolyte solutions. The main factors which appear to affect rechargeable oxygen electrode performance and life are: (1) the buildup of a refractory anodic layer on extended cycling, and (2) the dissolution of platinum.

A multiphase interfacial model for the dissolution of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Jerden, James L.; Frey, Kurt; Ebert, William

2015-07-01

The Fuel Matrix Dissolution Model (FMDM) is an electrochemical reaction/diffusion model for the dissolution of spent uranium oxide fuel. The model was developed to provide radionuclide source terms for use in performance assessment calculations for various types of geologic repositories. It is based on mixed potential theory and consists of a two-phase fuel surface made up of UO2 and a noble metal bearing fission product phase in contact with groundwater. The corrosion potential at the surface of the dissolving fuel is calculated by balancing cathodic and anodic reactions occurring at the solution interfaces with UO2 and NMP surfaces. Dissolved oxygen and hydrogen peroxide generated by radiolysis of the groundwater are the major oxidizing agents that promote fuel dissolution. Several reactions occurring on noble metal alloy surfaces are electrically coupled to the UO2 and can catalyze or inhibit oxidative dissolution of the fuel. The most important of these is the oxidation of hydrogen, which counteracts the effects of oxidants (primarily H2O2 and O2). Inclusion of this reaction greatly decreases the oxidation of U(IV) and slows fuel dissolution significantly. In addition to radiolytic hydrogen, large quantities of hydrogen can be produced by the anoxic corrosion of steel structures within and near the fuel waste package. The model accurately predicts key experimental trends seen in literature data, the most important being the dramatic depression of the fuel dissolution rate by the presence of dissolved hydrogen at even relatively low concentrations (e.g., less than 1 mM). This hydrogen effect counteracts oxidation reactions and can limit fuel degradation to chemical dissolution, which results in radionuclide source term values that are four or five orders of magnitude lower than when oxidative dissolution processes are operative. This paper presents the scientific basis of the model, the approach for modeling used fuel in a disposal system, and preliminary calculations to demonstrate the application and value of the model.

Very Large Arrays of Bipolar Electrodes

DTIC Science & Technology

2013-01-01

two driving electrodes and a simple power supply. The system was designed to have faradic reactions occurring at the cathode end of each electrode...related to sensing chemistry present at the cathode end. Accordingly, a series of experiments was designed to determine the amount of current passing...reduction reaction occurs at the cathodic end of the BPE, it triggers the oxidation and dissolution of Ag metal present at the anodic pole. The loss of Ag

Heat pump water heater and method of making the same

DOEpatents

Mei, Viung C.; Tomlinson, John J.; Chen, Fang C.

2001-01-01

An improved heat pump water heater wherein the condenser assembly of the heat pump is inserted into the water tank through an existing opening in the top of the tank, the assembly comprising a tube-in-a-tube construction with an elongated cylindrical outer body heat exchanger having a closed bottom with the superheated refrigerant that exits the compressor of the heat pump entering the top of the outer body. As the refrigerant condenses along the interior surface of the outer body, the heat from the refrigerant is transferred to the water through the outer body. The refrigerant then enters the bottom of an inner body coaxially disposed within the outer body and exits the top of the inner body into the refrigerant conduit leading into the expansion device of the heat pump. The outer body, in a second embodiment of the invention, acts not only as a heat exchanger but also as the sacrificial anode in the water tank by being constructed of a metal which is more likely to corrode than the metal of the tank.

Hydrothermal alteration of deep fractured granite: Effects of dissolution and precipitation

NASA Astrophysics Data System (ADS)

Nishimoto, Shoji; Yoshida, Hidekazu

2010-03-01

This paper investigates the mineralogical effects of hydrothermal alteration at depth in fractures in granite. A fracture accompanied by an alteration halo and filled with clay was found at a depth of 200 m in a drill core through Toki granite, Gifu, central Japan. Microscopic observation, XRD, XRF, EPMA and SXAM investigations revealed that the microcrystalline clays consist of illite, quartz and pyrite and that the halo round the fracture can be subdivided into a phyllic zone adjacent to the fracture, surrounded by a propylitic zone in which Fe-phyllosilicates are present, and a distinctive outer alteration front characterized by plagioclase breakdown. The processes that result in these changes took place in three successive stages: 1) partial dissolution of plagioclase with partial chloritization of biotite; 2) biotite dissolution and precipitation of Fe-phyllosilicate in the dissolution pores; 3) dissolution of K-feldspar and Fe-phyllosilicate, and illite precipitation associated with development of microcracks. These hydrothermal alterations of the granite proceed mainly by a dissolution-precipitation process resulting from the infiltration of hydrothermal fluid along microcracks. Such infiltration causes locally high mobility of Al and increases the ratio of fluid to rock in the alteration halo. These results contribute to an understanding of how granitic rock becomes altered in orogenic fields such as the Japanese island arc.

An Insoluble Titanium-Lead Anode for Sulfate Electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferdman, Alla

2005-05-11

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 compositemore » 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. Prototypes having optimized composition and structure were produced for testing in operating conditions of copper electrowinning and EMD production. Bench-scale, mini-pilot scale and pilot scale tests were performed. The test anodes were of both a plate design and a flow-through cylindrical design. The cylindrical anodes were composed of cylinders containing titanium inner rods and fitting over titanium-lead bushings. The cylindrical design allows the electrolyte to flow through the anode, which enhances diffusion of the electrolyte reactants. The cylindrical anodes demonstrate higher mass transport capabilities and increased electrical efficiency compared to the plate anodes. Copper electrowinning represents the primary target market for the titanium-lead anode. A full-size cylindrical anode performance in copper electrowinning conditions was monitored over a year. The test anode to cathode voltage was stable in the 1.8 to 2.0 volt range. Copper cathode morphology was very smooth and uniform. There was no measurable anode weight loss during this time period. Quantitative chemical analysis of the anode surface showed that the lead content after testing remained at its initial level. No lead dissolution or transfer from the anode to the product occurred.A key benefit of the titanium-lead anode design is that cobalt additions to copper electrolyte should be eliminated. Cobalt is added to the electrolyte to help stabilize the lead oxide surface of conventional lead anodes. The presence of the titanium intimately mixed with the lead should eliminate the need for cobalt stabilization of the lead surface. The anode should last twice as long as the conventional lead anode. Energy savings should be achieved due to minimizing and stabilizing the anode-cathode distance in the electrowinning cells. The anode is easily substitutable into existing tankhouses without a rectifier change.The copper electrowinning test data indicate that the titanium-lead anode is a good candidate for further testing as a possible replacement for a conventional lead anode. A key consideration is the cost. Titanium costs have increased. One of the ways to get the anode cost down is manufacturing the anodes with fewer cylinders. Additional prototypes having different number of cylinders were constructed for a long-term commercial testing in a circuit without cobalt. The objective of the testing is to evaluate the need for cobalt, investigate the effect of decreasing the number of cylinders on the anode performance, and to optimize further the anode design in order to meet the operating requirements, minimize the voltage, maximize the life of the anode, and to balance this against a reasonable cost for the anode. It is anticipated that after testing of the additional prototypes, a whole cell commercial test will be conducted to complete evaluation of the titanium-lead anode costs/benefits.« less

GEIGER-MULLER TYPE COUNTER TUBE

DOEpatents

Fowler, I.L.; Watt, L.A.K.

1959-12-15

A single counter tube capable of responding to a wide range of intensities is described. The counter tube comprises a tubular cathode and an anode extending centrally of the cathode. The spacing between the outer surface of the anode and the inner surface of the cathode is varied along the length of the tube to provide different counting volumes in adjacent portions of the tube. A large counting volume in one portion adjacent to a low-energy absorption window gives adequate sensitivity for measuring lowintensity radiation, while a smaller volume with close electrode spacing is provided in the counter to make possible measurement of intense garnma radiation fields.

New insights into pre-lithiation kinetics of graphite anodes via nuclear magnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

Holtstiege, Florian; Schmuch, Richard; Winter, Martin; Brunklaus, Gunther; Placke, Tobias

2018-02-01

Pre-lithiation of anode materials can be an effective method to compensate active lithium loss which mainly occurs in the first few cycles of a lithium ion battery (LIB), due to electrolyte decomposition and solid electrolyte interphase (SEI) formation at the surface of the anode. There are many different pre-lithiation methods, whereas pre-lithiation using metallic lithium constitutes the most convenient and widely utilized lab procedure in literature. In this work, for the first time, solid state nuclear magnetic resonance spectroscopy (NMR) is applied to monitor the reaction kinetics of the pre-lithiation process of graphite with lithium. Based on static 7Li NMR, we can directly observe both the dissolution of lithium metal and parallel formation of LiCx species in the obtained NMR spectra with time. It is also shown that the degree of pre-lithiation as well as distribution of lithium metal on the electrode surface have a strong impact on the reaction kinetics of the pre-lithiation process and on the remaining amount of lithium metal. Overall, our findings are highly important for further optimization of pre-lithiation methods for LIB anode materials, both in terms of optimized pre-lithiation time and appropriate amounts of lithium metal.

Anodic activation of iron corrosion in clay media under water-saturated conditions at 90 degrees C: characterization of the corrosion interface.

PubMed

Schlegel, Michel L; Bataillon, Christian; Blanc, Cécile; Prêt, Dimitri; Foy, Eddy

2010-02-15

To understand the process governing iron corrosion in clay over centuries, the chemical and mineralogical properties of solids formed by free or anodically activated corrosion of iron in water-saturated clay at 90 degrees C over 4 months were probed using microscopic and spectroscopic techniques. Free corrosion led to the formation of an internal discontinuous thin (<3 microm thick) magnetite layer, an external layer of Fe-rich phyllosilicate, and a clay transformation layer containing Ca-doped siderite (Ca(0.2)Fe(0.8)CO(3)). The thickness of corroded iron equaled approximately 5-7 microm, consistent with previous studies. Anodic polarization resulted in unequally distributed corrosion, with some areas corrosion-free and others heavily corroded. Activated corrosion led to the formation of an inner magnetite layer, an intermediate Fe(2)CO(3)(OH)(2) (chukanovite) layer, an outer layer of Fe-rich 7 A-phyllosilicate, and a transformed matrix layer containing siderite (FeCO(3)). The corroded thickness was estimated to 85 microm, less than 30% of the value expected from the supplied anodic charge. The difference was accounted for by reoxidation at the anodically polarized surface of cathodically produced H(2)(g). Thus, free or anodically activated corroding conditions led to structurally similar interfaces, indicating that anodic polarization can be used to probe the long-term corrosion of iron in clay. Finally, corrosion products retained only half of Fe oxidized by anodic activation. Missing Fe probably migrated in the clay, where it could interact with radionuclides released by alteration of nuclear glass.

Antibacterial activity of microstructured sacrificial anode thin films by combination of silver with platinum group elements (platinum, palladium, iridium).

PubMed

Köller, Manfred; Bellova, Petri; Javid, Siyamak Memar; Motemani, Yahya; Khare, Chinmay; Sengstock, Christina; Tschulik, Kristina; Schildhauer, Thomas A; Ludwig, Alfred

2017-05-01

Five different Ag dots arrays (16 to 400dots/mm 2 ) were fabricated on a continuous platinum, palladium, or iridium thin film and for comparison also on titanium film by sputter deposition and photolithographic patterning. To analyze the antibacterial activity of these microstructured films Staphylococcus aureus (S. aureus) were placed onto the array surfaces and cultivated overnight. To analyze the viability of planktonic as well as surface adherent bacteria, the applied bacterial fluid was subsequently aspirated, plated on blood agar plates and adherent bacteria were detected by fluorescence microscopy. A particular antibacterial effect towards S. aureus was induced by Ag dot arrays on each of the platinum group thin film (sacrificial anode system for Ag) in contrast to Ag dot arrays fabricated on the Ti thin films (non-sacrificial anode system for Ag). Among platinum group elements the Ir-Ag system exerted the highest antibacterial activity which was accompanied by most advanced dissolution of the Ag dots and Ag ion release compared to Ag dots on Pt or Pd. Copyright © 2016 Elsevier B.V. All rights reserved.

Can CO-tolerant Anodes be Economically Viable for PEMFC Applications with Reformates?

DOE PAGES

He, P.; Zhang, Y.; Ye., S.; ...

2014-10-05

Several years ago, the answer to this question was negative based on the criteria for an anode with <0.1 mg cm-2 of platinum group metals to perform similarly without and with 50 ppm CO in hydrogen proton exchange membrane fuel cells (PEMFCs). Now, with the amount of CO impurities reduced to 10 ppm in reformates, a <1% performance loss with a 1.5% air-bleed has become a reasonable target. The CO-tolerant catalyst also needs to be dissolution resistant up to 0.93 V, viz., the potential experienced at the anode during startup and shutdown of the fuel cells. We recently demonstrated ourmore » ability to simultaneously enhance activity and stability by using single crystalline Ru@Pt core-shell nanocatalysts. Here, we report that the performance target with reformates was met using bilayer-thick Ru@Pt core-shell nanocatalysts with 0.047 mg cm-2 Pt and 0.024 mg cm-2 Ru loading, supporting a positive prognosis for the economically viable use of reformates in PEMFC applications.« less

Effect of various de-anodizing techniques on the surface stability of non-colored and colored nanoporous AAO films in acidic solution

NASA Astrophysics Data System (ADS)

Awad, Ahmed M.; Shehata, Omnia S.; Heakal, Fakiha El-Taib

2015-12-01

Anodic aluminum oxide (AAO) is well known as an important nanostructured material, and a useful template in the fabrication of nanostructures. Nanoporous anodic alumina (PAA) with high open porosity was prepared by adopting three de-anodizing regimes following the first anodizing step and preceding the second one. The de-anodizing methods include electrolytic etching (EE) and chemical etching using either phosphoric acid (PE) or sodium hydroxide (HE) solutions. Three of the obtained AAO samples were black colored by electrodeposition of copper nanoparticles in their pores. Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques were used to characterize the electrochemical performance of the two sets of the prepared samples. In general, the data obtained in aggressive aerated 0.5 M HCl solution demonstrated dissimilar behavior for the three prepared samples despite that the second anodizing step was the same for all of them. The data indicated that the resistance and thickness of the inner barrier part of nano-PAA film, are the main controlling factors determining its stability. On the other hand, coloring the film decreased its stability due to the galvanic effect. The difference in the electrochemical behavior of the three colored samples was discussed based on the difference in both the pore size and thickness of the outer porous part of PAA film as supported by SEM, TEM and cross-sectional micrographs. These results can thus contribute for better engineering applications of nanoporous AAO.

Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cell Stacks

NASA Technical Reports Server (NTRS)

Valdez, Thomas I.; Firdosy, S.; Koel, B. E.; Narayanan, S. R.

2005-01-01

Dissolution of ruthenium was observed in the 80-cell stack. Duration testing was performed in single cell MEAs to determine the pathway of cell degradation. EDAX analysis on each of the single cell MEAs has shown that the Johnson Matthey commercial catalyst is stable in DMFC operation for 250 hours, no ruthenium dissolution was observed. Changes in the hydrophobicity of the cathode backing papers was minimum. Electrode polarization analysis revealed that the MEA performance loss is attributed to changes in the cathode catalyst layer. Ruthenium migration does not seem to occur during cell operation but can occur when methanol is absent from the anode compartment, the cathode compartment has access to air, and the cells in the stack are electrically connected to a load (Shunt Currents). The open-to-air cathode stack design allowed for: a) The MEAs to have continual access to oxygen; and b) The stack to sustain shunt currents. Ruthenium dissolution in a DMFC stack can be prevented by: a) Developing an internally manifolded stacks that seal reactant compartments when not in operation; b) Bringing the cell voltages to zero quickly when not in operation; and c) Limiting the total number of cells to 25 in an effort to limit shunt currents.

Monopolar fuel cell stack coupled together without use of top or bottom cover plates or tie rods

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R. (Inventor); Valdez, Thomas I. (Inventor)

2009-01-01

A monopolar fuel cell stack comprises a plurality of sealed unit cells coupled together. Each unit cell comprises two outer cathodes adjacent to corresponding membrane electrode assemblies and a center anode plate. An inlet and outlet manifold are coupled to the anode plate and communicate with a channel therein. Fuel flows from the inlet manifold through the channel in contact with the anode plate and flows out through the outlet manifold. The inlet and outlet manifolds are arranged to couple to the inlet and outlet manifolds respectively of an adjacent one of the plurality of unit cells to permit fuel flow in common into all of the inlet manifolds of the plurality of the unit cells when coupled together in a stack and out of all of the outlet manifolds of the plurality of unit cells when coupled together in a stack.

The microbe electric: conversion of organic matter to electricity.

PubMed

Lovley, Derek R

2008-12-01

Broad application of microbial fuel cells will require substantial increases in current density. A better understanding of the microbiology of these systems may help. Recent studies have greatly expanded the range of microorganisms known to function either as electrode-reducing microorganisms at the anode or as electrode-oxidizing microorganisms at the cathode. Microorganisms that can completely oxidize organic compounds with an electrode serving as the sole electron acceptor are expected to be the primary contributors to power production. Several mechanisms for electron transfer to anodes have been proposed including: direct electron transfer via outer-surface c-type cytochromes, long-range electron transfer via microbial nanowires, electron flow through a conductive biofilm matrix containing cytochromes, and soluble electron shuttles. Which mechanisms are most important depend on the microorganisms and the thickness of the anode biofilm. Emerging systems biology approaches to the study, design, and evolution of microorganisms interacting with electrodes are expected to contribute to improved microbial fuel cells.

Uranium Anodic Dissolution under Slightly Alkaline Conditions Progress Report Full-Scale Demonstration with DU Foil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gelis, A.; Brown, M. A.; Wiedmeyer, S.

2014-02-18

Argonne National Laboratory (Argonne) is developing an alternative method for digesting irradiated low enriched uranium (LEU) foil targets to produce 99Mo in neutral/alkaline media. This method consists of the electrolytic dissolution of irradiated uranium foil in sodium bicarbonate solution, followed by precipitation of base-insoluble fission and activation products, and uranyl-carbonate species with CaO. The addition of CaO is vital for the effective anion exchange separation of 99MoO 4 2- from the fission products, since most of the interfering anions (e.g., CO 3 2-) are removed from the solution, while molybdate remains in solution. An anion exchange is used to retainmore » and to purify the 99Mo from the filtrate. The electrochemical dissolver has been designed and fabricated in 304 stainless-steel (SS), and tested for the dissolution of a full-size depleted uranium (DU) target, wrapped in Al foil. Future work will include testing with low-burn-up DU foil at Argonne and later with high-burn-up LEU foils at Oak Ridge National Laboratory.« less

Manufacturing of Dysprosium-Iron Alloys by Electrolysis in Fluoride-Based Electrolytes. Electrolysis in a Laboratory-Scale Cell

NASA Astrophysics Data System (ADS)

Martinez, Ana Maria; Osen, Karen Sende; Støre, Anne; Gudbrandsen, Henrik; Kjos, Ole Sigmund; Solheim, Asbjørn; Wang, Zhaohui; Oury, Alexandre; Namy, Patrick

2018-04-01

Electrolytic production of light rare earth elements and rare earth alloys with transition elements takes place in a fluoride-based electrolyte using rare earth oxides as raw material. The optimization of this method, mainly in terms of the energy efficiency and environmental impact control, is rather challenging. Anode effects, evolution of fluorine-containing compounds and side cathode reactions could largely be minimized by good control of the amount of rare earth oxide species dissolved in the fluoride-based electrolyte and their dissolution rate. The Dy2O3 feed rate needed for stable cell operation was studied by following up the anode voltage and gas analysis. On-line analysis of the cell off-gases by FTIR showed that the electrochemical reaction for the formation of Dy-Fe alloy gives mainly CO gas and that CF4 is starting to evolve gradually at anode voltages of ca. 3.25 V. The limiting current density for the discharge of the oxide ions at the graphite anode was in the range of 0.1 to 0.18 A cm-2 at dissolved Dy2O3 contents of ca. 1 wt pct. Modeling of the laboratory cell reactor was also carried out by implementing two models, i.e., an electrical model simulating the current density distribution at the electrodes and a laminal bubbly flow model that explains the electrolyte velocity induced by gas bubble production at the anode.

Al-Air Batteries: Fundamental Thermodynamic Limitations from First Principles Theory

NASA Astrophysics Data System (ADS)

Chen, Leanne D.; Noerskov, Jens K.; Luntz, Alan C.

2015-03-01

The Al-air battery possesses high theoretical specific energy (4140 Wh/kg) and is therefore an attractive candidate for vehicle propulsion applications. However, the experimentally observed open-circuit potential is much lower than what thermodynamics predicts, and this potential loss is widely believed to be an effect of corrosion. We present a detailed study of the Al-air battery using density functional theory. The results suggest that the difference between bulk thermodynamic and surface potentials is due to both the effects of asymmetry in multi-electron transfer reactions that define the anodic dissolution of Al and, more importantly, a large chemical step inherent to the formation of bulk Al(OH)3 from surface intermediates. The former results in an energy loss of 3%, while the latter accounts for 14 -29% of the total thermodynamic energy depending on the surface site where dissolution occurs. Therefore, the maximum open-circuit potential of the Al anode is only -1.87 V vs. SHE in the absence of thermal excitations, contrary to -2.34 V predicted by bulk thermodynamics at pH 14.6. This is a fundamental limitation of the system and governs the maximum output potential, which cannot be improved even if corrosion effects were completely suppressed. Supported by the Natural Sciences and Engineering Research Council of Canada and the ReLiable Project (#11-116792) funded by the Danish Council for Strategic Research.

Electron transfer processes occurring on platinum neural stimulating electrodes: pulsing experiments for cathodic-first/charge-balanced/biphasic pulses for 0.566 ≤ k ≤ 2.3 in oxygenated and deoxygenated sulfuric acid.

PubMed

Kumsa, Doe W; Montague, Fred W; Hudak, Eric M; Mortimer, J Thomas

2016-10-01

The application of a train of cathodic-first/charge-balanced/biphasic pulses applied to a platinum electrode resulted in a positive creep of the anodic phase potential that increases with increasing charge injection but reaches a steady-state value before 1000 pulses have been delivered. The increase follows from the fact that charge going into irreversible reactions occurring during the anodic phase must equal the charge going into irreversible reactions during the cathodic phase for charge-balanced pulses. In an oxygenated electrolyte the drift of the measured positive potential moved into the platinum oxidation region of the i(V e) profile when the charge injection level exceeds k = 1.75. Platinum dissolution may occur in this region and k = 1.75 defines a boundary between damaging and non-damaging levels on the Shannon Plot. In a very low oxygen environment, the positive potential remained below the platinum oxidation region for the highest charge injection values studied, k = 2.3. The results support the hypothesis that platinum dissolution is the defining factor for the Shannon limit, k = 1.75. Numerous instrumentation issues were encountered in the course of making measurements. The solutions to these issues are provided.

Chemical stability of Lithium 2-trifluoromethyl-4,5-dicyanoimidazolide, an electrolyte salt for Li-ion cells

DOE PAGES

Shkrob, Ilya A.; Pupek, Krzysztof Z.; Gilbert, James A.; ...

2016-12-01

Lithium hexafluorophosphate (LiPF 6) is ubiquitous in commercial lithium-ion batteries, but it is hydrolytically unstable and corrosive on electrode surfaces. Using a more stable salt would confer multiple benefits for high-voltage operation, but many such electrolyte systems facilitate anodic dissolution and pitting corrosion of aluminum current collectors that negate their advantages. Lithium 2-trifluoromethyl-4,5-dicyanoimidazolide (LiTDI) is a new salt that was designed specifically for high-voltage cells. In this study we demonstrate that in carbonate electrolytes, LiTDI prevents anodic dissolution of Al current collectors, which places it into a select group of corrosion inhibitors. However, we also demonstrate that LiTDI becomes reducedmore » on lithiated graphite, undergoing sequential defluorination and yielding a thick and resistive solid-electrolyte interphase (SEI), which increases impedance and lowers electrode capacity. The mechanistic causes for this behavior are examined using computational chemistry methods in the light of recent spectroscopic studies. Here, we demonstrate that LiTDI reduction can be prevented by certain electrolyte additives, which include fluoroethylene carbonate, vinylene carbonate and lithium bis(oxalato)borate. This beneficial action is due to preferential reduction of these additives over LiTDI at a higher potential vs. Li/Li +, so the resulting SEI can prevent the direct reduction of LiTDI at lower potentials on the graphite electrode.« less

Dissolution of aragonite-strontianite solid solutions in nonstoichiometric Sr (HCO3)2-Ca (HCO3)2-CO2-H2O solutions

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.; Glynn, P.D.; Blum, A.E.

1992-01-01

Synthetic strontianite-aragonite solid-solution minerals were dissolved in CO2-saturated non-stoichiometric solutions of Sr(HCO3)2 and Ca(HCO3)2 at 25??C. The results show that none of the dissolution reactions reach thermodynamic equilibrium. Congruent dissolution in Ca(HCO3)2 solutions either attains or closely approaches stoichiometric saturation with respect to the dissolving solid. In Sr(HCO3)2 solutions the reactions usually become incongruent, precipitating a Sr-rich phase before reaching stoichiometric saturation. Dissolution of mechanical mixtures of solids approaches stoichiometric saturation with respect to the least stable solid in the mixture. Surface uptake from subsaturated bulk solutions was observed in the initial minutes of dissolution. This surficial phase is 0-10 atomic layers thick in Sr(HCO3)2 solutions and 0-4 layers thick in Ca(HCO3)2 solutions, and subsequently dissolves and/or recrystallizes, usually within 6 min of reaction. The initial transient surface precipitation (recrystallization) process is followed by congruent dissolution of the original solid which proceeds to stoichiometric saturation, or until the precipitation of a more stable Sr-rich solid. The compositions of secondary precipitates do not correspond to thermodynamic equilibrium or stoichiometric saturation states. X-ray photoelectron spectroscopy (XPS) measurements indicate the formation of solid solutions on surfaces of aragonite and strontianite single crystals immersed in Sr(HCO3)2 and Ca(HCO3)2 solutions, respectively. In Sr(HCO3)2 solutions, the XPS signal from the outer ~ 60 A?? on aragonite indicates a composition of 16 mol% SrCO3 after only 2 min of contact, and 14-18 mol% SrCO3 after 3 weeks of contact. The strontianite surface averages approximately 22 mol% CaCO3 after 2 min of contact with Ca(HCO3)2 solution, and is 34-39 mol% CaCO3 after 3 weeks of contact. XPS analysis suggests the surface composition is zoned with somewhat greater enrichment in the outer ~25 A?? (as much as 26 mol% SrCO3 on aragonite and 44 mol% CaCO3 on strontianite). The results indicate rapid formation of a solid-solution surface phase from subsaturated aqueous solutions. The surface phase continually adjusts in composition in response to changes in composition of the bulk fluid as net dissolution proceeds. Dissolution rates of the endmembers are greatly reduced in nonstoichiometric solutions relative to dissolution rates observed in stoichiometric solutions. All solids dissolve more slowly in solutions spiked with the least soluble component ((Sr(HCO3)2)) than in solutions spiked with the more soluble component (Ca(HCO3)2), an effect that becomes increasingly significant as stoichiometric saturation is approached. It is proposed that the formation of a non-stoichiometric surface reactive zone significantly decreases dissolution rates. ?? 1992.

Lithium-sulfur batteries: electrochemistry, materials, and prospects.

PubMed

Yin, Ya-Xia; Xin, Sen; Guo, Yu-Guo; Wan, Li-Jun

2013-12-09

With the increasing demand for efficient and economic energy storage, Li-S batteries have become attractive candidates for the next-generation high-energy rechargeable Li batteries because of their high theoretical energy density and cost effectiveness. Starting from a brief history of Li-S batteries, this Review introduces the electrochemistry of Li-S batteries, and discusses issues resulting from the electrochemistry, such as the electroactivity and the polysulfide dissolution. To address these critical issues, recent advances in Li-S batteries are summarized, including the S cathode, Li anode, electrolyte, and new designs of Li-S batteries with a metallic Li-free anode. Constructing S molecules confined in the conductive microporous carbon materials to improve the cyclability of Li-S batteries serves as a prospective strategy for the industry in the future. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbon-shell-constrained silicon cluster derived from Al-Si alloy as long-cycling life lithium ion batteries anode

NASA Astrophysics Data System (ADS)

Su, Junming; Zhang, Congcong; Chen, Xiang; Liu, Siyang; Huang, Tao; Yu, Aishui

2018-03-01

Although silicon is the most promising anode material for Li-ion batteries, large volume expansion during lithiation and delithiation is the main obstacle limiting the commercial application of silicon anodes. There are two ways to alleviate volume expansion and prevent further pulverization of a Si anode: fabrication of a rational nanostructure possessing void spaces and uniform distribution of the conducting sites, without a good balance effect in mitigating the limiting factors and enhancing battery performance. In this paper, we propose a novel nanostructure - a carbon-shell-constrained Si cluster (Si/C shell) with both adequate void space and good distribution of electrical contact sites to guarantee homogeneous lithiation in the initial cycle. Benefiting from the ability to maintain electrical conductivity of the outer carbon shell, even after cluster fragmentation, the Si/C shell synthesized from low-cost commercial Al-Si alloy spheres can deliver 0.03% capacity loss from 100th to 1000th cycles at a current density of 1 A g-1. The Si/C shell sample with the dual functional structure mentioned above can also maintain its own nanostructure during cycling and deliver excellent rate performance. It is a concise and scalable strategy which can simplify the preparation of other alloy anode materials for Li-ion batteries.

Thermionic energy converters

DOEpatents

Monroe, Jr., James E.

1977-08-09

A thermionic device for converting nuclear energy into electrical energy comprising a tubular anode spaced from and surrounding a cylindrical cathode, the cathode having an outer emitting surface of ruthenium, and nuclear fuel on the inner cylindrical surface. The nuclear fuel is a ceramic composition of fissionable material in a metal matrix. An axial void is provided to collect and contain fission product gases.

Transmission-line-circuit model of an 85-TW, 25-MA pulsed-power accelerator

NASA Astrophysics Data System (ADS)

Hutsel, B. T.; Corcoran, P. A.; Cuneo, M. E.; Gomez, M. R.; Hess, M. H.; Hinshelwood, D. D.; Jennings, C. A.; Laity, G. R.; Lamppa, D. C.; McBride, R. D.; Moore, J. K.; Myers, A.; Rose, D. V.; Slutz, S. A.; Stygar, W. A.; Waisman, E. M.; Welch, D. R.; Whitney, B. A.

2018-03-01

We have developed a physics-based transmission-line-circuit model of the Z pulsed-power accelerator. The 33-m-diameter Z machine generates a peak electrical power as high as 85 TW, and delivers as much as 25 MA to a physics load. The circuit model is used to design and analyze experiments conducted on Z. The model consists of 36 networks of transmission-line-circuit elements and resistors that represent each of Zs 36 modules. The model of each module includes a Marx generator, intermediate-energy-storage capacitor, laser-triggered gas switch, pulse-forming line, self-break water switches, and tri-plate transmission lines. The circuit model also includes elements that represent Zs water convolute, vacuum insulator stack, four parallel outer magnetically insulated vacuum transmission lines (MITLs), double-post-hole vacuum convolute, inner vacuum MITL, and physics load. Within the vacuum-transmission-line system the model conducts analytic calculations of current loss. To calculate the loss, the model simulates the following processes: (i) electron emission from MITL cathode surfaces wherever an electric-field threshold has been exceeded; (ii) electron loss in the MITLs before magnetic insulation has been established; (iii) flow of electrons emitted by the outer-MITL cathodes after insulation has been established; (iv) closure of MITL anode-cathode (AK) gaps due to expansion of cathode plasma; (v) energy loss to MITL conductors operated at high lineal current densities; (vi) heating of MITL-anode surfaces due to conduction current and deposition of electron kinetic energy; (vii) negative-space-charge-enhanced ion emission from MITL anode surfaces wherever an anode-surface-temperature threshold has been exceeded; and (viii) closure of MITL AK gaps due to expansion of anode plasma. The circuit model is expected to be most accurate when the fractional current loss is small. We have performed circuit simulations of 52 Z experiments conducted with a variety of accelerator configurations and load-impedance time histories. For these experiments, the apparent fractional current loss varies from 0% to 20%. Results of the circuit simulations agree with data acquired on 52 shots to within 2%.

Application of Electro Chemical Machining for materials used in extreme conditions

NASA Astrophysics Data System (ADS)

Pandilov, Z.

2018-03-01

Electro-Chemical Machining (ECM) is the generic term for a variety of electrochemical processes. ECM is used to machine work pieces from metal and metal alloys irrespective of their hardness, strength or thermal properties, through the anodic dissolution, in aerospace, automotive, construction, medical equipment, micro-systems and power supply industries. The Electro Chemical Machining is extremely suitable for machining of materials used in extreme conditions. General overview of the Electro-Chemical Machining and its application for different materials used in extreme conditions is presented.

Effect of hydrogen on cathodic corrosion of titanium aluminide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, K.W.; Jin, J.W.; Qiao, L.J.

1996-01-01

Cathodic corrosion of titanium aluminide (TiAl) during hydrogen charging in various acidic aqueous solutions and in molten salt at 160 C was studied. At constant potential, the rate of cathodic corrosion (V) was much higher than during anodic dissolution, and V increased linearly with increasing current. V was 10 times higher in the acid solution than in the salt solution under the same current. Disruption of the surface film by local hydride formation during cathodic polarization was shown to be the key step.

Interfacial Chemistry Regulation via a Skin-Grafting Strategy Enables High-Performance Lithium-Metal Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Yue; Zhao, Yuming; Li, Yuguang C.

The lithium (Li) metal anode suffers severe interfacial instability from its high reactivity toward liquid electrolytes, especially carbonate-based electrolytes, resulting in poor electrochemical performance of batteries that use 4 V high-capacity cathodes. In this paper, we report a new skin-grafting strategy that stabilizes the Li metal–liquid electrolyte interface by coating the Li metal surface with poly((N-2,2-dimethyl-1,3-dioxolane-4-methyl)-5-norbornene-exo-2,3-dicarboximide), a chemically and electrochemically active polymer layer. This layer, composed of cyclic ether groups with a stiff polycyclic main chain, serves as a grafted polymer skin on the Li metal anode not only to incorporate ether-based polymeric components into the solid-electrolyte interphase (SEI) butmore » also to accommodate Li deposition/dissolution under the skin in a dendrite/moss-free manner. Consequently, a Li-metal battery employing a Li metal anode with the grafted skin paired with LiNi 0.5Co 0.2Mn 0.3O 2 cathode has a 90.0% capacity retention after 400 charge/discharge cycles and a capacity of 1.2 mAh/cm 2 in a carbonate-based electrolyte. Finally, this proof-of-concept study provides a new direction for regulating the interfacial chemistry of Li metal anodes and for enabling high-performance Li-metal batteries.« less

Interfacial Chemistry Regulation via a Skin-Grafting Strategy Enables High-Performance Lithium-Metal Batteries

DOE PAGES

Gao, Yue; Zhao, Yuming; Li, Yuguang C.; ...

2017-10-06

The lithium (Li) metal anode suffers severe interfacial instability from its high reactivity toward liquid electrolytes, especially carbonate-based electrolytes, resulting in poor electrochemical performance of batteries that use 4 V high-capacity cathodes. In this paper, we report a new skin-grafting strategy that stabilizes the Li metal–liquid electrolyte interface by coating the Li metal surface with poly((N-2,2-dimethyl-1,3-dioxolane-4-methyl)-5-norbornene-exo-2,3-dicarboximide), a chemically and electrochemically active polymer layer. This layer, composed of cyclic ether groups with a stiff polycyclic main chain, serves as a grafted polymer skin on the Li metal anode not only to incorporate ether-based polymeric components into the solid-electrolyte interphase (SEI) butmore » also to accommodate Li deposition/dissolution under the skin in a dendrite/moss-free manner. Consequently, a Li-metal battery employing a Li metal anode with the grafted skin paired with LiNi 0.5Co 0.2Mn 0.3O 2 cathode has a 90.0% capacity retention after 400 charge/discharge cycles and a capacity of 1.2 mAh/cm 2 in a carbonate-based electrolyte. Finally, this proof-of-concept study provides a new direction for regulating the interfacial chemistry of Li metal anodes and for enabling high-performance Li-metal batteries.« less

Molten Salt Electrolysis of MgCl2 in a Cell with Rapid Chlorine Removal Feature

NASA Astrophysics Data System (ADS)

Demirci, Gökhan; Karakaya, İshak

An experimental electrolytic magnesium production cell was designed to remove chlorine gas from the electrolyte rapidly and demonstrate the beneficial effects of reduced chlorine dissolution into the molten salt electrolyte. The back reaction that is the main cause of current losses in electrolytic magnesium production was reduced as a result of effective separation of electrode products and decreased contact time of chlorine gas with the electrolyte. Moreover, smaller inter electrode distances employed and lower chlorine gas present on the anode surface made it possible to work at low cell voltages. Electrolytic cell was tested at different current densities. Energy consumption of 7.0 kWh kg-1 Mg that is slightly above the theoretical minimum, 6.2 kWh kg-1 Mg, at 0.68 Acm-2 anodic current density was achieved for a MgCl2/NaCl/KCl electrolyte.

Corrosion behavior and microstructures of experimental Ti-Au alloys.

PubMed

Takahashi, Masatoshi; Kikuchi, Masafumi; Takada, Yukyo; Okuno, Osamu; Okabe, Toru

2004-06-01

Anodic polarization was performed in 0.9% NaCl and 1% lactic acid solutions to characterize the relationship between the corrosion behavior and microstructures of cast Ti-Au (5-40%) alloys. An abrupt increase in the current density occurred at approximately 0.6 V vs. SCE for the 30% and 40% Au alloys in the 0.9% NaCl solution. The microstructures after corrosion testing indicated that this breakdown may have been caused by the preferential dissolution of the Ti3Au. However, the potential for preferential dissolution was higher than the breakdown potential of stainless steel or Co-Cr alloy, which meant that the corrosion resistance of the Ti-Au alloys was superior. In 1% lactic acid solution, the corrosion resistance of the Ti-Au alloys was excellent, with no breakdown at any composition. In the present test solutions, the Ti-Au alloys up to 20% Au had good corrosion resistance comparable to that for pure titanium.

Microstructural Aspects of Localized Corrosion Behavior of Mg Alloys

NASA Astrophysics Data System (ADS)

Chu, Peng-Wei

Combining high specific strength and unique electrochemical properties, magnesium (Mg) alloys are promising lightweight materials for various applications from automotive, consumer electronics, biomedical body implant, to battery electrodes. Engineering solutions such as coatings have enabled the use of Mg alloys, despite their intrinsic low corrosion resistance. Consequently, the fundamental mechanisms responsible for the unique localized corrosion behavior of bare Mg alloys, the associated abnormal hydrogen evolution response, and the relationships between corrosion behavior and alloy microstructure are still unsolved. This thesis aims to uncover the specificities of Mg corrosion and the roles of alloy chemistry and microstructure. To this end, multiscale site-specific microstructure characterization techniques, including in situ optical microscopy, scanning electron microscopy with focused ion beam milling, and transmission electron microscopy, combined with electrochemical analysis and hydrogen evolution rate monitoring, were performed on pure Mg and selected Mg alloys under free corrosion and anodic polarization, revealing key new information on the propagation mode of localized corrosion and the role of alloy microstructures, thereby confirming or disproving the validity of previously proposed corrosion models. Uniform surface corrosion film on Mg alloys immersed in NaCl solution consisted a bi-layered structure, with a porous Mg(OH)2 outer layer on top of a MgO inner layer. Presence of fine scale precipitates in Mg alloys interacted with the corrosion reaction front, reducing the corrosion rate and surface corrosion film thickness. Protruding hemispherical dome-like corrosion products, accompanied by growing hydrogen bubbles, formed on top of the impurity particles in Mg alloys by deposition of Mg(OH)2 via a microgalvanic effect. Localized corrosion on Mg alloys under both free immersion and anodic polarization was found to be governed by a common mechanism, with the corrosion front propagating laterally a few mum inside the alloy and underneath the surface corrosion film, with finger-like features aligned with (0001) Mg basal planes at the localized corrosion/alloy interface. Rising streams of hydrogen bubbles were found to follow the anodic dissolution of Mg and formation of Mg(OH)2 corrosion products at the propagating localized corrosion fronts. Alloying elements segregation to the grain boundaries showed the ability to stop localized corrosion propagation momentarily. By revealing the microstructure of corrosion features on Mg alloys, a descriptive model was proposed. Relationships between the corrosion behavior and alloy microstructures were also identified. This microscopic information can serve as a guideline for future development of Mg alloys by tailoring the microstructure to achieve proper corrosion responses for applications under different environments.

Dry compliant seal for phosphoric acid fuel cell

DOEpatents

Granata, Jr., Samuel J.; Woodle, Boyd M.

1990-01-01

A dry compliant overlapping seal for a phosphoric acid fuel cell preformed f non-compliant Teflon to make an anode seal frame that encircles an anode assembly, a cathode seal frame that encircles a cathode assembly and a compliant seal frame made of expanded Teflon, generally encircling a matrix assembly. Each frame has a thickness selected to accommodate various tolerances of the fuel cell elements and are either bonded to one of the other frames or to a bipolar or end plate. One of the non-compliant frames is wider than the other frames forming an overlap of the matrix over the wider seal frame, which cooperates with electrolyte permeating the matrix to form a wet seal within the fuel cell that prevents process gases from intermixing at the periphery of the fuel cell and a dry seal surrounding the cell to keep electrolyte from the periphery thereof. The frames may be made in one piece, in L-shaped portions or in strips and have an outer perimeter which registers with the outer perimeter of bipolar or end plates to form surfaces upon which flanges of pan shaped, gas manifolds can be sealed.

Tuning the Outward to Inward Swelling in Lithiated Silicon Nanotubes via Surface Oxide Coating

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jiangwei; Luo, Hao; Liu, Yang

2016-09-14

The electrochemically-induced mechanical degradation hinders the application of Si anodes in advanced lithium-ion batteries. Hollow structures and surface coatings have been often used to mitigate the degradation of Si-based anodes. However, the structural change and degradation mechanism during lithiation/delithiation of hollow Si structures with coatings remain unclear. Here, we combine in situ TEM experiment and chemomechanical modeling to study the electrochemically induced swelling of amorphous-Si (a-Si) nanotubes with different thicknesses of surface SiOx layers. Surprisingly, we find that no inward expansion occurs at the inner surface during lithiation of a-Si nanotubes with native oxides. In contrast, inward expansion can bemore » induced by increasing the thickness of SiOx on the outer surface. Moreover, both the sandwich lithiation mechanism and two-stage lithiation process in a-Si nanotubes remain unchanged with the increasing thickness of surface coatings. Our chemomechanical modeling reveals the mechanical confinement effects in lithiated a-Si nanotubes with and without SiOx coatings. This work not only provides insights into the degradation of nanotube anodes with surface coatings, but also sheds light onto the optimal design of hollow anodes for high-performance lithium-ion batteries.« less

Tin anode for sodium-ion batteries using natural wood fiber as a mechanical buffer and electrolyte reservoir.

PubMed

Zhu, Hongli; Jia, Zheng; Chen, Yuchen; Weadock, Nicholas; Wan, Jiayu; Vaaland, Oeyvind; Han, Xiaogang; Li, Teng; Hu, Liangbing

2013-07-10

Sodium (Na)-ion batteries offer an attractive option for low cost grid scale storage due to the abundance of Na. Tin (Sn) is touted as a high capacity anode for Na-ion batteries with a high theoretical capacity of 847 mAh/g, but it has several limitations such as large volume expansion with cycling, slow kinetics, and unstable solid electrolyte interphase (SEI) formation. In this article, we demonstrate that an anode consisting of a Sn thin film deposited on a hierarchical wood fiber substrate simultaneously addresses all the challenges associated with Sn anodes. The soft nature of wood fibers effectively releases the mechanical stresses associated with the sodiation process, and the mesoporous structure functions as an electrolyte reservoir that allows for ion transport through the outer and inner surface of the fiber. These properties are confirmed experimentally and computationally. A stable cycling performance of 400 cycles with an initial capacity of 339 mAh/g is demonstrated; a significant improvement over other reported Sn nanostructures. The soft and mesoporous wood fiber substrate can be utilized as a new platform for low cost Na-ion batteries.

Flavin redox bifurcation as a mechanism for controlling the direction of electron flow during extracellular electron transfer.

PubMed

Okamoto, Akihiro; Hashimoto, Kazuhito; Nealson, Kenneth H

2014-10-06

The iron-reducing bacterium Shewanella oneidensis MR-1 has a dual directional electronic conduit involving 40 heme redox centers in flavin-binding outer-membrane c-type cytochromes (OM c-Cyts). While the mechanism for electron export from the OM c-Cyts to an anode is well understood, how the redox centers in OM c-Cyts take electrons from a cathode has not been elucidated at the molecular level. Electrochemical analysis of live cells during switching from anodic to cathodic conditions showed that altering the direction of electron flow does not require gene expression or protein synthesis, but simply redox potential shift about 300 mV for a flavin cofactor interacting with the OM c-Cyts. That is, the redox bifurcation of the riboflavin cofactor in OM c-Cyts switches the direction of electron conduction in the biological conduit at the cell-electrode interface to drive bacterial metabolism as either anode or cathode catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recovery of critical and value metals from mobile electronics enabled by electrochemical processing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tedd E. Lister; Peiming Wang; Andre Anderko

2014-10-01

Electrochemistry-based schemes were investigated as a means to recover critical and value metals from scrap mobile electronics. Mobile electronics offer a growing feedstock for replenishing value and critical metals and reducing need to exhaust primary sources. The electrorecycling process generates oxidizing agents at an anode to dissolve metals from the scrap matrix while reducing dissolved metals at the cathode. The process uses a single cell to maximize energy efficiency. E vs pH diagrams and metals dissolution experiments were used to assess effectiveness of various solution chemistries. Following this work, a flow chart was developed where two stages of electrorecycling weremore » proposed: 1) initial dissolution of Cu, Sn, Ag and magnet materials using Fe+3 generated in acidic sulfate and 2) final dissolution of Pd and Au using Cl2 generated in an HCl solution. Experiments were performed using a simulated metal mixture equivalent to 5 cell phones. Both Cu and Ag were recovered at ~ 97% using Fe+3 while leaving Au and Pd intact. Strategy for extraction of rare earth elements (REE) from dissolved streams is discussed as well as future directions in process development.« less

Effects of magnetic field strength in the discharge channel on the performance of a multi-cusped field thruster

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Peng; Liu, Hui; Gao, Yuanyuan

The performance characteristics of a Multi-cusped Field Thruster depending on the magnetic field strength in the discharge channel were investigated. Four thrusters with different outer diameters of the magnet rings were designed to change the magnetic field strength in the discharge channel. It is found that increasing the magnetic field strength could restrain the radial cross-field electron current and decrease the radial width of main ionization region, which gives rise to the reduction of propellant utilization and thruster performance. The test results in different anode voltage conditions indicate that both the thrust and anode efficiency are higher for the weakermore » magnetic field in the discharge channel.« less

The impact of galaxy geometry and mass evolution on the survival of star clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Madrid, Juan P.; Hurley, Jarrod R.; Martig, Marie

2014-04-01

Direct N-body simulations of globular clusters in a realistic Milky-Way-like potential are carried out using the code NBODY6 to determine the impact of the host galaxy disk mass and geometry on the survival of star clusters. A relation between disk mass and star-cluster dissolution timescale is derived. These N-body models show that doubling the mass of the disk from 5 × 10{sup 10} M {sub ☉} to 10 × 10{sup 10} M {sub ☉} halves the dissolution time of a satellite star cluster orbiting the host galaxy at 6 kpc from the galactic center. Different geometries in a disk ofmore » identical mass can determine either the survival or dissolution of a star cluster orbiting within the inner 6 kpc of the galactic center. Furthermore, disk geometry has measurable effects on the mass loss of star clusters up to 15 kpc from the galactic center. N-body simulations performed with a fine output time step show that at each disk crossing the outer layers of star clusters experiences an increase in velocity dispersion of ∼5% of the average velocity dispersion in the outer section of star clusters. This leads to an enhancement of mass loss—a clearly discernable effect of disk shocking. By running models with different inclinations, we determine that star clusters with an orbit that is perpendicular to the Galactic plane have larger mass loss rates than do clusters that evolve in the Galactic plane or in an inclined orbit.« less

Vulnerability of the paper Nautilus (Argonauta nodosa) shell to a climate-change ocean: potential for extinction by dissolution.

PubMed

Wolfe, Kennedy; Smith, Abigail M; Trimby, Patrick; Byrne, Maria

2012-10-01

Shell calcification in argonauts is unique. Only females of these cephalopods construct the paper nautilus shell, which is used as a brood chamber for developing embryos in the pelagic realm. As one of the thinnest (225 μm) known adult mollusc shells, and lacking an outer protective periostracum-like cover, this shell may be susceptible to dissolution as the ocean warms and decreases in pH. Vulnerability of the A. nodosa shell was investigated through immersion of shell fragments in multifactorial experiments of control (19 °C/pH 8.1; pCO(2) 419; Ω(Ca) = 4.23) and near-future conditions (24 °C/pH 7.8-7.6; pCO(2) 932-1525; Ω(Ca) = 2.72-1.55) for 14 days. More extreme pH treatments (pH 7.4-7.2; pCO(2) 2454-3882; Ω(Ca) = 1.20-0.67) were used to assess tipping points in shell dissolution. X-ray diffractometry revealed no change in mineralogy between untreated and treated shells. Reduced shell weight due to dissolution was evident in shells incubated at pH 7.8 (projected for 2070) after 14 days at control temperature, with increased dissolution in warmer and lower pH treatments. The greatest dissolution was recorded at 24 °C (projected for local waters by 2100) compared to control temperature across all low-pH treatments. Scanning electron microscopy revealed dissolution and etching of shell mineral in experimental treatments. In the absence of compensatory mineralization, the uncovered female brood chamber will be susceptible to dissolution as ocean pH decreases. Since the shell was a crucial adaptation for the evolution of the argonauts' holopelagic existence, persistence of A. nodosa may be compromised by shell dissolution in an ocean-change world.

Anodized titanium and stainless steel in contact with CFRP: an electrochemical approach considering galvanic corrosion.

PubMed

Mueller, Yves; Tognini, Roger; Mayer, Joerg; Virtanen, Sannakaisa

2007-09-15

The combination of different materials in an implant gives the opportunity to better fulfill the requirements that are needed to improve the healing process. However, using different materials increases the risk of galvanic coupling corrosion. In this study, coupling effects of gold-anodized titanium, stainless steel for biomedical applications, carbon fiber reinforced polyetheretherketone (CFRP), and CFRP containing tantalum fibers are investigated electrochemically and by long-term immersion experiments in simulated body fluid (SBF). Potentiodynamic polarization experiments (i/E curves) and electrochemical impedance spectroscopy (EIS) of the separated materials showed a passive behavior of the metallic samples. Anodized titanium showed no corrosion attacks, whereas stainless steel is highly susceptibility for localized corrosion. On the other side, an active dissolution behavior of both of the CFRPs in the given environment could be determined, leading to delaminating of the carbon fibers from the matrix. Long-term immersion experiments were carried out using a set-up especially developed to simulate coupling conditions of a point contact fixator system (PC-Fix) in a biological environment. Electrochemical data were acquired in situ during the whole immersion time. The results of the immersion experiments correlate with the findings of the electrochemical investigation. Localized corrosion attacks were found on stainless steel, whereas anodized titanium showed no corrosion attacks. No significant differences between the two CFRP types could be found. Galvanic coupling corrosion in combination with crevice conditions and possible corrosion mechanisms are discussed. Copyright 2007 Wiley Periodicals, Inc.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stygar, W.A.; Spielman, R.B.; Allshouse, G.O.

The 36-module Z accelerator was designed to drive z-pinch loads for weapon-physics and inertial-confinement-fusion experiments, and to serve as a testing facility for pulsed-power research required to develop higher-current drivers. The authors have designed and tested a 10-nH 1.5-m-radius vacuum section for the Z accelerator. The vacuum section consists of four vacuum flares, four conical 1.3-m-radius magnetically-insulated transmission lines, a 7.6-cm-radius 12-post double-post-hole convolute which connects the four outer MITLs in parallel, and a 5-cm-long inner MITL which connects the output of the convolute to a z-pinch load. IVORY and ELECTRO calculations were performed to minimize the inductance of themore » vacuum flares with the constraint that there be no significant electron emission from the insulator-stack grading rings. Iterative TLCODE calculations were performed to minimize the inductance of the outer MITLs with the constraint that the MITL electron-flow-current fraction be {le} 7% at peak current. The TLCODE simulations assume a 2.5 cm/{micro}s MITL-cathode-plasma expansion velocity. The design limits the electron dose to the outer-MITL anodes to 50 J/g to prevent the formation of an anode plasma. The TLCODE results were confirmed by SCREAMER, TRIFL, TWOQUICK, IVORY, and LASNEX simulations. For the TLCODE, SCREAMER, and TRIFL calculations, the authors assume that after magnetic insulation is established, the electron-flow current launched in the outer MITLs is lost at the convolute. This assumption has been validated by 3-D QUICKSILVER simulations for load impedances {le} 0.36 ohms. LASNEX calculations suggest that ohmic resistance of the pinch and conduction-current-induced energy loss to the MITL electrodes can be neglected in Z power-flow modeling that is accurate to first order. To date, the Z vacuum section has been tested on 100 shots. They have demonstrated they can deliver a 100-ns rise-time 20-MA current pulse to the baseline z-pinch load.« less

Effect of Initial Conditions on Gas-Puff Z-Pinch Dynamics.

NASA Astrophysics Data System (ADS)

Peterson, Gus Gordon

This dissertation concerns the effects initial conditions have on the dynamics of an imploded, annular gas-puff z-pinch. The influence of axial magnetic fields, nozzle size and composition, different gases, pre-ionization, and electrode design on pinch quality and x-ray yield is investigated. The experiment uses a 5-kJ capacitor bank to deliver 0.35 MA to the pinch load in 1.4 mu rm s. This research establishes parameters important to increasing the x-ray yield of dense z-pinches. The initial stage of the implosion is diagnosed with a framing camera that photographs visible light emitted from z-pinch gas breakdown. Data from subsequent stages of the pinch is recorded with a B-dot probe, filtered x-ray diodes, an x-ray filtered pinhole camera, and a nitrogen laser interferometer. Applied axial magnetic fields of ~100 gauss increase average x-ray yield by more than 20%. A substantial increase of K-shell x -ray yield of more than 200% was obtained by increasing the energy delivered to the plasma by enlarging the nozzle diameter from 4 to 5 cm. The use of a Teflon outer-mantle for the nozzle resulted in less uniform gas breakdown as compared to graphite and copper outer-mantles, but x-ray yield and final state uniformity were not reduced. Lower Z gases showed poorer breakdown uniformity. Pre-ionization improved the uniformity of helium and neon breakdown but did not appear to affect subsequent dynamics. X-ray yield was significantly higher using a knife-edge annular anode, as opposed to a flat stainless steel honeycomb anode. Annular anodes with diameters more than a few millimeters different than the nozzle diameter produced low quality pinches with substantially lower x-ray yield.

Compact-Nanobox Engineering of Transition Metal Oxides with Enhanced Initial Coulombic Efficiency for Lithium-Ion Battery Anodes.

PubMed

Zhu, Yanfei; Hu, Aiping; Tang, Qunli; Zhang, Shiying; Deng, Weina; Li, Yanhua; Liu, Zheng; Fan, Binbin; Xiao, Kuikui; Liu, Jilei; Chen, Xiaohua

2018-03-14

A novel strategy is proposed to construct a compact-nanobox (CNB) structure composed of irregular nanograins (average diameter ≈ 10 nm), aiming to confine the electrode-electrolyte contact area and enhance initial Coulombic efficiency (ICE) of transition metal oxide (TMO) anodes. To demonstrate the validity of this attempt, CoO-CNB is taken as an example which is synthesized via a carbothermic reduction method. Benefiting from the compact configuration, electrolyte can only contact the outer surface of the nanobox, keeping the inner CoO nanograins untouched. Therefore, the solid electrolyte interphase (SEI) formation is reduced. Furthermore, the internal cavity leaves enough room for volume variation upon lithiation and delithiation, resulting in superior mechanical stability of the CNB structure and less generation of fresh SEI. Consequently, the SEI remains stable and spatially confined without degradation, and hence, the CoO-CNB electrode delivers an enhanced ICE of 82.2%, which is among the highest values reported for TMO-based anodes in lithium-ion batteries. In addition, the CoO-CNB electrode also demonstrates excellent cyclability with a reversible capacity of 811.6 mA h g -1 (90.4% capacity retention after 100 cycles). These findings open up a new way to design high-ICE electrodes and boost the practical application of TMO anodes.

Scallop-Inspired Shell Engineering of Microparticles for Stable and High Volumetric Capacity Battery Anodes.

PubMed

Zhang, Xinghao; Guo, Ruiying; Li, Xianglong; Zhi, Linjie

2018-06-01

Building stable and efficient electron and ion transport pathways are critically important for energy storage electrode materials and systems. Herein, a scallop-inspired shell engineering strategy is proposed and demonstrated to confine high volume change silicon microparticles toward the construction of stable and high volumetric capacity binder-free lithium battery anodes. As for each silicon microparticle, the methodology involves an inner sealed but adaptable overlapped graphene shell, and an outer open hollow shell consisting of interconnected reduced graphene oxide, mimicking the scallop structure. The inner closed shell enables simultaneous stabilization of the interfaces of silicon with both carbon and electrolyte, substantially facilitates efficient and rapid transport of both electrons and lithium ions from/to silicon, the outer open hollow shell creates stable and robust transport paths of both electrons and lithium ions throughout the electrode without any sophisticated additives. The resultant self-supported electrode has achieved stable cycling with rapidly increased coulombic efficiency in the early stage, superior rate capability, and remarkably high volumetric capacity upon a facile pressing process. The rational design and engineering of graphene shells of the silicon microparticles developed can provide guidance for the development of a wide range of other high capacity but large volume change electrochemically active materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Degradation Mechanisms of Magnesium Metal Anodes in Electrolytes Based on (CF 3SO 2) 2N – at High Current Densities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoo, Hyun Deog; Han, Sang-Don; Bolotin, Igor L.

The energy density of rechargeable batteries utilizing metals as anodes surpasses that of Li ion batteries, which employ carbon instead. Among possible metals, magnesium represents a potential alternative to the conventional choice, lithium, in terms of storage density, safety,stability, and cost. However, a major obstacle for metal-based batteries is the identification of electrolytes that show reversible deposition/dissolution of the metal anode and support reversible intercalation of ions into a cathode. Traditional Grignard-based Mg electrolytes are excellent with respect to the reversible deposition of Mg, but their limited anodic stability and compatibility with oxide cathodes hinder their applicability in Mg batteriesmore » with higher voltage. Non-Grignard electrolytes, which consist of ethereal solutions of magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI) 2), remain fairly stable near the potential of Mg deposition. The slight reactivity of these electrolytes toward Mg metal can be remedied by the addition of surface-protecting agents, such as MgCl 2. Hence, ethereal solutions of Mg(TFSI) 2 salt with MgCl 2 as an additive have been suggested as a representative non-Grignard Mg electrolyte. In this work, the degradation mechanisms of a Mg metal anode in the TFSI-based electrolyte were studied using a current density of 1 mA cm -2 and an areal capacity of ~0.4 mAh cm -2, which is close to those used in practical applications. The degradation mechanisms identified include the corrosion of Mg metal, which causes the loss of electronic pathways and mechanical integrity, the nonuniform deposition of Mg, and the decomposition of TFSI - anions. This study not only represents an assessment of the behavior of Mg metal anodes at practical current density and areal capacity but also details the outcomes of interfacial passivation, which was detected by simple cyclic voltammetry experiments. This study also points out the absolute absence of any passivation at the electrode-electrolyte interface for the premise of developing electrolytes compatible with a metal anode.« less

Degradation Mechanisms of Magnesium Metal Anodes in Electrolytes Based on (CF 3SO 2) 2N – at High Current Densities

DOE PAGES

Yoo, Hyun Deog; Han, Sang-Don; Bolotin, Igor L.; ...

2017-06-21

The energy density of rechargeable batteries utilizing metals as anodes surpasses that of Li ion batteries, which employ carbon instead. Among possible metals, magnesium represents a potential alternative to the conventional choice, lithium, in terms of storage density, safety,stability, and cost. However, a major obstacle for metal-based batteries is the identification of electrolytes that show reversible deposition/dissolution of the metal anode and support reversible intercalation of ions into a cathode. Traditional Grignard-based Mg electrolytes are excellent with respect to the reversible deposition of Mg, but their limited anodic stability and compatibility with oxide cathodes hinder their applicability in Mg batteriesmore » with higher voltage. Non-Grignard electrolytes, which consist of ethereal solutions of magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI) 2), remain fairly stable near the potential of Mg deposition. The slight reactivity of these electrolytes toward Mg metal can be remedied by the addition of surface-protecting agents, such as MgCl 2. Hence, ethereal solutions of Mg(TFSI) 2 salt with MgCl 2 as an additive have been suggested as a representative non-Grignard Mg electrolyte. In this work, the degradation mechanisms of a Mg metal anode in the TFSI-based electrolyte were studied using a current density of 1 mA cm -2 and an areal capacity of ~0.4 mAh cm -2, which is close to those used in practical applications. The degradation mechanisms identified include the corrosion of Mg metal, which causes the loss of electronic pathways and mechanical integrity, the nonuniform deposition of Mg, and the decomposition of TFSI - anions. This study not only represents an assessment of the behavior of Mg metal anodes at practical current density and areal capacity but also details the outcomes of interfacial passivation, which was detected by simple cyclic voltammetry experiments. This study also points out the absolute absence of any passivation at the electrode-electrolyte interface for the premise of developing electrolytes compatible with a metal anode.« less

Electrochemical mineral scale prevention and removal on electrically conducting carbon nanotube--polyamide reverse osmosis membranes.

PubMed

Duan, Wenyan; Dudchenko, Alexander; Mende, Elizabeth; Flyer, Celeste; Zhu, Xiaobo; Jassby, David

2014-05-01

The electrochemical prevention and removal of CaSO4 and CaCO3 mineral scales on electrically conducting carbon nanotube - polyamide reverse osmosis membrane was investigated. Different electrical potentials were applied to the membrane surface while filtering model scaling solutions with high saturation indices. Scaling progression was monitored through flux measurements. CaCO3 scale was efficiently removed from the membrane surface through the intermittent application of a 2.5 V potential to the membrane surface, when the membrane acted as an anode. Water oxidation at the anode, which led to proton formation, resulted in the dissolution of deposited CaCO3 crystals. CaSO4 scale formation was significantly retarded through the continuous application of 1.5 V DC to the membrane surface, when the membrane was operated as an anode. The continuous application of a sufficient electrical potential to the membrane surface leads to the formation of a thick layer of counter-ions along the membrane surface that pushed CaSO4 crystal formation away from the membrane surface, allowing the formed crystals to be carried away by the cross-flow. We developed a simple model, based on a modified Poisson-Boltzmann equation, which qualitatively explained our observed experimental results.

The influence of surface roughness and high pressure torsion on the growth of anodic titania nanotubes on pure titanium

NASA Astrophysics Data System (ADS)

Hu, Nan; Gao, Nong; Starink, Marco J.

2016-11-01

Anodic titanium dioxide nanotube (TNT) arrays have wide applications in photocatalytic, catalysis, electronics, solar cells and biomedical implants. When TNT coatings are combined with severe plastic deformation (SPD), metal processing techniques which efficiently improve the strength of metals, a new generation of biomedical implant is made possible with both improved bulk and surface properties. This work investigated the effect of processing by high pressure torsion (HPT) and different mechanical preparations on the substrate and subsequently on the morphology of TNT layers. HPT processing was applied to refine the grain size of commercially pure titanium samples and substantially improved their strength and hardness. Subsequent anodization at 30 V in 0.25 wt.% NH4F for 2 h to form TNT layers on sample surfaces prepared with different mechanical preparation methods was carried out. It appeared that the local roughness of the titanium surface on a microscopic level affected the TNT morphology more than the macroscopic surface roughness. For HPT-processed sample, the substrate has to be pre-treated by a mechanical preparation finer than 4000 grit for HPT to have a significant influence on TNTs. During the formation of TNT layers the oxide dissolution rate was increased for the ultrafine-grained microstructure formed due to HPT processing.

A Host-Configured Lithium-Sulfur Cell Built on 3D Nickel Photonic Crystal with Superior Electrochemical Performances.

PubMed

Lin, Shengxuan; Yan, Yang; Cai, Zihe; Liu, Lin; Hu, Xiaobin

2018-04-18

The insulator of the sulfur cathode and the easy dendrites growth of the lithium anode are the main barriers for lithium-sulfur cells in commercial application. Here, a 3D NPC@S/3D NPC@Li full cell is reported based on 3D hierarchical and continuously porous nickel photonic crystal (NPC) to solve the problems of sulfur cathode and lithium anode at the same time. In this case, the 3D NPC@S cathode can not only offer a fast transfer of electron and lithium ion, but also effectively prevent the dissolution of polysulfides and the tremendous volume change during cycling, and the 3D NPC@Li anode can efficiently inhibit the growth of lithium dendrites and volume expansion, too. As a result, the cell exhibits a high reversible capacity of 1383 mAh g -1 at 0.5 C (the current density of 837 mA g -1 ), superior rate ability (the reversible capacity of 735 mAh g -1 at the extremely high current density of 16 750 mA g -1 ) with excellent coulombic efficiency of about 100% and an excellent cycle life over 500 cycles with only about 0.026% capacity loss per cycle. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Trends in reactivity of electrodeposited 3d transition metals on gold revealed by operando soft x-ray absorption spectroscopy during water splitting

NASA Astrophysics Data System (ADS)

Velasco-Vélez, J. J.; Jones, Travis E.; Pfeifer, Verena; Dong, Chung-Li; Chen, Yu-Xun; Chen, Chieh-Ming; Chen, Hsin-Yu; Lu, Ying-Rui; Chen, Jin-Ming; Schlögl, R.; Knop-Gericke, A.; Chuang, C.-H.

2017-01-01

We activated gold electrodes for their use as electrocatalyst for water splitting by electrodepositing Cu, Ni and Co. A combination of operando x-ray absorption spectroscopy and potentiometric control under aqueous conditions revealed the trends in reactivity yielded by these electrodes, which are directly associated with the cross- and overpotentials as well as the occupancy of the 3d orbitals. It was found that under anodic polarization the materials electrodeposited on gold suffer from a lack of stability, while under cathodic polarization they exhibit stable behavior. The observed activity is strongly related to the lack of stability shown by these composites under anodic polarization revealing a dynamic process ruled by corrosion. By operando x-ray absorption, we established that the overall enhancement of the activity for the oxygen evolution reaction is directly attributable to the cross-potential and corrosion process of the electrodeposited materials. It is associated with the high potential deposition, which is the origin of the incipient oxidation-corrosion resistance of the lattice. We conclude that the observed trends in the total current are directly associated with the loss of oxygen in the metal-oxide lattice and the subsequent dissolution of metallic ions in the electrolyte under anodic polarization.

The Synergistic Effect of Iodide and Sodium Nitrite on the Corrosion Inhibition of Mild Steel in Bicarbonate-Chloride Solution.

PubMed

Eyu, Gaius Debi; Will, Geoffrey; Dekkers, Willem; MacLeod, Jennifer

2016-10-26

The effect of potassium iodide (KI) and sodium nitrite (NaNO₂ inhibitor on the corrosion inhibition of mild steel in chloride bicarbonate solution has been studied using electrochemical techniques. Potentiodynamic polarisation data suggest that, when used in combination, KI and NaNO₂ function together to inhibit reactions at both the anode and the cathode, but predominantly anodic. KI/NO₂ - concentration ratios varied from 2:1 to 2:5; inhibition efficiency was optimized for a ratio of 1:1. The surface morphology and corrosion products were analysed using scanning electron microscopy (SEM) and X-ray diffractometry (XRD). The latter shows that the addition of I - to NO₂ facilitates the formation of a passivating oxide (γ-Fe₂O₃) as compared to NO₂ - alone, decreasing the rate of metal dissolution observed in electrochemical testing. The synergistic effect of KI/NO₂ - inhibition was enhanced under the dynamic conditions associated with testing in a rotating disc electrode.

Humidity Effect on Nanoscale Electrochemistry in Solid Silver Ion Conductors and the Dual Nature of Its Locality

DOE PAGES

Yang, Sangmo; Strelcov, Evgheni; Paranthaman, Mariappan Parans; ...

2015-01-07

Scanning probe microscopy (SPM) is a powerful tool to investigate electrochemistry in nanoscale volumes. While most SPM-based studies have focused on reactions at the tip-surface junction, charge and mass conservation requires coupled and intrinsically non-local cathodic and anodic processes that can be significantly affected by ambient humidity. Here, we explore the role of water in both cathodic and anodic processes, associated charge transport, and topographic volume changes depending on the polarity of tip bias. The first-order reversal curve current-voltage technique combined with simultaneous detection of the sample topography, referred to as FORC-IVz, was applied to a silver solid ion conductor.more » We found that the protons generated from water affect silver ionic conduction, silver particle formation and dissolution, and mechanical integrity of the material. This work highlights the dual nature (simultaneously local and non-local) of electrochemical SPM studies, which should be considered for comprehensive understanding of nanoscale electrochemistry.« less

Controllable construction of flower-like FeS/Fe2O3 composite for lithium storage

NASA Astrophysics Data System (ADS)

Wang, Jie; He, Huan; Wu, Zexing; Liang, Jianing; Han, Lili; Xin, Huolin L.; Guo, Xuyun; Zhu, Ye; Wang, Deli

2018-07-01

Transitions metal sulfides/oxides have been considered as promising anode candidates for next generation lithium-ion batteries (LIBs) due to high theoretical capacities. However, the large volume change during lithiation/delithiation process and poor electronic conductivity often result in a poor charging/discharging performance. Herein, we design a flower-like FeS/Fe2O3 composite via a simple "solvothermal-oxidation" method, in which the Fe2O3 is most distributed on the surface of the flower. The unique porous structure and synergistic effect between FeS and Fe2O3 not only accommodate the large volume expansion, but also facilitate Li ion and electron transport. The Fe2O3 shell effectively reduce the dissolution of Li2Sx during discharge/charge process. When serving as the anode material in lithium ion battery, FeS/Fe2O3 exhibits superior specific capacity, rate capacity and cycling stability compared with pure FeS and Fe2O3.

Humidity effect on nanoscale electrochemistry in solid silver ion conductors and the dual nature of its locality.

PubMed

Yang, Sang Mo; Strelcov, Evgheni; Paranthaman, M Parans; Tselev, Alexander; Noh, Tae Won; Kalinin, Sergei V

2015-02-11

Scanning probe microscopy (SPM) is a powerful tool to investigate electrochemistry in nanoscale volumes. While most SPM-based studies have focused on reactions at the tip-surface junction, charge and mass conservation requires coupled and intrinsically nonlocal cathodic and anodic processes that can be significantly affected by ambient humidity. Here, we explore the role of water in both cathodic and anodic processes, associated charge transport, and topographic volume changes depending on the polarity of tip bias. The first-order reversal curve current-voltage technique combined with simultaneous detection of the sample topography, referred to as FORC-IVz, was applied to a silver solid ion conductor. We found that the protons generated from water affect silver ionic conduction, silver particle formation and dissolution, and mechanical integrity of the material. This work highlights the dual nature (simultaneously local and nonlocal) of electrochemical SPM studies, which should be considered for comprehensive understanding of nanoscale electrochemistry.

Performance study of magnesium-sulfur battery using a graphene based sulfur composite cathode electrode and a non-nucleophilic Mg electrolyte.

PubMed

Vinayan, B P; Zhao-Karger, Zhirong; Diemant, Thomas; Chakravadhanula, Venkata Sai Kiran; Schwarzburger, Nele I; Cambaz, Musa Ali; Behm, R Jürgen; Kübel, Christian; Fichtner, Maximilian

2016-02-14

Here we report for the first time the development of a Mg rechargeable battery using a graphene-sulfur nanocomposite as the cathode, a Mg-carbon composite as the anode and a non-nucleophilic Mg based complex in tetraglyme solvent as the electrolyte. The graphene-sulfur nanocomposites are prepared through a new pathway by the combination of thermal and chemical precipitation methods. The Mg/S cell delivers a higher reversible capacity (448 mA h g(-1)), a longer cyclability (236 mA h g(-1) at the end of the 50(th) cycle) and a better rate capability than previously described cells. The dissolution of Mg polysulfides to the anode side was studied by X-ray photoelectron spectroscopy. The use of a graphene-sulfur composite cathode electrode, with the properties of a high surface area, a porous morphology, a very good electronic conductivity and the presence of oxygen functional groups, along with a non-nucleophilic Mg electrolyte gives an improved battery performance.

Computational Examination of Orientation-Dependent Morphological Evolution during the Electrodeposition and Electrodissolution of Magnesium

DOE PAGES

DeWitt, S.; Hahn, N.; Zavadil, K.; ...

2015-12-30

Here a new model of electrodeposition and electrodissolution is developed and applied to the evolution of Mg deposits during anode cycling. The model captures Butler-Volmer kinetics, facet evolution, the spatially varying potential in the electrolyte, and the time-dependent electrolyte concentration. The model utilizes a diffuse interface approach, employing the phase field and smoothed boundary methods. Scanning electron microscope (SEM) images of magnesium deposited on a gold substrate show the formation of faceted deposits, often in the form of hexagonal prisms. Orientation-dependent reaction rate coefficients were parameterized using the experimental SEM images. Three-dimensional simulations of the growth of magnesium deposits yieldmore » deposit morphologies consistent with the experimental results. The simulations predict that the deposits become narrower and taller as the current density increases due to the depletion of the electrolyte concentration near the sides of the deposits. Increasing the distance between the deposits leads to increased depletion of the electrolyte surrounding the deposit. Two models relating the orientation-dependence of the deposition and dissolution reactions are presented. Finally, the morphology of the Mg deposit after one deposition-dissolution cycle is significantly different between the two orientation-dependence models, providing testable predictions that suggest the underlying physical mechanisms governing morphology evolution during deposition and dissolution.« less

Ti film deposition process of a plasma focus: Study by an experimental design

NASA Astrophysics Data System (ADS)

Inestrosa-Izurieta, M. J.; Moreno, J.; Davis, S.; Soto, L.

2017-10-01

The plasma generated by plasma focus (PF) devices have substantially different physical characteristics from another plasma, energetic ions and electrons, compared with conventional plasma devices used for plasma nanofabrication, offering new and unique opportunities in the processing and synthesis of Nanomaterials. This article presents the use of a plasma focus of tens of joules, PF-50J, for the deposition of materials sprayed from the anode by the plasma dynamics in the axial direction. This work focuses on the determination of the most significant effects of the technological parameters of the system on the obtained depositions through the use of a statistical experimental design. The results allow us to give a qualitative understanding of the Ti film deposition process in our PF device depending on four different events provoked by the plasma dynamics: i) an electric erosion of the outer material of the anode; ii) substrate ablation generating an interlayer; iii) electron beam deposition of material from the center of the anode; iv) heat load provoking clustering or even melting of the deposition surface.

Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments

NASA Astrophysics Data System (ADS)

Borowski, Susan C.; Biswakarma, Jagannath; Kang, Kyounglim; Schenkeveld, Walter D. C.; Hering, Janet G.; Kubicki, James D.; Kraemer, Stephan M.; Hug, Stephan J.

2018-04-01

Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.

Probing off-Hugoniot states in Ta, Cu, and Al to 1000 GPa compression with magnetically driven liner implosions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lemke, R. W., E-mail: rwlemke@sandia.gov; Dolan, D. H.; Dalton, D. G.

We report on a new technique for obtaining off-Hugoniot pressure vs. density data for solid metals compressed to extreme pressure by a magnetically driven liner implosion on the Z-machine (Z) at Sandia National Laboratories. In our experiments, the liner comprises inner and outer metal tubes. The inner tube is composed of a sample material (e.g., Ta and Cu) whose compressed state is to be inferred. The outer tube is composed of Al and serves as the current carrying cathode. Another aluminum liner at much larger radius serves as the anode. A shaped current pulse quasi-isentropically compresses the sample as itmore » implodes. The iterative method used to infer pressure vs. density requires two velocity measurements. Photonic Doppler velocimetry probes measure the implosion velocity of the free (inner) surface of the sample material and the explosion velocity of the anode free (outer) surface. These two velocities are used in conjunction with magnetohydrodynamic simulation and mathematical optimization to obtain the current driving the liner implosion, and to infer pressure and density in the sample through maximum compression. This new equation of state calibration technique is illustrated using a simulated experiment with a Cu sample. Monte Carlo uncertainty quantification of synthetic data establishes convergence criteria for experiments. Results are presented from experiments with Al/Ta, Al/Cu, and Al liners. Symmetric liner implosion with quasi-isentropic compression to peak pressure ∼1000 GPa is achieved in all cases. These experiments exhibit unexpectedly softer behavior above 200 GPa, which we conjecture is related to differences in the actual and modeled properties of aluminum.« less

Probing off-Hugoniot states in Ta, Cu, and Al to 1000 GPa compression with magnetically driven liner implosions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lemke, R. W.; Dolan, D. H.; Dalton, D. G.

We report on a new technique for obtaining off-Hugoniot pressure vs. density data for solid metals compressed to extreme pressure by a magnetically driven liner implosion on the Z-machine (Z) at Sandia National Laboratories. In our experiments, the liner comprises inner and outer metal tubes. The inner tube is composed of a sample material (e.g., Ta and Cu) whose compressed state is to be inferred. The outer tube is composed of Al and serves as the current carrying cathode. Another aluminum liner at much larger radius serves as the anode. A shaped current pulse quasi-isentropically compresses the sample as itmore » implodes. The iterative method used to infer pressure vs. density requires two velocity measurements. Photonic Doppler velocimetry probes measure the implosion velocity of the free (inner) surface of the sample material and the explosion velocity of the anode free (outer) surface. These two velocities are used in conjunction with magnetohydrodynamic simulation and mathematical optimization to obtain the current driving the liner implosion, and to infer pressure and density in the sample through maximum compression. This new equation of state calibration technique is illustrated using a simulated experiment with a Cu sample. Monte Carlo uncertainty quantification of synthetic data establishes convergence criteria for experiments. Results are presented from experiments with Al/Ta, Al/Cu, and Al liners. Symmetric liner implosion with quasi-isentropic compression to peak pressure ~1000 GPa is achieved in all cases. Lastly, these experiments exhibit unexpectedly softer behavior above 200 GPa, which we conjecture is related to differences in the actual and modeled properties of aluminum.« less

Probing off-Hugoniot states in Ta, Cu, and Al to 1000 GPa compression with magnetically driven liner implosions

DOE PAGES

Lemke, R. W.; Dolan, D. H.; Dalton, D. G.; ...

2016-01-07

We report on a new technique for obtaining off-Hugoniot pressure vs. density data for solid metals compressed to extreme pressure by a magnetically driven liner implosion on the Z-machine (Z) at Sandia National Laboratories. In our experiments, the liner comprises inner and outer metal tubes. The inner tube is composed of a sample material (e.g., Ta and Cu) whose compressed state is to be inferred. The outer tube is composed of Al and serves as the current carrying cathode. Another aluminum liner at much larger radius serves as the anode. A shaped current pulse quasi-isentropically compresses the sample as itmore » implodes. The iterative method used to infer pressure vs. density requires two velocity measurements. Photonic Doppler velocimetry probes measure the implosion velocity of the free (inner) surface of the sample material and the explosion velocity of the anode free (outer) surface. These two velocities are used in conjunction with magnetohydrodynamic simulation and mathematical optimization to obtain the current driving the liner implosion, and to infer pressure and density in the sample through maximum compression. This new equation of state calibration technique is illustrated using a simulated experiment with a Cu sample. Monte Carlo uncertainty quantification of synthetic data establishes convergence criteria for experiments. Results are presented from experiments with Al/Ta, Al/Cu, and Al liners. Symmetric liner implosion with quasi-isentropic compression to peak pressure ~1000 GPa is achieved in all cases. Lastly, these experiments exhibit unexpectedly softer behavior above 200 GPa, which we conjecture is related to differences in the actual and modeled properties of aluminum.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ulin, V. P.; Ulin, N. V.; Soldatenkov, F. Yu., E-mail: f.soldatenkov@mail.ioffe.ru

The interaction of heavily doped p- and n-type Si crystals with hydrofluoric acid in the dark with and without contact with metals having greatly differing work functions (Ag and Pd) is studied. The dependences of the dissolution rates of Si crystals in HF solutions that contain oxidizing agents with different redox potentials (FeCl{sub 3}, V{sub 2}O{sub 5} and CrO{sub 3}) on the type and level of silicon doping are determined. Analysis of the experimental data suggests that valence-band holes in silicon are not directly involved in the anodic reactions of silicon oxidation and dissolution and their generation in crystals doesmore » not limit the rate of these processes. It is also shown that the character and rate of the chemical process leading to silicon dissolution in HF-containing electrolytes are determined by the interfacial potential attained at the semiconductor–electrolyte interface. The mechanism of electrochemical pore formation in silicon crystals is discussed in terms of selfconsistent cooperative reactions of nucleophilic substitution between chemisorbed fluorine anions and coordination- saturated silicon atoms in the crystal subsurface layer. A specific feature of these reactions for silicon crystals is that vacant nonbonding d{sup 2}sp{sup 3} orbitals of Si atoms, associated with sixfold degenerate states corresponding to the Δ valley of the conduction band, are involved in the formation of intermediate complexes. According to the suggested model, the pore-formation process spontaneously develops in local regions of the interface under the action of the interfacial potential in the adsorption layer and occurs as a result of the detachment of (SiF{sub 2}){sub n} polymer chains from the crystal. Just this process leads to the preferential propagation of pores along the <100> crystallographic directions. The thermodynamic aspects of pore nucleation and the effect of the potential drop across the interface, conduction type, and free-carrier concentration in the crystal on the pore size and structure are discussed. The concepts developed in the study can consistently account for experimental facts characterizing the etching of silicon crystals with various electrical parameters under various conditions providing the anodic polarization of crystals in HF-containing solutions.« less

Tissue dissolution by a novel multisonic ultracleaning system and sodium hypochlorite.

PubMed

Haapasalo, Markus; Wang, Zhejun; Shen, Ya; Curtis, Allison; Patel, Payal; Khakpour, Mehrzad

2014-08-01

This study aimed to evaluate the effectiveness of a novel Multisonic Ultracleaning System (Sonendo Inc, Laguna Hills, CA) in tissue dissolution in comparison with conventional irrigation devices. Pieces of bovine muscle tissue (68 ± 2 mg) were placed in 0.7-mL test tubes (height: 23.60 mm, inner diameter: 6.00 mm, outer diameter: 7.75 mm) and exposed to 5 minutes of irrigation by different devices. Endodontic devices included the Multisonic Ultracleaning System, the Piezon Master 700 (EMS, Dallas, TX) ultrasonic system with agitation, the EndoVac negative-pressure irrigation system (SybronEndo, Orange, CA), and a conventional positive-pressure 27-G irrigation needle at a flow rate of 10 mL/min. The systems were tested with 0.5%, 3%, and 6% sodium hypochlorite (NaOCl) at room temperature (21°C) as well as 40°C. Irrigation with sterile water was used as a control. The mass of tissue specimens was measured and recorded before and after the use of each device, and if the specimen was completely dissolved visually within 5 minutes, the dissolution time was recorded. The rate of tissue dissolution (%/s) was then calculated. The Multisonic Ultracleaning System had the fastest rate of tissue dissolution (P < .05), at 1.0% ± 0.1% per second using 0.5% NaOCl, 2.3% ± 0.9% per second using 3% NaOCl, and 2.9% ± 0.7% per second using 6% NaOCl. This tissue dissolution rate was more than 8 times greater than the second fastest device tested (P < .01), the Piezon Master 700 ultrasonic system, which resulted in a tissue dissolution rate of 0.328% ± 0.002% per second using 6% NaOCl at 40°C. For all irrigation devices tested, the rate of tissue dissolution increased with a higher concentration and temperature of the NaOCl solution. The novel Multisonic Ultracleaning System achieved a significantly faster tissue dissolution rate when compared with the other systems examined in vitro. Copyright © 2014 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Mathematical modelling of solar ultraviolet radiation induced optical degradation in anodized aluminum

NASA Technical Reports Server (NTRS)

Ruley, John D.

1986-01-01

In the design of spacecraft for proper thermal balance, accurate information on the long-term optical behavior of the spacecraft outer skin materials is necessary. A phenomenological model for such behavior is given. The underlying principles are explained and some examples are given of the model's fit to actual measurements under simulated Earth-orbit conditions. Comments are given on the applicability of the model to materials testing and thermal modelling.

Studies on applicability of press-coated tablets using hydroxypropylcellulose (HPC) in the outer shell for timed-release preparations.

PubMed

Fukui, E; Uemura, K; Kobayashi, M

2000-08-10

Press-coated tablets, containing diltiazem hydrochloride (DIL) in the core tablet and coated with hydroxypropylcellulose (HPC) as the outer shell, were examined for applicability as timed-release tablets with a predetermined lag time and subsequent rapid drug release phase. Various types of press-coated tablets were prepared using a rotary tabletting machine and their DIL dissolution behavior was evaluated by the JP paddle method. The results indicated that tablets with the timed-release function could be prepared, and that the lag times were prolonged as the viscosity of HPC and the amount of the outer shell were increased. The lag times could be controlled widely by the above method, however, the compression load had little effect. Two different kinds of timed-release press-coated tablets that showed lag times of 3 and 6 h in the in vitro test (denoted PCT(L3) and PCT(L6), respectively) were administered to beagle dogs. DIL was first detected in the plasma more than 3 h after administration, and both tablets showed timed-release. The lag times showed a good agreement between the in vivo and in vitro tests in PCT(L3). However, the in vivo lag times were about 4 h in PCT(L6) and were much shorter than the in vitro lag time. The dissolution test was performed at different paddle rotation speeds, and good agreement was obtained between the in vivo and in vitro lag times at 150 rpm. This suggested that the effects of gastrointestinal peristalsis and contraction should also be taken into consideration for the further development of drug delivery systems.

Solid oxide fuel cell matrix and modules

DOEpatents

Riley, B.

1988-04-22

Porous refractory ceramic blocks arranged in an abutting, stacked configuration and forming a three dimensional array provide a support structure and coupling means for a plurality of solid oxide fuel cells (SOFCs). The stack of ceramic blocks is self-supporting, with a plurality of such stacked arrays forming a matrix enclosed in an insulating refractory brick structure having an outer steel layer. The necessary connections for air, fuel, burnt gas, and anode and cathode connections are provided through the brick and steel outer shell. The ceramic blocks are so designed with respect to the strings of modules that by simple and logical design the strings could be replaced by hot reloading if one should fail. The hot reloading concept has not been included in any previous designs. 11 figs.

Preparation of titanium dioxide films on etched aluminum foil by vacuum infiltration and anodizing

NASA Astrophysics Data System (ADS)

Xiang, Lian; Park, Sang-Shik

2016-12-01

Al2O3-TiO2 (Al-Ti) composite oxide films are a promising dielectric material for future use in capacitors. In this study, TiO2 films were prepared on etched Al foils by vacuum infiltration. TiO2 films prepared using a sol-gel process were annealed at various temperatures (450, 500, and 550 °C) for different time durations (10, 30, and 60 min) for 4 cycles, and then anodized at 100 V. The specimens were characterized using X-ray diffraction, field emission scanning electron microscopy, and field emission transmission electron microscopy. The results show that the tunnels of the specimens feature a multi-layer structure consisting of an Al2O3 outer layer, an Al-Ti composite oxide middle layer, and an aluminum hydrate inner layer. The electrical properties of the specimens, such as the withstanding voltage and specific capacitance, were also measured. Compared to specimens without TiO2 coating, the specific capacitances of the TiO2-coated specimens are increased. The specific capacitance of the anode Al foil with TiO2 coating increased by 42% compared to that of a specimen without TiO2 coating when annealed at 550 °C for 10 min. These composite oxide films could enhance the specific capacitance of anode Al foils used in dielectric materials.

Transparent Nanotubular TiO₂ Photoanodes Grown Directly on FTO Substrates.

PubMed

Paušová, Šárka; Kment, Štěpán; Zlámal, Martin; Baudys, Michal; Hubička, Zdeněk; Krýsa, Josef

2017-05-10

This work describes the preparation of transparent TiO₂ nanotube (TNT) arrays on fluorine-doped tin oxide (FTO) substrates. An optimized electrolyte composition (0.2 mol dm -3 NH₄F and 4 mol dm -3 H₂O in ethylene glycol) was used for the anodization of Ti films with different thicknesses (from 100 to 1300 nm) sputtered on the FTO glass substrates. For Ti thicknesses 600 nm and higher, anodization resulted in the formation of TNT arrays with an outer nanotube diameter around 180 nm and a wall thickness around 45 nm, while for anodized Ti thicknesses of 100 nm, the produced nanotubes were not well defined. The transmittance in the visible region (λ = 500 nm) varied from 90% for the thinnest TNT array to 65% for the thickest TNT array. For the fabrication of transparent TNT arrays by anodization, the optimal Ti thickness on FTO was around 1000 nm. Such fabricated TNT arrays with a length of 2500 nm exhibit stable photocurrent densities in aqueous electrolytes (~300 µA cm -2 at potential 0.5 V vs. Ag/AgCl). The stability of the photocurrent response and a sufficient transparency (≥65%) enables the use of transparent TNT arrays in photoelectrochemical applications when the illumination from the support/semiconductor interface is a necessary condition and the transmitted light can be used for another purpose (photocathode or photochemical reaction in the electrolyte).

Direct electrolytic dissolution of silicate minerals for air CO2 mitigation and carbon-negative H2 production

PubMed Central

Rau, Greg H.; Carroll, Susan A.; Bourcier, William L.; Singleton, Michael J.; Smith, Megan M.; Aines, Roger D.

2013-01-01

We experimentally demonstrate the direct coupling of silicate mineral dissolution with saline water electrolysis and H2 production to effect significant air CO2 absorption, chemical conversion, and storage in solution. In particular, we observed as much as a 105-fold increase in OH− concentration (pH increase of up to 5.3 units) relative to experimental controls following the electrolysis of 0.25 M Na2SO4 solutions when the anode was encased in powdered silicate mineral, either wollastonite or an ultramafic mineral. After electrolysis, full equilibration of the alkalized solution with air led to a significant pH reduction and as much as a 45-fold increase in dissolved inorganic carbon concentration. This demonstrated significant spontaneous air CO2 capture, chemical conversion, and storage as a bicarbonate, predominantly as NaHCO3. The excess OH− initially formed in these experiments apparently resulted via neutralization of the anolyte acid, H2SO4, by reaction with the base mineral silicate at the anode, producing mineral sulfate and silica. This allowed the NaOH, normally generated at the cathode, to go unneutralized and to accumulate in the bulk electrolyte, ultimately reacting with atmospheric CO2 to form dissolved bicarbonate. Using nongrid or nonpeak renewable electricity, optimized systems at large scale might allow relatively high-capacity, energy-efficient (<300 kJ/mol of CO2 captured), and inexpensive (<$100 per tonne of CO2 mitigated) removal of excess air CO2 with production of carbon-negative H2. Furthermore, when added to the ocean, the produced hydroxide and/or (bi)carbonate could be useful in reducing sea-to-air CO2 emissions and in neutralizing or offsetting the effects of ongoing ocean acidification. PMID:23729814

Spontaneous Water Oxidation at Hematite (α-Fe2O3) Crystal Faces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chatman, Shawn ME; Zarzycki, Piotr P.; Rosso, Kevin M.

2015-01-28

Hematite (α-Fe2O3) persists as a promising candidate for photoelectrochemical water splitting but a slow oxygen evolution reaction (OER) at its surfaces remains a limitation. Here we extend a series of studies that examine pH-dependent surface potentials and electron transfer properties of effectively perfect low-index crystal faces of hematite in contact with simple electrolyte. Zero resistance amperometry was performed in a two electrode configuration to quantify spontaneous dark current between hematite crystal face pairs (001)/(012), (001)/(113), and (012)/(113) at pH 3. Exponentially decaying currents initially of up to 200 nA were reported between faces over four minute experiments. Fourth order ZRAmore » kinetics indicated rate limitation by the OER for current that flows between (001)/(012) and (001)/(113) face pairs, with the (012) and (113) faces serving as the anodes when paired with (001). The cathodic partner reaction is reductive dissolution of the (001) face, converting surface Fe3+ to solubilized aqueous Fe2+, at a rate maintained by the OER at the anode. In contrast, OER rate limitation does not manifest for the (012)/(113) pair. The uniqueness of the (001) face is established in terms of a faster intrinsic ability to accept the protons required for the reductive dissolution reaction. OER rate limitation inversely may thus arise from sluggish kinetics of hematite surfaces to dispense with the protons that accompany the four-electron OER. The results are explained in terms of semi-quantitative energy band diagrams. The finding may be useful as a consideration for tailoring the design of polycrystalline hematite photoanodes that present multiple terminations to the interface with electrolyte.« less

Real-Time Terahertz Imaging Using a Quantum Cascade Laser and Uncooled Microbolometer Focal Plane Array

DTIC Science & Technology

2008-06-01

reverse magnetron ” design (in which the polarity of the magnetron elements are reversed—such that the cathode constitutes the outer ring; the anode ...included as inset frames within Fig. 20. The dual nature of this figure (reporting both voltage and intensity vs. bias current) is useful in that it...tuned micro- magnetrons [60]-[61]. Conventional magnetrons (such as those used to generate microwaves) have physical dimensions which are excessively

Investigation of carbon supported PtW catalysts as CO tolerant anodes at high temperature in proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Hassan, Ayaz; Paganin, Valdecir A.; Ticianelli, Edson A.

2016-09-01

The CO tolerance mechanism and the stability of carbon supported PtW electrocatalysts are evaluated in the anode of a proton exchange membrane fuel cell (PEMFC) at two different temperatures. The electrocatalysts are characterized by energy dispersive spectroscopy, X-ray diffraction, and transmission electron spectroscopy. Employed electrochemical techniques include cyclic voltammetry, CO stripping, fuel cell polarization, and online mass spectrometry. At a cell temperature of 85 °C, the PtW/C catalyst shows higher CO tolerance compared to Pt/C due an electronic effect of WOx in the Pt 5d band, which reduces the CO adsorption. An increase in hydrogen oxidation activity in the presence of CO is observed for both the catalysts at a higher temperature, due to the decrease of the Pt-CO coverage. A reduction in the current densities occurs for the PtW/C catalyst in both polarization curves and cyclic voltammograms after 5000 cycles of the anode in the range of 0.1-0.7 V vs. RHE at 50 mVs-1. This decrease in performance is assigned to the dissolution of W, with a consequent increase in the membrane resistivity. However, the observed decline of performance is small either in the presence of pure H2 or in the presence of H2/CO.

Lithium rich cathode/graphite anode combination for lithium ion cells with high tolerance to near zero volt storage

NASA Astrophysics Data System (ADS)

Crompton, K. R.; Staub, J. W.; Hladky, M. P.; Landi, B. J.

2017-03-01

Management of reversible lithium is an advantageous approach to design lithium ion cells that are tolerant to near zero volt (NZV) storage under fixed resistive load towards highly controllable, enhanced user-inactive safety. Presently, the first cycle loss from a high energy density Li-rich HE5050 cathode is used to provide excess reversible lithium when paired with an appropriately capacity matched mesocarbon microbead (MCMB) anode. Cells utilizing 1.2 M LiPF6 3:7 v/v ethylene carbonate:ethyl methyl carbonate electrolyte and a lithium reference were used for 3-electrode testing. After conditioning, a fixed resistive load was applied to 3-electrode cells for 72 or 168-h during which the anode potential and electrode asymptotic potential (EAP) remained less than the copper dissolution potential. After multiple storage cycles (room temperature or 40 °C), the NZV coulombic efficiency (cell reversibility) exceeded 97% and the discharge capacity retention was >98%. Conventional 2-electrode HE5050/MCMB pouch cells stored at NZV or open circuit for 3 days had nearly identical rate capability (up to 5C) and discharge performance stability (for 500 cycles under a 30% depth of discharge low-earth-orbit regime). Thus, lithium ion cells with appropriately capacity matched HE5050/MCMB electrodes have excellent tolerance to prolonged NZV storage, which can lead to enhanced user-inactive safety.

Alumina-coated and manganese monoxide embedded 3D carbon derived from avocado as high-performance anode for lithium-ion batteries

NASA Astrophysics Data System (ADS)

rehman, Wasif ur; Xu, Youlong; Du, Xianfeng; Sun, Xiaofei; Ullah, Inam; Zhang, Yuan; Jin, Yanling; Zhang, Baofeng; Li, Xifei

2018-07-01

Derived from avocado fruit, a three dimension (3D) carbon is prepared via a hydrothermal/pyrolysis process followed by embedding with MnO nanoparticles by a wet chemical method and coating with Al2O3 through an atomic layer deposition technique. The obtained material presents a hierarchical structure that MnO nanocrystals wrapped in 3D carbon and then encapsulated in a uniform Al2O3 layer with a thickness of about 5 nm. Benefiting from this hierarchical structure in which 3D carbon offers numerous electronic pathways to enhance the conductivity and Al2O3 nanolayer provide a shelter to keep away from dissolution of Mn4+ and volume changes during charge/discharge process. This material (marked as C/MnO@Al2O3) has exhibited high rate performance and excellent cyclability as an anode for lithium ion batteries. A high specific capacity of about 600 mA h g-1 is achieved at a current density of 1000 mA g-1 and the electrode can still deliver a high specific capacity of about 1165 mA h g-1 at 150 mA g-1 after 100 cycles. These results facilitate a green and high potential of anode materials towards promising devices for advance performance of lithium-ion batteries.

Formation and Entrapment of Tris(8-hydroxyquinoline)aluminum from 8-Hydroxyquinoline in Anodic Porous Alumina

PubMed Central

Yamaguchi, Shohei; Matsui, Kazunori

2016-01-01

The formation and entrapment of tris(8-hydroxyquinoline)aluminum (Alq3) molecules on the surface of anodic porous alumina (APA) immersed in an ethanol solution of 8-hydroxyquinoline (HQ) were investigated by absorption, fluorescence, and Raman spectroscopies. The effects of the selected APA preparation conditions (galvanostatic or potentiostatic anodization method, anodizing current and voltage values, one- or two-step anodizing process, and sulfuric acid electrolyte concentration) on the adsorption and desorption of Alq3 species were examined. Among the listed parameters, sulfuric acid concentration was the most important factor in determining the Alq3 adsorption characteristics. The Alq3 content measured after desorption under galvanostatic conditions was 2.5 times larger than that obtained under potentiostatic ones, regardless of the adsorbed quantities. The obtained results suggest the existence of at least two types of adsorption sites on the APA surface characterized by different magnitudes of the Alq3 bonding strength. The related fluorescence spectra contained two peaks at wavelengths of 480 and 505 nm, which could be attributed to isolated Alq3 species inside nanovoids and aggregated Alq3 clusters in the pores of APA, respectively. The former species were attached to the adsorption sites with higher binding energies, whereas the latter ones were bound to the APA surface more weakly. Similar results were obtained for the Alq3 species formed from the HQ solution, which quantitatively exceeded the number of the Alq3 species adsorbed from the Alq3 solution. Alq3 molecules were formed in the HQ solution during the reaction of HQ molecules with the Al3+ ions in the oxide dissolution zone near the oxide/electrolyte interface through the cracks and the Al3+ ions adsorbed on surface of pore and cracks. In addition, it was suggested that HQ molecules could penetrate the nanovoids more easily than Alq3 species because of their smaller sizes, which resulted in higher magnitudes of the adsorption. PMID:28773840

Fabrication of CNT@void@SnO2@C with tube-in-tube nanostructure as high-performance anode for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Tian, Qinghua; Tian, Yang; Zhang, Zhengxi; Yang, Li; Hirano, Shin-ichi

2015-09-01

Tin dioxide/carbon composites is an important class of promising candidates for anode materials with superior electrochemical performance and thus have attracted extensive attention. Herein, a tube-in-tube nanostructure, denoted as CNT@void@SnO2@C, has been fabricated by a facile and novel strategy. The possible formation mechanism is also discussed and determined by TEM, XRD and XPS characterizations. As a promising anode material for lithium-ion batteries, the CNT@void@SnO2@C exhibits superior lithium storage properties, delivering a reversible capacity of 702.5 mAh g-1 at 200 mA g-1 even after 350 cycles. The excellent performances should be benefited from the peculiar tube-in-tube nanostructure, in which SnO2 located between CNT and outermost carbon coating layers can sure the structural integrity and high conductivity during long-term cycling, and one-dimensional void space formed between the inner CNT and outer SnO2@C nanotubes, in particular, can provide larger free space for alleviating the huge volume variation of SnO2 and accommodating the stress formed during repeated discharge/charge process.

Application of fuel cell for pyrite and heavy metal containing mining waste

NASA Astrophysics Data System (ADS)

Keum, H.; Ju, W. J.; Jho, E. H.; Nam, K.

2015-12-01

Once pyrite and heavy metal containing mining waste reacts with water and air it produces acid mine drainage (AMD) and leads to the other environmental problems such as contamination of surrounding soils. Pyrite is the major source of AMD and it can be controlled using a biological-electrochemical dissolution method. By enhancing the dissolution of pyrite using fuel cell technology, not only mining waste be beneficially utilized but also be treated at the same time by. As pyrite-containing mining waste is oxidized in the anode of the fuel cell, electrons and protons are generated, and electrons moves through an external load to cathode reducing oxygen to water while protons migrate to cathode through a proton exchange membrane. Iron-oxidizing bacteria such as Acidithiobacillus ferrooxidans, which can utilize Fe as an electron donor promotes pyrite dissolution and hence enhances electrochemical dissolution of pyrite from mining waste. In this study mining waste from a zinc mine in Korea containing 17 wt% pyrite and 9% As was utilized as a fuel for the fuel cell inoculated with A. ferrooxidans. Electrochemically dissolved As content and chemically dissolved As content was compared. With the initial pH of 3.5 at 23℃, the dissolved As concentration increased (from 4.0 to 13 mg/L after 20 d) in the fuel cell, while it kept decreased in the chemical reactor (from 12 to 0.43 mg/L after 20 d). The fuel cell produced 0.09 V of open circuit voltage with the maximum power density of 0.84 mW/m2. Dissolution of As from mining waste was enhanced through electrochemical reaction. Application of fuel cell technology is a novel treatment method for pyrite and heavy metals containing mining waste, and this method is beneficial for mining environment as well as local community of mining areas.

Fabrication of Nanopipette Arrays for Biosensing

NASA Technical Reports Server (NTRS)

Meyyappan, Meyya (Inventor)

2015-01-01

Method for providing a nanopipette array for biosensing applications. A thin substrate of anodizable metal ("AN-metal," such as Al, Mg, Zn, Ti, Ta and/or Nb) is anodized at temperature T=20-200.degree. C., chemical bath pH=4-6 and electrical potential 1-300 Volts, to produce an array of anodized nanopipette channels, having diameters 10-50 nm, with oxidized channel surfaces of thickness 5-20 nm. A portion of exposed non-oxidized AN-metal between adjacent nanopipette channels, of length 1-5 .mu.m, is etched away, exposing inner and outer surfaces of a nanopipette channel. A probe molecule, is deposited on one or both surfaces to provide biosensing capability for K(.gtoreq.1) target molecules. Target molecule presence, in an above-threshold concentration, in a fluid passed through or adjacent to a nanopipette channel, produces characteristic detection signals associated with the probe molecule site.

Si/Ge double-layered nanotube array as a lithium ion battery anode.

PubMed

Song, Taeseup; Cheng, Huanyu; Choi, Heechae; Lee, Jin-Hyon; Han, Hyungkyu; Lee, Dong Hyun; Yoo, Dong Su; Kwon, Moon-Seok; Choi, Jae-Man; Doo, Seok Gwang; Chang, Hyuk; Xiao, Jianliang; Huang, Yonggang; Park, Won Il; Chung, Yong-Chae; Kim, Hansu; Rogers, John A; Paik, Ungyu

2012-01-24

Problems related to tremendous volume changes associated with cycling and the low electron conductivity and ion diffusivity of Si represent major obstacles to its use in high-capacity anodes for lithium ion batteries. We have developed a group IVA based nanotube heterostructure array, consisting of a high-capacity Si inner layer and a highly conductive Ge outer layer, to yield both favorable mechanics and kinetics in battery applications. This type of Si/Ge double-layered nanotube array electrode exhibits improved electrochemical performances over the analogous homogeneous Si system, including stable capacity retention (85% after 50 cycles) and doubled capacity at a 3C rate. These results stem from reduced maximum hoop strain in the nanotubes, supported by theoretical mechanics modeling, and lowered activation energy barrier for Li diffusion. This electrode technology creates opportunities in the development of group IVA nanotube heterostructures for next generation lithium ion batteries. © 2011 American Chemical Society

[Preparation and evaluation of press-coated aminophylline tablet using crystalline cellulose and polyethylene glycol in the outer shell for timed-release dosage forms].

PubMed

Watanabe, Yoshiteru; Mukai, Baku; Kawamura, Ken-ichi; Ishikawa, Tatsuya; Namiki, Michihiro; Utoguchi, Naoki; Fujii, Makiko

2002-02-01

In an attempt to achieve chronopharmacotherapy for asthma, press-coated tablets (250 mg), which contained aminophylline in the core tablet in the form of low-substituted hydroxypropylcellulose (L-HPC) and coated with crystalline cellulose (PH-102) and polyethylene glycol (PEG) at various molecular weights and mixing ratios in the amounts of PH-102 and PEG as the outer shell (press-coating material), were prepared (chronopharmaceutics). Their applicability as timed-release (delayed-release) tablets with a lag time of disintegration and a subsequent rapid drug release phase was investigated. Various types of press-coated tablets were prepared using a tableting machine, and their aminophylline dissolution profiles were evaluated by the JP paddle method. Tablets with the timed-release characteristics could be prepared, and the lag time of disintegration was prolonged as the molecular weight and the amount of PEG, for example PEG 500,000, in the outer shell were increased. The lag time of disintegration could be controlled by the above-mentioned method, however, the pH of the medium had no effect on disintegration of the tablet and dissolution behavior of theophylline. The press-coated tablet (core tablet:aminophylline 50 mg, L-HPC and PEG 6000; outer shell:PH-102:PEG = 8:2 200 mg) with the timed-release characteristics was administered orally to rabbits for an in vivo test. Theophylline was first detected in plasma more than 2 h after administration; thus, this tablet showed a timed-release characteristics in the gastrointestinal tract. The time (tmax) required to reach the maximum plasma theophylline concentration (Cmax) observed after administration of the press-coated tablet was significantly (p < 0.05) delayed compared with that observed after administration of aminophylline solution in the control experiment. However, there was no difference in Cmax and area under the plasma theophylline concentration-time curve (AUC0-->24) between the press-coated tablet and aminophylline solution. These results suggest that the press-coated aminophylline tablet (with the timed-release characteristic) offers a promising forms of theophylline chronotherapy for asthma.

Al-Air Batteries: Fundamental Thermodynamic Limitations from First-Principles Theory.

PubMed

Chen, Leanne D; Nørskov, Jens K; Luntz, Alan C

2015-01-02

The Al-air battery possesses high theoretical specific energy (4140 W h/kg) and is therefore an attractive candidate for vehicle propulsion. However, the experimentally observed open-circuit potential is much lower than what bulk thermodynamics predicts, and this potential loss is typically attributed to corrosion. Similarly, large Tafel slopes associated with the battery are assumed to be due to film formation. We present a detailed thermodynamic study of the Al-air battery using density functional theory. The results suggest that the maximum open-circuit potential of the Al anode is only -1.87 V versus the standard hydrogen electrode at pH 14.6 instead of the traditionally assumed -2.34 V and that large Tafel slopes are inherent in the electrochemistry. These deviations from the bulk thermodynamics are intrinsic to the electrochemical surface processes that define Al anodic dissolution. This has contributions from both asymmetry in multielectron transfers and, more importantly, a large chemical stabilization inherent to the formation of bulk Al(OH)3 from surface intermediates. These are fundamental limitations that cannot be improved even if corrosion and film effects are completely suppressed.

Electrokinetic treatment of an agricultural soil contaminated with heavy metals.

PubMed

Figueroa, Arylein; Cameselle, Claudio; Gouveia, Susana; Hansen, Henrik K

2016-07-28

The high organic matter content in agricultural soils tends to complex and retain contaminants such as heavy metals. Electrokinetic remediation was tested in an agricultural soil contaminated with Co(+2), Zn(+2), Cd(+2), Cu(+2), Cr(VI), Pb(+2) and Hg(+2). The unenhanced electrokinetic treatment was not able to remove heavy metals from the soil due to the formation of precipitates in the alkaline environment in the soil section close to the cathode. Moreover, the interaction between metals and organic matter probably limited metal transportation under the effect of the electric field. Citric acid and ethylenediaminetetraacetic acid (EDTA) were used in the catholyte as complexing agents in order to enhance the extractability and removal of heavy metals from soil. These complexing agents formed negatively charged complexes that migrated towards the anode. The acid front electrogenerated at the anode favored the dissolution of heavy metals that were transported towards the cathode. The combined effect of the soil pH and the complexing agents resulted in the accumulation of heavy metals in the center of the soil specimen.

Long-term behaviour of solid oxide fuel cell interconnect materials in contact with Ni-mesh during exposure in simulated anode gas at 700 and 800 °C

NASA Astrophysics Data System (ADS)

Garcia-Fresnillo, L.; Shemet, V.; Chyrkin, A.; de Haart, L. G. J.; Quadakkers, W. J.

2014-12-01

In the present study the long-term behaviour of two ferritic steels, Crofer 22 APU and Crofer 22H, in contact with a Ni-mesh during exposure in simulated anode gas, Ar-4%H2-2%H2O, at 700 and 800 °C for exposure times up to 3000 h was investigated. Ni diffusion from the Ni-mesh into the steel resulted in the formation of an austenitic zone whereas diffusion of iron and chromium from the steel into the Ni-mesh resulted in the formation of chromia base oxides in the Ni-mesh. Depending on the chemical composition of the steel, the temperature and the exposure time, interdiffusion processes between ferritic steel and Ni-mesh also resulted in σ-phase formation at the austenite-ferrite interface and in Laves-phase dissolution in the austenitic zone. The extent and morphology of the σ-phase formation are discussed on the basis of thermodynamic considerations, including reaction paths in the ternary alloy system Fe-Ni-Cr.

Galvanic corrosion of nitinol under deaerated and aerated conditions.

PubMed

Pound, Bruce G

2016-10-01

Various studies have examined the corrosion rate of nitinol generally under deaerated conditions. Likewise, galvanic corrosion studies have typically involved deaerated solutions. This work addressed the effect of galvanic coupling on the corrosion current of electropolished nitinol in phosphate buffered saline and 0.9% sodium chloride under dearated and aerated conditions for times up to 24 h. Tests were performed on nitinol alone and coupled with MP35N in both the mechanically polished and passivated conditions. Aeration and galvanic coupling were found to have relatively little effect, indicating that the corrosion current is controlled by the anodic reaction. The current can be attributed entirely to Ni(2+) dissolution, which appears to be governed by solid-state mass transport of Ni(2+) through the passive oxide film. Because corrosion of EP nitinol is controlled by the anodic reaction, contact between EP nitinol and MP35N or other biomedical Co-Cr alloys is unlikely to result in significant galvanic effects in vivo. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1322-1327, 2016. © 2015 Wiley Periodicals, Inc.

Synthesis of zinc oxide porous structures by anodization with water as an electrolyte

NASA Astrophysics Data System (ADS)

Shetty, Amitha; Nanda, Karuna Kar

2012-10-01

We report a simple, reliable and one-step method of synthesizing ZnO porous structures at room temperature by anodization of zinc (Zn) sheet with water as an electrolyte and graphite as a counter electrode. We observed that the de-ionized (DI) water used in the experiment is slightly acidic (pH=5.8), which is due to the dissolution of carbon dioxide from the atmosphere forming carbonic acid. Porous ZnO is characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy and photoluminescence (PL) studies. The current-transient measurement is carried out using a Gamry Instruments Reference 3000 and the thickness of the deposited films is measured using a Dektak surface profilometer. The PL, Raman and X-ray photoelectron spectroscopy are used to confirm the presence of ZnO phase. We have demonstrated that the hybrid structures of ZnO and poly (3,4-ethylenedioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) exhibit good rectifying characteristics. The evaluated barrier height and the ideality factor are 0.45 eV and 3.6, respectively.

SiO2 decoration dramatically enhanced the stability of PtRu electrocatalysts with undetectable deterioration in fuel cell performance.

PubMed

Yu, Xinxin; Xu, Zejun; Yang, Zehui; Xu, Sen; Zhang, Quan; Ling, Ying; Zhang, Yunfeng; Cai, Weiwei

2018-06-15

Prevention of Ru dissolution is essential for steady CO tolerance of anodic electrocatalysts in direct methanol fuel cells. Here, we demonstrate a facile way to stabilize Ru atoms by decorating commercial CB/PtRu with SiO 2 , which shows a six-fold higher stability and similar activity toward a methanol oxidation reaction leading to no discernible degradation in fuel cell performance compared to commercial CB/PtRu electrocatalysts. The higher stability and stable CO tolerance of SiO 2 -decorated electrocatalysts originate from the SiO 2 coating, since Ru atoms are partially ionized during SiO 2 decorating, resulting in difficulties in dissolution; while, in the case of commercial CB/PtRu, the dissolved Ru offers active sites for Pt coalescences and CO species resulting in the rapid decay of the electrochemical surface area and fuel cell performance. To the best of our knowledge, this is the first study about the stabilization of Ru atoms by SiO 2 . The highest stability is obtained for a PtRu electrocatalyst with negligible effect on the electrochemical properties.

A study of X100 pipeline steel passivation in mildly alkaline bicarbonate solutions using electrochemical impedance spectroscopy under potentiodynamic conditions and Mott-Schottky

NASA Astrophysics Data System (ADS)

Gadala, Ibrahim M.; Alfantazi, Akram

2015-12-01

The key steps involved in X100 pipeline steel passivation in bicarbonate-based simulated soil solutions from the pre-passive to transpassive potential regions have been analyzed here using a step-wise anodizing-electrochemical impedance spectroscopy (EIS) routine. Pre-passive steps involve parallel dissolution-adsorption in early stages followed by clear diffusion-adsorption control shortly before iron hydroxide formation. Aggressive NS4 chlorides/sulfate promote steel dissolution whilst inhibiting diffusion in pre-passive steps. Diffusive and adsorptive effects remain during iron hydroxide formation, but withdraw shortly thereafter during its removal and the development of the stable iron carbonate passive layer. Passive layer protectiveness is evaluated using EIS fitting, current density analysis, and correlations with semiconductive parameters, consistently revealing improved robustness in colder, bicarbonate-rich, chloride/sulfate-free conditions. Ferrous oxide formation at higher potentials results in markedly lower impedances with disordered behavior, and the involvement of the iron(III) valence state is observed in Mott-Schottky tests exclusively for 75 °C conditions.

Negligible degradation upon in situ voltage cycling of a PEMFC using an electrospun niobium-doped tin oxide supported Pt cathode.

PubMed

Savych, Iuliia; Subianto, Surya; Nabil, Yannick; Cavaliere, Sara; Jones, Deborah; Rozière, Jacques

2015-07-14

Novel platinum-catalysed, corrosion-resistant, loose-tube-structured electrocatalysts for proton exchange membrane fuel cells have been obtained using single-needle electrospinning associated with a microwave-assisted polyol method. Monodisperse platinum particles supported on Nb-SnO2 demonstrated higher electrochemical stability than conventional Pt/C electrodes during ex situ potential cycling and comparable activity in the oxygen reduction reaction. In situ fuel cell operation under accelerated stress test conditions of a membrane electrode assembly elaborated using a Pt/C anode and Pt/Nb-SnO2 cathode confirmed that the voltage loss is significantly lower for the novel cathode than for an MEA prepared using conventional Pt/C supported electrocatalysts. Furthermore, the Nb-SnO2 stabilised the supported platinum nanoparticles against dissolution, migration and reprecipitation in the membrane. Pt/Nb-SnO2 loose-tubes constitute a mitigation strategy for two known degradation mechanisms in PEMFC: corrosion of the carbon support at the cathode, and dissolution of Pt at high cell voltages.

Friction Stir Welding of Al Alloy 2219-T8: Part II-Mechanical and Corrosion

NASA Astrophysics Data System (ADS)

Kang, Ju; Feng, Zhi-Cao; Li, Ji-Chao; Frankel, G. S.; Wang, Guo-Qing; Wu, Ai-Ping

2016-09-01

In Part I of this series, abnormal agglomerations of θ particles with size of about 100 to 1000 µm were observed in friction stir welded AA2219-T8 joints. In this work, the effects of these agglomerated θ particles on the mechanical and corrosion properties of the joints are studied. Tensile testing with in situ SEM imaging was utilized to monitor crack initiation and propagation in base metal and weld nugget zone (WNZ) samples. These tests showed that cracks initiated in the θ particles and at the θ/matrix interfaces, but not in the matrix. The WNZ samples containing abnormal agglomerated θ particles had a similar ultimate tensile stress but 3 pct less elongation than other WNZ samples with only normal θ particles. Measurements using the microcell technique indicated that the agglomerated θ particles acted as a cathode causing the dissolution of adjacent matrix. The abnormal θ particle agglomerations led to more severe localized attack due to the large cathode/anode ratio. Al preferential dissolution occurred in the abnormal θ particle agglomerations, which was different from the corrosion behavior of normal size θ particles.

Corrosion behavior of ODS steels with several chromium contents in hot nitric acid solutions

NASA Astrophysics Data System (ADS)

Tanno, Takashi; Takeuchi, Masayuki; Ohtsuka, Satoshi; Kaito, Takeji

2017-10-01

Oxide dispersion strengthened (ODS) steel cladding tubes have been developed for fast reactors. Tempered martensitic ODS steels with 9 and 11 wt% of chromium (9Cr-, 11Cr-ODS steel) are the candidate material in research being carried out at JAEA. In this work, fundamental immersion tests and electrochemical tests of 9 to 12Cr-ODS steels were systematically conducted in various nitric acid solutions at 95 °C. The corrosion rate decreased exponentially with effective solute chromium concentration (Creff) and nitric acid concentration. Addition of vanadium (V) and ruthenium (Ru) also decreased the corrosion rate. The combination of low Creff and dilute nitric acid could not avoid the active mass dissolution during active domain at the beginning of immersion, and the corrosion rate was high. Higher Creff decreased the partial anodic current during the active domain and assisted the passivation of the surface of the steel. Concentrated nitric acid and addition of Ru and V increased partial cathodic current and shifted the corrosion potential to noble side. These effects should have prevented the active mass dissolution and decreased the corrosion rate.

SiO2 decoration dramatically enhanced the stability of PtRu electrocatalysts with undetectable deterioration in fuel cell performance

NASA Astrophysics Data System (ADS)

Yu, Xinxin; Xu, Zejun; Yang, Zehui; Xu, Sen; Zhang, Quan; Ling, Ying; Zhang, Yunfeng; Cai, Weiwei

2018-06-01

Prevention of Ru dissolution is essential for steady CO tolerance of anodic electrocatalysts in direct methanol fuel cells. Here, we demonstrate a facile way to stabilize Ru atoms by decorating commercial CB/PtRu with SiO2, which shows a six-fold higher stability and similar activity toward a methanol oxidation reaction leading to no discernible degradation in fuel cell performance compared to commercial CB/PtRu electrocatalysts. The higher stability and stable CO tolerance of SiO2-decorated electrocatalysts originate from the SiO2 coating, since Ru atoms are partially ionized during SiO2 decorating, resulting in difficulties in dissolution; while, in the case of commercial CB/PtRu, the dissolved Ru offers active sites for Pt coalescences and CO species resulting in the rapid decay of the electrochemical surface area and fuel cell performance. To the best of our knowledge, this is the first study about the stabilization of Ru atoms by SiO2. The highest stability is obtained for a PtRu electrocatalyst with negligible effect on the electrochemical properties.

Dissolution of Nickel Ferrite in Aqueous Solutions Containing Oxalic Acid and Ferrous Salts.

PubMed

Figueroa, Carlos A.; Sileo, Elsa E.; Morando, Pedro J.; Blesa, Miguel A.

2000-05-15

The dissolution of nickel ferrite in oxalic acid and in ferrous oxalate-oxalic acid aqueous solution was studied. Nickel ferrite was synthesized by thermal decomposition of a mixed tartrate; the particles were shown to be coated with a thin ferric oxide layer. Dissolution takes place in two stages, the first one corresponding to the dissolution of the ferric oxide outer layer and the second one being the dissolution of Ni(1.06)Fe(1.96)O(4). The kinetics of dissolution during this first stage is typical of ferric oxides: in oxalic acid, both a ligand-assisted and a redox mechanism operates, whereas in the presence of ferrous ions, redox catalysis leads to a faster dissolution. The rate dependence on both oxalic acid and on ferrous ion is described by the Langmuir-Hinshelwood equation; the best fitting corresponds to K(1)(ads)=25.6 mol(-1) dm(-3) and k(1)(max)=9.17x10(-7) mol m(-2) s(-1) and K(2)(ads)=37.1x10(3) mol(-1) dm(-3) and k(2)(max)=62.3x10(-7) mol m(-2) s(-1), respectively. In the second stage, Langmuir-Hinshelwood kinetics also describes the dissolution of iron and nickel from nickel ferrite, with K(1)(ads)=20.8 mol(-1) dm(3) and K(2)(ads)=1.16x10(5) mol(-1) dm(3). For iron, k(1)(max)=1.02x10(-7) mol of Fe m(-2) s(-1) and k(2)(max)=2.38x10(-7) mol of Fe m(-2) s(-1); for nickel, the rate constants k(1)(max) and k(2)(max) are 2.4 and 1.79 times smaller, respectively. The factor 1.79 agrees nicely with the stoichiometric ratio, whereas the factor 2.4 implies the accumulation of some nickel in the residual particles. The rate of nickel dissolution in oxalic acid is higher than that in bunsenite by a factor of 8, whereas hematite is more reactive by a factor of 9 (in the absence of Fe(II)) and 27 (in the presence of Fe (II)). It may be concluded that oxalic acid operates to dissolve iron, and the ensuing disruption of the solid framework accelerates the release of nickel. Copyright 2000 Academic Press.

Dosage form design and in vitro/in vivo evaluation of cevimeline extended-release tablet formulations.

PubMed

Tajiri, Shinichiro; Kanamaru, Taro; Kamada, Makoto; Makoto, Kamada; Konno, Tsutomu; Nakagami, Hiroaki

2010-01-04

The objective of the present work is to develop an extended-release dosage form of cevimeline. Two types of extended-release tablets (simple matrix tablets and press-coated tablets) were prepared and their potential as extended-release dosage forms were assessed. Simple matrix tablets have a large amount of hydroxypropylcellulose as a rate-controlling polymer and the matrix is homogeneous throughout the tablet. The press-coated tablets consisted of a matrix core tablet, which was completely surrounded by an outer shell containing a large amount of hydroxypropylcellulose. The simple matrix tablets could not sustain the release of cevimeline effectively. In contrast, the press-coated tablets showed a slower dissolution rate compared with simple matrix tablets and the release curve was nearly linear. The dissolution of cevimeline from the press-coated tablets was not markedly affected by the pH of the dissolution medium or by a paddle rotating speed over the range of 50-200 rpm. Furthermore, cevimeline was constantly released from the press-coated tablets in the gastrointestinal tract and the steady-state plasma drug levels were maintained in beagle dogs. These results suggested that the designed PC tablets have a potential for extended-release dosage forms.

Development of a novel drug release system, time-controlled explosion system (TES). I. Concept and design.

PubMed

Ueda, S; Hata, T; Asakura, S; Yamaguchi, H; Kotani, M; Ueda, Y

1994-01-01

A novel controlled drug release system. Time-Controlled Explosion System (TES) has been developed. TES has a four-layered spherical structure, which consists of core, drug, swelling agent and water insoluble polymer membrane. TES is characterized by a rapid drug release with a precisely programmed lag time; i.e. expansion of the swelling agent by water penetrating through the outer membrane, destruction of the membrane by stress due to swelling force and subsequent rapid drug release. For establishing the concept and development strategy, TES was designed using metoprolol and polystyrene balls (size: 3.2 mm in diameter) as a model drug and core particles. Among the polymers screened, low-substituted hydroxypropylcellulose (L-HPC) and ethylcellulose (EC) were selected for a swelling agent and an outer water insoluble membrane, respectively. The release profiles of metoprolol from the system were not affected by the pH of the dissolution media. Lag time was controlled by the thickness of the outer EC membrane; thus, a combination of TES particles possessing different lag times could offer any desired release profile of the model compound, metoprolol.

Solid oxide fuel cell matrix and modules

DOEpatents

Riley, Brian

1990-01-01

Porous refractory ceramic blocks arranged in an abutting, stacked configuration and forming a three dimensional array provide a support structure and coupling means for a plurality of solid oxide fuel cells (SOFCs). Each of the blocks includes a square center channel which forms a vertical shaft when the blocks are arranged in a stacked array. Positioned within the channel is a SOFC unit cell such that a plurality of such SOFC units disposed within a vertical shaft form a string of SOFC units coupled in series. A first pair of facing inner walls of each of the blocks each include an interconnecting channel hole cut horizontally and vertically into the block walls to form gas exit channels. A second pair of facing lateral walls of each block further include a pair of inner half circular grooves which form sleeves to accommodate anode fuel and cathode air tubes. The stack of ceramic blocks is self-supporting, with a plurality of such stacked arrays forming a matrix enclosed in an insulating refractory brick structure having an outer steel layer. The necessary connections for air, fuel, burnt gas, and anode and cathode connections are provided through the brick and steel outer shell. The ceramic blocks are so designed with respect to the strings of modules that by simple and logical design the strings could be replaced by hot reloading if one should fail. The hot reloading concept has not been included in any previous designs.

Preparation and characterization of fast dissolving flurbiprofen and esomeprazole solid dispersion using spray drying technique.

PubMed

Pradhan, Roshan; Tran, Tuan Hiep; Kim, Sung Yub; Woo, Kyu Bong; Choi, Yong Joo; Choi, Han-Gon; Yong, Chul Soon; Kim, Jong Oh

2016-04-11

We aimed to develop an immediate-release flurbiprofen (FLU) and esomeprazole (ESO) combination formulation with enhanced gastric aqueous solubility and dissolution rate. Aqueous solubility can be enhanced by formulating solid dispersions (SDs) with a polyvinylpyrrolidone (PVP)-K30 hydrophilic carrier, using spray-drying technique. Aqueous and gastric pH dissolution can be achieved by macro-environmental pH modulation using sodium bicarbonate (NaHCO3) and magnesium hydroxide (Mg(OH)2) as the alkaline buffer. FLU/ESO-loaded SDs (FLU/ESO-SDs) significantly improved aqueous solubility of both drugs, compared to each drug powder. Dissolution studies in gastric pH and water were compared with the microenvironmental pH modulated formulations. The optimized FLU/ESO-SD powder formulation consisted of FLU/ESO/PVP-K30/sodium carbonate (Na2CO3) in a weight ratio 1:0.22:1.5:0.3, filled in the inner capsule. The outer capsule consisted of NaHCO3 and Mg(OH)2, which created the macro-environmental pH modulation. Increased aqueous and gastric pH dissolution of FLU and ESO from the SD was attributed to the alkaline buffer effects and most importantly, to drug transformation from crystalline to amorphous SD powder, clearly revealed by scanning electron microscopy, differential scanning calorimetry, and powder X-ray diffraction studies. Thus, the combined FLU and ESO SD powder can be effectively delivered as an immediate-release formulation using the macro-environmental pH modulation concept. Copyright © 2016. Published by Elsevier B.V.

Photoresponsive Molecular Memory Films Composed of Sequentially Assembled Heterolayers Containing Ruthenium Complexes.

PubMed

Nagashima, Takumi; Ozawa, Hiroaki; Suzuki, Takashi; Nakabayashi, Takuya; Kanaizuka, Katsuhiko; Haga, Masa-Aki

2016-01-26

Photoresponsive molecular memory films were fabricated by a layer-by-layer (LbL) assembling of two dinuclear Ru complexes with tetrapodal phosphonate anchors, containing either 2,3,5,6-tetra(2-pyridyl)pyrazine or 1,2,4,5-tetra(2-pyridyl)benzene as a bridging ligand (Ru-NP and Ru-CP, respectively), using zirconium phosphonate to link the layers. Various types of multilayer homo- and heterostructures were constructed. In the multilayer heterofilms such as ITO||(Ru-NP)m |(Ru-CP)n , the difference in redox potentials between Ru-NP and Ru-CP layers was approximately 0.7 V, which induced a potential gradient determined by the sequence of the layers. In the ITO||(Ru-NP)m |(Ru-CP)n multilayer heterofilms, the direct electron transfer (ET) from the outer Ru-CP layers to the ITO were observed to be blocked for m>2, and charge trapping in the outer Ru-CP layers became evident from the appearance of an intervalence charge transfer (IVCT) band at 1140 nm from the formation of the mixed-valent state of Ru-CP units, resulting from the reductive ET mediation of the inner Ru-NP layers. Therefore, the charging/discharging ("1"and "0") states in the outer Ru-CP layers could be addressed and interconverted by applying potential pulses between -0.5 and +0.7 V. The two states could be read out by the direction of the photocurrent (anodic or cathodic). The molecular heterolayer films thus represent a typical example of a photoresponsive memory device; that is, the writing process may be achieved by the applied potential (-0.5 or +0.7 V), while the readout process is achieved by measuring the direction of the photocurrent (anodic or cathodic). Sequence-sensitive multilayer heterofilms, using redox-active complexes as building blocks, thus demonstrate great potential for the design of molecular functional devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Discharge properties of Mg-Al-Mn-Ca and Mg-Al-Mn alloys as anode materials for primary magnesium-air batteries

NASA Astrophysics Data System (ADS)

Yuasa, Motohiro; Huang, Xinsheng; Suzuki, Kazutaka; Mabuchi, Mamoru; Chino, Yasumasa

2015-11-01

The discharge behaviors of rolled Mg-6 mass%Al-0.3 mass%Mn-2 mass%Ca (AMX602) and Mg-6 mass%Al-0.3 mass%Mn (AM60) alloys used as anodes for Magnesium-air batteries were investigated. The AMX602 alloy exhibited superior discharge properties compared to the AM60 alloy, especially at low current density. The discharge products of the AMX602 alloy were dense and thin, and many cracks were observed at all current densities. In addition, the discharge products were detached at some sites. These sites often corresponded to the positions of Al2Ca particles. The comparison of the discharge and corrosion tests indicated that the dense and thin discharge products of AMX602 were easily cracked by dissolution of the Mg matrix around Al2Ca particles, and the cracks promoted the penetration of the electrolyte into the discharge products, retaining the discharge activity. In contrast, concerning the AM60 alloy, thick discharge products were formed on the surface during discharge, and cracking of the discharge products hardly occurred, degrading the discharge properties. Localized and deeply corroded pits that could result from the detachment of metal pieces from the anode during discharge were partly observed in the AM60 alloy. It is suggested that these detached metal pieces are another reason for the low discharge properties of the AM60 alloy.

[Studies on preparation of sustained-release Shuxiong formulation, a traditional Chinese medicine compound recipe, using time-controlled release techniques].

PubMed

Song, Hong-Tao; Zhang, Qian; Jiang, Peng; Guo, Tao; Chen, Da-Wei; He, Zhong-Gui

2006-09-01

To prepare a sustained-release formulation of traditional Chinese medicine compound recipe by adopting time-controlled release techniques. Shuxiong tablets were chosen as model drug. The prescription and technique of core tablets were formulated with selecting disintegrating time and swelling volume of core tablets in water as index. The time-controlled release tablets were prepared by adopting press-coated techniques, using PEG6000, HCO and EVA as coating materials. The influences of compositions, preparation process and dissolution conditions in vitro on the lag time (T(lag)) of drug release were investigated. The composition of core tablets was as follow: 30% of drug, 50% MCC and 20% CMS-Na. The T(lag) of time-controlled release tablets was altered remarkably by PEG6000 content of the outer layer, the amount of outer layer and hardness of tablet. The viscosity of dissolution media and basket rotation had less influence on the T(lag) but more on rate of drug release. The core tablets pressed with the optimized composition had preferable swelling and disintegrating properties. The shuxiong sustained-release formulations which contained core tablet and two kinds of time-controlled release tablets with 3 h and 6 h of T(lag) could release drug successively at 0 h, 3 h and 6 h in vitro. The technique made it possible that various components with extremely different physicochemical properties in these preparations could release synchronously.

P(VDF-TrFE) ferroelectric nanotube array for high energy density capacitor applications.

PubMed

Li, Xue; Lim, Yee-Fun; Yao, Kui; Tay, Francis Eng Hock; Seah, Kar Heng

2013-01-14

Poly(vinylidene-fluoride-co-trifluoroethylene) (P(VDF-TrFE)) ferroelectric nanotube arrays were fabricated using an anodized alumina membrane (AAM) as a template and silver electrodes were deposited on both the outer and inner sides of the nanotubes by an electroless plating method. The nanotubes have the unique structure of being sealed at one end and linked at the open end, thus preventing electrical shorting between the inner and outer electrodes. Compared with a P(VDF-TrFE) film with a similar overall thickness, the idealized nanotube array has a theoretical capacitance that is 763 times larger due to the greatly enlarged contact area between the electrodes and the polymer dielectric. A capacitance that is 95 times larger has been demonstrated experimentally, thus indicating that such nanotube arrays are promising for realizing high density capacitance and high power dielectric energy storage.

Research on rechargeable oxygen electrodes.

NASA Technical Reports Server (NTRS)

Giner, J.; Holleck, G.; Malachesky, P. A.

1970-01-01

A research program is described which consisted of studying the effects of electrode cycling in very pure KOH solutions, with and without controlled additions of impurities, on oxide formation, oxygen evolution kinetics, oxygen reduction kinetics (including hydrogen peroxide formation), and changes in electrode structure. Bright platinum, platinized platinum, and Teflon-bonded platinum black electrodes were studied. Three main problem areas are identified: the buildup of a refractory anodic layer on prolonged cycling, which leads to a degradation of performance; the dissolution and subsequent deposition of dendritic platinum in the separator, leading to short-circuit ing and loss of electrocatalyst; and the disruptive effect of bubbling during gas evolution on charge. Each of these problem areas is analyzed, and remedial solutions are proposed.

Influence of Dy in solid solution on the degradation behavior of binary Mg-Dy alloys in cell culture medium.

PubMed

Yang, Lei; Ma, Liangong; Huang, Yuanding; Feyerabend, Frank; Blawert, Carsten; Höche, Daniel; Willumeit-Römer, Regine; Zhang, Erlin; Kainer, Karl Ulrich; Hort, Norbert

2017-06-01

Rare earth element Dy is one of the promising alloying elements for magnesium alloy as biodegradable implants. To understand the effect of Dy in solid solution on the degradation of Mg-Dy alloys in simulated physiological conditions, the present work studied the microstructure and degradation behavior of Mg-Dy alloys in cell culture medium. It is found the corrosion resistance enhances with the increase of Dy content in solid solution in Mg. This can be attributed to the formation of a relatively more corrosion resistant Dy-enriched film which decreases the anodic dissolution of Mg. Copyright © 2017 Elsevier B.V. All rights reserved.

[Study on electrochemical mechanism of coronary stent used austenitic stainless steel in flowing artificial body fluid].

PubMed

Liang, Chenghao; Guo, Liang; Chen, Wan; Wang, Hua

2005-08-01

The electrochemical mechanism of austenitic stainless steel (SUS316L and SUS317L) coronary stents in flowing artificial body fluid has been investigated with electrochemical technologies. The results indicated that the flowing medium coursed the samples' pitting potential Eb shift negatively, increased the pitting corrosion sensitivity, accelerated its anodic dissolution, but had little effects on repassivated potential. The flowing environment had great effects on cathodic process. The oxygen reaction on the samples' surface became faster as the cathodic process was not controlled by oxygen diffusion but by mixed diffusion and electrochemical process. With the increase of velocity of solution, the pitting corrosion becomes liable to occur under this circumstance.

[Complex technology for water and wastewater disinfection and its industrial realization in prototype unit].

PubMed

Arakcheev, E N; Brunman, V E; Brunman, M V; Konyashin, A V; Dyachenko, V A; Petkova, A P

Usage of complex automated electrolysis unit for drinking water disinfection and wastewater oxidation and coagulation is scoped, its ecological and energy efficiency is shown. Properties of technological process of anolyte production using membrane electrolysis of brine for water disinfection in municipal pipelines and potassium ferrate production using electrochemical dissolution of iron anode in NaOH solution for usage in purification plants are listed. Construction of modules of industrial prototype for anolyte and ferrate production and applied aspects of automation of complex electrolysis unit are proved. Results of approbation of electrolytic potassium ferrate for drinking water disinfection and wastewater, rain water and environmental water oxidation and coagulation are shown.

Influence of depositional environment on diagenesis in St. Peter sandstone, Michigan basin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lundgren, C.E. Jr.; Barnes, D.A.

1989-03-01

The Middle Ordovician St. Peter Sandstone in the Michigan basin was deposited in marine peritidal to storm-dominated, outer shelf depositional environments that evolved in a regionally significant transgressive pattern. The formation is bounded by carbonate and shaly clastic strata of the Prairie du Chien Group below and is transitional to condensed sequence clastics and carbonates of the Glenwood Formation above. Sedimentologic and petrographic analysis of conventional core from 25 wells suggests that reservoir quality in the formation is strongly dependent on a complex diagenetic history, especially the nature and subsequent dissolution of intergranular carbonate in the sandstone. Petrographic evidence indicatesmore » that porosity in the formation formed by dissolution of precursor dolomite of various origins and, locally, the formation of pore-filling authigenic clay (chlorite-illite). Authigenic clay is the incongruent dissolution product of dolomite, detrital K-feldspar, and, possibly, muscovite and results in diminished reservoir quality where abundant in the St. Peter Sandstone. Authigenic clay is volumetrically more significant in the upper portions of the formation and is associated with higher concentrations of detrital K-feldspar. Depositional facies controlled the distribution and types of intergranular carbonate (now dolomite) and detrital K-feldspar in the St. Peter Sandstone and hence reservoir quality; both components were more significant in storm-shelf sandstone facies.« less

Quantitative ultra-fast MRI of HPMC swelling and dissolution.

PubMed

Chen, Ya Ying; Hughes, L P; Gladden, L F; Mantle, M D

2010-08-01

For the first time quantitative Rapid Acquisition with Relaxation Enhancement (RARE) based ultra-fast two-dimensional magnetic resonance imaging has been used to follow the dissolution of hydroxypropylmethyl cellulose (HPMC) in water. Quantitative maps of absolute water concentration, spin-spin relaxation times and water self-diffusion coefficient are obtained at a spatial resolution of 469 microm in less than 3 min each. These maps allow the dynamic development of the medium release rate HPMC/water system to be followed. It is demonstrated that the evolution of the gel layer and, in particular, the gradient in water concentration across it, is significantly different when comparing the quantitative RARE sequence with a standard (nonquantitative) implementation of RARE. The total gel thickness in the axial direction grows faster than that in the radial direction and that the dry core initially expands anisotropically. Additionally, while HPMC absorbs a large amount of water during the dissolution process, the concentration gradient of water within the gel layer is relatively small. For the first time MRI evidence is presented for a transition swollen glassy layer which resides between the outer edge of the dry tablet core and the inner edge of the gel layer. (c) 2010 Wiley-Liss, Inc. and the American Pharmacists Association

An investigation using atomic force microscopy nanoindentation of dental enamel demineralization as a function of undissociated acid concentration and differential buffer capacity

NASA Astrophysics Data System (ADS)

Barbour, Michele E.; Shellis, R. Peter

2007-02-01

Acidic drinks and foodstuffs can demineralize dental hard tissues, leading to a pathological condition known as dental erosion, which is of increasing clinical concern. The first step in enamel dissolution is a demineralization of the outer few micrometres of tissue, which results in a softening of the structure. The primary determinant of dissolution rate is pH, but the concentration of undissociated acid, which is related to buffer capacity, also appears to be important. In this study, atomic force microscopy nanoindentation was used to measure the first initial demineralization (softening) induced within 1 min by exposure to solutions with a range of undissociated acid concentration and natural pH of 3.3 or with an undissociated acid concentration of 10 mmol l-1 and pH adjusted to 3.3. The results indicate that differential buffering capacity is a better determinant of softening than undissociated acid concentration. Under the conditions of these experiments, a buffer capacity of >3 mmol l-1 pH-1 does not have any further effect on dissolution rate. These results imply that differential buffering capacity should be used for preference over undissociated acid concentration or titratable acidity, which are more commonly employed in the literature.

Salt dissolution sinkhole at the Weeks Island, Louisiana, Strategic Petroleum Reserve storage site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neal, J.T.; Myers, R.E.

1994-12-31

A sinkhole was first observed in May 1992 over the outer edge of the two-tiered former salt mine that was converted for oil storage by the US Strategic Petroleum Reserve (SPR). Results of diagnostic studies which included geophysical, geochemical, drilling, and hydrological methods suggest a direct connection exists between the surface collapse area and the underground mine. The connection was confirmed by correlative measurements of sediment slump rates, piezometric surface deflection, and brine influx rates into the mine. The dissolution of salt below the sinkhole that initiated the leak into the mine was likely caused by several confluent geologic processes,more » and exacerbated by mining-induced stresses that created fractures which severed as hydrologic flowpaths. Modeling studies of mine stresses show that years of tensional stresses may be required before cracking begins to occur, but once begun can continue to develop, and relieve the stress in that specific regime. The crack regime creates the avenue for incursion of groundwater, very slowly initially, but gradually enlarging as undersaturated groundwater dissolves salt on the sides of the crack. Mitigative measures include increasing the mine pressurization, slowing the dissolution by injecting brine into the sinkhole throat, and permeation grouting in hydrologic flowpaths.« less

Capacitively coupled pickup in MCP-based photodetectors using a conductive metallic anode

NASA Astrophysics Data System (ADS)

Angelico, E.; Seiss, T.; Adams, B.; Elagin, A.; Frisch, H.; Spieglan, E.

2017-02-01

We have designed and tested a robust 20×20 cm2 thin metal film internal anode capacitively coupled to an external array of signal pads or micro-strips for use in fast microchannel plate photodetectors. The internal anode, in this case a 10 nm-thick NiCr film deposited on a 96% pure Al2O3 3 mm-thick ceramic plate and connected to HV ground, provides the return path for the electron cascade charge. The multi-channel pickup array consists of a printed-circuit card or glass plate with metal signal pickups on one side and the signal ground plane on the other. The pickup can be put in close proximity to the bottom outer surface of the sealed photodetector, with no electrical connections through the photodetector hermetic vacuum package other than a single ground connection to the internal anode. Two pickup patterns were tested using a small commercial MCP-PMT as the signal source: 1) parallel 50 Ω 25-cm-long micro-strips with an analog bandwidth of 1.5 GHz, and 2) a 20×20 cm2 array of 2-dimensional square 'pads' with sides of 1.27 cm or 2.54 cm. The rise-time of the fast input pulse is maintained for both pickup patterns. For the pad pattern, we observe 80% of the directly coupled amplitude. For the strip pattern we measure 34% of the directly coupled amplitude on the central strip of a broadened signal. The physical decoupling of the photodetector from the pickup pattern allows easy customization for different applications while maintaining high analog bandwidth.

Performance characteristics of No-Wall-Losses Hall Thruster

NASA Astrophysics Data System (ADS)

Ding, Yongjie; Peng, Wuji; Sun, Hezhi; Wei, Liqiu; Zeng, Ming; Wang, Fufeng; Yu, Daren

2017-08-01

A 200 W No-Wall-Losses Hall Thruster (NWLHT-200 W) is designed and processed to verify the technology of pushing down magnetic field with two permanent magnetic rings. To create a magnetic field, NWLHT-200 W uses two permanent magnetic rings (inner and outer) in the absence of magnetic screen or magnetic component. The anode is at the internal magnetic separatrix position, and the thruster shell is hollow to enhance the heat dissipation of ceramics. The magnetic field strength at the channel outlet is 90% of the maximum magnetic field. In this study, the experimental results concerning the thrust, discharge current, specific impulse, and efficiency are presented and examined. Our experiments show that "no erosive discharge" of wall is achieved within the range of 120-460 W; the maximum efficiency of the anode may reach 49%. The thruster designed can work stably for a long time, without any auxiliary heat dissipation equipment (heat pipe or radiator), which significantly prolongs the life of Hall thrusters.

Heterogeneous nanocrystals assembled TiO2/SnO2/C composite for improved lithium storage

NASA Astrophysics Data System (ADS)

Tian, Qinghua; Mao, Yuning; Zhang, Xuzhen; Yang, Li

2018-07-01

Using stable TiO2 and flexible carbon as double-functional structure protector of nanostructural SnO2 to fabricate TiO2/SnO2/C composites is widely considered as a favorable strategy for improving the lithium storage performance of SnO2 anodes. But, it is still a challenge to obtain a satisfying TiO2/SnO2/C composite. Herein, an interesting porous nanostructure of TiO2/SnO2/C nanosphere composite assembled by TiO2 and SnO2 nanocrystals with an outer carbon coating has been fabricated by a well-designed approach. Thanks to the perfectly combined action of porous spherical nanostructure, TiO2 and SnO2 nanocrystals and carbon coating, the as-prepared composite obtains excellent structure stability and improved electrochemcial properties. When used as a promising anode for lithium-ion batteres, it exhibits outstanding lithium storage performance, delivering a high capacity of 687.2 mAh g-1 after even 400 cycles.

The Effects of Diet Calcium, Protein and Acidity on Calcium Retention in the Rat, Particularly as Related to the Inner and Outer Surfaces of Tubular Bone: A Possible Model for the Treatment or Prevention of Osteoporosis

DTIC Science & Technology

1979-10-01

transformed, by dissolution and reprecipitation, Into the crystalline constituent (85). It has also been suggested that crystalline hydroxyapatite ...a Ca:P molar ratio of 8:6), and finally hydroxyapatite (115). The apatites of bone are primarily hydroxvapatite which has the composition Ca 1 0 (P0...Thus bone always contains a large variety of materials other than those which compose hydroxyapatite . ____ ____ ___..~rr? - -- lt- - -11- The amount

Assessment of capacitor electrodes for intracortical neural stimulation.

PubMed

Rose, T L; Kelliher, E M; Robblee, L S

1985-01-01

Capacitor electrodes offer the potential for the safest method of stimulation of neural tissue because they operate without any faradaic process occurring at the electrode-electrolyte interface. Their use eliminates problems associated with metal dissolution or water electrolysis which may occur with electrodes of noble metals. This paper reviews recent work aimed at increasing the charge storage density of capacitor electrodes to allow their application with the small areas of 10(-4) mm2 required for intracortical stimulation of single neurons. Increased charge storage with electrodes using anodic films such as TiO2 and Ta2O5 has been obtained by increasing the real surface area of microelectrodes. Experiments have also been done with BaTiO3 films which have a much higher dielectric constant than the anodic film dielectrics. State-of-the-art electrodes made with these materials, however, have a charge storage density which at best is comparable to that obtained with Pt and is considerably lower than electrochemically safe charge densities that have been reported for activated Ir. It is concluded that for very small intracortical electrodes, capacitor electrodes will not be competitive with electrodes which operate using surface localized faradaic reactions.

Integrated fuel cell stack shunt current prevention arrangement

DOEpatents

Roche, Robert P.; Nowak, Michael P.

1992-01-01

A fuel cell stack includes a plurality of fuel cells juxtaposed with one another in the stack and each including a pair of plate-shaped anode and cathode electrodes that face one another, and a quantity of liquid electrolyte present at least between the electrodes. A separator plate is interposed between each two successive electrodes of adjacent ones of the fuel cells and is unified therewith into an integral separator plate. Each integral separator plate is provided with a circumferentially complete barrier that prevents flow of shunt currents onto and on an outer peripheral surface of the separator plate. This barrier consists of electrolyte-nonwettable barrier members that are accommodated, prior to the formation of the integral separator plate, in corresponding edge recesses situated at the interfaces between the electrodes and the separator plate proper. Each barrier member extends over the entire length of the associated marginal portion and is flush with the outer periphery of the integral separator plate. This barrier also prevents cell-to-cell migration of any electrolyte that may be present at the outer periphery of the integral separator plate while the latter is incorporated in the fuel cell stack.

Intensified nitrogen and phosphorus removal in a novel electrolysis-integrated tidal flow constructed wetland system.

PubMed

Ju, Xinxin; Wu, Shubiao; Zhang, Yansheng; Dong, Renjie

2014-08-01

A novel electrolysis-integrated tidal flow constructed wetland (CW) system was developed in this study. The dynamics of intensified nitrogen and phosphorus removal and that of hydrogen sulphide control were evaluated. Ammonium removal of up to 80% was achieved with an inflow concentration of 60 mg/L in wetland systems with and without electrolysis integration. Effluent nitrate concentration decreased from 2 mg/L to less than 0.5 mg/L with the decrease in current intensity from 1.5 mA/cm(2) to 0.57 mA/cm(2) in the electrolysis-integrated wetland system, thus indicating that the current intensity of electrolysis plays an important role in nitrogen transformations. Phosphorus removal was significantly enhanced, exceeding 95% in the electrolysis-integrated CW system because of the in-situ formation of a ferric iron coagulant through the electro-dissolution of a sacrificial iron anode. Moreover, the electrolyzed wetland system effectively inhibits sulphide accumulation as a result of a sulphide precipitation coupled with ferrous-iron electro-dissolution and/or an inhibition of bacterial sulphate reduction under increased aerobic conditions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Rare earth elements in Hamersley BIF minerals

NASA Astrophysics Data System (ADS)

Alibert, Chantal

2016-07-01

Minerals from the Hamersley banded iron formation, Western Australia, were analyzed for Y and rare earth elements (YREEs) by laser ablation ICP-MS to investigate diagenetic pathways, from precursor phases to BIF minerals. One group of apatites carries the seawater REE signature, giving evidence that P and REEs, thoroughly scavenged from the water column by Si-ferrihydrite particles, were released upon microbial Fe3+ reductive dissolution of Si-ferrihydrite in pore-water and finally sequestered mainly in authigenic apatite. The absence of fractionation between apatite and seawater suggests that REE were first incorporated into an amorphous calcium phosphate as fully hydrated cations, i.e. as outer-sphere complexes. The iron oxides and carbonates carry only a small fraction of the whole-rock REE budget. Their REE patterns are distinctly enriched in Yb and show some M-type tetrad effect consistent with experimental Kd(REE) between solid and saline solution with low carbonate ion concentrations. It is deduced that hematite formed at an incipient stage of Fe2+-catalyzed dissolution of Si-ferrihydrite, via a dissolution-reprecipitation pathway. The REE pattern of greenalite, found as sub-micron particles in quartz in a chert-siderite sample, is consistent with its authigenic origin by precipitation in pore-water after dissolution of a small amount of Si-ferrihydrite. Magnetite carries very low YREEs (ppb-level), has an homogeneous pattern distinctly enriched in the mid-REEs compared to hematite, and includes a late population depleted in light-REEs, Ba and As. Magnetite forming aggregates and massive laminae is tentatively interpreted as reflecting some fluid-aided hematite-magnetite re-equilibration or transformation at low-grade metamorphic temperatures.

Amorphous and crystalline TiO2 nanotube arrays for enhanced Li-ion intercalation properties.

PubMed

Guan, Dongsheng; Cai, Chuan; Wang, Ying

2011-04-01

We have employed a simple process of anodizing Ti foils to prepare TiO2 nanotube arrays which show enhanced electrochemical properties for applications as Li-ion battery electrode materials. The lengths and pore diameters of TiO2 nanotubes can be finely tuned by varying voltage, electrolyte composition, or anodization time. The as-prepared nanotubes are amorphous and can be converted into anatase nanotubes with heat treatment at 480 degrees C. Rutile crystallites emerge in the anatase nanotube when the annealing temperature is increased to 580 degrees C, resulting in TiO2 nanotubes of mixed phases. The morphological features of nanotubes remain unchanged after annealing. Li-ion insertion performance has been studied for amorphous and crystalline TiO2 nanotube arrays. Amorphous nanotubes with a length of 3.0 microm and an outer diameter of 125 nm deliver a capacity of 91.2 microA h cm(-2) at a current density of 400 microA cm(-2), while those with a length of 25 microm and an outer diameter of 158 nm display a capacity of 533 microA h cm-2. When the 3-microm long nanotubes become crystalline, they deliver lower capacities: the anatase nanotubes and nanotubes of mixed phases show capacities of 53.8 microA h cm-2 and 63.1 microA h cm(-2), respectively at the same current density. The amorphous nanotubes show excellent capacity retention ability over 50 cycles. The cycled nanotubes show little change in morphology compared to the nanotubes before electrochemical cycling. All the TiO2 nanotubes demonstrate higher capacities than amorphous TiO2 compact layer reported in literature. The amorphous TiO2 nanotubes with a length of 1.9 microm exhibit a capacity five times higher than that of TiO2 compact layer even when the nanotube array is cycled at a current density 80 times higher than that for the compact layer. These results suggest that anodic TiO2 nanotube arrays are promising electrode materials for rechargeable Li-ion batteries.

In situ monitoring of corrosion mechanisms and phosphate inhibitor surface deposition during corrosion of zinc-magnesium-aluminium (ZMA) alloys using novel time-lapse microscopy.

PubMed

Sullivan, James; Cooze, Nathan; Gallagher, Callum; Lewis, Tom; Prosek, Tomas; Thierry, Dominique

2015-01-01

In situ time-lapse optical microscopy was used to examine the microstructural corrosion mechanisms in three zinc-magnesium-aluminium (ZMA) alloy coated steels immersed in 1% NaCl pH 7. Preferential corrosion of MgZn(2) lamellae within the eutectic phases was observed in all the ZMA alloys followed by subsequent dissolution of Zn rich phases. The total extent and rate of corrosion, measured using time-lapse image analysis and scanning vibrating electrode technique (SVET) estimated mass loss, decreased as Mg and Al alloying additions were increased up to a level of 3 wt% Mg and 3.7 wt% Al. This was probably due to the increased presence of MgO and Al(2)O(3) at the alloy surface retarding the kinetics of cathodic oxygen reduction. The addition of 1 × 10(-2) mol dm(-3) Na(3)PO(4) to 1% NaCl pH 7 had a dramatic influence on the corrosion mechanism for a ZMA with passivation of anodic sites through phosphate precipitation observed using time-lapse image analysis. Intriguing rapid precipitation of filamentous phosphate was also observed and it is postulated that these filaments nucleate and grow due to super saturation effects. Polarisation experiments showed that the addition of 1 × 10(-2) mol dm(-3) Na(3)PO(4) to the 1% NaCl electrolyte promoted an anodic shift of 50 mV in open circuit potential for the ZMA alloy with a reduction in anodic current of 2.5 orders of magnitude suggesting that it was acting primarily as an anodic inhibitor supporting the inferences from the time-lapse investigations. These phosphate additions resulted in a 98% reduction in estimated mass loss as measured by SVET demonstrating the effectiveness of phosphate inhibitors for this alloy system.

Electro-kinetic remediation coupled with phytoremediation to remove lead, arsenic and cesium from contaminated paddy soil

PubMed Central

Mao, Xinyu; Han, Fengxiang X.; Shao, Xiaohou; Guo, Kai; McComb, Jacqueline; Arslan, Zikri; Zhang, Zhanyu

2017-01-01

The objectives of this study were to investigate distribution and solubility of Pb, Cs and As in soils under electrokinetic field and examine the processes of coupled electrokinetic phytoremediation of polluted soils. The elevated bioavailability and bioaccumulation of Pb, As and Cs in paddy soil under an electrokinetic field (EKF) were studied. The results show that the EKF treatment is effective on lowering soil pH to around 1.5 near the anode which is beneficial for the dissolution of metal(loid)s, thus increasing their overall solubility. The acidification in the anode soil efficiently increased the water soluble (SOL) and exchangeable (EXC) Pb, As and Cs, implying enhanced solubility and elevated overall potential bioavailability in the anode region while lower solubility in the cathode areas. Bioaccumulations of Pb, As and Cs were largely determined by the nature of elements, loading levels and EKF treatment. The native Pb in soil usually is not bioavailable. However, EKF treatment tends to transfer Pb to the SOL and EXC fractions improving the phytoextraction efficiency. Similarly, EKF transferred more EXC As and Cs to the SOL fraction significantly increasing their bioaccumulation in plant roots and shoots. Pb and As were accumulated more in plant roots than in shoots while Cs was accumulated more in shoots due to its similarity of chemical properties to potassium. Indian mustard, spinach and cabbage are good accumulators for Cs. Translocation of Pb, As and Cs from plant roots to shoots were enhanced by EKF. However, this study indicated the overall low phytoextraction efficiency of these plants. PMID:26650421

Water oxidation by size selected Co 27 clusters supported on Fe 2O 3

DOE PAGES

Pellin, Michael J.; Riha, Shannon C.; Tyo, Eric C.; ...

2016-09-22

The complexity of the water oxidation reaction makes understanding the role of individual catalytic sites critical to improving the process. Here, size-selected 27-atom cobalt clusters (Co 27) deposited on hematite (Fe 2O 3) anodes were tested for water oxidation activity. The uniformity of these anodes allows measurement of the activity of catalytic sites of well-defined nuclearity and known density. Grazing incidence X-ray absorption near-edge spectroscopy (GIXANES) characterization of the anodes before and after electrochemical cycling demonstrates that these Co 27 clusters are stable to dissolution even in the harsh water oxidation electrochemical environment. They are also stable under illumination atmore » the equivalent of 0.4suns irradiation. The clusters show turnover rates for water oxidation that are comparable or higher than those reported for Pd- and Co-based materials or for hematite. The support for the Co 27 clusters is Fe 2O 3 grown by atomic layer deposition on a Si chip. We have chosen to deposit a Fe2O3 layer that is only a few unit cells thick (2nm), to remove complications related to exciton diffusion. We find that the electrocatalytic and the photoelectrocatalytic activity of the Co 27/Fe 2O 3 material is significantly improved when the samples are annealed (with the clusters already deposited). Lastly, given that the support is thin and that the cluster deposition density is equivalent to approximately 5% of an atomic monolayer, we suggest that annealing may significantly improve the exciton diffusion from the support to the catalytic moiety.« less

Numerical experiments on neutron yield and soft x-ray study of a ˜100 kJ plasma focus using the current profile fitting technique

NASA Astrophysics Data System (ADS)

Ong, S. T.; Chaudhary, K.; Ali, J.; Lee, S.

2014-07-01

Numerical experiments using the Lee model were performed to study the neutron yield and soft x-ray emission from the IR-MPF-100 plasma focus using the current fitting technique. The mass sweeping factor and the current factor for the axial and radial phase were used to represent the imperfections encountered in experiments. All gross properties including the yields were realistically simulated once the computed and measured current profiles were well fitted. The computed neutron yield Yn was in agreement with the experimentally measured Yn at 20 kV (E0 ˜ 30 kJ) charging voltage. The optimum computed neutron yield of Yn = 1.238 × 109 neutrons per shot was obtained at optimum physics parameters of the plasma focus operated with deuterium gas. It was also observed that no soft x-rays were emitted from the IR-MPF-100 plasma focus operated with argon gas due to the absence of helium-like and hydrogen-like ions at a low plasma temperature (˜0.094 keV) and axial speed (8.12 cm µs-1). However, the soft x-ray yield can be achieved by increasing the charging voltage, using a higher ratio of outer anode radius to inner anode radius c or shorter anode length z0, or using neon as the operating gas.

Aligned TiO₂ nanotube/nanoparticle heterostructures with enhanced electrochemical performance as three-dimensional anode for lithium-ion microbatteries.

PubMed

Xie, Keyu; Guo, Min; Lu, Wei; Huang, Haitao

2014-11-14

A novel TiO₂ three-dimensional (3D) anode with an aligned TiO₂ nanotube/nanoparticle heterostructure (TiO₂ NTs/NPs) is developed by simply immersing as-anodized TiO₂ NTs into water and further crystallizing the TiO₂ NTs by post-annealing. The heterostructure, with its core in a tubular morphology and with both the outer and inner surface consisting of nanoparticles, is confirmed by FESEM and TEM. A reversible areal capacity of 0.126 mAh · cm(-2) is retained after 50 cycles for the TiO₂ NTs/NPs heterostructure electrode, which is higher than that of the TiO₂ NTs electrode (0.102 mAh · cm(-2) after 50 cycles). At the current densities of 0.02, 0.04, 0.06, 0.08, 0.10 and 0.20 mA · cm(-2), the areal capacities are 0.142, 0.127, 0.117, 0.110, 0.104 and 0.089 mAh · cm(-2), respectively, for the TiO₂ NTs/NPs heterostructure electrode compared to the areal capacities of 0.123, 0.112, 0.105, 0.101, 0.094 and 0.083 mAh · cm(-2), respectively, for the the TiO₂ NTs electrode. The enhanced electrochemical performance is attributed to the unique microstructure of the TiO₂ NTs/NPs heterostructure electrode with the TiO₂ NT core used as a straight pathway for electronic transport and with TiO₂ NP offering enhanced surface areas for facile Li+ insertion/extraction. The results described here inspire a facile approach to fabricate a 3D anode with an enhanced electrochemical performance for lithium-ion microbattery applications.

Erbium Doped Quantum Dot and Si:O and Plasmon Resonance Enabled Quantum Dot Nanoscale Lasers

DTIC Science & Technology

2009-08-31

electroluminescence has to be coupled with a high-Q cavity for lasing. Alq3 PEDOT:PSS ITO — • MEHPPV +PbSe QDs . • •A iz^————— Gold (Au...PEDOT:PSS on the ITO anode and Alq3 /Ca/Al cathode. The inset is a SEM image of the L3 defect photonic crystal microcavity in silicon. Outer air holes at...consisting of tris(8-hydroxyquinoline)aluminum ( Alq3 ), calcium, and aluminum. The device heterostructure is schematically shown in Fig. 5(a). The ITO

An internal affinity-tag for purification and crystallization of the siderophore receptor FhuA, integral outer membrane protein from Escherichia coli K-12.

PubMed

Ferguson, A D; Breed, J; Diederichs, K; Welte, W; Coulton, J W

1998-07-01

FhuA (Mr 78,992, 714 amino acids), siderophore receptor for ferrichrome-iron in the outer membrane of Escherichia coli, was affinity tagged, rapidly purified, and crystallized. To obtain FhuA in quantities sufficient for crystallization, a hexahistidine tag was genetically inserted into the fhuA gene after amino acid 405, which resides in a known surface-exposed loop. Recombinant FhuA405.H6 was overexpressed in an E. coli strain that is devoid of several major porins and using metal-chelate chromatography was purified in large amounts to homogeneity. FhuA crystals were grown using the hanging drop vapor diffusion technique and were suitable for X-ray diffraction analysis. On a rotating anode X-ray source, diffraction was observed to 3.0 A resolution. The crystals belong to space group P6(1) or P6(5) with unit cell dimensions of a=b=174 A, c=88 A (alpha=beta=90 degrees, gamma=120 degrees).

Experimental and Theoretical Demonstrations for the Mechanism behind Enhanced Microbial Electron Transfer by CNT Network

NASA Astrophysics Data System (ADS)

Liu, Xian-Wei; Chen, Jie-Jie; Huang, Yu-Xi; Sun, Xue-Fei; Sheng, Guo-Ping; Li, Dao-Bo; Xiong, Lu; Zhang, Yuan-Yuan; Zhao, Feng; Yu, Han-Qing

2014-01-01

Bioelectrochemical systems (BESs) share the principle of the microbially catalyzed anodic substrate oxidation. Creating an electrode interface to promote extracellular electron transfer from microbes to electrode and understanding such mechanisms are crucial for engineering BESs. In this study, significantly promoted electron transfer and a 10-times increase in current generation in a BES were achieved by the utilization of carbon nanotube (CNT) network, compared with carbon paper. The mechanisms for the enhanced current generation with the CNT network were elucidated with both experimental approach and molecular dynamic simulations. The fabricated CNT network was found to be able to substantially enhance the interaction between the c-type cytochromes and solid electron acceptor, indicating that the direct electron transfer from outer-membrane decaheme c-type cytochromes to electrode might occur. The results obtained in this study will benefit for the optimized design of new materials to target the outer membrane proteins for enhanced electron exchanges.

Pulsed electromagnetic gas acceleration

NASA Technical Reports Server (NTRS)

Jahn, R. G.; Vonjaskowsky, W. F.; Clark, K. E.

1974-01-01

Detailed measurements of the axial velocity profile and electromagnetic structure of a high power, quasi-steady MPD discharge are used to formulate a gasdynamic model of the acceleration process. Conceptually dividing the accelerated plasma into an inner flow and an outer flow, it is found that more than two-thirds of the total power in the plasma is deposited in the inner flow, accelerating it to an exhaust velocity of 12.5 km/sec. The outer flow, which is accelerated to a velocity of only 6.2 km/sec, appears to provide a current conduction path between the inner flow and the anode. Related cathode studies have shown that the critical current for the onset of terminal voltage fluctuations, which was recently shown to be a function of the cathode area, appears to reach an asymptote for cathodes of very large surface area. Detailed floating potential measurements show that the fluctuations are confined to the vicinity of the cathode and hence reflect a cathode emission process rather than a fundamental limit on MPD performance.

Barium isotope fractionation during witherite (BaCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; van Zuilen, Kirsten; Purgstaller, Bettina; Baldermann, Andre; Nägler, Thomas F.; Dietzel, Martin

2016-10-01

This study examines the behavior of Ba isotope fractionation between witherite and fluid during mineral dissolution, precipitation and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 10-2 M NaCl solution where the pH was adjusted by continuous bubbling of a water saturated gas phase of CO2 or atmospheric air. During witherite dissolution no Ba isotope fractionation was observed between solid and fluid. In contrast, during witherite precipitation, caused by a pH increase, a preferential uptake of the lighter 134Ba isotopomer in the solid phase was observed. In this case, the isotope fractionation factor αwitherite-fluid is calculated to be 0.99993 ± 0.00004 (or Δ137/134Bawitherite-fluid ≈ -0.07 ± 0.04‰, 2 sd). The most interesting feature of this study, however, is that after the attainment of chemical equilibrium, the Ba isotope composition of the aqueous phase is progressively becoming lighter, indicating a continuous exchange of Ba2+ ions between witherite and fluid. Mass balance calculations indicate that the detachment of Ba from the solid is not only restricted to the outer surface layer of the solid, but affects several (∼7 unit cells) subsurface layers of the crystal. This observation comes in excellent agreement with the concept of a dynamic system at chemical equilibrium in a mineral-fluid system, denoting that the time required for the achievement of isotopic equilibrium in the witherite-fluid system is longer compared to that observed for chemical equilibrium. Overall, these results indicate that the isotopic composition of Ba bearing carbonates in natural environments may be altered due to changes in fluid composition without a net dissolution/precipitation to be observed.

Preparation of yolk-shell MoS2 nanospheres covered with carbon shell for excellent lithium-ion battery anodes

NASA Astrophysics Data System (ADS)

Guo, Bangjun; Feng, Yu; Chen, Xiaofan; Li, Bo; Yu, Ke

2018-03-01

Molybdenum disulfide is regarded as one of the most promising electrode materials for high performance lithium-ion batteries. Designing firm basal structure is a key point to fully utilize the high capacity of layered MoS2 nanomaterials. Here, yolk-shell structured MoS2 nanospheres is firstly designed and fabricated to meet this needs. This unique yolk-shell nanospheres are transformed from solid nanospheres by a simply weak alkaline etching method. Then, the yolk-shell MoS2/C is synthesized by a facile process to protect the outside MoS2 shell and promote the conductivity. Taking advantages of high capacity and well-defined cavity space, allowing the core MoS2 to expand freely without breaking the outer shells, yolk-shell MoS2/C nanospheres delivers long cycle life (94% of capacity retained after 200 cycles) and high rate behaviour (830 mA h g-1 at 5 A g-1). This design of yolk-shell structure may set up a new strategy for preparing next generation anode materials for LIBs.

Multi-Physics Modeling of Molten Salt Transport in Solid Oxide Membrane (SOM) Electrolysis and Recycling of Magnesium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Powell, Adam; Pati, Soobhankar

2012-03-11

Solid Oxide Membrane (SOM) Electrolysis is a new energy-efficient zero-emissions process for producing high-purity magnesium and high-purity oxygen directly from industrial-grade MgO. SOM Recycling combines SOM electrolysis with electrorefining, continuously and efficiently producing high-purity magnesium from low-purity partially oxidized scrap. In both processes, electrolysis and/or electrorefining take place in the crucible, where raw material is continuously fed into the molten salt electrolyte, producing magnesium vapor at the cathode and oxygen at the inert anode inside the SOM. This paper describes a three-dimensional multi-physics finite-element model of ionic current, fluid flow driven by argon bubbling and thermal buoyancy, and heat andmore » mass transport in the crucible. The model predicts the effects of stirring on the anode boundary layer and its time scale of formation, and the effect of natural convection at the outer wall. MOxST has developed this model as a tool for scale-up design of these closely-related processes.« less

Aspects on mediated glucose oxidation at a supported cubic phase.

PubMed

Aghbolagh, Mahdi Shahmohammadi; Khani Meynaq, Mohammad Yaser; Shimizu, Kenichi; Lindholm-Sethson, Britta

2017-12-01

A supported liquid crystalline cubic phase housing glucose oxidase on an electrode surface has been suggested as bio-anode in a biofuel. The purpose of this investigation is to clarify some aspect on the mediated enzymatic oxidation of glucose in such a bio-anode where the mediator ferrocene-carboxylic acid and glucose were dissolved in the solution. The enzyme glucose oxidase was housed in the water channels of the mono-olein cubic phase. The system was investigated with cyclic voltammetry at different scan rates and the temperature was varied between 15°C and 30°C. The diffusion coefficient of the mediator and also the film resistance was estimated showing a large decrease in the mass-transport properties as the temperature was decreased. The current from mediated oxidation of glucose at the electrode surface increased with decreasing film thickness. The transport of the mediator in the cubic phase was the rate-limiting step in the overall reaction, where the oxidation of glucose took place at the outer surface of the cubic phase. Copyright © 2017 Elsevier B.V. All rights reserved.

Nafion-coating of the electrodes improves the flow-stability of the Ag/SiO2/Ag2O electroosmotic pump.

PubMed

Shin, Woonsup; Zhu, Enhua; Nagarale, Rajaram Krishna; Kim, Chang Hwan; Lee, Jong Myung; Shin, Samuel Jaeho; Heller, Adam

2011-06-15

When a current or a voltage is applied across the ceramic membrane of the nongassing Ag/Ag(2)O-SiO(2)-Ag/Ag(2)O pump, protons produced in the anodic reaction 2Ag(s) + H(2)O → Ag(2)O(s) + 2H(+) + 2e(-) are driven to the cathode, where they are consumed by the reaction Ag(2)O(s) + H(2)O + 2e(-) → 2Ag(s) + 2 OH(-). The flow of water is induced by momentum transfer from the electric field-driven proton-sheet at the surface of the ceramic membrane. About 10(4) water molecules flowed per reacted electron. Because dissolved ions decrease the field at the membrane surface, the flow decreases upon increasing the ionic strength. For this reason Ag(+) ions introduced through the anodic reaction and by dissolution of Ag(2)O decrease the flow. Their accumulation is reduced by applying Nafion-films to the electrodes. The 20 μL min(-1) flow rate of 6 mm i.d. pumps with Nafion coated electrodes operate daily for 5 min at 1 V for 1 month, for 70 h when the pump is pulsed for 30 s every 30 min, and for 2 h when operating continuously.

Fabrication and characterization of conductive anodic aluminum oxide substrates

NASA Astrophysics Data System (ADS)

Altuntas, Sevde; Buyukserin, Fatih

2014-11-01

Biomaterials that allow the utilization of electrical, chemical and topographic cues for improved neuron-material interaction and neural regeneration hold great promise for nerve tissue engineering applications. The nature of anodic aluminum oxide (AAO) membranes intrinsically provides delicate control over topographic and chemical cues for enhanced cell interaction; however their use in nerve regeneration is still very limited. Herein, we report the fabrication and characterization of conductive AAO (CAAO) surfaces for the ultimate goal of integrating electrical cues for improved nerve tissue behavior on the nanoporous substrate material. Parafilm was used as a protecting polymer film, for the first time, in order to obtain large area (50 cm2) free-standing AAO membranes. Carbon (C) was then deposited on the AAO surface via sputtering. Morphological characterization of the CAAO surfaces revealed that the pores remain open after the deposition process. The presence of C on the material surface and inside the nanopores was confirmed by XPS and EDX studies. Furthermore, I-V curves of the surface were used to extract surface resistance values and conductive AFM demonstrated that current signals can only be achieved where conductive C layer is present. Finally, novel nanoporous C films with controllable pore diameters and one dimensional (1-D) C nanostructures were obtained by the dissolution of the template AAO substrate.

Gas Evolution in Operating Lithium-Ion Batteries Studied In Situ by Neutron Imaging

PubMed Central

Michalak, Barbara; Sommer, Heino; Mannes, David; Kaestner, Anders; Brezesinski, Torsten; Janek, Jürgen

2015-01-01

Gas generation as a result of electrolyte decomposition is one of the major issues of high-performance rechargeable batteries. Here, we report the direct observation of gassing in operating lithium-ion batteries using neutron imaging. This technique can be used to obtain qualitative as well as quantitative information by applying a new analysis approach. Special emphasis is placed on high voltage LiNi0.5Mn1.5O4/graphite pouch cells. Continuous gassing due to oxidation and reduction of electrolyte solvents is observed. To separate gas evolution reactions occurring on the anode from those associated with the cathode interface and to gain more insight into the gassing behavior of LiNi0.5Mn1.5O4/graphite cells, neutron experiments were also conducted systematically on other cathode/anode combinations, including LiFePO4/graphite, LiNi0.5Mn1.5O4/Li4Ti5O12 and LiFePO4/Li4Ti5O12. In addition, the data were supported by gas pressure measurements. The results suggest that metal dissolution in the electrolyte and decomposition products resulting from the high potentials adversely affect the gas generation, particularly in the first charge cycle (i.e., during graphite solid-electrolyte interface layer formation). PMID:26496823

Mechanism of Zn Insertion into Nanostructured δ-MnO 2 : A Nonaqueous Rechargeable Zn Metal Battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Sang-Don; Kim, Soojeong; Li, Dongguo

2017-05-19

Unlike the more established lithium-ion based energy storage chemistries, the complex intercalation chemistry of multivalent cations in a host lattice is not well understood, especially the relationship between the intercalating species solution chemistry and the prevalence and type of side reactions. Among multivalent metals, a promising model system can be based on nonaqueous Zn2+ ion chemistry. Several examples of these systems support the use of a Zn metal anode, and reversible intercalation cathodes have been reported. This study utilizes a combination of analytical tools to probe the chemistry of a nanostructured delta-MnO2 cathode in association with a nonaqueous acetonitrile-Zn(TFSI)(2) electrolytemore » and a Zn metal anode. As many of the issues related to understanding a multivalent battery relate to the electrolyte electrode interface, the high surface area of a nanostructured cathode provides a significant interface between the electrolyte and cathode host that maximizes the spectroscopic signal of any side reactions or minor mechanistic pathways. Numerous factors affecting capacity fade and issues associated with the second phase formation including Mn dissolution in heavily cycled Zn/delta-MnO2 cells are presented including dramatic mechanistic differences in the storage mechanism of this couple when compared to similar aqueous electrolytes are noted.« less

Recovery of Metal Values from Spent Zinc-Carbon Dry Cell Batteries

NASA Astrophysics Data System (ADS)

Khan, Majharul Haque; Gulshan, Fahmida; Kurny, A. S. W.

2013-04-01

Spent zinc-carbon dry cell batteries were characterized in the process of recovery of metal values. Zinc, manganese and steel were the major metallic materials constituting 63 % of the weight of spent batteries. Different components of the spent batteries were separately processed to extract the metallic values. A maximum of 92 % of total amount of zinc contained in the anodes could be extracted with a purity of over 99.0 % from the anodes by heating at 600 °C for 10 min in presence of 12 % NH4Cl flux. Spent electrolyte paste containing manganese and zinc as major metallic elements, was leached in sulfuric acid solution in presence of hydrogen peroxide as a reducing agent. The optimum condition for leaching was found to be concentration of sulfuric acid: 2.5 M, concentration of hydrogen peroxide: 10 %, temperature: 60 °C, stirring speed: 600 rpm and solid/liquid ratio 1:12. A maximum of 88 % manganese contained in the paste could be dissolved within 27 min of leaching under the optimized conditions. Dissolution of zinc under the same conditions was 97 %. A maximum of 69.89 % of manganese and 83.29 % of zinc contained in the leach liquor could be precipitated in the form of manganese carbonate and zinc oxalate.

Effects of Anion Mobility on Electrochemical Behaviors of Lithium–Sulfur Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Kee Sung; Chen, Junzheng; Cao, Ruiguo

The electrolyte is a crucial component of lithium-sulfur (Li-S) batteries, as it controls polysulfide dissolution, charge shuttling processes, and solid-electrolyte interphase (SEI) layer formation. Experimentally, the overall performance of Li-S batteries varies with choice of solvent system and Li-salt used in the electrolyte, and a lack of predictive understanding about the effects of individual electrolyte components inhibits the rational design of electrolytes for Li-S batteries. Here we analyze the role of the counter anions of common Li salts (such as TfO-, FSI-, TFSI-, and TDI-) when dissolved in DOL/DME (1:1 vol.) for use in Li-S batteries. The evolution of ion-ionmore » and ion-solvent interactions due to vari-ous anions was analyzed using 17O NMR and pulsed-field gradient (PFG) NMR and then correlated with electrochemi-cal performance in Li-S cells. These data reveal that the for-mation of the passivation layer on the anode and the loss of active materials from the cathode (evidenced by polysulfide dissolution) are related to anion mobility and affinity with lithium polysulfide, respectively. For future electrolyte de-sign, anions with lower mobility and weaker interactions with lithium polysulfides may be superior candidates for increasing the long-term stability of Li-S batteries.« less

A Universal Strategy To Prepare Sulfur-Containing Polymer Composites with Desired Morphologies for Lithium-Sulfur Batteries.

PubMed

Zeng, Shao-Zhong; Zeng, Xierong; Tu, Wenxuan; Huang, Haitao; Yu, Liang; Yao, Yuechao; Jin, Nengzhi; Zhang, Qi; Zou, Jizhao

2018-06-19

Lithium-sulfur (Li-S) batteries are probably the most promising candidates for the next-generation batteries owing to their high energy density. However, Li-S batteries face severe technical problems where the dissolution of intermediate polysulfides is the biggest problem because it leads to the degradation of the cathode and the lithium anode, and finally the fast capacity decay. Compared with the composites of elemental sulfur and other matrices, sulfur-containing polymers (SCPs) have strong chemical bonds to sulfur and therefore show low dissolution of polysulfides. Unfortunately, most SCPs have very low electron conductivity and their morphologies can hardly be controlled, which undoubtedly depress the battery performances of SCPs. To overcome these two weaknesses of SCPs, a new strategy was developed for preparing SCP composites with enhanced conductivity and desired morphologies. With this strategy, macroporous SCP composites were successfully prepared from hierarchical porous carbon. The composites displayed discharge/charge capacities up to 1218/1139, 949/922, and 796/785 mA h g -1 at the current rates of 5, 10, and 15 C, respectively. Considering the universality of this strategy and the numerous morphologies of carbon materials, this strategy opens many opportunities for making carbon/SCP composites with novel morphologies.

Pulsed electrodeposition of two-dimensional Ag nanostructures on Au(111).

PubMed

Borissov, D; Tsekov, R; Freyland, W

2006-08-17

One-step pulsed potential electrodeposition of Ag on Au(111) in the underpotential deposition (UPD) region has been studied in 0.5 mM Ag2SO4 + 0.1 M H2SO4 aqueous electrolyte at various pulse durations from 0.2 to 500 ms. Evolution of the deposited Ag nanostructures was followed by in situ scanning tunneling microscopy (STM) and by measurement of the respective current transients. At short pulse durations a relatively high number density (4 x 10(11) cm(-2)) of two-dimensional Ag clusters with a narrow size and distance distribution is observed. They exhibit a remarkably high stability characterized by a dissolution potential which lies about 200 mV more anodically than the typical potential of Ag-(1 x 1) monolayer dissolution. To elucidate the underlying nucleation and growth mechanism, two models have been considered: two-dimensional lattice incorporation and a newly developed coupled diffusion-adsorption model. The first one yields a qualitative description of the current transients, whereas the second one is in nearly quantitative agreement with the experimental data. In this model the transformation of a Ag-(3 x 3) into a Ag-(1 x 1) structure indicated in the cyclic voltammogram (peaks at 520 vs 20 mV) is taken into account.

Moisture-Induced Spallation and Interfacial Hydrogen Embrittlement of Alumina Scales

NASA Technical Reports Server (NTRS)

Smialek, James L.

2005-01-01

Thermal expansion mismatch stresses and interfacial sulfur activity are the major factors producing primary Al2O3 scale spallation on high temperature alloys. However, moisture-induced delayed spallation appears as a secondary, but often dramatic, illustration of an additional mechanistic detail. A historical review of delayed failure of alumina scales and TBC s on superalloys is presented herein. Similarities with metallic phenomena suggest that hydrogen embrittlement from ambient humidity, resulting from the reaction Al+3H2O=Al(OH)3+3H(+)+3e(-), is the operative mechanism. This proposal was tested by standard cathodic hydrogen charging in 1N H2SO4, applied to Rene N5 pre-oxidized at 1150 C for 1000 1-hr cycles, and monitored by weight change, induced current, and microstructure. Here cathodic polarization at -2.0 V abruptly stripped mature Al2O3 scales at the oxide-metal interface. Anodic polarization at +2.0 V, however, produced alloy dissolution. Finally, with no applied voltage, the electrolyte alone produced neither scale spallation nor alloy dissolution. These experiments thus highlight the detrimental effects of hydrogen charging on alumina scale adhesion. It is proposed that interfacial hydrogen embrittlement is produced by moist air and is the root cause of both moisture-induced, delayed scale spallation and desktop TBC failures.

Membrane-less hybrid flow battery based on low-cost elements

NASA Astrophysics Data System (ADS)

Leung, P. K.; Martin, T.; Shah, A. A.; Mohamed, M. R.; Anderson, M. A.; Palma, J.

2017-02-01

The capital cost of conventional redox flow batteries is relatively high (>USD 200/kWh) due to the use of expensive active materials and ion-exchange membranes. This paper presents a membrane-less hybrid organic-inorganic flow battery based on the low-cost elements zinc (92.7% with the use of carbon felt electrodes. In the presence of a fully oxidized active species close to its solubility limit, dissolution of the deposited anode is relatively slow (<2.37 g h-1 cm-2) with an equivalent corrosion current density of <1.9 mA cm-2. In a parallel plate flow configuration, the resulting battery was charge-discharge cycled at 30 mA cm-2 with average coulombic and energy efficiencies of c.a. 71.8 and c.a. 42.0% over 20 cycles, respectively.

DTT-doped MWCNT coating for checking shuttle effect of lithium-sulfur battery

NASA Astrophysics Data System (ADS)

Xiaogang, Sun; Jie, Wang; Xu, Li; Wei, Chen

2018-01-01

In order to improve the rate and reversible capacity of lithium-sulfur (Li-S) battery, a reagent of dithiothreitol (DTT) was utilized to check the dissolution and shuttle of long-chain lithium polysulfides (LiPSs) by cutting the disulfide bond (-S-S- bonds) in them. The slurry of DTT-doped multi-walled carbon nanotubes (MWCNTs) was coated on the surface of sulfur cathode as a shield to slice the long-chain LiPSs to short-chain ones for checking the dissolution and migration of LiPSs to lithium anode. The morphology and structure of the electrodes were observed by scanning electron microscopy (SEM). The electrochemical performance was tested by galvanostatic charge-discharge, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The initial discharge capacity of S-DTT- carbon nanotube paper (CNTP) electrode reached 1670 and 949 mAh/g at 0.05 and 2 C respectively with a coulombic efficiency of over 99%. The electrode maintained a reversible specific capacity of 949 mAh/g after 45 cycles at 2 C. This suggested that the DTT-doped MWCNT coating can restrain shuttle effect and improve the rate and capacity of Li-S battery. The S-DTT-CNTP electrode not only accommodates the volume expansion but also provides stable electronics and ions channels.

Preliminary studies of the CHIM electrogeochemical method at the Kokomo Mine, Russell Gulch, Colorado

USGS Publications Warehouse

Smith, D.B.; Hoover, D.B.; Sanzolone, R.F.

1993-01-01

The CHIM electrogeochemical exploration technique was developed in the former Soviet Union about 20 years ago and is claimed to be effective in exploration for concealed mineral deposits that are not detectable by other geochemical or geophysical techniques. The method involves providing a high-voltage direct current to an anode and an array of special collector cathodes. Cations mobile in the electric field are collected at the cathodes and their concentrations determined. The U.S. Geological Survey started a study of the CHIM method by conducting tests over a precious- and base-metal-bearing quartz vein covered with 3 m of colluvial soil and weathered bedrock near the Kokomo Mine, Colorado. The tests show that the CHIM method gives better definition of the vein than conventional soil geochemistry based on a total-dissolution technique. The CHIM technique gives reproducible geochemical anomaly patterns, but the absolute concentrations depend on local site variability as well as temporal variations. Weak partial dissolutions of soils at the Kokomo Mine by an enzyme leach, a dilute acetic acid leach, and a dilute hydrochloric acid leach show results comparable to those from the CHIM method. This supports the idea that the CHIM technique is essentially a weak in-situ partial extraction involving only ions able to move in a weak electric field. ?? 1993.

Electro-kinetic remediation coupled with phytoremediation to remove lead, arsenic and cesium from contaminated paddy soil.

PubMed

Mao, Xinyu; Han, Fengxiang X; Shao, Xiaohou; Guo, Kai; McComb, Jacqueline; Arslan, Zikri; Zhang, Zhanyu

2016-03-01

The objectives of this study were to investigate distribution and solubility of Pb, Cs and As in soils under electrokinetic field and examine the processes of coupled electrokinetic phytoremediation of polluted soils. The elevated bioavailability and bioaccumulation of Pb, As and Cs in paddy soil under an electro-kinetic field (EKF) were studied. The results show that the EKF treatment is effective on lowering soil pH to around 1.5 near the anode which is beneficial for the dissolution of metal(loid)s, thus increasing their overall solubility. The acidification in the anode soil efficiently increased the water soluble (SOL) and exchangeable (EXC) Pb, As and Cs, implying enhanced solubility and elevated overall potential bioavailability in the anode region while lower solubility in the cathode areas. Bioaccumulations of Pb, As and Cs were largely determined by the nature of elements, loading levels and EKF treatment. The native Pb in soil usually is not bioavailable. However, EKF treatment tends to transfer Pb to the SOL and EXC fractions improving the phytoextraction efficiency. Similarly, EKF transferred more EXC As and Cs to the SOL fraction significantly increasing their bioaccumulation in plant roots and shoots. Pb and As were accumulated more in plant roots than in shoots while Cs was accumulated more in shoots due to its similarity of chemical properties to potassium. Indian mustard, spinach and cabbage are good accumulators for Cs. Translocation of Pb, As and Cs from plant roots to shoots were enhanced by EKF. However, this study indicated the overall low phytoextraction efficiency of these plants. Copyright © 2015 Elsevier Inc. All rights reserved.

Electrolyte additives for lithium metal anodes and rechargeable lithium metal batteries: progresses and perspectives.

PubMed

Zhang, Heng; Eshetu, Gebrekidan Gebresilassie; Judez, Xabier; Li, Chunmei; Rodriguez-Martínez, Lide M; Armand, Michel

2018-02-14

Lithium metal (Li°) - based rechargeable batteries (LMBs), such as Li° anode vs. intercalation and/or conversion type cathode batteries, lithium-sulphur (Li-S), and lithium-oxygen (O2)/air (Li-O2/air) are becoming increasingly important for electrifying the modern transportation system, enabling sustainable mobility in the near future. Though some rechargeable LMBs batteries (e.g., Li°/LiFePO4 batteries from Bolloré Bluecar®, Li-S batteries from OXIS Energy and Sion Power) are already commercially viable in niche applications, their large-scale deployment is still hampered due to the existence of a number of formidable challenges, including lithium dendrite growth, electrolyte instability towards high voltage intercalation type cathode, poor electronic and ionic conductivities of sulphur (S8) and O2, as well as their corresponding reduction products (e.g., Li2S and Li2O), dissolution and shuttling of polysulphide (PS) intermediates etc. This ultimately results in short cycle life, low coulombic/energy efficiency, poor safety, and a high self-discharge rate. Among other mitigating strategies, the use of electrolyte additives is considered as one of the most economical, and effective approach for circumventing these dilemmas. Set out to offer an in-depth insight into the rapidly growing research on the account of electrolyte additives for rechargeable LMBs, this review presents an overview of the various functional additives, that are being applied in Li-anode/intercalation cathode-based, Li-S and Li-O2 batteries. This review is believed to assess the status quo of the research and thereby arouse new thoughts and opportunities, opening new avenues for the practical realization of these appealing devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Activity and Stability of Dispersed Multi Metallic Pt-based Catalysts for CO Tolerance in Proton Exchange Membrane Fuel Cell Anodes.

PubMed

Hassan, Ayaz; Ticianelli, Edson A

2018-01-01

Studies aiming at improving the activity and stability of dispersed W and Mo containing Pt catalysts for the CO tolerance in proton exchange membrane fuel cell (PEMFC) anodes are revised for the following catalyst systems: (1) a carbon supported PtMo electrocatalyst submitted to heat treatments; (2) Pt and PtMo nanoparticles deposited on carbon-supported molybdenum carbides (Mo2C/C); (3) ternary and quaternary materials formed by PtMoFe/C, PtMoRu/C and PtMoRuFe/C and; (4) Pt nanoparticles supported on tungsten carbide/carbon catalysts and its parallel evaluation with carbon supported PtW catalyst. The heat-treated (600 oC) Pt-Mo/C catalyst showed higher hydrogen oxidation activity in the absence and in the presence of CO and better stability, compared to all other Mo-containing catalysts. PtMoRuFe, PtMoFe, PtMoRu supported on carbon and Pt supported on Mo2C/C exhibited similar CO tolerances but better stability, as compared to as-prepared PtMo supported on carbon. Among the tungsten-based catalysts, tungsten carbide supported Pt catalyst showed reasonable performance and reliable stability in comparison to simple carbon supported PtW catalyst, though an uneven level of catalytic activity towards H2 oxidation in presence of CO is observed for the former as compared to Mo containing catalyst. However, a small dissolution of Mo, Ru, Fe and W from the anodes and their migration toward cathodes during the cell operation is observed. These results indicate that the fuel cell performance and stability has been improved but not yet totally resolved.

Effect of inflammatory conditions and H2O2 on bare and coated Ti-6Al-4V surfaces: Corrosion behavior, metal ion release and Ca-P formation under long-term immersion in DMEM

NASA Astrophysics Data System (ADS)

Höhn, Sarah; Virtanen, Sannakaisa

2015-12-01

The surface oxide film and calcium-phosphate (Ca-P) formation on Ti-6Al-4V during long-term immersion in biological environments play a decisive role for the biocompatibility of the implant. Hence, the aim of the study was to evaluate the corrosion resistance, metal ion release and Ca-P formation in DMEM under physiological conditions at pH values of 7.4 and in comparison under simulated inflammatory conditions with pH 5 and in presence of H2O2. Furthermore, the influence of the immersion conditions was investigated on different surface treatments: on bare Ti-6Al-4V, after anodization, and for TiO2 nanoparticle (NP) and hydroxyapatite (HA)-incorporated TiO2-NP coatings. In the absence of H2O2, the impedance response indicated a stable thin oxide film and Ca-P formation after 28 days or 56 days depending on the coating, while under inflammatory conditions the Ca-P formation on the surface is time-delayed and dissolution of the anodized oxide layer as well as selective etching of the β-phase and phase boundaries in case of the bare alloy occur. Electrochemical impedance spectroscopy (EIS), however, indicates a good general corrosion behavior in all cases. The quantities of Ti, Al and V released from the bare and coated Ti-6Al-4V alloy markedly increased with decreasing pH (pH ≤ 5). Although the rapid increase of metal release was observed for all samples at pH 5, the quantities were significantly higher for the bare and anodized alloy than after coating with TiO2-NP or HA.

In vitro study of electrodeposited fluoridated hydroxyapatite coating on G-II titanium with a nanostructured TiO2 interlayer.

PubMed

Lin, Jin-Shyong; Tsai, Tzung-Bau; Say, Wen-Ching; Chiu, Chun; Chen, Shih-Hsun

2017-04-04

Titanium and its alloys have been widely used as orthopedic and dental implants for several decades due to their superior mechanical properties, corrosion resistance and biocompatibility. Recently, many researches revealed that the hydroxyapatite coatings on biomedical materials can further improve their biocompatibility and bioactivity. However, hydroxyapatite coatings are easily decomposed, weakening the bonding between implants and bone tissues and resulting in a high dissolution rate in the biological environment. Prolonging the lifetime of hydroxyapatite in implants is valuable for improving postoperative quality. Hydroxyapatite is the primary inorganic component of bones and teeth. A suitable amount of fluoride ions would be beneficial for the formation of fluoridated hydroxyapatite, which can enhance bone-cell response and the acid resistance of enamel. In this study, G-II titanium substrate was anodized to form a TiO 2 interlayer with a nanotube structure. An electrolyte composed of fluoride, calcium and phosphorus ions was prepared for electroplating fluoridated hydroxyapatite (FHA) coatings onto anodized G-II titanium substrates at a constant voltage. The obtained coatings were examined for their microstructure, mechanical properties; moreover, the changes of apatite structure, surface morphology and corrosion resistance were further investigated after immersion in simulated body fluid (SBF) for a number of weeks. The results show that FHA coatings have a higher surface roughness and hardness than plain hydroxyapatite. After immersion in SBF, the FHA coatings induced the nucleation and growth of apatite on the surface and increased their crystallinity. In a potentiodynamic polarization test, FHA coatings exhibited a better anti-corrosion ability than bare G-II titanium substrate in SBF. Additionally, the anodized TiO 2 nanotube improved the adhesion and corrosion resistance of FHA as well.

Preparation and characterization of ultraflat Pt facets by atom-height-resolved differential optical microscopy

NASA Astrophysics Data System (ADS)

Azhagurajan, M.; Wen, R.; Kim, Y. G.; Itoh, T.; Sashikata, K.; Itaya, K.

2015-01-01

We recently demonstrated that improvements to our technique, laser confocal microscopy with differential interference microscopy (LCM-DIM), has rendered it fully capable of resolving monatomic steps with heights of ca. 0.25 nm on Au(111) and Pd(111) surfaces, even as low as 0.14 nm on Si(100), in aqueous solution. In this paper, we describe in detail a method to prepare and characterize, via atomic-layer-resolved LCM-DIM, ultraflat Pt(111) and Pt(100) facets over a wide surface area. The preparation of ultraflat surfaces is important in the characterization at the atomic scale of electrochemical processes under reaction conditions. To showcase the elegance of LCM-DIM, the anodic dissolution of Pt in aqueous HCl is briefly recounted.

Complexity of Products of Tungsten Corrosion: Comparison of the 3D Pourbaix Diagrams with the Experimental Data

NASA Astrophysics Data System (ADS)

Nave, Maryana I.; Kornev, Konstantin G.

2017-03-01

Tungsten is one of the most attractive metals in applications where materials are subject to high temperature and strong fields. However, in harsh aqueous environment, tungsten is prone to corrosion. Control of tungsten corrosion in aqueous solutions is a challenging task: as a transition metal, tungsten is able to produce a vast variety of oxides and hydrates. To reveal the thermodynamic pathway of corrosion at different conditions, the 3D Pourbaix diagrams relating the reduction potential, pH, and concentration of different tungsten-based compounds were constructed. These diagrams allow one to identify the most thermodynamically stable tungsten-based compounds. The 3D Pourbaix diagrams were used to explain different regimes of anodic dissolution of tungsten in aqueous solutions of potassium hydroxide.

Investigation of hexagonal boron nitride as an atomically thin corrosion passivation coating in aqueous solution.

PubMed

Zhang, Jing; Yang, Yingchao; Lou, Jun

2016-09-09

Hexagonal boron nitride (h-BN) atomic layers were utilized as a passivation coating in this study. A large-area continuous h-BN thin film was grown on nickel foil using a chemical vapor deposition method and then transferred onto sputtered copper as a corrosion passivation coating. The corrosion passivation performance in a Na2SO4 solution of bare and coated copper was investigated by electrochemical methods including cyclic voltammetry (CV), Tafel polarization and electrochemical impedance spectroscopy (EIS). CV and Tafel analysis indicate that the h-BN coating could effectively suppress the anodic dissolution of copper. The EIS fitting result suggests that defects are the dominant leakage source on h-BN films, and improved anti-corrosion performances could be achieved by further passivating these defects.

Hydrochemical and water quality assessment of groundwater in Doon Valley of Outer Himalaya, Uttarakhand, India.

PubMed

Dudeja, Divya; Bartarya, Sukesh Kumar; Biyani, A K

2011-10-01

The present study discusses ion sources and assesses the chemical quality of groundwater of Doon Valley in Outer Himalayan region for drinking and irrigational purposes. Valley is almost filled with Doon gravels that are main aquifers supplying water to its habitants. Recharged only by meteoric water, groundwater quality in these aquifers is controlled essentially by chemical processes occurring between water and lithology and locally altered by human activities. Seventy-six water samples were collected from dug wells, hand pumps and tube wells and were analysed for their major ion concentrations. The pH is varying from 5.6 to 7.4 and electrical conductivity from 71 to 951 μmho/cm. Groundwater of Doon valley is dominated by bicarbonate contributing 83% in anionic abundance while calcium and magnesium dominate in cationic concentrations with 88%. The seasonal and spatial variation in ionic concentration, in general, is related to discharge and lithology. The high ratio of (Ca + Mg)/(Na + K), i.e. 10, low ratio of (Na + K)/TZ+, i.e.0.2 and also the presence of carbonate lithology in the northern part of valley, is indicative of carbonate dissolution as the main controlling solute acquisition process in the valley. The low abundance of silica content and high HCO₃/H₄SiO₄ ratio also supports carbonate dissolution and less significant role of silicate weathering as the major source for dissolved ions in Doon Valley. The analytical results computed for various indices show that water is of fairly good quality, although, hard but have moderate dissolved solid content. It is free from sodium hazard lying in C₁-S₁ and C₂-S₁ class of USSL diagram and in general suitable for drinking and irrigation except few locations having slightly high salinity hazard.

Preparation of enteric coated timed-release press-coated tablets and evaluation of their function by in vitro and in vivo tests for colon targeting.

PubMed

Fukui, E; Miyamura, N; Uemura, K; Kobayashi, M

2000-08-25

As a new oral drug delivery system for colon targeting, enteric coated timed-release press-coated tablets (ETP tablets) were developed by coating enteric polymer on timed-release press-coated tablets composed of an outer shell of hydroxypropylcellulose and core tablet containing diltiazem hydrochloride (DIL) as a model drug. The results of the in vitro dissolution tests in JP 1st fluid (pH 1.2) and JP 2nd fluid (pH 6.8) indicated that these tablets showed both acid resistance and timed-release. To clarify whether ETP tablets could have been of use in the gastrointestinal tract, ETP tablets with a layer of phenylpropanolamine hydrochloride (PPA) (a marker of gastric emptying) between the enteric coating layer and outer shell were prepared, and were administered to beagle dogs. The gastric emptying time and lag time after gastric emptying were evaluated by determining the times at which PPA and DIL first appeared in the plasma (TFA(PPA) and TFA(DIL), respectively). TFA(PPA) and TFA(DIL) were about 4 and 7 h, respectively. This value of TFA(PPA) indicated that ETP tablets displayed acid resistance in the stomach as well as in JP Ist fluid. Subtraction of TFA(PPA) from TFA(DIL) gave a value of about 3 h which agreed well with the lag time determined by in vitro dissolution test in JP 2nd fluid. Also, the results seemed to be in accordance with the time at which the tablets reached the colon after gastric emptying. Therefore, ETP tablets seemed to be an effective tool for oral site-specific delivery including targeting of the colon.

Electrochemical behavior of tube-fin assembly for an aluminum automotive condenser with improved corrosion resistance

NASA Astrophysics Data System (ADS)

Pech-Canul, M. A.; Guía-Tello, J. C.; Pech-Canul, M. I.; Aguilar, J. C.; Gorocica-Díaz, J. A.; Arana-Guillén, R.; Puch-Bleis, J.

An aluminum automotive condenser was designed to exhibit high corrosion resistance in the seawater acetic acid test (SWAAT) combining zinc coated microchannel tubes and fins made with AA4343/AA3003(Zn)/AA4343 brazing sheet. Electrochemical measurements in SWAAT solution were carried out under laboratory conditions using tube-fin assembly and individual fin and tube samples withdrawn from the condenser core. The aim was to gain information on the protective role of the zinc sacrificial layer and about changes in corrosion behavior as a function of immersion time. External corrosion of the tube-fin system was simulated by immersion of mini-core samples under open circuit conditions. The corrosion rate increased rapidly during the first 6 h and slowly afterwards. The short time behavior was related to the dissolution of the oxide film and fast dissolution of the outermost part of the zinc diffusion layer. With the aid of cross-sectional depth corrosion potential profiles, it was shown that as the sacrificial layer gets dissolved, the surface concentration of zinc decreases and the potential shifts to less negative values. The results of galvanic coupling of tube and fins in a mini-cell showed that the tube became the anode while the fins exhibited cathodic behavior. An evolution in the galvanic interaction was observed, due to the progressive dissolution of the sacrificial zinc layer. The difference of uncoupled potentials between tube and fins decreased from 71 mV to 32 mV after 84 h of galvanic coupling. At the end of such period there was still a part of the zinc sacrificial layer remaining which would serve for protection of the tube material for even longer periods and there were indications of slight corrosion in the fins.

The effect of grain boundary chemistry on Intergranular stress corrosion cracking of Ni-Cr-Fe alloys in 50 Pct NaOH at 140 °C

NASA Astrophysics Data System (ADS)

Sung, J. K.; Koch, J.; Angeliu, T.; Was, G. S.

1992-10-01

The role of chromium, carbon, chromium carbides, and phosphorus on the intergranular stress corrosion cracking (IGSCC) resistance of Ni-Cr-Fe alloys in 50 pct NaOH at 140 °C is studied using controlled-purity alloys. The effect of carbon is studied using heats in which the carbon level is varied between 0.002 and 0.063 wt pct while the Cr level is fixed at 16.8 wt pct. The effect of Cr is studied using alloys with Cr concentrations between 5 and 30 wt pct. The effect of grain boundary Cr and C together is studied by heat-treating the nominal alloy composition of Ni-16Cr-9Fe-0.035C, and the effect of P is studied using a high-purity, P-doped alloy and a carbon-containing, P-doped alloy. Constant extension rate tensile (CERT) results show that the crack depth increases with decreasing alloy Cr content and increasing alloy C content. Crack- ing severity also correlates inversely with thermal treatment time at 700 °C, during which the grain boundary Cr content rises and the grain boundary C content falls. Phosphorus is found to have a slightly beneficial effect on IG cracking susceptibility. Potentiodynamic polarization and potentiostatic current decay experiments confirm that Cr depletion or grain boundary C enhances the dissolution at the grain boundary. Results support a film rupture-anodic dissolution model in which Cr depletion or grain boundary C (independently or additively) enhances dissolution of nickel from the grain boundary region and leads to increased IG cracking.

Coupling thermoelectricity and electrocatalysis for hydrogen production via PbTesbnd PbS/TiO2 heterojunction

NASA Astrophysics Data System (ADS)

Liu, Zhongqing; Cao, Xiaohao; Wang, Bin; Xia, Min; Lin, Sidney; Guo, Zhanhu; Zhang, Xiaoming; Gao, Shiyuan

2017-02-01

PbTesbnd PbS/TiO2 electrodes are produced via wet chemical routes for splitting water into hydrogen at the ambient temperatures. PbTe nano-crystals are firstly deposited via the successive ionic layer adsorption and reaction (SILAR) treatment onto TiO2 nanotube arrays (TNAs) prepared by anodic oxidation of Ti substrates. Subsequently, linear sweep voltammetry (LSV) is employed to convert the outer PbTe into PbS, producing PbTesbnd PbS/TiO2 electrodes with a gradient p-n-n band configuration. With the external electric field, the vector charge transfer effect of the TNAs and the gradient energy band structure of PbTesbnd PbS/TNAs, the two electrode system in which PbTesbnd PbS/TNAs functions as the anode illustrates excellent hydrogen production activities. The whole electrochemical system consisted of anode, cathode, electrolyte serves as a hot side while the endothermic electrochemical reactions in hydrogen production as an in situ cold side. At 70 °C and 1.0 V bath voltage, the system registers 6.1 mL cm-2 h-1 rate of hydrogen generation, consuming electric power of 26.2 kW h kg-1 H2, with an energy efficiency of 88.5% and a heat efficiency of 49.9%. This method demonstrates a novel pathway to produce chemical energy from low quality waste heat, benefitting from thermoelectric and electrocatalytic coupling.

Interior and Exterior Laser-Induced Fluorescence and Plasma Potential Measurements on a Laboratory Hall Thruster (Postprint)

DTIC Science & Technology

1999-06-01

Hall thruster is provided by a 1 mm axial slot in the insulator outer wall. Axial ion velocity profiles for four discharge voltages (100 V, 160 V, 200 V, 250 V) are measured as are radial velocity profiles in the near field plume. Internal neutral xenon axial velocity profiles are also measured at these conditions. For comparison, the plume plasma potential profile is measured with an emissive probe. These probe based potential measurements extend from 50 mm outside the plume to the near anode region for all but the highest discharge voltage condition. For each condition,

Effect of Minor Alloying Elements on Localized Corrosion Behavior of Aluminum-Copper-Magnesium based Solid Solution Alloys

NASA Astrophysics Data System (ADS)

Aburada, Tomohiro

2011-12-01

The effects and mechanistic roles of a minor alloying element, Ni, on the localized corrosion behavior were explored by studying (Al75Cu 17Mg8)97Ni3 and Al70Cu 18Mg12 amorphous alloys. To explore the minor alloying element limited to the outer surface layers, the corrosion behavior of Al70Cu 18Mg12 amorphous alloy in solutions with and without Ni 2+ was also studied. Both Ni alloying and Ni2+ in solution improved the localized corrosion resistance of the alloys by ennobling the pitting and repassivation potentials. Pit growth by the selective dissolution of Al and Mg was also suppressed by Ni alloying. Remaining Cu and Ni reorganized into a Cu-rich polycrystalline nanoporous structure with continuous ligaments in pits. The minor Ni alloying and Ni2+ in solution suppressed the coarsening of the ligaments in the dealloyed nanoporous structure. The presence of relatively immobile Ni atoms at the surface suppressed the surface diffusion of Cu, which reduced the coarsening of the nanoporous structure, resulting in the formation of 10 to 30 nm wide Cu ligaments. Two mechanistic roles of minor alloying elements in the improvement of the pitting corrosion resistance of the solid solution alloys are elucidated. The first role is the suppression of active dissolution by altering the atomic structure. Ni in solid solution formed stronger bonds with Al, and reduces the probability of weaker Al-Al bonds. The second role is to hinder dissolution by producing a greater negative shift of the true interfacial potential at the dissolution front under the dealloyed layer due to the greater Ohmic resistance through the finer porous structure. These effects contributed to the elevation of pitting potentials by ennobling the applied potential required to produce enough dissolution for the stabilization of pits. Scientifically, this thesis advances the state of understanding of alloy dissolution, particularly the role of minor alloying elements on preferential oxidation at the atomic, nanometer, and micrometer scales. Technological implementations of the findings of the research are also discussed, including a new route to synthesize nanoporous materials with tunable porosity and new corrosion mitigation strategies for commercial Al-based alloys containing the detrimental Al2CuMg phase.

Biofilm Matrix Proteins.

PubMed

Fong, Jiunn N C; Yildiz, Fitnat H

2015-04-01

Proteinaceous components of the biofilm matrix include secreted extracellular proteins, cell surface adhesins, and protein subunits of cell appendages such as flagella and pili. Biofilm matrix proteins play diverse roles in biofilm formation and dissolution. They are involved in attaching cells to surfaces, stabilizing the biofilm matrix via interactions with exopolysaccharide and nucleic acid components, developing three-dimensional biofilm architectures, and dissolving biofilm matrix via enzymatic degradation of polysaccharides, proteins, and nucleic acids. In this article, we will review functions of matrix proteins in a selected set of microorganisms, studies of the matrix proteomes of Vibrio cholerae and Pseudomonas aeruginosa, and roles of outer membrane vesicles and of nucleoid-binding proteins in biofilm formation.

Dissolution flowsheet for high flux isotope reactor fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Foster, T.

2016-09-27

As part of the Spent Nuclear Fuel (SNF) processing campaign, H-Canyon is planning to begin dissolving High Flux Isotope Reactor (HFIR) fuel in late FY17 or early FY18. Each HFIR fuel core contains inner and outer fuel elements which were fabricated from uranium oxide (U 3O 8) dispersed in a continuous Al phase using traditional powder metallurgy techniques. Fuels fabricated in this manner, like other SNF’s processed in H-Canyon, dissolve by the same general mechanisms with similar gas generation rates and the production of H 2. The HFIR fuel cores will be dissolved and the recovered U will be down-blendedmore » into low-enriched U. HFIR fuel was previously processed in H-Canyon using a unique insert in both the 6.1D and 6.4D dissolvers. Multiple cores will be charged to the same dissolver solution maximizing the concentration of dissolved Al. The objective of this study was to identify flowsheet conditions through literature review and laboratory experimentation to safely and efficiently dissolve the HFIR fuel in H-Canyon. Laboratory-scale experiments were performed to evaluate the dissolution of HFIR fuel using both Al 1100 and Al 6061 T6 alloy coupons. The Al 1100 alloy was considered a representative surrogate which provided an upper bound on the generation of flammable (i.e., H 2) gas during the dissolution process. The dissolution of the Al 6061 T6 alloy proceeded at a slower rate than the Al 1100 alloy and was used to verify that the target Al concentration in solution could be achieved for the selected Hg concentration. Mass spectrometry and Raman spectroscopy were used to provide continuous monitoring of the concentration of H 2 and other permanent gases in the dissolution offgas allowing the development of H 2 generation rate profiles. The H 2 generation rates were subsequently used to evaluate if a full HFIR core could be dissolved in an H-Canyon dissolver without exceeding 60% of the calculated lower flammability limit (LFL) for H 2 at a given Hg concentration.« less

The Nonbarred Double-Ringed Galaxy, PGC 1000714

NASA Astrophysics Data System (ADS)

Seigar, Marc; Mutlu Pakdil, Burcin; Mangedarage, Mithila; Treuthardt, Patrick M.

2017-01-01

Hoag-type galaxies are rare peculiar systems which bear strong resemblance to Hoag's Object with an elliptical-like core, a detached outer ring, and no signs of a bar or stellar disk. They represent extreme cases and help us understand the formation of galaxies in general by providing clues on formation mechanisms. The nature of outer rings in Hoag-type galaxies is still debated and may be related either to slow secular evolution, such as dissolution of a barlike structure or to environmental processes, such as galaxy-galaxy interactions or gas infall. Due to a fairly superficial resemblance to Hoag's Object, PGC 1000714 is a good target for detailed study of the peculiar structure of this type. We present the first photometric study of PGC 1000714 that has not yet been described in the literature. Our aim is to evaluate its structure and properties as well as understand the origin of outer rings in such galaxies. Surface photometry of the central body is performed using near-UV, BVRI and JHK images. Based on the photometric data, the nearly round central body follows a de Vaucouleurs profile almost all the way to the center. The detailed photometry reveals a reddish inner ring-shaped structure that shares the same center as the central body. However, no sign of a bar or stellar disk is detected. The outer ring appears as a bump in the surface brightness profile with a peak brightness of 25.8 mag/arcsec^{2} in the B-band and shows no sharp outer boundary. By reconstructing the observed SED for the central body and the rings, we recover the stellar population properties of the galaxy components. Our work suggests different formation histories for the inner and outer rings. We rule out the secular evolution model as being a formation mechanism for the outer ring. The colors of the outer ring are consistent with a feature that may have experienced a burst of star formation due to a possible recent accretion event. In addition, our work supports that the central body may be formed by a relatively dry major merger or in a single, short and highly effective star formation burst, and the inner ring may be formed as a result of intergalactic medium accretion or secular evolution of a possible gaseous disk

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Moonsoo; Kim, Jongmin; Cho, Jaehee

Graphical abstract: The presence of Chlorine in the outer surface resulted in a highly electro-negative surface states and an increase in the vacuum energy level. - Highlights: • We investigated the influence of chlorine surface treatment on ITO properties. • Chlorination induced the change of the electro-static potential in the outer surface. • Chlorine electro-chemical treatment of ITO is a simple, fast and effective technique. - Abstract: In this work, we investigate the influence of a chlorine-based electro-chemical surface treatment on the characteristics of indium tin oxide (ITO) including the work function, chemical composition, and phase transition. The treated ITOsmore » were characterized using X-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS), 4-point probe measurements, and grazing incidence X-ray diffraction (GI-XRD). We confirmed a change of the chemical composition in the near-surface region of the ITO and the formation of indium-chlorine (In-Cl) bonds and surface dipoles (via XPS). In particular, the change of the electro-static potential in the outer surface was caused by chlorination. Due to the vacuum-level shift after the electro-chemical treatment in a dilute hydrochloric acid, the ITO work function was increased by ∼0.43 eV (via UPS); furthermore, the electro-negativity of the chlorine anions attracted electrons to emit them from the hole transport layer (HTL) to the ITO anodes, resulting in an increase of the hole-injection efficiency.« less

Advances in space power research and technology at the National Aeronautics and Space Administration

NASA Technical Reports Server (NTRS)

Mullin, J. P.; Randolph, L. P.; Hudson, W. R.; Ambrus, J. H.

1981-01-01

Progress and plans in various areas of the NASA Space Power Program are discussed. Solar cell research is narrowed to GaAs, multibandgap, and thin Si cells for arrays in planar and concentrator configurations, with further work to increase cell efficiency, radiation hardness, develop flexible encapsulants, and reduce cost. Electrochemical research is concentrating on increasing energy and power density, cycle and wet stand life, reliability and cost reduction of batteries. Further development of the Ni-H2 battery and O2-H2 fuel cell to multihundred kW with a 5 year life and 30,000 cycles is noted. Basic research is ongoing for alkali metal anodes for high energy density secondary cells. Nuclear thermoelectric propulsion is being developed for outer planets exploration propulsion systems, using Si-Ge generators, and studies with rare earth chalcogenides and sulfides are mentioned. Power Systems Management seeks to harmonize increasing power supply levels with inner and outer spacecraft environments, circuits, demands, and automatic monitoring. Concomitant development of bipolar transistors, an infrared rectenna, spacecraft charging measurement, and larger heat pipe transport capacity are noted.

Mechanical Properties of TRIP Steel Microalloyed with Ti

NASA Astrophysics Data System (ADS)

Krizan, Daniel; De Cooman, Bruno C.

2014-07-01

The precipitation state, microstructure, retained austenite stability, and mechanical properties of cold-rolled Ti-microalloyed CMnAlSiP TRIP steel were investigated. The precipitation state was analyzed in each processing step by means of transmission electron microscopy, chemical analysis using the anodic dissolution method, and by model calculations. Ti additions refined the microstructure mainly by the pinning of austenite and ferrite grain boundaries by various Ti-containing precipitates. Ti additions also resulted in a refinement of the size of the retained austenite islands and caused a slight decrease of the volume fraction and carbon content of the retained austenite. The morphology of the retained austenite was also changed and the stability of the retained austenite decreased, but Ti addition still resulted in an adequate strength-ductility balance and a tensile strength close to 1 GPa.

Graphene oxide wrapped croconic acid disodium salt for sodium ion battery electrodes

NASA Astrophysics Data System (ADS)

Luo, Chao; Zhu, Yujie; Xu, Yunhua; Liu, Yihang; Gao, Tao; Wang, Jing; Wang, Chunsheng

2014-03-01

Croconic acid disodium salt (CADS), a renewable or recyclable organic compound, is investigated as an anode material in sodium ion battery for the first time. The pristine micro-sized CADS delivers a high capacity of 246.7 mAh g-1, but it suffers from fast capacity decay during charge/discharge cycles. The detailed investigation reveals that the severe capacity loss is mainly attributed to the pulverization of CADS particles induced by the large volume change during sodiation/desodiation rather than the generally believed dissolution of CADS in the organic electrolyte. Minimizing the particle size can effectively suppress the pulverization, thus improving the cycling stability. Wrapping CADS with graphene oxide by ultrasonic spray pyrolysis can enhance the integration and conductivity of CADS electrodes, thus providing a high capacity of 293 mAh g-1.

Stress Corrosion Cracking Behavior of Interstitial Free Steel Via Slow Strain Rate Technique

NASA Astrophysics Data System (ADS)

Murkute, Pratik; Ramkumar, J.; Mondal, K.

2016-07-01

An interstitial free steel is subjected to slow strain rate tests to investigate the stress corrosion cracking (SCC) behavior at strain rates ranging from 10-4 to 10-6s-1 in air and 3.5 wt.% NaCl solution. The ratios of time to failure, failure strain, and ultimate tensile stress at different strain rates in air to that in corrosive were considered as SCC susceptibility. Serrated stress-strain curve observed at lowest strain rate is explained by the Portevin-Le Chatelier effect. Maximum susceptibility to SCC at lowest strain rate is attributed to the soluble γ-FeOOH in the rust analyzed by Fourier Transformed Infrared spectroscopy. Mechanism for SCC relates to the anodic dissolution forming the groove, where hydrogen embrittlement can set in and finally fracture happens due to triaxiality.

Electrochemical characterization of p(+)n and n(+)p diffused InP structures

NASA Technical Reports Server (NTRS)

Wilt, David M.; Faur, Maria; Faur, Mircea; Goradia, M.; Vargas-Aburto, Carlos

1993-01-01

The relatively well documented and widely used electrolytes for characterization and processing of Si and GaAs-related materials and structures by electrochemical methods are of little or no use with InP because the electrolytes presently used either dissolve the surface preferentially at the defect areas or form residual oxides and introduce a large density of surface states. Using an electrolyte which was newly developed for anodic dissolution of InP, and was named the 'FAP' electrolyte, accurate characterization of InP related structures including nature and density of surface states, defect density, and net majority carrier concentration, all as functions of depth was performed. A step-by-step optimization of n(+)p and p(+)n InP structures made by thermal diffusion was done using the electrochemical techniques, and resulted in high performance homojunction InP structures.

Electrochemical behavior of zinc particles with silica based coatings as anode material for zinc air batteries with improved discharge capacity

NASA Astrophysics Data System (ADS)

Schmid, M.; Willert-Porada, M.

2017-05-01

Silica coatings on zinc particles as anode material for alkaline zinc air batteries are expected to reduce early formation of irreversible ZnO passivation layers during discharge by controlling zinc dissolution and precipitation of supersaturated zincates, Zn(OH)42-. Zinc particles were coated with SiO2 (thickness: 15 nm) by chemical solution deposition and with Zn2SiO4 (thickness: 20 nm) by chemical vapor deposition. These coatings formed a Si(OH)4 gel in aqueous KOH and retarded hydrogen evolution by 40%. By treatment in aqueous KOH and drying afterwards, the silica coatings were changed into ZnO-K2O·SiO2 layers. In this work, the electrochemical performance of such coated zinc particles is investigated by different electrochemical methods in order to gain a deeper understanding of the mechanisms of the coatings, which reduce zinc passivation. In particular, zinc utilization and changes in internal resistance are investigated. Moreover, methods for determination of diffusion coefficients, charge carrier numbers and activation energies for electrochemical oxidation are determined. SiO2-coated zinc particles show improved discharge capacity (CVD-coated zinc: 69% zinc utilization, CSD-coated zinc: 62% zinc utilization) as compared to as-received zinc (57% zinc utilization) at C/20 rate, by reducing supersaturation of zincates. Additionally, KOH-modified SiO2-coated zinc particles enhance rechargeability after 100% depth-of-discharge.

Stabilizing the Performance of High-Capacity Sulfur Composite Electrodes by a New Gel Polymer Electrolyte Configuration.

PubMed

Agostini, Marco; Lim, Du Hyun; Sadd, Matthew; Fasciani, Chiara; Navarra, Maria Assunta; Panero, Stefania; Brutti, Sergio; Matic, Aleksandar; Scrosati, Bruno

2017-09-11

Increased pollution and the resulting increase in global warming are drawing attention to boosting the use of renewable energy sources such as solar or wind. However, the production of energy from most renewable sources is intermittent and thus relies on the availability of electrical energy-storage systems with high capacity and at competitive cost. Lithium-sulfur batteries are among the most promising technologies in this respect due to a very high theoretical energy density (1675 mAh g -1 ) and that the active material, sulfur, is abundant and inexpensive. However, a so far limited practical energy density, life time, and the scaleup of materials and production processes prevent their introduction into commercial applications. In this work, we report on a simple strategy to address these issues by using a new gel polymer electrolyte (GPE) that enables stable performance close to the theoretical capacity of a low cost sulfur-carbon composite with high loading of active material, that is, 70 % sulfur. We show that the GPE prevents sulfur dissolution and reduces migration of polysulfide species to the anode. This functional mechanism of the GPE membranes is revealed by investigating both its morphology and the Li-anode/GPE interface at various states of discharge/charge using Raman spectroscopy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanism of Zn Insertion into Nanostructured δ-MnO 2 : A Nonaqueous Rechargeable Zn Metal Battery

DOE PAGES

Han, Sang-Don; Kim, Soojeong; Li, Dongguo; ...

2017-05-08

Unlike the more established lithium-ion based energy storage chemistries, the complex intercalation chemistry of multivalent cations in a host lattice is not well understood, especially the relationship between the intercalating species solution chemistry and the prevalence and type of side reactions. Among multivalent metals, a promising model system can be based on nonaqueous Zn 2+ ion chemistry. There are several examples of these systems support the use of a Zn metal anode, and reversible intercalation cathodes have been reported. Our study utilizes a combination of analytical tools to probe the chemistry of a nanostructured δ-MnO 2 cathode in association withmore » a nonaqueous acetonitrile–Zn(TFSI) 2 electrolyte and a Zn metal anode. As many of the issues related to understanding a multivalent battery relate to the electrolyte–electrode interface, the high surface area of a nanostructured cathode provides a significant interface between the electrolyte and cathode host that maximizes the spectroscopic signal of any side reactions or minor mechanistic pathways. There are numerous factors affecting capacity fade and issues associated with the second phase formation including Mn dissolution in heavily cycled Zn/δ-MnO 2 cells are presented including dramatic mechanistic differences in the storage mechanism of this couple when compared to similar aqueous electrolytes are noted.« less

Oxygen ion irradiation effect on corrosion behavior of titanium in nitric acid medium

NASA Astrophysics Data System (ADS)

Ningshen, S.; Kamachi Mudali, U.; Mukherjee, P.; Barat, P.; Raj, Baldev

2011-01-01

The corrosion assessment and surface layer properties after O 5+ ion irradiation of commercially pure titanium (CP-Ti) has been studied in 11.5 N HNO 3. CP-Ti specimen was irradiated at different fluences of 1 × 10 13, 1 × 10 14 and 1 × 10 15 ions/cm 2 below 313 K, using 116 MeV O 5+ ions source. The corrosion resistance and surface layer were evaluated by using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and glancing-angle X-ray diffraction (GXRD) methods. The potentiodynamic anodic polarization results of CP-Ti revealed that increased in ion fluence (1 × 10 13-1 × 10 15 ions/cm 2) resulted in increased passive current density due to higher anodic dissolution. SEM micrographs and GXRD analysis corroborated these results showing irradiation damage after corrosion test and modified oxide layer by O 5+ ion irradiation was observed. The EIS studies revealed that the stability and passive film resistance varied depending on the fluence of ion irradiation. The GXRD patterns of O 5+ ion irradiated CP-Ti revealed the oxides formed are mostly TiO 2, Ti 2O 3 and TiO. In this paper, the effects of O 5+ ion irradiation on material integrity and corrosion behavior of CP-Ti in nitric acid are described.

Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

PubMed

Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

2018-01-31

The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

Characterization of Pulse Reverses Electroforming on Hard Gold Coating.

PubMed

Byoun, Young-Min; Noh, Young-Tai; Kim, Young-Geun; Ma, Seung-Hwan; Kim, Gwan-Hoon

2018-03-01

Effect of pulse reverse current (PRC) method on brass coatings electroplated from gold solution was investigated by various plating parameters such as plating duration, the anodic duty cycle, the anodic current density and the cathodic current density. The reversed current results in a significant change in the morphology of electrodeposits, improvement of the overall current efficiency and reduction of deposit porosity. With longer pulses, hemispherical surface features are generated, while larger grains result from shorter pulse widths. The porosity of the plated samples is found to decrease compared with results at the same time-average plating rate obtained from DC or Pulse plating. A major impediment to reducing gold later thickness is the corrosion of the underlying substrate, which is affected by the porosity of the gold layer. Both the morphology and the hydrogen evolution reaction have significant impact on porosity. PRC plating affect hydrogen gold and may oxidize hydrogen produced during the cathodic portion of the waveform. Whether the dissolution of gold and oxidation of hydrogen occur depends on the type of plating bath and the plating conditions adapted. In reversed pulse plating, the amount of excess near-surface cyanide is changed after the cathodic current is applied, and the oxidation of gold under these conditions has not been fully addressed. The effects of the current density, pulse-reverse ratio and brightener concentration of the electroplating process were investigated and optimized for suitable performance.

The cuticle modulates ultraviolet reflectance of avian eggshells

PubMed Central

Fecheyr-Lippens, Daphne C.; Igic, Branislav; D'Alba, Liliana; Hanley, Daniel; Verdes, Aida; Holford, Mande; Waterhouse, Geoffrey I. N.; Grim, Tomas; Hauber, Mark E.; Shawkey, Matthew D.

2015-01-01

ABSTRACT Avian eggshells are variedly coloured, yet only two pigments, biliverdin and protoporphyrin IX, are known to contribute to the dramatic diversity of their colours. By contrast, the contributions of structural or other chemical components of the eggshell are poorly understood. For example, unpigmented eggshells, which appear white to the human eye, vary in their ultraviolet (UV) reflectance, which may be detectable by birds. We investigated the proximate mechanisms for the variation in UV-reflectance of unpigmented bird eggshells using spectrophotometry, electron microscopy, chemical analyses, and experimental manipulations. We specifically tested how UV-reflectance is affected by the eggshell cuticle, the outermost layer of most avian eggshells. The chemical dissolution of the outer eggshell layers, including the cuticle, increased UV-reflectance for only eggshells that contained a cuticle. Our findings demonstrate that the outer eggshell layers, including the cuticle, absorb UV-light, probably because they contain higher levels of organic components and other chemicals, such as calcium phosphates, compared to the predominantly calcite-based eggshell matrix. These data highlight the need to examine factors other than the known pigments in studies of avian eggshell colour. PMID:25964661

Dissolution Flowsheet for High Flux Isotope Reactor Fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daniel, W. E.; Rudisill, T. S.; O'Rourke, P. E.

2016-09-27

As part of the Spent Nuclear Fuel (SNF) processing campaign, H-Canyon is planning to begin dissolving High Flux Isotope Reactor (HFIR) fuel in late FY17 or early FY18. Each HFIR fuel core contains inner and outer fuel elements which were fabricated from uranium oxide (U 3O 8) dispersed in a continuous Al phase using traditional powder metallurgy techniques. Fuels fabricated in this manner, like other SNF’s processed in H-Canyon, dissolve by the same general mechanisms with similar gas generation rates and the production of H 2. The HFIR fuel cores will be dissolved and the recovered U will be down-blendedmore » into low-enriched U. HFIR fuel was previously processed in H-Canyon using a unique insert in both the 6.1D and 6.4D dissolvers. Multiple cores will be charged to the same dissolver solution maximizing the concentration of dissolved Al. The objective of this study was to identify flowsheet conditions through literature review and laboratory experimentation to safely and efficiently dissolve the HFIR fuel in H-Canyon. Laboratory-scale experiments were performed to evaluate the dissolution of HFIR fuel using both Al 1100 and Al 6061 T6 alloy coupons. The Al 1100 alloy was considered a representative surrogate which provided an upper bound on the generation of flammable (i.e., H 2) gas during the dissolution process. The dissolution of the Al 6061 T6 alloy proceeded at a slower rate than the Al 1100 alloy, and was used to verify that the target Al concentration in solution could be achieved for the selected Hg concentration. Mass spectrometry and Raman spectroscopy were used to provide continuous monitoring of the concentration of H 2 and other permanent gases in the dissolution offgas, allowing the development of H 2 generation rate profiles. The H 2 generation rates were subsequently used to evaluate if a full HFIR core could be dissolved in an H-Canyon dissolver without exceeding 60% of the calculated lower flammability limit (LFL) for H 2 at a given Hg concentration. Complete dissolution of the Al 1100 and Al 6061 T6 alloys up to a final Al concentration of 2 M was obtained using a 7 M HNO 3 solution containing a 0.002 M Hg catalyst. However, following the dissolutions, solids were observed in the solution. The solids were amorphous, but likely originated from the Si present in the alloys. No crystalline materials, such as Al(NO 3) 3 were observed. During the course of the dissolution experiments, it was determined that delaying the addition of Hg once the HNO 3 solution reached the boiling point can reduce the total offgas and H 2 generation rates. The delay in starting the Hg addition is not necessary for HFIR fuel dissolution, but could be useful in other research reactor dissolution campaigns. The potential to generate flammable concentrations of H 2 in the offgas during a HFIR fuel dissolution was evaluated using the experimental data. The predicted H 2 concentration in the dissolver offgas stream was compared with 60% of the calculated H 2 LFL at 200 °C using several prototypical experiments. The calculations showed that a full HFIR core can be dissolved using nominally 0.002 M Hg to catalyze the dissolution. The margin between the predicted H 2 concentration and the calculated LFL was greater when the solution was allowed to boil for 45 min prior to initiating the Hg addition. When the Hg was increased to 0.004 M, the predicted H 2 concentration exceeded the calculated LFL early in the dissolution. The dissolution experiments also demonstrated that additional Hg (beyond the initial 0.002 M) could be added as the Al concentration increases. The ability to add more Hg during a HFIR fuel dissolution could be beneficial if slow dissolution rates are observed at high Al concentrations. Experimental data were used to demonstrate that the predicted H 2 concentration in a dissolver was below 60% of the calculated LFL at 200 °C when 0.004 M Hg was used to catalyze the dissolution if the Al concentration is conservatively greater than 0.5 M. Data also show that the Hg concentration during a HFIR fuel dissolution can be increased from 0.002 to 0.008 M at an Al concentration of 1.3 M.« less

Atomic-Scale Control of Silicon Expansion Space as Ultrastable Battery Anodes.

PubMed

Zhu, Jian; Wang, Tao; Fan, Fengru; Mei, Lin; Lu, Bingan

2016-09-27

Development of electrode materials with high capability and long cycle life are central issues for lithium-ion batteries (LIBs). Here, we report an architecture of three-dimensional (3D) flexible silicon and graphene/carbon nanofibers (FSiGCNFs) with atomic-scale control of the expansion space as the binder-free anode for flexible LIBs. The FSiGCNFs with Si nanoparticles surrounded by accurate and controllable void spaces ensure excellent mechanical strength and afford sufficient space to overcome the damage caused by the volume expansion of Si nanoparticles during charge and discharge processes. This 3D porous structure possessing built-in void space between the Si and graphene/carbon matrix not only limits most solid-electrolyte interphase formation to the outer surface, instead of on the surface of individual NPs, and increases its stability but also achieves highly efficient channels for the fast transport of both electrons and lithium ions during cycling, thus offering outstanding electrochemical performance (2002 mAh g(-1) at a current density of 700 mA g(-1) over 1050 cycles corresponding to 3840 mAh g(-1) for silicon alone and 582 mAh g(-1) at the highest current density of 28 000 mA g(-1)).

Nanoporous Pirani sensor based on anodic aluminum oxide

NASA Astrophysics Data System (ADS)

Jeon, Gwang-Jae; Kim, Woo Young; Shim, Hyun Bin; Lee, Hee Chul

2016-09-01

A nanoporous Pirani sensor based on anodic aluminum oxide (AAO) is proposed, and the quantitative relationship between the performance of the sensor and the porosity of the AAO membrane is characterized with a theoretical model. The proposed Pirani sensor is composed of a metallic resistor on a suspended nanoporous membrane, which simultaneously serves as the sensing area and the supporting structure. The AAO membrane has numerous vertically-tufted nanopores, resulting in a lower measurable pressure limit due to both the increased effective sensing area and the decreased effective thermal loss through the supporting structure. Additionally, the suspended AAO membrane structure, with its outer periphery anchored to the substrate, known as a closed-type design, is demonstrated using nanopores of AAO as an etch hole without a bulk micromachining process used on the substrate. In a CMOS-compatible process, a 200 μm × 200 μm nanoporous Pirani sensor with porosity of 25% was capable of measuring the pressure from 0.1 mTorr to 760 Torr. With adjustment of the porosity of the AAO, the measurable range could be extended toward lower pressures of more than one decade compared to a non-porous membrane with an identical footprint.

Hard x-ray response of a CdZnTe ring-drift detector

DOE Office of Scientific and Technical Information (OSTI.GOV)

Owens, A.; Hartog, R. den; Quarati, F.

We present the results of an experimental study of a special type of CdZnTe detector of hard x and {gamma} rays--A-drift detector. The device consists of a double ring electrode structure surrounding a central point anode with a guard plane surrounding the outer anode ring. The detector can be operated in two distinctively different modes of charge collection--pseudohemispherical and pseudodrift. We study the detector response profiles obtained by scanning the focused x-ray beam over the whole detector area, specifically the variations in count rate, peak position, and energy resolution for x rays from 10 to 100 keV. In addition, atmore » 662 keV the energy resolution was shown to be 4.8 keV, more than a factor of 2 better than for CdZnTe coplanar grid detectors. To interpret the experimental data, we derive an analytical expression for the spatial distribution of the electric field inside the detector and neglecting carrier diffusion, and identify carrier collection patterns for both modes of operation within the drift model approximation. We show that this model provides a good understanding of measured profiles.« less

Method for preparing a sodium/sulfur cell

DOEpatents

Weiner, Steven A.

1978-01-01

A method for preparing a sodium/sulfur cell comprising (A) inserting a solid sodium slug, adapted to be connected to an external circuit, into the anodic reaction zone of a cell subassembly maintained within an inert atmosphere, said cell subassembly comprising a cell container and a tubular cation-permeable barrier disposed within said container such that a first reaction zone is located within cation-permeable barrier and a second reaction zone is located between the outer surface of said cation-permeable barrier and the inner surface of said container, one of said reaction zones being said anodic reaction zone and the other of said reaction zone being a cathodic reaction zone containing a precast composite cathodic reactant comprising a sulfur impregnated porous conductive material connected to said cation permeable barrier and adapted to be connected to said external circuit; and (B) providing closure means for said subassembly and sealing the same to said subassembly at a temperature less than about 100.degree. C. The method of the invention overcomes deficiencies of the prior art methods by allowing preparation of a sodium/sulfur cell without the use of molten reactants and the fill spouts which are required when the cell is filled with molten reactants.

Transmission electron microscopy of coatings formed by plasma electrolytic oxidation of titanium.

PubMed

Matykina, E; Arrabal, R; Skeldon, P; Thompson, G E

2009-05-01

Transmission electron microscopy and supporting film analyses are used to investigate the changes in composition, morphology and structure of coatings formed on titanium during DC plasma electrolytic oxidation in a calcium- and phosphorus-containing electrolyte. The coatings are of potential interest as bioactive surfaces. The initial barrier film, of mixed amorphous and nanocrystalline structure, formed below the sparking voltage of 180 V, incorporates small amounts of phosphorus and calcium species, with phosphorus confined to the outer approximately 63% of the coating thickness. On commencement of sparking, calcium- and phosphorus-rich amorphous material forms at the coating surface, with local heating promoting crystallization in underlying and adjacent anodic titania. The amorphous material thickens with increased treatment time, comprising almost the whole of the approximately 5.7-microm-thick coating formed at 340 V. At this stage, the coating is approximately 4.4 times thicker than the oxidized titanium, with a near-surface composition of about 12 at.% Ti, 58 at.% O, 19 at.% P and 11 at.% Ca. Further, the amount of titanium consumed in forming the coating is similar to that calculated from the anodizing charge, although there may be non-Faradaic contributions to the coating growth.

Interaction of CuS and sulfur in Li-S battery system

DOE PAGES

Sun, Ke; Su, Dong; Zhang, Qing; ...

2015-10-27

Lithium-Sulfur (Li-S) battery has been a subject of intensive research in recent years due to its potential to provide much higher energy density and lower cost than the current state of the art lithiumion battery technology. In this work, we have investigated Cupric Sulfide (CuS) as a capacitycontributing conductive additive to the sulfur electrode in a Li-S battery. Galvanostatic charge/discharge cycling has been used to compare the performance of both sulfur electrodes and S:CuS hybrid electrodes with various ratios. We found that the conductive CuS additive enhanced the utilization of the sulfur cathode under a 1C rate discharge. However, undermore » a C/10 discharge rate, S:CuS hybrid electrodes exhibited lower sulfur utilization in the first discharge and faster capacity decay in later cycles than a pure sulfur electrode due to the dissolution of CuS. The CuS dissolution is found to be the result of strong interaction between the soluble low order polysulfide Li 2S 3 and CuS. As a result, we identified the presence of conductive copper-containing sulfides at the cycled lithium anode surface, which may degrade the effectiveness of the passivation function of the solid-electrolyte-interphase (SEI) layer, accounting for the poor cycling performance of the S:CuS hybrid cells at low rate.« less

Facile and quantitative electrochemical detection of yeast cell apoptosis

NASA Astrophysics Data System (ADS)

Yue, Qiulin; Xiong, Shiquan; Cai, Dongqing; Wu, Zhengyan; Zhang, Xin

2014-03-01

An electrochemical method based on square wave anodic stripping voltammetry (SWASV) was developed to detect the apoptosis of yeast cells conveniently and quantitatively through the high affinity between Cu2+ and phosphatidylserine (PS) translocated from the inner to the outer plasma membrane of the apoptotic cells. The combination of negatively charged PS and Cu2+ could decrease the electrochemical response of Cu2+ on the electrode. The results showed that the apoptotic rates of cells could be detected quantitatively through the variations of peak currents of Cu2+ by SWASV, and agreed well with those obtained through traditional flow cytometry detection. This work thus may provide a novel, simple, immediate and accurate detection method for cell apoptosis.

Solenoid and monocusp ion source

DOEpatents

Brainard, John Paul; Burns, Erskine John Thomas; Draper, Charles Hadley

1997-01-01

An ion source which generates hydrogen ions having high atomic purity incorporates a solenoidal permanent magnets to increase the electron path length. In a sealed envelope, electrons emitted from a cathode traverse the magnetic field lines of a solenoid and a monocusp magnet between the cathode and a reflector at the monocusp. As electrons collide with gas, the molecular gas forms a plasma. An anode grazes the outer boundary of the plasma. Molecular ions and high energy electrons remain substantially on the cathode side of the cusp, but as the ions and electrons are scattered to the aperture side of the cusp, additional collisions create atomic ions. The increased electron path length allows for smaller diameters and lower operating pressures.

Solenoid and monocusp ion source

DOEpatents

Brainard, J.P.; Burns, E.J.T.; Draper, C.H.

1997-10-07

An ion source which generates hydrogen ions having high atomic purity incorporates a solenoidal permanent magnets to increase the electron path length. In a sealed envelope, electrons emitted from a cathode traverse the magnetic field lines of a solenoid and a monocusp magnet between the cathode and a reflector at the monocusp. As electrons collide with gas, the molecular gas forms a plasma. An anode grazes the outer boundary of the plasma. Molecular ions and high energy electrons remain substantially on the cathode side of the cusp, but as the ions and electrons are scattered to the aperture side of the cusp, additional collisions create atomic ions. The increased electron path length allows for smaller diameters and lower operating pressures. 6 figs.

Accelerating the dissolution of enteric coatings in the upper small intestine: evolution of a novel pH 5.6 bicarbonate buffer system to assess drug release.

PubMed

Varum, Felipe J O; Merchant, Hamid A; Goyanes, Alvaro; Assi, Pardis; Zboranová, Veronika; Basit, Abdul W

2014-07-01

Despite rapid dissolution in compendial phosphate buffers, gastro resistant (enteric coated) products can take up to 2 h to disintegrate in the human small intestine, which clearly highlights the inadequacy of the in vitro test method to predict in vivo behaviour of these formulations. The aim of this study was to establish the utility of a novel pH 5.6 bicarbonate buffer, stabilized by an Auto pH™ System, as a better surrogate of the conditions of the proximal small intestine to investigate the dissolution behaviour of standard and accelerated release enteric double coating formulations. Prednisolone tablets were coated with 3 or 5 mg/cm(2) of partially neutralized EUDRAGIT(®) L 30 D-55, HP-55 or HPMC adjusted to pH 6 or 8. An outer layer of EUDRAGIT(®) L 30 D-55 was applied at 5mg/cm(2). For comparison purposes, a standard single layer of EUDRAGIT(®) L 30 D-55 was applied to the tablets. Dissolution was carried out using USP II apparatus in 0.1 M HCl for 2 h, followed by pH 5.6 bicarbonate buffer. EUDRAGIT(®) L 30 D-55 single-coated tablets showed a slow drug release with a lag time of 75 min in buffer, whereas release from the EUDRAGIT(®) L 30 D-55 double-coated tablets was accelerated. These in vitro lag times closely match the in vivo disintegration times for these coated tablets reported previously. Drug release was further accelerated from modified double coatings, particularly in the case of coatings with a thinner inner layer of HP-55 or HPMC (pH 8 and KH2PO4). This study confirms that the pH 5.6 bicarbonate buffer system offers significant advantages during the development of dosage forms designed to release the drug in the upper small intestine. Copyright © 2014. Published by Elsevier B.V.

Development and evaluation of a collection apparatus for recoil products for study of the deexcitation process of (235m)U.

PubMed

Shigekawa, Y; Kasamatsu, Y; Shinohara, A

2016-05-01

The nucleus (235m)U is an isomer with extremely low excitation energy (76.8 eV) and decays dominantly through the internal conversion (IC) process. Because outer-shell electrons are involved in the IC process, the decay constant of (235m)U depends on its chemical environment. We plan to study the deexcitation process of (235m)U by measuring the energy spectra of IC electrons in addition to the decay constants for various chemical forms. In this paper, the preparation method of (235m)U samples from (239)Pu by using alpha-recoil energy is reported. A Collection Apparatus for Recoil Products was fabricated, and then collection efficiencies under various conditions were determined by collecting (224)Ra recoiling out of (228)Th electrodeposited and precipitated sources. The pressure in the apparatus (vacuum or 1 atm of N2 gas) affected the variations of the collection efficiencies depending on the negative voltage applied to the collector. The maximum values of the collection efficiencies were mainly affected by the thickness of the (228)Th sources. From these results, the suitable conditions of the (239)Pu sources for preparation of (235m)U were determined. In addition, dissolution efficiencies were determined by washing collected (224)Ra with solutions. When (224)Ra was collected in 1 atm of N2 gas and dissolved with polar solutions such as water, the dissolution efficiencies were nearly 100%. The method of rapid dissolution of recoil products would be applicable to rapid preparation of short-lived (235m)U samples for various chemical forms.

Ceria-Based Anodes for Next Generation Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Mirfakhraei, Behzad

Mixed ionic and electronic conducting materials (MIECs) have been suggested to represent the next generation of solid oxide fuel cell (SOFC) anodes, primarily due to their significantly enhanced active surface area and their tolerance to fuel components. In this thesis, the main focus has been on determining and tuning the physicochemical and electrochemical properties of ceria-based MIECs in the versatile perovskite or fluorite crystal structures. In one direction, BaZr0.1Ce0.7Y0.1 M0.1O3-delta (M = Fe, Ni, Co and Yb) (BZCY-M) perovskites were synthesized using solid-state or wet citric acid combustion methods and the effect of various transition metal dopants on the sintering behavior, crystal structure, chemical stability under CO2 and H 2S, and electrical conductivity, was investigated. BZCY-Ni, synthesized using the wet combustion method, was the best performing anode, giving a polarization resistance (RP) of 0.4 O.cm2 at 800 °C. Scanning electron microscopy and X-ray diffraction analysis showed that this was due to the exsolution of catalytic Ni nanoparticles onto the oxide surface. Evolving from this promising result, the effect of Mo-doped CeO 2 (nCMO) or Ni nanoparticle infiltration into a porous Gd-doped CeO 2 (GDC) anode (in the fluorite structure) was studied. While 3 wt. % Ni infiltration lowered RP by up to 90 %, giving 0.09 O.cm2 at 800 °C and exhibiting a ca. 5 times higher tolerance towards 10 ppm H2, nCMO infiltration enhanced the H2 stability by ca. 3 times, but had no influence on RP. In parallel work, a first-time study of the Ce3+ and Ce 4+ redox process (pseudocapacitance) within GDC anode materials was carried out using cyclic voltammetry (CV) in wet H2 at high temperatures. It was concluded that, at 500-600 °C, the Ce3+/Ce 4+ reaction is diffusion controlled, probably due to O2- transport limitations in the outer 5-10 layers of the GDC particles, giving a very high capacitance of ca. 70 F/g. Increasing the temperature ultimately diminished the observed capacitance, likely as the chemical reduction of GDC at high temperatures is irreversible.

Analytic model of a magnetically insulated transmission line with collisional flow electrons

NASA Astrophysics Data System (ADS)

Stygar, W. A.; Wagoner, T. C.; Ives, H. C.; Corcoran, P. A.; Cuneo, M. E.; Douglas, J. W.; Gilliland, T. L.; Mazarakis, M. G.; Ramirez, J. J.; Seamen, J. F.; Seidel, D. B.; Spielman, R. B.

2006-09-01

We have developed a relativistic-fluid model of the flow-electron plasma in a steady-state one-dimensional magnetically insulated transmission line (MITL). The model assumes that the electrons are collisional and, as a result, drift toward the anode. The model predicts that in the limit of fully developed collisional flow, the relation between the voltage Va, anode current Ia, cathode current Ik, and geometric impedance Z0 of a 1D planar MITL can be expressed as Va=IaZ0h(χ), where h(χ)≡[(χ+1)/4(χ-1)]1/2-ln⁡⌊χ+(χ2-1)1/2⌋/2χ(χ-1) and χ≡Ia/Ik. The relation is valid when Va≳1MV. In the minimally insulated limit, the anode current Ia,min⁡=1.78Va/Z0, the electron-flow current If,min⁡=1.25Va/Z0, and the flow impedance Zf,min⁡=0.588Z0. {The electron-flow current If≡Ia-Ik. Following Mendel and Rosenthal [Phys. Plasmas 2, 1332 (1995)PHPAEN1070-664X10.1063/1.871345], we define the flow impedance Zf as Va/(Ia2-Ik2)1/2.} In the well-insulated limit (i.e., when Ia≫Ia,min⁡), the electron-flow current If=9Va2/8IaZ02 and the flow impedance Zf=2Z0/3. Similar results are obtained for a 1D collisional MITL with coaxial cylindrical electrodes, when the inner conductor is at a negative potential with respect to the outer, and Z0≲40Ω. We compare the predictions of the collisional model to those of several MITL models that assume the flow electrons are collisionless. We find that at given values of Va and Z0, collisions can significantly increase both Ia,min⁡ and If,min⁡ above the values predicted by the collisionless models, and decrease Zf,min⁡. When Ia≫Ia,min⁡, we find that, at given values of Va, Z0, and Ia, collisions can significantly increase If and decrease Zf. Since the steady-state collisional model is valid only when the drift of electrons toward the anode has had sufficient time to establish fully developed collisional flow, and collisionless models assume there is no net electron drift toward the anode, we expect these two types of models to provide theoretical bounds on Ia, If, and Zf.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, Gang, E-mail: dugang@hdu.edu.cn; Li, Hongxia; Mao, Qinan

A bidirectional threshold switching (TS) characteristic was demonstrated in Ag/ZrO{sub 2}/Pt electrochemical metallization cells by using the electrochemical active Ag electrode and appropriate programming operation strategies The volatile TS was stable and reproducible and the rectify ratio could be tuned to ∼10{sup 7} by engineering the compliance current. We infer that the volatile behavior is essentially due to the moisture absorption in the electron beam evaporated films, which remarkably improved the anodic oxidation as well as the migration of Ag{sup +} ions. The resultant electromotive force would act as a driving force for the metal filaments dissolution, leading to themore » spontaneous volatile characteristics. Moreover, conductance quantization behaviors were also achieved owing to formation and annihilation of atomic scale metal filaments in the film matrix. Our results illustrate that the Ag/ZrO{sub 2}/Pt device with superior TS performances is a promising candidate for selector applications in passive crossbar arrays.« less

Electrolysis of a molten semiconductor

PubMed Central

Yin, Huayi; Chung, Brice; Sadoway, Donald R.

2016-01-01

Metals cannot be extracted by electrolysis of transition-metal sulfides because as liquids they are semiconductors, which exhibit high levels of electronic conduction and metal dissolution. Herein by introduction of a distinct secondary electrolyte, we reveal a high-throughput electro-desulfurization process that directly converts semiconducting molten stibnite (Sb2S3) into pure (99.9%) liquid antimony and sulfur vapour. At the bottom of the cell liquid antimony pools beneath cathodically polarized molten stibnite. At the top of the cell sulfur issues from a carbon anode immersed in an immiscible secondary molten salt electrolyte disposed above molten stibnite, thereby blocking electronic shorting across the cell. As opposed to conventional extraction practices, direct sulfide electrolysis completely avoids generation of problematic fugitive emissions (CO2, CO and SO2), significantly reduces energy consumption, increases productivity in a single-step process (lower capital and operating costs) and is broadly applicable to a host of electronically conductive transition-metal chalcogenides. PMID:27553525

Influence of albumin on the electrochemical behaviour of Zr in phosphate buffered saline solutions.

PubMed

Wang, Lu-Ning; Huang, Xian-Qiu; Shinbine, Alyssa; Luo, Jing-Li

2013-02-01

The corrosion behaviour of Zr in phosphate buffered saline (PBS) solutions with various concentrations (0-4 g L(-1)) of albumin was studied by electrochemical techniques and surface analysis. Addition of albumin to PBS solutions moved the open circuit potential (OCP) to less nobler direction. OCP, polarization resistance and impedance increased and the corrosion current decreased over immersion duration. At early stages of immersion, the resistance was increased with the concentration of albumin because of the high adsorption kinetics of albumin on metal. After the long term immersion, the resistance in PBS without albumin was higher than PBS with albumin owing to the anodic dissolution effect of albumin on metal. According to the analysis of effective capacitances, a normal distribution of time-constants was proposed to estimate the surface film on Zr. A corrosion mechanism of Zr in PBS with different albumin was proposed based on electrochemical analysis.

A comparative study on the electrochemical corrosion behavior of iron and X-65 steel in 4.0 wt % sodium chloride solution after different exposure intervals.

PubMed

Sherif, El-Sayed M

2014-07-09

In this work, the results obtained from studying the anodic dissolution of pure iron and API X-65 5L pipeline steel after 40 min and 12 h exposure period in 4.0 wt % NaCl solutions at room temperature were reported. Potential-time, electrochemical impedance spectroscopy, potentiodynamic polarization, and chronoamperometric current-time at constant potential techniques were employed. It has been found that the iron electrode corrodes in the chloride test solutions faster than the API X-65 5L steel does under the same conditions. Increasing the exposure period for the electrodes from 40 min to 12 h showed a significant reduction in the corrosion parameters for both iron and steel in the 4.0 wt % NaCl solution. Results together confirmed clearly that the X-65 steel is superior to iron against corrosion in sodium chloride solutions.

Enhancing lithium-sulphur battery performance by strongly binding the discharge products on amino-functionalized reduced graphene oxide.

PubMed

Wang, Zhiyu; Dong, Yanfeng; Li, Hongjiang; Zhao, Zongbin; Wu, Hao Bin; Hao, Ce; Liu, Shaohong; Qiu, Jieshan; Lou, Xiong Wen David

2014-09-25

Lithium-sulphur batteries are one very appealing power source with high energy density. But their practical use is still hindered by several issues including short lifespan, low efficiency and safety concern from the lithium anode. Polysulphide dissolution and insulating nature of sulphur are generally considered responsible for the capacity degradation. However, the detachment of discharge products, that is, highly polar lithium sulphides, from nonpolar carbon matrix (for example, graphene) has been rarely studied as one critical factor. Here we report the strongly covalent stabilization of sulphur and its discharge products on amino-functionalized reduced graphene oxide that enables stable capacity retention of 80% for 350 cycles with high capacities and excellent high-rate response up to 4 C. The present study demonstrates a feasible and effective strategy to solve the long-term cycling difficulty for lithium-sulphur batteries and also helps to understand the capacity decay mechanism involved.

Autonomous colloidal crystallization in a galvanic microreactor

NASA Astrophysics Data System (ADS)

Punckt, Christian; Jan, Linda; Jiang, Peng; Frewen, Thomas A.; Saville, Dudley A.; Kevrekidis, Ioannis G.; Aksay, Ilhan A.

2012-10-01

We report on a technique that utilizes an array of galvanic microreactors to guide the assembly of two-dimensional colloidal crystals with spatial and orientational order. Our system is comprised of an array of copper and gold electrodes in a coplanar arrangement, immersed in a dilute hydrochloric acid solution in which colloidal micro-spheres of polystyrene and silica are suspended. Under optimized conditions, two-dimensional colloidal crystals form at the anodic copper with patterns and crystal orientation governed by the electrode geometry. After the aggregation process, the colloidal particles are cemented to the substrate by co-deposition of reaction products. As we vary the electrode geometry, the dissolution rate of the copper electrodes is altered. This way, we control the colloidal motion as well as the degree of reaction product formation. We show that particle motion is governed by a combination of electrokinetic effects acting directly on the colloidal particles and bulk electrolyte flow generated at the copper-gold interface.

Overcharge tolerant high-temperature cells and batteries

DOEpatents

Redey, Laszlo; Nelson, Paul A.

1989-01-01

In a lithium-alloy/metal sulfide high temperature electrochemical cell, cell damage caused by overcharging is avoided by providing excess lithium in a high-lithium solubility phase alloy in the negative electrode and a specified ratio maximum of the capacity of a matrix metal of the negative electrode in the working phase to the capacity of a transition metal of the positive electrode. In charging the cell, or a plurality of such cells in series and/or parallel, chemical transfer of elemental lithium from the negative electrode through the electrolyte to the positive electrode provides sufficient lithium to support an increased self-charge current to avoid anodic dissolution of the positive electrode components above a critical potential. The lithium is subsequently electrochemically transferred back to the negative electrode in an electrochemical/chemical cycle which maintains high self-discharge currents on the order of 3-15 mA/cm.sup.2 in the cell to prevent overcharging.

Electricity generation from bio-treatment of sewage sludge with microbial fuel cell.

PubMed

Jiang, Junqiu; Zhao, Qingliang; Zhang, Jinna; Zhang, Guodong; Lee, Duu-Jong

2009-12-01

A two-chambered microbial fuel cell (MFC) with potassium ferricyanide as its electron acceptor was utilized to degrade excess sewage sludge and to generate electricity. Stable electrical power was produced continuously during operation for 250 h. Total chemical oxygen demand (TCOD) of sludge was reduced by 46.4% when an initial TCOD was 10,850 mg/l. The MFC power output did not significantly depend on process parameters such as substrate concentration, cathode catholyte concentration, and anodic pH. However, the MFC produced power was in close correlation with the soluble chemical oxygen demand (SCOD) of sludge. Furthermore, ultrasonic pretreatment of sludge accelerated organic matter dissolution and, hence, TCOD removal rate in the MFC was increased, but power output was insignificantly enhanced. This study demonstrates that this MFC can generate electricity from sewage sludge over a wide range of process parameters.

Electrolysis of a molten semiconductor.

PubMed

Yin, Huayi; Chung, Brice; Sadoway, Donald R

2016-08-24

Metals cannot be extracted by electrolysis of transition-metal sulfides because as liquids they are semiconductors, which exhibit high levels of electronic conduction and metal dissolution. Herein by introduction of a distinct secondary electrolyte, we reveal a high-throughput electro-desulfurization process that directly converts semiconducting molten stibnite (Sb2S3) into pure (99.9%) liquid antimony and sulfur vapour. At the bottom of the cell liquid antimony pools beneath cathodically polarized molten stibnite. At the top of the cell sulfur issues from a carbon anode immersed in an immiscible secondary molten salt electrolyte disposed above molten stibnite, thereby blocking electronic shorting across the cell. As opposed to conventional extraction practices, direct sulfide electrolysis completely avoids generation of problematic fugitive emissions (CO2, CO and SO2), significantly reduces energy consumption, increases productivity in a single-step process (lower capital and operating costs) and is broadly applicable to a host of electronically conductive transition-metal chalcogenides.

Electrolysis of a molten semiconductor

NASA Astrophysics Data System (ADS)

Yin, Huayi; Chung, Brice; Sadoway, Donald R.

2016-08-01

Metals cannot be extracted by electrolysis of transition-metal sulfides because as liquids they are semiconductors, which exhibit high levels of electronic conduction and metal dissolution. Herein by introduction of a distinct secondary electrolyte, we reveal a high-throughput electro-desulfurization process that directly converts semiconducting molten stibnite (Sb2S3) into pure (99.9%) liquid antimony and sulfur vapour. At the bottom of the cell liquid antimony pools beneath cathodically polarized molten stibnite. At the top of the cell sulfur issues from a carbon anode immersed in an immiscible secondary molten salt electrolyte disposed above molten stibnite, thereby blocking electronic shorting across the cell. As opposed to conventional extraction practices, direct sulfide electrolysis completely avoids generation of problematic fugitive emissions (CO2, CO and SO2), significantly reduces energy consumption, increases productivity in a single-step process (lower capital and operating costs) and is broadly applicable to a host of electronically conductive transition-metal chalcogenides.

In Situ NMR Observation of the Temporal Speciation of Lithium Sulfur Batteries during Electrochemical Cycling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hao; Sa, Niya; He, Meinan

The understanding of the reaction mechanism and temporal speciation of the lithium sulfur batteries is challenged by complex polysulfide disproportionation chemistry coupled with the precipitation and dissolution of species. In this report, for the first time, we present a comprehensive method to investigate lithium sulfur electrochemistry using in situ 7Li NMR spectroscopy, a technique that is capable of quantitatively capturing the evolution of the soluble and precipitated lithium (poly)sulfides during electrochemical cycling. Furthermore, through deconvolution and quantification, every lithium-bearing species was closely tracked and four-step soluble lithium polysulfide-mediated lithium sulfur electrochemistry was demonstrated in never before seen detail. Significant irreversiblemore » accumulation of Li 2S is observed on the Li metal anode after four cycles because of sulfur shuttling. We present the application of the method in order to study electrolyte/additive development and lithium protection research can be readily envisaged.« less

In Situ NMR Observation of the Temporal Speciation of Lithium Sulfur Batteries during Electrochemical Cycling

DOE PAGES

Wang, Hao; Sa, Niya; He, Meinan; ...

2017-03-03

The understanding of the reaction mechanism and temporal speciation of the lithium sulfur batteries is challenged by complex polysulfide disproportionation chemistry coupled with the precipitation and dissolution of species. In this report, for the first time, we present a comprehensive method to investigate lithium sulfur electrochemistry using in situ 7Li NMR spectroscopy, a technique that is capable of quantitatively capturing the evolution of the soluble and precipitated lithium (poly)sulfides during electrochemical cycling. Furthermore, through deconvolution and quantification, every lithium-bearing species was closely tracked and four-step soluble lithium polysulfide-mediated lithium sulfur electrochemistry was demonstrated in never before seen detail. Significant irreversiblemore » accumulation of Li 2S is observed on the Li metal anode after four cycles because of sulfur shuttling. We present the application of the method in order to study electrolyte/additive development and lithium protection research can be readily envisaged.« less

Electrochemical Interpretation of a Stress Corrosion Cracking of Thermally Treated Ni base Alloys in a Lead Contaminated Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hwang, Seong Sik; Lim, Yun Soo; Kim, Hong Pyo

2007-08-20

Since the PbSCC(Lead stress corrosion cracking) of alloy 600 tubing materials was reported by Copson and Dean in 1965, the effect of lead on a corrosion film and cracking morphology have been continually debated. An electrochemical interaction of lead with the alloying elements of SG tubings was studied and the corrosion products were analyzed. It was found that lead enhanced the anodic dissolution of alloy 600 and alloy 690 in the electrochemical test. The lead preferentially dissolved the Cr from the corrosion film of alloy 600 and alloy 690 in alkaline water. The lead ion seemed to penetrate into themore » TG crack tip and react with the corrosion film. A selective Cr depletion was observed to weaken the stability of the passive film on the alloys. Whereas passivity of Ni became stable in lead containing solution, Cr and Fe passivity became unstable.« less

Corrosion fatigue crack propagation in metals

NASA Technical Reports Server (NTRS)

Gangloff, Richard P.

1990-01-01

This review assesses fracture mechanics data and mechanistic models for corrosion fatigue crack propagation in structural alloys exposed to ambient temperature gases and electrolytes. Extensive stress intensity-crack growth rate data exist for ferrous, aluminum and nickel based alloys in a variety of environments. Interactive variables (viz., stress intensity range, mean stress, alloy composition and microstructure, loading frequency, temperature, gas pressure and electrode potential) strongly affect crack growth kinetics and complicate fatigue control. Mechanistic models to predict crack growth rates were formulated by coupling crack tip mechanics with occluded crack chemistry, and from both the hydrogen embrittlement and anodic dissolution/film rupture perspectives. Research is required to better define: (1) environmental effects near threshold and on crack closure; (2) damage tolerant life prediction codes and the validity of similitude; (3) the behavior of microcrack; (4) probes and improved models of crack tip damage; and (5) the cracking performance of advanced alloys and composites.

Role of thermal resistance on the performance of superconducting radio frequency cavities

DOE PAGES

Dhakal, Pashupati; Ciovati, Gianluigi; Myneni, Ganapati Rao

2017-03-07

Thermal stability is an important parameter for the operation of the superconducting radio frequency (SRF) cavities used in particle accelerators. The rf power dissipated on the inner surface of the cavities is conducted to the helium bath cooling the outer cavity surface and the equilibrium temperature of the inner surface depends on the thermal resistance. In this manuscript, we present the results of direct measurements of thermal resistance on 1.3 GHz single cell SRF cavities made from high purity large-grain and fine-grain niobium as well as their rf performance for different treatments applied to outer cavity surface in order tomore » investigate the role of the Kapitza resistance to the overall thermal resistance and to the SRF cavity performance. The results show no significant impact of the thermal resistance to the SRF cavity performance after chemical polishing, mechanical polishing or anodization of the outer cavity surface. Temperature maps taken during the rf test show nonuniform heating of the surface at medium rf fields. Calculations of Q 0(B p) curves using the thermal feedback model show good agreement with experimental data at 2 and 1.8 K when a pair-braking term is included in the calculation of the Bardeen-Cooper-Schrieffer surface resistance. In conclusion, these results indicate local intrinsic nonlinearities of the surface resistance, rather than purely thermal effects, to be the main cause for the observed field dependence of Q 0(B p).« less

Role of thermal resistance on the performance of superconducting radio frequency cavities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dhakal, Pashupati; Ciovati, Gianluigi; Myneni, Ganapati Rao

Thermal stability is an important parameter for the operation of the superconducting radio frequency (SRF) cavities used in particle accelerators. The rf power dissipated on the inner surface of the cavities is conducted to the helium bath cooling the outer cavity surface and the equilibrium temperature of the inner surface depends on the thermal resistance. In this manuscript, we present the results of direct measurements of thermal resistance on 1.3 GHz single cell SRF cavities made from high purity large-grain and fine-grain niobium as well as their rf performance for different treatments applied to outer cavity surface in order tomore » investigate the role of the Kapitza resistance to the overall thermal resistance and to the SRF cavity performance. The results show no significant impact of the thermal resistance to the SRF cavity performance after chemical polishing, mechanical polishing or anodization of the outer cavity surface. Temperature maps taken during the rf test show nonuniform heating of the surface at medium rf fields. Calculations of Q 0(B p) curves using the thermal feedback model show good agreement with experimental data at 2 and 1.8 K when a pair-braking term is included in the calculation of the Bardeen-Cooper-Schrieffer surface resistance. In conclusion, these results indicate local intrinsic nonlinearities of the surface resistance, rather than purely thermal effects, to be the main cause for the observed field dependence of Q 0(B p).« less

Macroscopic and molecular-scale assessment of soil lead contamination impacted by seasonal dove hunting activities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arai, Y.; Tappero, R.; Rick, A.R.

Environmental contamination of lead (Pb) in soils and sediments poses serious threats to human and ecological health. The objective of this study is to investigate the effect of seasonal dove sports hunting activities on Pb contamination in acid forest soils. A grid sampling method was used to investigate the spatial distribution of Pb contamination in surface soils. Soils were analyzed for total metal(loid) concentration and characterized for physicochemical properties and mineralogy. Adsorption isotherm experiments were also conducted to understand the reactivity and retention capacity of Pb(II) in soils. Finally, synchrotron-based X-ray microprobe and X-ray absorption spectroscopy were used to understandmore » the chemical speciation of Pb that controls the retention/release mechanisms of Pb in soils. There was no excessive accumulation of Pb at the site. However, the concentration of Pb in surface soils was greater than the background level (<16 mg kg{sup -1}). The contamination level of Pb was as high as 67 mg kg{sup -1} near a patch of corn field where lime was frequently applied. A microfocused X-ray microprobe analysis showed the presence of Pb pellet fragments that predominantly contain oxidized Pb(II), suggesting that oxidative dissolution was occurring in soils. Dissolved Pb(II) can be readily retained in soils up to {approx}3,600 mg kg{sup -1} via inner-sphere and outer-sphere surface complexation on carbon and aluminol functional groups of soil components, suggesting that partitioning reactions control the concentration of Pb in soil solution. The fate of Pb is likely to be controlled by (1) oxidative dissolution process of Pb(0) pellets and (2) the release of outer-sphere and/or inner-sphere Pb surface complexes in humic substances and aluminosilicate/Al oxyhydroxides. Although no remedial actions are immediately required, the long-term accumulation of Pb in soils should be carefully monitored in protecting ecosystem and water quality at the dove hunting field.« less

Macroscopic and microscopic investigation of Ni(II) sequestration on diatomite by batch, XPS, and EXAFS techniques.

PubMed

Sheng, Guodong; Yang, Shitong; Sheng, Jiang; Hu, Jun; Tan, Xiaoli; Wang, Xiangke

2011-09-15

Sequestration of Ni(II) on diatomite as a function of time, pH, and temperature was investigated by batch, XPS, and EXAFS techniques. The ionic strength-dependent sorption at pH < 7.0 was consistent with outer-sphere surface complexation, while the ionic strength-independent sorption at pH = 7.0-8.6 was indicative of inner-sphere surface complexation. EXAFS results indicated that the adsorbed Ni(II) consisted of ∼6 O at R(Ni-O) ≈ 2.05 Å. EXAFS analysis from the second shell suggested that three phenomena occurred at the diatomite/water interface: (1) outer-sphere and/or inner-sphere complexation; (2) dissolution of Si which is the rate limiting step during Ni uptake; and (3) extensive growth of surface (co)precipitates. Under acidic conditions, outer-sphere complexation is the main mechanism controlling Ni uptake, which is in good agreement with the macroscopic results. At contact time of 1 h or 1 day or pH = 7.0-8.0, surface coprecipitates occur concurrently with inner-sphere complexes on diatomite surface, whereas at contact time of 1 month or pH = 10.0, surface (co)precipitates dominate Ni uptake. Furthermore, surface loading increases with temperature increasing, and surface coprecipitates become the dominant mechanism at elevated temperature. The results are important to understand Ni interaction with minerals at the solid-water interface, which is helpful to evaluate the mobility of Ni(II) in the natural environment.

Plasma development in the accelerator of a 2-kJ focus discharge.

PubMed

Fischer, H; Haering, K H

1979-07-01

Optical image structures from early breakdown ( approximately 200 nsec) to focus formation (~1300 nsec) in 3 Torr hydrogen were studied by means of 2 image converter shutters having 50-nsec and 10-nsec exposure. Space charge limited cathode spots at the outer electrode (OE)-spoke-shaped positive columns across the gap-and an extended electron cloud along the center electrode (CE) determine the current flow during early breakdown. Ionization increases exponentially within the center gap plasma. This is separated from the CE by a pattern of anode drop filaments. Filament structures grow into the z-axis accelerated current sheath, which in addition carries the early spoke pattern. The sheath appears homogeneous after leaving the accelerator exit.

A Field Test of Electromigration as a Method for Remediating Sulfate from Shallow Ground Water

USGS Publications Warehouse

Patterson, C.G.; Runnells, D.D.

1996-01-01

Electromigration offers a potential tool for remediating ground water contaminated with highly soluble components, such as Na+, Cl-, NO3-, and SO4-. A field experiment was designed to test the efficacy of electromigration for preconcentrating dissolved SO42- in ground water associated with a fossil-fuel power plant. Two shallow wells, 25 feet apart (one 25 feet deep, the other 47 feet deep), were constructed in the upper portion of an unconfined alluvial aquifer. The wells were constructed with a double-wall design, with an outer casing of 4-inch PVC and an inner tube of 2-inch PVC; both were fully slotted (0.01 inch). Electrodes were constructed by wrapping the inner tubing with a 100-foot length of rare-earth metal oxide/copper wire. An electrical potential of 10.65 volts DC was applied, and tests were run for periods of 12, 44, and 216 hours. Results showed large changes in the pH from the initial pH of ground water of about 7.5 to values of approximately 2 and 12 at the anode and cathode, respectively. Despite the fact that the test conditions were far from ideal, dissolved SO42- was significantly concentrated at the anode. Over a period of approximately nine days, the concentration of SO42- at the anode reached what appeared to be a steady-state value of 2200 mg/L, compared to the initial value in ground water of approximately 1150 mg/L. The results of this field test should encourage further investigation of electromigration as a tool in the remediation of contaminated ground water.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Yun; Chen, Song; Hackett, Gregory

The interaction of trace (ppm) phosphine with the nickel/yttria stabilized zirconia (YSZ) anode of commercial solid oxide fuel cells has been investigated and evaluated for both synthesis gas and hydrogen fuels in an effort to examine P–Y reactions. The Ni poisoning effects reported in literature were confirmed and degradation was examined by electrochemical methods and post-test microstructural and chemical analyses. The results indicate that P-induced degradation rates and mechanisms are fuel dependent and that degradation of cells operated in synthesis gas (syngas) with phosphine is more severe than that of cells operated in hydrogen with phosphine. As reported in publishedmore » literature, a cell operated in syngas containing 10 ppm phosphine demonstrated significant microstructural degradation within the Ni phase, including formation of Ni–P phases concentrated on the outer layer of the anode and significant pitting corrosion in the Ni grains. In this research, a previously undetected YPO{sub 4} phase is observed at the YSZ/YSZ/Ni triple grain junctions located at the interface with the YSZ electrolyte. Tetragonal YSZ (t-YSZ) and cubic-YSZ (c-YSZ) domains with sizes of several tens of nanometers are also newly observed along the Ni/YSZ interface. These observations contrast with data obtained for a cell operated in dry hydrogen with phosphine, where no YPO{sub 4} phase is observed and the alternating t-YSZ and c-YSZ domains at the Ni/YSZ interface are smaller with typical sizes of 5–10 nm. The data imply that electrolyte attack by P is a potentially debilitating mode of degradation in SOFC anodes, and that the associated reaction mechanisms and rates are worthy of further examination.« less

Cylindrical Asymmetrical Capacitors for Use in Outer Space

NASA Technical Reports Server (NTRS)

Campbell, Jonathan W.

2007-01-01

A report proposes that cylindrical asymmetrical capacitors (CACs) be used to generate small thrusts for precise maneuvering of spacecraft on long missions. The report notes that it has been known for decades that when high voltages are applied to CACs in air, thrusts are generated - most likely as a result of ionization of air molecules and acceleration of the ions by the high electric fields. The report goes on to discuss how to optimize the designs of CACs for operation as thrusters in outer space. Components that could be used to enable outerspace operation include a supply of gas and a shroud, partly surrounding a CAC, into which the gas would flow. Other elements of operation and design discussed in the report include variation of applied voltage and/or of gas flow to vary thrust, effects of CAC and shroud dimensions on thrust and weight, some representative electrode configurations, and several alternative designs, including one in which the basic CAC configuration would be modified into something shaped like a conventional rocket engine with converging/diverging nozzle and an anode with gas feed in the space that, in a conventional rocket engine, would be the combustion chamber.

Kinetic Monte Carlo Simulations and Molecular Conductance Measurements of the Bacterial Decaheme Cytochrome MtrF

DOE Office of Scientific and Technical Information (OSTI.GOV)

Byun, H. S.; Pirbadian, S.; Nakano, Aiichiro

2014-09-05

Microorganisms overcome the considerable hurdle of respiring extracellular solid substrates by deploying large multiheme cytochrome complexes that form 20 nanometer conduits to traffic electrons through the periplasm and across the cellular outer membrane. Here we report the first kinetic Monte Carlo simulations and single-molecule scanning tunneling microscopy (STM) measurements of the Shewanella oneidensis MR-1 outer membrane decaheme cytochrome MtrF, which can perform the final electron transfer step from cells to minerals and microbial fuel cell anodes. We find that the calculated electron transport rate through MtrF is consistent with previously reported in vitro measurements of the Shewanella Mtr complex, asmore » well as in vivo respiration rates on electrode surfaces assuming a reasonable (experimentally verified) coverage of cytochromes on the cell surface. The simulations also reveal a rich phase diagram in the overall electron occupation density of the hemes as a function of electron injection and ejection rates. Single molecule tunneling spectroscopy confirms MtrF's ability to mediate electron transport between an STM tip and an underlying Au(111) surface, but at rates higher than expected from previously calculated heme-heme electron transfer rates for solvated molecules.« less

Two Isoforms of Geobacter sulfurreducens PilA Have Distinct Roles in Pilus Biogenesis, Cytochrome Localization, Extracellular Electron Transfer, and Biofilm Formation

PubMed Central

Richter, Lubna V.; Sandler, Steven J.

2012-01-01

Type IV pili of Geobacter sulfurreducens are composed of PilA monomers and are essential for long-range extracellular electron transfer to insoluble Fe(III) oxides and graphite anodes. A previous analysis of pilA expression indicated that transcription was initiated at two positions, with two predicted ribosome-binding sites and translation start codons, potentially producing two PilA preprotein isoforms. The present study supports the existence of two functional translation start codons for pilA and identifies two isoforms (short and long) of the PilA preprotein. The short PilA isoform is found predominantly in an intracellular fraction. It seems to stabilize the long isoform and to influence the secretion of several outer-surface c-type cytochromes. The long PilA isoform is required for secretion of PilA to the outer cell surface, a process that requires coexpression of pilA with nine downstream genes. The long isoform was determined to be essential for biofilm formation on certain surfaces, for optimum current production in microbial fuel cells, and for growth on insoluble Fe(III) oxides. PMID:22408162

An ultrafast rechargeable aluminium-ion battery.

PubMed

Lin, Meng-Chang; Gong, Ming; Lu, Bingan; Wu, Yingpeng; Wang, Di-Yan; Guan, Mingyun; Angell, Michael; Chen, Changxin; Yang, Jiang; Hwang, Bing-Joe; Dai, Hongjie

2015-04-16

The development of new rechargeable battery systems could fuel various energy applications, from personal electronics to grid storage. Rechargeable aluminium-based batteries offer the possibilities of low cost and low flammability, together with three-electron-redox properties leading to high capacity. However, research efforts over the past 30 years have encountered numerous problems, such as cathode material disintegration, low cell discharge voltage (about 0.55 volts; ref. 5), capacitive behaviour without discharge voltage plateaus (1.1-0.2 volts or 1.8-0.8 volts) and insufficient cycle life (less than 100 cycles) with rapid capacity decay (by 26-85 per cent over 100 cycles). Here we present a rechargeable aluminium battery with high-rate capability that uses an aluminium metal anode and a three-dimensional graphitic-foam cathode. The battery operates through the electrochemical deposition and dissolution of aluminium at the anode, and intercalation/de-intercalation of chloroaluminate anions in the graphite, using a non-flammable ionic liquid electrolyte. The cell exhibits well-defined discharge voltage plateaus near 2 volts, a specific capacity of about 70 mA h g(-1) and a Coulombic efficiency of approximately 98 per cent. The cathode was found to enable fast anion diffusion and intercalation, affording charging times of around one minute with a current density of ~4,000 mA g(-1) (equivalent to ~3,000 W kg(-1)), and to withstand more than 7,500 cycles without capacity decay.

NaTi2(PO4)3 as an Aqueous Anode: Degradation Mechanisms and Mitigation Techniques

NASA Astrophysics Data System (ADS)

Mohamed, Alexander I.

With the proliferation of renewable energy sources, there has been a growing interest in battery chemistries for grid scale energy storage. Aqueous sodium ion batteries are particularly interesting for large scale energy storage because of their low cost and high safety, however, they tend to show poor long term stability. NaTi2(PO4)3 (NTP) shows promise as an anode for these systems with excellent long term stability when cycled quickly. When cycled slowly, NaTi2(PO4) 3 shows rapid capacity fade. The reasons for this rate depend capacity fade is poorly understood and is the topic of this document. It has been found that the products of the hydrogen evolution reaction, H2(g) and OH-, are the two largest contributors to capacity fade. High electrolyte pH caused by generation of OH- promotes dissolution of NTP during extend cycling, this is exacerbated when the pH increase above 11. The single greatest cause of apparent capacity fade for this material is loss of electrochemical surface area due to hydrogen gas entrapment within the porous structure of the electrode. Capacity lost in this manner can be recovered through reinfiltration of the electrode. The detrimental effects of gas entrapment within the electrode can be partially mitigated through compositing of the electrode with activated carbon and enhancing the wettability of the pores through addition of a surfactant to the electrolyte.

Influence of laser surface treated on the characterization and corrosion behavior of Al-Fe aerospace alloys

NASA Astrophysics Data System (ADS)

Pariona, Moisés Meza; Teleginski, Viviane; dos Santos, Kelly; de Lima, Angela A. O. C.; Zara, Alfredo J.; Micene, Katieli Tives; Riva, Rudimar

2013-07-01

In this research laser surface remelting without protective coating with a 2 kW Yb-fiber laser (IPG YLR-2000S) was applied in the Al-1.5 wt.%Fe alloy in order to investigate the layer treated with different techniques of superficial characterization, thereby, the technique of optical microscopy, atomic force microscopy and low-angle X-ray diffraction were used. The present work mainly focuses on the corrosion study by diverse techniques in aggressive environment of the laser-treated area and the substrate material was carried out, thereby, at open circuit potential testing, the results have shown a displacement to more anodic values in the corrosion potential for the laser-treated specimen when compared to the untreated specimen; in potentiodynamic polarization tests have shown that as a result of the laser treatment, the corrosion current can be reduced by as much as ten times, and a passive region was obtained, which served as an effective barrier for reducing anodic dissolution and finally, the result in cyclic polarization curves of the untreated sample there was a greater area of the hysteresis loop, implying that it is more susceptible to corrosion. This study was complemented by other techniques mentioned above in order to elucidate this study. Laser surface remelting process has definitely modified the surface film, which results in higher corrosion resistance, a large range of passivation and a lower area of the hysteresis loop.

Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover

DOE PAGES

Li, Wangda; Kim, Un-Hyuck; Dolocan, Andrei; ...

2017-05-14

The formation of metallic lithium microstructures in the form of dendrites or mosses at the surface of anode electrodes (e.g., lithium metal, graphite, and silicon) leads to rapid capacity fade and poses grave safety risks in rechargeable lithium batteries. In this work, we present here a direct, relative quantitative analysis of lithium deposition on graphite anodes in pouch cells under normal operating conditions, paired with a model cathode material, the layered nickel-rich oxide LiNi 0.61Co 0.12Mn 0.27O 2, over the course of 3000 charge-discharge cycles. Secondary-ion mass spectrometry chemically dissects the solid-electrolyte interphase (SEI) on extensively cycled graphite with virtuallymore » atomic depth resolution and reveals substantial growth of Li-metal deposits. With the absence of apparent kinetic (e.g., fast charging) or stoichiometric restraints (e.g., overcharge) during cycling, we show lithium deposition on graphite is triggered by certain transition-metal ions (manganese in particular) dissolved from the cathode in a disrupted SEI. This insidious effect is found to initiate at a very early stage of cell operation (<200 cycles) and can be effectively inhibited by substituting a small amount of aluminum (~1 mol %) in the cathode, resulting in much reduced transition-metal dissolution and drastically improved cyclability. In conclusion, our results may also be applicable to studying the unstable electrodeposition of lithium on other substrates, including Li metal.« less

Innovative approach for the valorization of useful metals from waste electric and electronic equipment (WEEE)

NASA Astrophysics Data System (ADS)

Soare, V.; Burada, M.; Dumitrescu, D. V.; Constantin, I.; Soare, V.; Popescu, A.-M. J.; Carcea, I.

2016-08-01

Waste electric and electronic equipment are an important secondary source of rare and precious metals and their processing through ecological technologies constitutes a major concern in the European Union and significantly contributes to the reduction of environmental pollution and to the preservation of valuable resources of nonferrous metals. The paper presents an innovative approach for the complex valorization of useful metals contained in WEEE. The method consists in the melting of WEEE in a furnace in a microwave field at temperatures of 1000 ÷1200°C, for the complete separation of the metallic fraction from the organic components. The gases resulting from the melting process were also treated/neutralized in a microwave environment and the obtained metallic bulk (multi-component alloy) was processed through combined hydrometallurgical and electrochemical methods. The major elements in the metallic bulk (Cu, Sn, Zn, Pb) were separated/recovered by anodic dissolution, respectively by leaching in nitric acid followed by cementation using various agents, or by electrodeposition. Depending on the electrochemical parameters, cathodic deposits consisting of Cu, with a purity higher than 99.9%, or of Cu-Sn and Cu-Sn-Zn alloys were obtained. Silver was valorized by leaching/precipitation with NaCl and the gold concentrated in the anodic slime will be recovered by thiourea extraction. The experiments performed demonstrate the possibility of ecological and efficient processing of WEEE in a microwave field and the recovery of nonferrous and precious metals through combined hydrometallurgical and electrochemical methods.

Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Wangda; Kim, Un-Hyuck; Dolocan, Andrei

The formation of metallic lithium microstructures in the form of dendrites or mosses at the surface of anode electrodes (e.g., lithium metal, graphite, and silicon) leads to rapid capacity fade and poses grave safety risks in rechargeable lithium batteries. In this work, we present here a direct, relative quantitative analysis of lithium deposition on graphite anodes in pouch cells under normal operating conditions, paired with a model cathode material, the layered nickel-rich oxide LiNi 0.61Co 0.12Mn 0.27O 2, over the course of 3000 charge-discharge cycles. Secondary-ion mass spectrometry chemically dissects the solid-electrolyte interphase (SEI) on extensively cycled graphite with virtuallymore » atomic depth resolution and reveals substantial growth of Li-metal deposits. With the absence of apparent kinetic (e.g., fast charging) or stoichiometric restraints (e.g., overcharge) during cycling, we show lithium deposition on graphite is triggered by certain transition-metal ions (manganese in particular) dissolved from the cathode in a disrupted SEI. This insidious effect is found to initiate at a very early stage of cell operation (<200 cycles) and can be effectively inhibited by substituting a small amount of aluminum (~1 mol %) in the cathode, resulting in much reduced transition-metal dissolution and drastically improved cyclability. In conclusion, our results may also be applicable to studying the unstable electrodeposition of lithium on other substrates, including Li metal.« less

Comparative studies of thin film growth on aluminium by AFM, TEM and GDOES characterization

NASA Astrophysics Data System (ADS)

Qi, Jiantao; Thompson, George E.

2016-07-01

In this present study, comparative studies of trivalent chromium conversion coating formation, associated with aluminium dissolution process, have been investigated using atomic force microscopy (AFM), transmission electron microscopy (TEM) and glow-discharge optical emission spectroscopy (GDOES). High-resolution electron micrographs revealed the evident and uniform coating initiation on the whole surface after conversion treatment for only 30 s, although a network of metal ridges was created by HF etching pre-treatment. In terms of conversion treatment process on electropolished aluminium, constant kinetics of coating growth, ∼0.30 ± 0.2 nm/s, were found after the prolonged conversion treatment for 600 s. The availability of electrolyte anions for coating deposition determined the growth process. Simultaneously, a proceeding process of aluminium dissolution during conversion treatment, of ∼0.11 ± 0.02 nm/s, was found for the first time, indicating constant kinetics of anodic reactions. The distinct process of aluminium consumption was assigned with loss of corrosion protection of the deposited coating material as evidenced in the electrochemical impedance spectroscopy. Based on the present data, a new mechanism of coating growth on aluminium was proposed, and it consisted of an activation period (0-30 s), a linear growth period (0.30 nm/s, up for 600 s) and limited growth period (0.17 nm/s, 600-1200 s). In addition, the air-drying post-treatment and a high-vacuum environment in the microscope revealed a coating shrinkage, especially in the coatings after conversion treatments for longer time.

Polyaniline-encapsulated silicon on three-dimensional carbon nanotubes foam with enhanced electrochemical performance for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhou, Xiaoming; Liu, Yang; Du, Chunyu; Ren, Yang; Mu, Tiansheng; Zuo, Pengjian; Yin, Geping; Ma, Yulin; Cheng, Xinqun; Gao, Yunzhi

2018-03-01

Seeking free volume around nanostructures for silicon-based anodes has been a crucial strategy to improve cycling and rate performance in the next generation Li-ion batteries. Herein, through a simple pyrolysis and in-situ polymerization approach, the low cost commercially available melamine foam as a soft template converts carbon nanotubes into highly dispersed and three-dimensionally interconnected framework with encapsulated silicon/polyaniline hierarchical nanoarchitecture. This unique core-sheath structure based on carbon nanotubes foam integrates a large number of mesoporous, thus providing well-accessible space for electrolyte wetting, whereas the carbon nanotubes matrix serves as conductive thoroughfares for electron transport. Meanwhile, the outer polyaniline coated on silicon nanoparticles provides effective space for volume expansion of silicon, further inhibiting the active material escape from the current collector. As expected, the PANI-Si@CNTs foam exhibits a high initial specific capacity of 1954 mAh g-1 and retains 727 mAh g-1 after 100 cycles at 100 mA g-1, which can be attributed to highly electrical conductivity of carbon nanotubes and protective layer of polyaniline sheath, together with three-dimensionally interconnected porous skeleton. This facile structure can pave a way for large scale synthesis of high durable silicon-based anodes or other electrode materials with huge volume expansion.

In situ nano- to microscopic imaging and growth mechanism of electrochemical dissolution (e.g., corrosion) of a confined metal surface

PubMed Central

Merola, C.; Cheng, H.-W.; Schwenzfeier, K.; Kristiansen, K.; Chen, Y.-J.; Dobbs, H. A.; Valtiner, M.

2017-01-01

Reactivity in confinement is central to a wide range of applications and systems, yet it is notoriously difficult to probe reactions in confined spaces in real time. Using a modified electrochemical surface forces apparatus (EC-SFA) on confined metallic surfaces, we observe in situ nano- to microscale dissolution and pit formation (qualitatively similar to previous observation on nonmetallic surfaces, e.g., silica) in well-defined geometries in environments relevant to corrosion processes. We follow “crevice corrosion” processes in real time in different pH-neutral NaCl solutions and applied surface potentials of nickel (vs. Ag|AgCl electrode in solution) for the mica–nickel confined interface of total area ∼0.03 mm2. The initial corrosion proceeds as self-catalyzed pitting, visualized by the sudden appearance of circular pits with uniform diameters of 6–7 μm and depth ∼2–3 nm. At concentrations above 10 mM NaCl, pitting is initiated at the outer rim of the confined zone, while below 10 mM NaCl, pitting is initiated inside the confined zone. We compare statistical analysis of growth kinetics and shape evolution of individual nanoscale deep pits with estimates from macroscopic experiments to study initial pit growth and propagation. Our data and experimental techniques reveal a mechanism that suggests initial corrosion results in formation of an aggressive interfacial electrolyte that rapidly accelerates pitting, similar to crack initiation and propagation within the confined area. These results support a general mechanism for nanoscale material degradation and dissolution (e.g., crevice corrosion) of polycrystalline nonnoble metals, alloys, and inorganic materials within confined interfaces. PMID:28827338

Semisolid matrix filled capsules: an approach to improve dissolution stability of phenytoin sodium formulation.

PubMed

El Massik, M A; Abdallah, O Y; Galal, S; Daabis, N A

2003-05-01

Seven semisolid fill bases were selected for the formulation of 24 capsule formulations, each containing 100 mg of phenytoin sodium. The fill materials were selected based on the water absorption capacity of their mixtures with phenytoin sodium. The fill matrices included lipophilic bases (castor oil, soya oil, and Gelucire (G) 33/01), amphiphilic bases (G 44/14 and Suppocire BP), and water-soluble bases (PEG 4000 and PEG 6000). The drug:base ratio was 1:2. Excipients such as lecithin, docusate sodium, and poloxamer 188 were added to some formulations. The dissolution rate study indicated that formulations containing lipophilic and amphiphilic bases showed the best release profiles. These are F4 (castor oil-1% docusate sodium); F10 (castor oil-3% poloxamer 188); F14 (G33/01-10% lecithin); F17 (G33/01-1% docusate sodium), and F20 (Suppocire BP). Further, the dissolution stability of the five formulations above was assessed by an accelerated stability study at 30 degrees C and 75% RH using standard Epanutin capsules for comparison. The study included the test and standard capsules either packed in the container of marketed Epanutin capsules (packed) or removed from their outer pack (unpacked). Release data indicated superior release rates of castor oil based formulations (F4 and F10) relative to standard capsules in both the unpacked and packed forms. For instance, the extent of drug release at 30 min after 1 month was 91% for F4 and F10 and 20% for standard capsules. Drug release from packed capsules after 6 months storage was 88% for both formulations F4 and F10 and 35% for standard capsules. In conclusion, the pharmaceutical quality of phenytoin sodium capsules can be improved by using a semisolid lipophilic matrix filled in hard gelatin capsules.

Prediction of plasma properties in mercury ion thrusters

NASA Technical Reports Server (NTRS)

Longhurst, G. R.

1978-01-01

A simplified theoretical model was developed which obtains to first order the plasma properties in the discharge chamber of a mercury ion thruster from basic thruster design and controllable operating parameters. The basic operation and design of ion thrusters is discussed, and the important processes which influence the plasma properties are described in terms of the design and control parameters. The conservation for mass, charge and energy were applied to the ion production region, which was defined as the region of the discharge chamber having as its outer boundary the surface of revolution of the innermost field line to intersect the anode. Mass conservation and the equations describing the various processes involved with mass addition and removal from the ion production region are satisfied by a Maxwellian electron density spatial distribution in that region.

Glass-silicon column

DOEpatents

Yu, Conrad M.

2003-12-30

A glass-silicon column that can operate in temperature variations between room temperature and about 450.degree. C. The glass-silicon column includes large area glass, such as a thin Corning 7740 boron-silicate glass bonded to a silicon wafer, with an electrode embedded in or mounted on glass of the column, and with a self alignment silicon post/glass hole structure. The glass/silicon components are bonded, for example be anodic bonding. In one embodiment, the column includes two outer layers of silicon each bonded to an inner layer of glass, with an electrode imbedded between the layers of glass, and with at least one self alignment hole and post arrangement. The electrode functions as a column heater, and one glass/silicon component is provided with a number of flow channels adjacent the bonded surfaces.

Larger sized wire arrays on 1.5 MA Z-pinch generator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Safronova, A. S., E-mail: alla@unr.edu; Kantsyrev, V. L., E-mail: alla@unr.edu; Weller, M. E., E-mail: alla@unr.edu

Experiments on the UNR Zebra generator with Load Current Multiplier (LCM) allow for implosions of larger sized wire array loads than at standard current of 1 MA. Advantages of larger sized planar wire array implosions include enhanced energy coupling to plasmas, better diagnostic access to observable plasma regions, and more complex geometries of the wire loads. The experiments with larger sized wire arrays were performed on 1.5 MA Zebra with LCM (the anode-cathode gap was 1 cm, which is half the gap used in the standard mode). In particular, larger sized multi-planar wire arrays had two outer wire planes frommore » mid-atomic-number wires to create a global magnetic field (gmf) and plasma flow between them. A modified central plane with a few Al wires at the edges was put in the middle between outer planes to influence gmf and to create Al plasma flow in the perpendicular direction (to the outer arrays plasma flow). Such modified plane has different number of empty slots: it was increased from 6 up to 10, hence increasing the gap inside the middle plane from 4.9 to 7.7 mm, respectively. Such load configuration allows for more independent study of the flows of L-shell mid-atomic-number plasma (between the outer planes) and K-shell Al plasma (which first fills the gap between the edge wires along the middle plane) and their radiation in space and time. We demonstrate that such configuration produces higher linear radiation yield and electron temperatures as well as advantages of better diagnostics access to observable plasma regions and how the load geometry (size of the gap in the middle plane) influences K-shell Al radiation. In particular, K-shell Al radiation was delayed compared to L-shell mid-atomic-number radiation when the gap in the middle plane was large enough (when the number of empty slots was increased up to ten)« less

Nitridation of a Super-Ferritic Stainless Steel for PEMFC Bipolar Plate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, H.; Turner, J. A.; Brady, M. P.

2007-01-01

AL29-4C alloy nitrided in pure nitrogen resulted in a nitrogen-modified oxide surface, which is the same as AISI446 nitrided under identical conditions. When the alloy was nitrided 24h at 900 C in N2-4H2, XRD and XPS analysis indicated that the surface layer consisted of a nitride outer layer ({approx}0.20 {micro}m) and an oxide inner layer ({approx} 0.82 {micro}m). According to XPS, the nitride outer layer is composed of CrN and [Cr(N),Fe]2N1-x, with much more Cr2N than Fe2N. Mn is migrated and enriched in the oxide inner layer and combined with chromium oxide.AL29-4C alloy nitrided in N2-4H2 resulted in low ICRmore » and excellent corrosion resistance in simulated PEMFC environments. Current was at ca. -3.0 {micro}A/cm2 in the PEMFC anode environment, and at ca. 0.3 {approx} 0.5 {micro}A/cm2 in the cathode environment. This is considered to be rather stable. After being polarized in a PEMFC environment, the ICR increased slightly compared with the as-nitrided sample, but was still rather low.« less

Lipopolysaccharide inhibits or accelerates biomedical titanium corrosion depending on environmental acidity

PubMed Central

Yu, Fei; Addison, Owen; Baker, Stephen J; Davenport, Alison J

2015-01-01

Titanium and its alloys are routinely used as biomedical implants and are usually considered to be corrosion resistant under physiological conditions. However, during inflammation, chemical modifications of the peri-implant environment including acidification occur. In addition certain biomolecules including lipopolysaccharide (LPS), a component of Gram-negative bacterial cell walls and driver of inflammation have been shown to interact strongly with Ti and modify its corrosion resistance. Gram-negative microbes are abundant in biofilms which form on dental implants. The objective was to investigate the influence of LPS on the corrosion properties of relevant biomedical Ti substrates as a function of environmental acidity. Inductively coupled plasma mass spectrometry was used to quantify Ti dissolution following immersion testing in physiological saline for three common biomedical grades of Ti (ASTM Grade 2, Grade 4 and Grade 5). Complementary electrochemical tests including anodic and cathodic polarisation experiments and potentiostatic measurements were also conducted. All three Ti alloys were observed to behave similarly and ion release was sensitive to pH of the immersion solution. However, LPS significantly inhibited Ti release under the most acidic conditions (pH 2), which may develop in localized corrosion sites, but promoted dissolution at pH 4–7, which would be more commonly encountered physiologically. The observed pattern of sensitivity to environmental acidity of the effect of LPS on Ti corrosion has not previously been reported. LPS is found extensively on the surfaces of skin and mucosal penetrating Ti implants and the findings are therefore relevant when considering the chemical stability of Ti implant surfaces in vivo. PMID:25634122

Electrochemical characteristics of bioresorbable binary MgCa alloys in Ringer's solution: Revealing the impact of local pH distributions during in-vitro dissolution.

PubMed

Mareci, D; Bolat, G; Izquierdo, J; Crimu, C; Munteanu, C; Antoniac, I; Souto, R M

2016-03-01

Biodegradable magnesium-calcium (MgCa) alloy is a very attractive biomaterial. Two MgCa alloys below the solid solubility of Ca were considered, as to solely investigate the effect of Ca content on the behavior of magnesium and the pH changes associated to metal dissolution. X-ray diffraction analysis and optical microscopy showed that both Mg-0.63Ca and Mg-0.89Ca alloys were solely composed of α(Mg) phase. Degradation characteristics and electrochemical characterization of MgCa alloys were investigated during exposure to Ringer's solution at 37 °C by electrochemical impedance spectroscopy and scanning electrochemical microscopy. The impedance behavior showed both capacitive and inductive features that are related to the alloy charge transfer reaction and the relaxation of the absorbed corrosion compounds, and can be described in terms of an equivalent circuit. Scanning electron microscopy (SEM) was employed to view the surface morphology of the MgCa samples after 1 week immersion in Ringer's solution showing extensive precipitation of corrosion products, whereas the substrate shows evidence of a non-uniform corrosion process. Energy dispersive analysis showed that the precipitates contained oxygen, calcium, magnesium and chlorine, and the Mg:Ca ratios were smaller than in the alloys. Scanning electrochemical microscopy (SECM) was used to visualize local pH changes associated to these physicochemical processes with high spatial resolution. The occurrence of pH variations in excess of 3 units between anodic and cathodic half-cell reactions was monitored in situ. Copyright © 2015 Elsevier B.V. All rights reserved.

A method of lead determination in human teeth by energy dispersive X-ray fluorescence (EDXRF).

PubMed

Sargentini-Maier, M L; Frank, R M; Leroy, M J; Turlot, J C

1988-12-01

A systematic sampling procedure was combined with a method of energy dispersive X-ray fluorescence (EDXRF) to study lead content and its variations in human teeth. On serial ground sections made on unembedded permanent teeth of inhabitants of Strasbourg with a special diamond rotating disk, 2 series of 500 microns large punch biopsies were made systematically in 5 directions from the tooth surface to the inner pulpal dentine with a micro-punching unit. In addition, pooled fragments of enamel and dentine were made for each tooth. On each punched fragment or pooled sample, lead content was determined after dissolution in ultrapure nitric acid, on a 4 microns thick polypropylene film, and irradiation with a Siemens EDXRF prototype with direct sample excitation by a high power X-ray tube with a molybdenum anode. Fluorescence was detected by a Si(Li) detector and calcium was used as an internal standard. This technique allowed a rapid, automatic, multielementary and non-destructive analysis of microsamples with good detection limits.

Effect of electromagnetic interaction during fusion welding of AISI 2205 duplex stainless steel on the corrosion resistance

NASA Astrophysics Data System (ADS)

García-Rentería, M. A.; López-Morelos, V. H.; González-Sánchez, J.; García-Hernández, R.; Dzib-Pérez, L.; Curiel-López, F. F.

2017-02-01

The effect of electromagnetic interaction of low intensity (EMILI) applied during fusion welding of AISI 2205 duplex stainless steel on the resistance to localised corrosion in natural seawater was investigated. The heat affected zone (HAZ) of samples welded under EMILI showed a higher temperature for pitting initiation and lower dissolution under anodic polarisation in chloride containing solutions than samples welded without EMILI. The EMILI assisted welding process developed in the present work enhanced the resistance to localised corrosion due to a modification on the microstructural evolution in the HAZ and the fusion zone during the thermal cycle involved in fusion welding. The application of EMILI reduced the size of the HAZ, limited coarsening of the ferrite grains and promoted regeneration of austenite in this zone, inducing a homogeneous passive condition of the surface. EMILI can be applied during fusion welding of structural or functional components of diverse size manufactured with duplex stainless steel designed to withstand aggressive environments such as natural seawater or marine atmospheres.

Cadmium sulfide nanocluster-based electrochemical stripping detection of DNA hybridization.

PubMed

Zhu, Ningning; Zhang, Aiping; He, Pingang; Fang, Yuzhi

2003-03-01

A novel, sensitive electrochemical DNA hybridization detection assay, using cadmium sulfide (CdS) nanoclusters as the oligonucleotide labeling tag, is described. The assay relies on the hybridization of the target DNA with the CdS nanocluster oligonucleotide DNA probe, followed by the dissolution of the CdS nanoclusters anchored on the hybrids and the indirect determination of the dissolved cadmium ions by sensitive anodic stripping voltammetry (ASV) at a mercury-coated glassy carbon electrode (GCE). The results showed that only a complementary sequence could form a double-stranded dsDNA-CdS with the DNA probe and give an obvious electrochemical response. A three-base mismatch sequence and non-complementary sequence had negligible response. The combination of the large number of cadmium ions released from each dsDNA hybrid with the remarkable sensitivity of the electrochemical stripping analysis for cadmium at mercury-film GCE allows detection at levels as low as 0.2 pmol L(-1) of the complementary sequence of DNA.

The mutual co-regulation of extracellular polymeric substances and iron ions in biocorrosion of cast iron pipes.

PubMed

Jin, Juntao; Guan, Yuntao

2014-10-01

New insights into the biocorrosion process may be gained through understanding of the interaction between extracellular polymeric substances (EPS) and iron. Herein, the effect of iron ions on the formation of biofilms and production of EPS was investigated. Additionally, the impact of EPS on the corrosion of cast iron coupons was explored. The results showed that a moderate concentration of iron ions (0.06 mg/L) promoted both biofilm formation and EPS production. The presence of EPS accelerated corrosion during the initial stage, while inhibited corrosion at the later stage. The functional groups of EPS acted as electron shuttles to enable the binding of iron ions. Binding of iron ions with EPS led to anodic dissolution and promoted corrosion, while corrosion was later inhibited through oxygen reduction and availability of phosphorus from EPS. The presence of EPS also led to changes in crystalline phases of corrosion products. Copyright © 2014 Elsevier Ltd. All rights reserved.

Electrolysis of a molten semiconductor

DOE PAGES

Yin, Huayi; Chung, Brice; Sadoway, Donald R.

2016-08-24

Metals cannot be extracted by electrolysis of transition-metal sulfides because as liquids they are semiconductors, which exhibit high levels of electronic conduction and metal dissolution. Herein by introduction of a distinct secondary electrolyte, we reveal a high-throughput electro-desulfurization process that directly converts semiconducting molten stibnite (Sb 2S 3) into pure (99.9%) liquid antimony and sulfur vapour. At the bottom of the cell liquid antimony pools beneath cathodically polarized molten stibnite. At the top of the cell sulfur issues from a carbon anode immersed in an immiscible secondary molten salt electrolyte disposed above molten stibnite, thereby blocking electronic shorting across themore » cell. In conclusion, as opposed to conventional extraction practices, direct sulfide electrolysis completely avoids generation of problematic fugitive emissions (CO 2, CO and SO 2), significantly reduces energy consumption, increases productivity in a single-step process (lower capital and operating costs) and is broadly applicable to a host of electronically conductive transition-metal chalcogenides.« less

Hierarchical Tubular Structures Composed of Co3 O4 Hollow Nanoparticles and Carbon Nanotubes for Lithium Storage.

PubMed

Chen, Yu Ming; Yu, Le; Lou, Xiong Wen David

2016-05-10

Hierarchical tubular structures composed of Co3 O4 hollow nanoparticles and carbon nanotubes (CNTs) have been synthesized by an efficient multi-step route. Starting from polymer-cobalt acetate (Co(Ac)2 ) composite nanofibers, uniform polymer-Co(Ac)2 @zeolitic imidazolate framework-67 (ZIF-67) core-shell nanofibers are first synthesized via partial phase transformation with 2-methylimidazole in ethanol. After the selective dissolution of polymer-Co(Ac)2 cores, the resulting ZIF-67 tubular structures can be converted into hierarchical CNTs/Co-carbon hybrids by annealing in Ar/H2 atmosphere. Finally, the hierarchical CNT/Co3 O4 microtubes are obtained by a subsequent thermal treatment in air. Impressively, the as-prepared nanocomposite delivers a high reversible capacity of 1281 mAh g(-1) at 0.1 A g(-1) with exceptional rate capability and long cycle life over 200 cycles as an anode material for lithium-ion batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improving the Performance at Elevated Temperature of High Voltage Graphite/LiNi 0.5Mn 1.5O 4 Cells with Added Lithium Catechol Dimethyl Borate

DOE PAGES

Dong, Yingnan; Demeaux, Julien; Zhang, Yuzi; ...

2016-12-13

Performance of LiNi 0.5Mn 1.5O 4/graphite cells cycled to 4.8 V at 55°C with the 1.2 M LiPF 6 in EC/EMC (3/7, STD electrolyte) with and without added lithium catechol dimethyl borate (LiCDMB) has been investigated. The incorporation of 0.5 wt% LiCDMB to the STD electrolyte results in an improved capacity retention and coulombic efficiency upon cycling at 55°C. Ex-situ analysis of the electrode surfaces via a combination of SEM, TEM, and XPS reveals that oxidation of LiCDMB at high potential results in the deposition of a passivation layer on the electrode surface, preventing transition metal ion dissolution from themore » cathode and subsequent deposition on the anode. NMR investigations of the bulk electrolyte stored at 85°C reveals that added LiCDMB prevents the thermal decomposition of LiPF 6.« less

Improving the Performance at Elevated Temperature of High Voltage Graphite/LiNi 0.5Mn 1.5O 4 Cells with Added Lithium Catechol Dimethyl Borate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Yingnan; Demeaux, Julien; Zhang, Yuzi

Performance of LiNi 0.5Mn 1.5O 4/graphite cells cycled to 4.8 V at 55°C with the 1.2 M LiPF 6 in EC/EMC (3/7, STD electrolyte) with and without added lithium catechol dimethyl borate (LiCDMB) has been investigated. The incorporation of 0.5 wt% LiCDMB to the STD electrolyte results in an improved capacity retention and coulombic efficiency upon cycling at 55°C. Ex-situ analysis of the electrode surfaces via a combination of SEM, TEM, and XPS reveals that oxidation of LiCDMB at high potential results in the deposition of a passivation layer on the electrode surface, preventing transition metal ion dissolution from themore » cathode and subsequent deposition on the anode. NMR investigations of the bulk electrolyte stored at 85°C reveals that added LiCDMB prevents the thermal decomposition of LiPF 6.« less

Structure-Property Relationships of Organic Electrolytes and Their Effects on Li/S Battery Performance.

PubMed

Kaiser, Mohammad Rejaul; Chou, Shulei; Liu, Hua-Kun; Dou, Shi-Xue; Wang, Chunsheng; Wang, Jiazhao

2017-12-01

Electrolytes, which are a key component in electrochemical devices, transport ions between the sulfur/carbon composite cathode and the lithium anode in lithium-sulfur batteries (LSBs). The performance of a LSB mostly depends on the electrolyte due to the dissolution of polysulfides into the electrolyte, along with the formation of a solid-electrolyte interphase. The selection of the electrolyte and its functionality during charging and discharging is intricate and involves multiple reactions and processes. The selection of the proper electrolyte, including solvents and salts, for LSBs strongly depends on its physical and chemical properties, which is heavily controlled by its molecular structure. In this review, the fundamental properties of organic electrolytes for LSBs are presented, and an attempt is made to determine the relationship between the molecular structure and the properties of common organic electrolytes, along with their effects on the LSB performance. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effects of temperature and aeration on the corrosion of A508III low alloy steel in boric acid solutions at 25-95 °C

NASA Astrophysics Data System (ADS)

Xiao, Qian; Lu, Zhanpeng; Chen, Junjie; Yao, Meiyi; Chen, Zhen; Ejaz, Ahsan

2016-11-01

The effects of temperature, solution composition and dissolved oxygen on the corrosion rate and electrochemical behavior of an A508III low alloy steel in boric acid solution with lithium hydroxide at 25-95 °C are investigated. In aerated solutions, increasing the boric acid concentration increases the corrosion rate and the anodic current density. The corrosion rate in deaerated solutions increases with increasing temperature. A corrosion rate peak value is found at approximately 75 °C in aerated solutions. Increasing temperature increases the oxygen diffusion coefficient, decreases the dissolved oxygen concentration, accelerates the hydrogen evolution reaction, and accelerates both the active dissolution and the film forming reactions. Increasing dissolved oxygen concentration does not significantly affect the corrosion rate at 50 and 60 °C, increases the corrosion rate at 70 and 80 °C, and decreases the corrosion rate at 87.5 and 95 °C in a high concentration boric acid solution with lithium hydroxide.

An iridium oxide microelectrode for monitoring acute local pH changes of endothelial cells.

PubMed

Ng, Shu Rui; O'Hare, Danny

2015-06-21

pH sensors were fabricated by anodically electrodepositing iridium oxide films (AEIROFs) onto microelectrodes on chips and coated with poly(ethyleneimine) (PEI) for mechanical stability. These demonstrate super-Nernstian response to pH from pH 4.0 to 7.7 in chloride-free phosphate buffer. The surface of the chip was coated with fibronectin for the attachment of porcine aortic endothelial cells (PAECs). The working capability of the pH sensor for monitoring acute local pH changes was investigated by stimulating the PAECs with thrombin. Our results show that thrombin induced acute extracellular acidification of PAECs and dissolution of fibronectin, causing the local pH to decrease. The use of PD98059, a mitogen-activated protein kinase (MAPK) inhibitor, reduced extracellular acidification and an increase in local pH was observed. This study shows that our pH sensors can facilitate the investigation of acute cellular responses to stimulation by monitoring the real-time, local pH changes of cells attached to the sensors.

Enhanced stress corrosion cracking resistance and electrical conductivity of a T761 treated Al-Zn-Mg-Cu alloy thin plate

NASA Astrophysics Data System (ADS)

Chen, Xu; Zhai, Sudan; Gao, Di; Liu, Ye; Xu, Jing; Liu, Yang

2018-01-01

The stress corrosion cracking (SCC) behavior, electrical conductivity and mechanical properties of an Al-Zn-Mg-Cu alloy pre-stretched thin plate for wing skin were researched in this paper. The microstructures and SCC fracture surfaces of the alloy treated at different conditions were characterized by transmission electron microscopy, optical microscopy and scanning electron microscopy. Results indicated that with the increasing of aging temperature, the electrical conductivity and the elongation increased greatly, while the strength decreased gradually which were closely associated with the type and morphology of the precipitates. Compared with the T6 treated alloy, the SCC resistance of the T761 treated Al-Zn-Mg-Cu alloy was improved greatly. The SCC behavior of the T6 treated alloy was dominated by anodic dissolution theory, whereas the hydrogen induced cracking controlled the fracture behavior of the T761 treated alloy which was influenced by the morphology of grain boundary precipitates in this investigated alloy.

Stress Corrosion Cracking Behavior of X80 Pipeline Steel in Acid Soil Environment with SRB

NASA Astrophysics Data System (ADS)

Wang, Dan; Xie, Fei; Wu, Ming; Liu, Guangxin; Zong, Yue; Li, Xue

2017-06-01

Self-designed experimental device was adopted to ensure the normal growth of sulphate-reducing bacteria (SRB) in sterile simulated Yingtan soil solution. Stress corrosion cracking (SCC) behavior of X80 pipeline steel in simulated acid soil environment was investigated by electrochemical impedance spectroscopy, slow strain rate test, and scanning electron microscope. Results show that the presence of SRB could promote stress corrosion cracking susceptibility. In a growth cycle, polarization resistance first presents a decrease and subsequently an increase, which is inversely proportional to the quantities of SRB. At 8 days of growth, SRB reach their largest quantity of 1.42 × 103 cells/g. The corrosion behavior is most serious at this time point, and the SCC mechanism is hydrogen embrittlement. In other SRB growth stages, the SCC mechanism of X80 steel is anodic dissolution. With the increasing SRB quantities, X80 steel is largely prone to SCC behavior, and the effect of hydrogen is considerably obvious.

Controlling the corrosion and cathodic activation of magnesium via microalloying additions of Ge

PubMed Central

Liu, R. L.; Hurley, M. F.; Kvryan, A.; Williams, G.; Scully, J. R.; Birbilis, N.

2016-01-01

The evolution of corrosion morphology and kinetics for magnesium (Mg) have been demonstrated to be influenced by cathodic activation, which implies that the rate of the cathodic partial reaction is enhanced as a result of anodic dissolution. This phenomenon was recently demonstrated to be moderated by the use of arsenic (As) alloying as a poison for the cathodic reaction, leading to significantly improved corrosion resistance. The pursuit of alternatives to toxic As is important as a means to imparting a technologically safe and effective corrosion control method for Mg (and its alloys). In this work, Mg was microalloyed with germanium (Ge), with the aim of improving corrosion resistance by retarding cathodic activation. Based on a combined analysis herein, we report that Ge is potent in supressing the cathodic hydrogen evolution reaction (reduction of water) upon Mg, improving corrosion resistance. With the addition of Ge, cathodic activation of Mg subject to cyclic polarisation was also hindered, with beneficial implications for future Mg electrodes. PMID:27350286

Halogen-free boron based electrolyte solution for rechargeable magnesium batteries

NASA Astrophysics Data System (ADS)

Zhu, Jinjie; Guo, Yongsheng; Yang, Jun; Nuli, Yanna; Zhang, Fan; Wang, Jiulin; Hirano, Shin-ichi

2014-02-01

All halogen containing electrolytes for Mg battery are apt to corrode conventional metal current collectors. In this paper, a new type of halogen-free boron based electrolyte (Mg[Mes3BPh]2/THF) is designed and prepared. Electrochemical tests show that this electrolyte system possesses high ion conductivity (1.5 × 10-3 S cm-1) and good Mg deposition-dissolution reversibility. More importantly, the same electrochemical window (2.6 V vs. Mg RE) of the electrolyte on Pt and stainless steel electrodes indicates that halogen-free electrolyte indeed lessens the corrosion to conventional metal current collectors. The surface morphologies of stainless steel, aluminum and copper are further observed after their anodic potentiostatic polarization in 0.25 mol L-1 Mg[Mes3BPh]2/THF electrolyte solution for 2 days. A comparison with halogen containing electrolytes proves that the presence of halogen in electrolyte is the reason for corrosion. This work provides a stepping stone for developing new halogen-free electrolyte systems for rechargeable Mg batteries.

Carbon-Supported Nickel Selenide Hollow Nanowires as Advanced Anode Materials for Sodium-Ion Batteries.

PubMed

Yang, Xuming; Zhang, Jiaolong; Wang, Zhenguang; Wang, Hongkang; Zhi, Chunyi; Yu, Denis Y W; Rogach, Andrey L

2018-02-01

Carbon-supported nickel selenide (Ni 0.85 Se/C) hollow nanowires are prepared from carbon-coated selenium nanowires via a self-templating hydrothermal method, by first dissolving selenium in the Se/C nanowires in hydrazine, allowing it to diffuse out of the carbon layer, and then reacting with nickel ions into Ni 0.85 Se nanoplates on the outer surface of the carbon. Ni 0.85 Se/C hollow nanowires are employed as anode materials for sodium-ion batteries, and their electrochemical performance is evaluated via the cyclic voltammetry and electrochemical impedance spectroscopy combined with ex situ X-ray photoelectron spectroscopy and X-ray diffraction measurements. It is found that Ni 0.85 Se/C hollow nanowires exhibit greatly enhanced cycle stability and rate capability as compared to Ni 0.85 Se nanoparticles, with a reversible capacity around 390 mA h g -1 (the theoretical capacity is 416 mA h g -1 ) at the rate of 0.2 C and 97% capacity retention after 100 cycles. When the current rate is raised to 5 C, they still deliver capacity of 219 mA h g -1 . The synthetic methodology introduced here is general and can easily be applied to building similar structures for other metal selenides in the future. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of substrate microstructure on the formation of oriented oxide nanotube arrays on Ti and Ti alloys

NASA Astrophysics Data System (ADS)

Ferreira, C. P.; Gonçalves, M. C.; Caram, R.; Bertazzoli, R.; Rodrigues, C. A.

2013-11-01

The formation of nanotubular oxide layers on Ti and Ti alloys has been widely investigated for the photocatalytic degradation of organic compounds due to their excellent catalytic efficiency, chemical stability, and low cost and toxicity. Aiming to improve the photocatalytic efficiency of this nanostructured oxide, this work investigated the influence of substrate grain size on the growth of nanotubular oxide layers. Ti and Ti alloys (Ti-6Al, Ti-6Al-7Nb) were produced by arc melting with non-consumable tungsten electrode and water-cooled copper hearth under argon atmosphere. Some of the ingots were heat-treated at 1000 °C for 12 and 24 h in argon atmosphere, followed by slow cooling rates to reduce crystalline defects and increase the grain size of their microstructures. Three types of samples were anodized: commercial substrate, as-prepared and heat-treated samples. The anodization was performed using fluoride solution and a cell potential of 20 V. The samples were characterized by optical microscopy, field-emission scanning electron microscopy and X-ray diffraction. The heat treatment preceding the anodization process increased the grain size of pure Ti and Ti alloys and promoted the formation of Widmanstätten structures in Ti6Al7Nb. The nanotubes layers grown on smaller grain and thermally untreated samples were more regular and homogeneous. In the case of Ti-6Al-7Nb alloy, which presents a α + β phase microstructure, the morphology of nanotubes nucleated on α matrix was more regular than those of nanotubes nucleated on β phase. After the annealing process, the Ti-6Al-7Nb alloy presented full diffusion process and the growth of equilibrium phases resulting in the appearance of regions containing higher concentrations of Nb, i.e. beta phase. In those regions the dissolution rate of Nb2O5 is lower than that of TiO2, resulting in a nanoporous layer. In general, heat treating reduces crystalline defects and promotes the increasing of the grain sizes, not favoring the process of nanotube nucleation and growth on the metallic surface.

Electrorecycling of Critical and Value Metals from Mobile Electronics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tedd E. Lister; Peming Wang; Andre Anderko

2014-09-01

Mobile electronic devices such as smart phones and tablets are a significant source of valuable metals that should be recycled. Each year over a billion devices are sold world-wide and the average life is only a couple years. Value metals in phones are gold, palladium, silver, copper, cobalt and nickel. Devices now contain increasing amounts of rare earth elements (REE). In recent years the supply chain for REE has moved almost exclusively to China. They are contained in displays, speakers and vibrators within the devices. By US Department of Energy (DOE) classification, specific REEs (Nd, Dy, Eu, Tb and Y)more » are considered critical while others (Ce, La and Pr) are deemed near critical. Effective recycling schemes should include the recovery of these critical materials. By including more value materials in a recovery scheme, more value can be obtained by product diversification and less waste metals remains to be disposed of. REEs are mined as a group such that when specific elements become critical significantly more ore must be processed to capture the dilute but valuable critical elements. Targeted recycling of items containing the more of the less available critical materials could address their future criticality. This presentation will describe work in developing aqueous electrochemistry-based schemes for recycling metals from scrap mobile electronics. The electrorecycling process generates oxidizing agents at an anode while reducing dissolved metals at the cathode. E vs pH diagrams and metals dissolution experiments are used to assess effectiveness of various solution chemistries. Although several schemes were envisioned, a two stages process has been the focus of work: 1) initial dissolution of Cu, Sn, Ag and magnet materials using Fe+3 generated in acidic sulfate and 2) final dissolution of Pd and Au using Cl2 generated in an HCl solution. Experiments were performed using simulated metal mixtures. Both Cu and Ag were recovered at ~ 97% using Fe+3 while leaving Au and Ag intact. REE were extracted from the dissolved mixture using conventional methods. A discussion of future research directions will be discussed.« less

A dual coaxial nanocable sulfur composite for high-rate lithium-sulfur batteries.

PubMed

Li, Zhen; Yuan, Lixia; Yi, Ziqi; Liu, Yang; Xin, Ying; Zhang, Zhaoliang; Huang, Yunhui

2014-01-01

Lithium-sulfur batteries have great potential for some high energy applications such as in electric vehicles and smart grids due to their high capacity, natural abundance, low cost and environmental friendliness. But they suffer from rapid capacity decay and poor rate capability. The problems are mainly related to the dissolution of the intermediate polysulfides in the electrolyte, and to the poor conductivity of sulfur and the discharge products. In this work, we propose a novel dual coaxial nanocable sulfur composite fabricated with multi-walled nanotubes (MWCNT), nitrogen-doped porous carbon (NPC) and polyethylene glycol (PEG), i.e. MWCNTs@S/NPC@PEG nanocable, as a cathode material for Li-S batteries. In such a coaxial structure, the middle N-doped carbon with hierarchical porous structure provides a nanosized capsule to contain and hold the sulfur particles; the inner MWCNTs and the outer PEG layer can further ensure the fast electronic transport and prevent the dissolution of the polysulfides into the electrolyte, respectively. The as-designed MWCNT@S/NPC@PEG composite shows good cycling stability and excellent rate capability. The capacity is retained at 527 mA h g(-1) at 1 C after 100 cycles, and 791 mA h g(-1) at 0.5 C and 551 mA h g(-1) at 2 C after 50 cycles. Especially, the high-rate capability is outstanding with 400 mA h g(-1) at 5 C.

Pyrite nanoparticles as a Fenton-like reagent for in situ remediation of organic pollutants

PubMed Central

Losa-Adams, Elisabeth; F.-Dávila, Alfonso; Gago-Duport, Luis

2014-01-01

Summary The Fenton reaction is the most widely used advanced oxidation process (AOP) for wastewater treatment. This study reports on the use of pyrite nanoparticles and microparticles as Fenton reagents for the oxidative degradation of copper phthalocyanine (CuPc) as a representative contaminant. Upon oxidative dissolution in water, pyrite (FeS2) particles can generate H2O2 at their surface while simultaneously promoting recycling of Fe3+ into Fe2+ and vice versa. Pyrite nanoparticles were synthesized by the hot injection method. The use of a high concentration of precursors gave individual nanoparticles (diameter: 20 nm) with broader crystallinity at the outer interfaces, providing a greater number of surface defects, which is advantageous for generating H2O2. Batch reactions were run to monitor the kinetics of CuPc degradation in real time and the amount of H2O2. A markedly greater degradation of CuPc was achieved with nanoparticles as compared to microparticles: at low loadings (0.08 mg/L) and 20 h reaction time, the former enabled 60% CuPc removal, whereas the latter enabled only 7% removal. These results confirm that the use of low concentrations of synthetic nanoparticles can be a cost effective alternative to conventional Fenton procedures for use in wastewater treatment, avoiding the potential risks caused by the release of heavy metals upon dissolution of natural pyrites. PMID:24991522

Pyrite nanoparticles as a Fenton-like reagent for in situ remediation of organic pollutants.

PubMed

Gil-Lozano, Carolina; Losa-Adams, Elisabeth; F-Dávila, Alfonso; Gago-Duport, Luis

2014-01-01

The Fenton reaction is the most widely used advanced oxidation process (AOP) for wastewater treatment. This study reports on the use of pyrite nanoparticles and microparticles as Fenton reagents for the oxidative degradation of copper phthalocyanine (CuPc) as a representative contaminant. Upon oxidative dissolution in water, pyrite (FeS2) particles can generate H2O2 at their surface while simultaneously promoting recycling of Fe(3+) into Fe(2+) and vice versa. Pyrite nanoparticles were synthesized by the hot injection method. The use of a high concentration of precursors gave individual nanoparticles (diameter: 20 nm) with broader crystallinity at the outer interfaces, providing a greater number of surface defects, which is advantageous for generating H2O2. Batch reactions were run to monitor the kinetics of CuPc degradation in real time and the amount of H2O2. A markedly greater degradation of CuPc was achieved with nanoparticles as compared to microparticles: at low loadings (0.08 mg/L) and 20 h reaction time, the former enabled 60% CuPc removal, whereas the latter enabled only 7% removal. These results confirm that the use of low concentrations of synthetic nanoparticles can be a cost effective alternative to conventional Fenton procedures for use in wastewater treatment, avoiding the potential risks caused by the release of heavy metals upon dissolution of natural pyrites.

Growth and FIB-SEM analyses of C60 microtubes vertically synthesized on porous alumina membranes

NASA Astrophysics Data System (ADS)

Miyazawa, Kun'ichi; Kuriyama, Ryota; Shimomura, Shuichi; Wakahara, Takatsugu; Tachibana, Masaru

2014-02-01

The vertical growth of C60 microtubes (C60MTs) on anodic aluminum oxide (AAO) membranes was investigated. The C60MT size dependence on isopropyl alcohol (IPA) injection rate, into C60-saturated toluene solutions through AAO membranes, was measured. A longitudinal section of the interface between a vertically grown C60MT (V-C60MT) and a membrane was prepared by focused ion beam processing, and observed with scanning electron microscopy. No cracking was observed along the interface, suggesting good bonding. V-C60MTs exhibited spiral growth. V-C60MT planar density, wall thickness and aspect ratio all decreased with increasing IPA injection rate. The relationships among length, inner and outer diameters of V-C60MTs were also investigated by varying IPA injection rate.

Fuel cell cassette with compliant seal

DOEpatents

Karl, Haltiner, Jr. J.; Anthony, Derose J.; Klotzbach, Darasack C.; Schneider, Jonathan R.

2017-11-07

A fuel cell cassette for forming a fuel cell stack along a fuel cell axis includes a cell retainer, a plate positioned axially to the cell retainer and defining a space axially with the cell retainer, and a fuel cell having an anode layer and a cathode layer separated by an electrolyte layer. The outer perimeter of the fuel cell is positioned in the space between the plate and the cell retainer, thereby retaining the fuel cell and defining a cavity between the cell retainer, the fuel cell, and the plate. The fuel cell cassette also includes a seal disposed within the cavity for sealing the edge of the fuel cell. The seal is compliant at operational temperatures of the fuel cell, thereby allowing lateral expansion and contraction of the fuel cell within the cavity while maintaining sealing at the edge of the fuel cell.

Selective growth of palladium and titanium dioxide nanostructures inside carbon nanotube membranes

NASA Astrophysics Data System (ADS)

Hevia, Samuel; Homm, Pía; Cortes, Andrea; Núñez, Verónica; Contreras, Claudia; Vera, Jenniffer; Segura, Rodrigo

2012-06-01

Hybrid nanostructured arrays based on carbon nanotubes (CNT) and palladium or titanium dioxide materials have been synthesized using self-supported and silicon-supported anodized aluminum oxide (AAO) as nanoporous template. It is well demonstrated that carbon nanotubes can be grown using these membranes and hydrocarbon precursors that decompose at temperatures closer to 600°C without the use of a metal catalyst. In this process, carbonic fragments condensate to form stacked graphitic sheets, which adopt the shape of the pores, yielding from these moulds' multi-walled carbon nanotubes. After this process, the ends of the tubes remain open and accessible to other substances, whereas the outer walls are protected by the alumina. Taking advantage of this fact, we have performed the synthesis of palladium and titanium dioxide nanostructures selectively inside carbon nanotubes using these CNT-AAO membranes as nanoreactors.

Selective growth of palladium and titanium dioxide nanostructures inside carbon nanotube membranes.

PubMed

Hevia, Samuel; Homm, Pía; Cortes, Andrea; Núñez, Verónica; Contreras, Claudia; Vera, Jenniffer; Segura, Rodrigo

2012-06-25

Hybrid nanostructured arrays based on carbon nanotubes (CNT) and palladium or titanium dioxide materials have been synthesized using self-supported and silicon-supported anodized aluminum oxide (AAO) as nanoporous template. It is well demonstrated that carbon nanotubes can be grown using these membranes and hydrocarbon precursors that decompose at temperatures closer to 600°C without the use of a metal catalyst. In this process, carbonic fragments condensate to form stacked graphitic sheets, which adopt the shape of the pores, yielding from these moulds' multi-walled carbon nanotubes. After this process, the ends of the tubes remain open and accessible to other substances, whereas the outer walls are protected by the alumina. Taking advantage of this fact, we have performed the synthesis of palladium and titanium dioxide nanostructures selectively inside carbon nanotubes using these CNT-AAO membranes as nanoreactors.

Electrodeionization Using Microseparated Bipolar Membranes

NASA Technical Reports Server (NTRS)

Lyons, Donald; Jackson, George; Andrews, Craig C.; Tennakoon, Charles L, K.; Singh, Waheguru; Hitchens, G. Duncan; Jabs, Harry; Chepin, James F.; Archer, Shivaun; Gonzalez-Martinez, Anukia;

Optimization of Time Controlled 6-mercaptopurine Delivery for Site- Specific Targeting to Colon Diseases.

PubMed

Hude, Rahul U; Jagdale, Swati C

2016-01-01

6-MP has short elimination time (<2 h) and low bioavailability (~ 50%). Present study was aimed to develop time controlled and site targeted delivery of 6-Mercaptopurine (6-MP) for treatment of colon diseases. Compression coating technique was used. 32 full factorial design was designed for optimization of the outer coat for the core tablet. For outer coat amount of Eudragit RS 100 and hydroxypropyl methylcellulose (HPMC K100) were employed as independent variables each at three levels while responses evaluated were swelling index and bursting time. Direct compression method was used for tablets formulation. 80% w/w of microcrystalline cellulose and 20% w/w of croscarmellose sodium were found to be optimum concentration for the core tablet. The outer coat of optimized batch (ED) contains 21.05% w/w Eudragit RS 100 and 78.95% w/w HPMC K100 of total polymer weight. In-vitro dissolution study indicated that combination of polymer retards the drug release in gastric region and releases ≥95% of drug in colonic region after ≥7 h. Whereas in case of in-vivo placebo x-ray imaging study had shown that the tablet reaches colonic part after 5±0.5 h providing the proof of arrival in the colon. Stability study indicated that the optimized formulation were physically and chemically stable. Present research work concluded that compression coating by Eudragit RS 100 and HPMC K100 to 6-MP core provides potential colon targeted system with advantages of reduced gastric exposure and enhanced bioavailability. Formulation can be considered as potential and promising candidate for the treatment of colon diseases.

Chemical Reaction at the Core-Mantle Boundary from Experimental Study with a Diamond-Anvil Cell (Invited)

NASA Astrophysics Data System (ADS)

Ozawa, H.; Hirose, K.

2010-12-01

Element partitioning between molten iron and mantle minerals was investigated to 146 GPa by a combination of laser-heated diamond-anvil cell and analytical transmission electron microscope. The chemical compositions of co-existing quenched molten iron and (Mg,Fe)SiO3 perovskite/ferropericlase were determined quantitatively with energy-dispersive X-ray spectrometry and electron energy loss spectroscopy. The results demonstrate that the oxygen solubility in liquid iron co-existing with ferropericlase decreases with pressure to 38 GPa and, whereas the pressure effect is small at higher pressures. It was also revealed that the quenched liquid iron in contact with perovskite contained substantial amounts of oxygen and silicon at the core-mantle boundary (CMB) pressure. The chemical equilibrium between perovskite, ferropericlase, and molten iron at the P-T conditions of the CMB was calculated in Mg-Fe-Si-O system from these experimental results. Note that perovskite is a predominant phase instead of post-perovskite above 3500 K at the CMB pressure. We found that molten iron should include oxygen and silicon more than required to account for the core density deficit of below 10% when co-existing with both perovskite and ferropericlase at the CMB. This suggests that the bulk outer core liquid with <10% density deficit is not in direct contact with the mantle. Dissolutions of light elements from the mantle can produce a gravitationally stratified liquid layer at the topmost outer core, which can be responsible for the low-P wave velocity layer observed there. Such layer physically separates the mantle from the bulk outer core liquid, hindering the chemical reaction between them.

New Insights in the Long-Term Atmospheric Corrosion Mechanisms of Low Alloy Steel Reinforcements of Cultural Heritage Buildings

PubMed Central

Bouchar, Marie; Dillmann, Philippe; Neff, Delphine

2017-01-01

Reinforcing clamps made of low alloy steel from the Metz cathedral and corroded outdoors during 500 years were studied by OM, FESEM/EDS, and micro-Raman spectroscopy. The corrosion product layer is constituted of a dual structure. The outer layer is mainly constituted of goethite and lepidocrocite embedding exogenous elements such as Ca and P. The inner layer is mainly constituted of ferrihydrite. The behaviour of the inner layer under conditions simulating the wetting stage of the RH wet/dry atmospheric corrosion cycle was observed by in situ micro-Raman spectroscopy. The disappearance of ferrihydrite near the metal/oxide interface strongly suggests a mechanism of reductive dissolution caused by the oxidation of the metallic substrate and was observed for the first time in situ on an archaeological system. PMID:28773030

In-vitro characterization of 5-aminosalicylic acid release from MMX mesalamine tablets and determination of tablet coating thickness.

PubMed

Tenjarla, Srini; Abinusawa, Adeyinka

2011-01-01

Substantial variability in gastrointestinal pH is observed in patients with ulcerative colitis (UC). We characterized the effect of pH on 5-aminosalicylic acid (5-ASA) release from MMX mesalamine tablets (Shire Pharmaceuticals Inc., Wayne, PA, USA), examined thickness/uniformity of tablet film coatings, and explored the influence of simulating altered gastrointestinal motility. Nondestructive, three-dimensional, terahertz pulse imaging (TPI) was used to characterize the film coating of three lots of MMX mesalamine tablets (n=36). Thereafter, 5-ASA release from these tablets was evaluated using United States Pharmacopeia (USP) apparatus II at pH 6.8 and 7.2. Onset of tablet film-coat breach and mean dissolution time were determined for each lot. 5-ASA release was also assessed at three different paddle rotation speeds (50, 75, and 100 rpm) at pH 7.2. The mean ± SD film-coating thickness of the three lots of MMX mesalamine tablets were 109.2 ± 16.8, 113.1 ± 19.5, and 113.8 ± 19.8 μM, respectively. At pH 6.8 (100 rpm), the onset of film-coat breach was 10-30 minutes, whereas at pH 7.2 this was observed within 10 minutes. 5-ASA release was uniform at both pH conditions, with minimal lot-to-lot variability. Complete drug release was achieved within 6 hours under both pH conditions. 5-ASA release increased in proportion with paddle speed, but remained prolonged at all speeds. 5-ASA release from MMX mesalamine is unaffected by normal variations in simulated intracolonic pH. The dissolution profile of 5-ASA from MMX mesalamine tablets may be attributed to consistent outer film coatings and the hydrogel-forming matrix that controls the drug release after dissolution of the film coating.

Ultra-High Density Single Nanometer-Scale Anodic Alumina Nanofibers Fabricated by Pyrophosphoric Acid Anodizing

NASA Astrophysics Data System (ADS)

Kikuchi, Tatsuya; Nishinaga, Osamu; Nakajima, Daiki; Kawashima, Jun; Natsui, Shungo; Sakaguchi, Norihito; Suzuki, Ryosuke O.

2014-12-01

Anodic oxide fabricated by anodizing has been widely used for nanostructural engineering, but the nanomorphology is limited to only two oxides: anodic barrier and porous oxides. Therefore, the discovery of an additional anodic oxide with a unique nanofeature would expand the applicability of anodizing. Here we demonstrate the fabrication of a third-generation anodic oxide, specifically, anodic alumina nanofibers, by anodizing in a new electrolyte, pyrophosphoric acid. Ultra-high density single nanometer-scale anodic alumina nanofibers (1010 nanofibers/cm2) consisting of an amorphous, pure aluminum oxide were successfully fabricated via pyrophosphoric acid anodizing. The nanomorphologies of the anodic nanofibers can be controlled by the electrochemical conditions. Anodic tungsten oxide nanofibers can also be fabricated by pyrophosphoric acid anodizing. The aluminum surface covered by the anodic alumina nanofibers exhibited ultra-fast superhydrophilic behavior, with a contact angle of less than 1°, within 1 second. Such ultra-narrow nanofibers can be used for various nanoapplications including catalysts, wettability control, and electronic devices.

Ultra-High Density Single Nanometer-Scale Anodic Alumina Nanofibers Fabricated by Pyrophosphoric Acid Anodizing

PubMed Central

Kikuchi, Tatsuya; Nishinaga, Osamu; Nakajima, Daiki; Kawashima, Jun; Natsui, Shungo; Sakaguchi, Norihito; Suzuki, Ryosuke O.

2014-01-01

Anodic oxide fabricated by anodizing has been widely used for nanostructural engineering, but the nanomorphology is limited to only two oxides: anodic barrier and porous oxides. Therefore, the discovery of an additional anodic oxide with a unique nanofeature would expand the applicability of anodizing. Here we demonstrate the fabrication of a third-generation anodic oxide, specifically, anodic alumina nanofibers, by anodizing in a new electrolyte, pyrophosphoric acid. Ultra-high density single nanometer-scale anodic alumina nanofibers (1010 nanofibers/cm2) consisting of an amorphous, pure aluminum oxide were successfully fabricated via pyrophosphoric acid anodizing. The nanomorphologies of the anodic nanofibers can be controlled by the electrochemical conditions. Anodic tungsten oxide nanofibers can also be fabricated by pyrophosphoric acid anodizing. The aluminum surface covered by the anodic alumina nanofibers exhibited ultra-fast superhydrophilic behavior, with a contact angle of less than 1°, within 1 second. Such ultra-narrow nanofibers can be used for various nanoapplications including catalysts, wettability control, and electronic devices. PMID:25491282

Dissolution of Hydrocarbon Gas Hydrates in Seawater at 1030-m; Effects of Porosity, Structure, and Compositional Variation as Determined by High-Definition Video and SEM Imaging.

NASA Astrophysics Data System (ADS)

Stern, L. A.; Peltzer, E. T.; Durham, W. B.; Kirby, S. H.; Brewer, P. G.; Circone, S.; Rehder, G.

2002-12-01

We compare dissolution rates of pure, porous, compacted, and oil-contaminated sI methane hydrate and sII methane-ethane hydrate to rates measured previously on pure, compacted, sI methane hydrate and sI carbon dioxide hydrate (Rehder et al., Fall AGU 2001). Laboratory-synthesized test specimens were used in both studies, allowing characterization of test materials prior to their transport and exposure to seawater at 1030-meter depth on the Monterey Canyon seafloor, off coastal Moss Landing, CA. Although pressure and temperature (P-T) conditions at this site are within the nominal P-T equilibrium fields of all gas hydrates tested here, the seawater is undersaturated with respect to the hydrate-forming gas species. Hence, samples dissolve with time, at a rate dependent on water current flow. Four samples were deployed in this second experiment: (1) pure, 30% porous methane hydrate; (2) pure, compacted methane hydrate; (3) pure methane hydrate compacted and then contaminated with a low-T mineral oil; and (4) pure, compacted sII methane-ethane hydrate with methane:ethane molar ratio 0.72. Samples were transferred by pressure vessel at 0 ° C and 15 MPa to the seafloor observatory via the MBARI remotely operated vehicle Ventana. Samples were then exposed to the deep ocean environment and monitored by HDTV camera for several hours at the beginning and end of a 25-hour period. Local current speed and direction were also measured throughout the experiment. Those samples that did not undergo complete dissolution after 25 h were successfully recovered to the laboratory for subsequent analysis by scanning electron microscopy (SEM). Previously, video analysis showed dissolution rates corresponding to 4.0 +/- 0.5 mmole CO2/m2 s for compacted CO2 hydrate samples, and 0.37 +/- 0.03 mmole CH4/m2s for compacted methane hydrate samples (Rehder et al, AGU 2001). The ratio of dissolution rates fits a simple diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site. These calculations assume that dissolution occurred only along the outer (i.e. imaged) surface of the samples. This assumption is now validated by SEM analysis of recovered samples from the second dive, showing little to no internal alteration of compacted material following their partial dissolution. Quantitative comparison of results from the two dives poses challenges due to variations in sample size and orientation. However, both compacted methane hydrate samples from the second dive in fact exhibited comparable behavior to that measured in the previous experiment; the oily sample did not dissolve at a slower rate, as might be expected if a hydrophobic contaminant inhibits seawater contact. Surprisingly, the porous methane hydrate exhibited significantly slower face retreat than its compacted counterparts. The sII methane-ethane hydrate dissolved measurably slower than all other samples, consistent with the solubility properties of its guest components. While these results represent only a first step in emulating the more complex interactions of seawater with naturally occurring hydrate-bearing sediments, such end member studies should aid preliminary modelling investigations of the chemical stability and lifetime of gas hydrates exposed at the seafloor.

The role of stress in self-ordered porous anodic oxide formation and corrosion of aluminum

NASA Astrophysics Data System (ADS)

Capraz, Omer Ozgur

The phenomenon of plastic flow induced by electrochemical reactions near room temperature is significant in porous anodic oxide (PAO) films, charging of lithium batteries and stress-corrosion cracking (SCC). As this phenomenon is poorly understood, fundamental insight into flow from our work may provide useful information for these problems. In-situ monitoring of the stress state allows direct correlation between stress and the current or potential, thus providing fundamental insight into technologically important deformation and failure mechanisms induced by electrochemical reactions. A phase-shifting curvature interferometry was designed to investigate the stress generation mechanisms on different systems. Resolution of our curvature interferometry was found to be ten times more powerful than that obtained by state-of-art multiple deflectometry technique and the curvature interferometry helps to resolve the conflicting reports in the literature. During this work, formation of surface patterns during both aqueous corrosion of aluminum and formation of PAO films were investigated. Interestingly, for both cases, stress induced plastic flow controls the formation of surface patterns. Pore formation mechanisms during anodizing of the porous aluminum oxide films was investigated . PAO films are formed by the electrochemical oxidation of metals such as aluminum and titanium in a solution where oxide is moderately soluble. They have been used extensively to design numerous devices for optical, catalytic, and biological and energy related applications, due to their vertically aligned-geometry, high-specific surface area and tunable geometry by adjusting process variables. These structures have developed empirically, in the absence of understanding the process mechanism. Previous experimental studies of anodizing-induced stress have extensively focused on the measurement of average stress, however the measurement of stress evolution during anodizing does not provide sufficient information to understand the potential stress mechanisms. We developed a new method, which enables us to discriminate the potential stress mechanisms during anodizing and characterize the evolution of the stress profile during film growth. Using stress measurement and characterization techniques, we demonstrated the evolution of the stress profile during the film formation and discussed the role of stress on the PAO film formation. Compressive stress builds up linearly during the anodizing, while barrier oxide film gets thicker until the onset of the pore initiation. Both barrier layer thickness and the integrated oxide stress decreased rapidly to the steady-state period when pore initiation began. The morphology change and stress transients points out the transition from elastic to plastic oxide behavior, similar to those observed in other situations such as lithium intercalation into silicon. The stress profile is consistent with the stress gradient needed to drive plastic flow observed experimentally. We also addressed the dependence of overall stress generation on applied current density. Apparently, stress caused by expansion or contraction of oxide and metal interface depends on the volume change due to overall reactions. In the last chapter, the stress generation during alkaline Al corrosion will be discussed. The enhancement of mechanical degradation by corrosion is the basis for the damage process such as stress-corrosion cracking. Understanding the synergistic effect of stress on stress-corrosion cracking mechanism is necessary to design new materials to improve the safety and viability of existing energy conversion systems. the high-resolution in-situ stress measurements during Al corrosion in alkaline solution was presented, supported by characterization techniques and Fast Fourier Transform analysis. Unprecedented curvature resolution of curvature interferometry permits the monitoring of stress during extended periods of corrosion of thick metal samples. Evolution of concaved-shaped surface patterns is in a great harmony with recorded tensile stress. Furthermore, absolute value of tensile stress onset of the plasticity depends on the dissolution rate of metal and yield stress of metal. The measurements reveal corrosion-induced tensile stress generation, leading to surface plasticity. This finding is evidence that corrosion can directly bring about plasticity, and may be relevant to mechanism of corrosion-induced degradation.

Anode power deposition in applied-field MPD thrusters

NASA Technical Reports Server (NTRS)

Myers, Roger M.; Soulas, George C.

1992-01-01

Anode power deposition is the principle performance limiter of magnetoplasmadynamic (MPD) thrusters. Current thrusters lose between 50 and 70 percent of the input power to the anode. In this work, anode power deposition was studied for three cylindrical applied magnetic field thrusters for a range of argon propellant flow rates, discharge currents, and applied-field strengths. Between 60 and 95 percent of the anode power deposition resulted from electron current conduction into the anode, with cathode radiation depositing between 5 and 35 percent of the anode power, and convective heat transfer from the hot plasma accounting for less than 5 percent. While the fractional anode power loss decreased with increasing applied-field strength and anode size, the magnitude of the anode power increased. The rise in anode power resulted from a linear rise in the anode fall voltage with applied-field strength and anode radius. The anode fall voltage also rose with decreasing propellant flow rate. The trends indicate that the anode fall region is magnetized, and suggest techniques for reducing the anode power loss in MPD thrusters.

Long-term corrosion of a Ga-containing restorative material.

PubMed

Sarkar, N K; Moiseyeva, R; Berzins, D W; Osborne, J W

2000-03-01

The aim was to simulate and characterize the long-term corrosion of a Ga-containing alloy (Galloy, SDI). To induce corrosion, cylindrical specimens, 8 x 4 mm, of the material were subject to potentiostatic polarization at -0.1 V (SCE) in a phosphated buffered saline (PBS) solution at 20 degrees C for d. The current-time transients during polarization were recorded and the corresponding anodic charge, Q, was calculated. Parallel potentiostatic corrosion tests in a Cl-free PBS solution were also conducted to demonstrate the significance of the Cl- ion in corrosion. In addition, potentiodynamic anodic polarization tests were performed to characterize the overall corrosion behavior of the alloy in both electrolytes. The external and internal corroded layers, formed during potentiostatic corrosion in PBS, were measured by optical microscopy. SEM and EDXA were used to characterize the morphology and composition of the potentiostatically polarized surfaces. Galloy was passive in Cl-free PBS. The Cl- ion in PBS destroyed passivity and initiated a "dissolution-precipitation" type reaction during potentiostatic corrosion. The latter led to circumferential internal corrosion and growth of a layer of external corrosion products. The thickness of the internal and external corrosion layers was 0.77 +/- 0.07 and 0.86 +/- 0.37 mm, respectively. The Q value (89.3 +/- 13.7 C/cm2) in PBS was about two orders of magnitude higher than that (0.66 +/- 0.24 C/cm2) in Cl-free PBS. The corrosion products contained Sn, Ga, In, Cu, O and Cl. Massive internal and external corrosion in a Cl-containing medium as in saliva, accumulation of corrosion products at the cavity wall, and the consequent stress build-up contribute to post-operative pain, tooth straining, marginal breakdown and fractured teeth reported with the clinical use of Galloy.

Long-Chain Polysulfide Retention at the Cathode of Li–S Batteries

DOE PAGES

Kamphaus, Ethan P.; Balbuena, Perla B.

2016-02-10

Lithium–sulfur batteries present a complex interconnected chemistry where the three components—anode, electrolyte, and cathode—strongly interact with each other. One of the main issues associated with these interactions is the dissolution in the electrolyte solution of part of the sulfur reduction products (mainly long-chain polysulfides) during the discharge reactions at the cathode. These dissolved species can migrate and react at the anode surface producing undesired insulating films. A potential solution to mitigate this problem is to resort to additional materials which can act as anchors of the soluble species thus avoiding their migration. Density functional theory and ab initio molecular dynamicsmore » simulations are employed to investigate the ability of certain substrates to retain long-chain polysulfides (Li 2S 6 and Li 2S 8) at their surfaces in the presence of a pure solvent or a lithiated solution. Nanopores of graphene are first tested because the cathode is usually a mix of sulfur and carbon. Then, MoS 2 and Mo-doped graphene are evaluated because of the well-known Mo–S affinity. Finally, a material which has been reported successful in experimental studies, MnO 2, is analyzed and compared with another oxide surface, Fe 2O 3. Adsorption energies of the polysulfides to the surfaces and the detailed interactions of the Li ions and S atoms with the substrate are characterized via charge and geometric analyses. Both the Mo-containing materials and the oxides adsorb the polysulfides much more strongly than graphene nanopores do. However, some of these surfaces are found to be excessively reactive. Thus, a balance between affinity for S and moderate surface reactivity is found as a promising guideline for designing these materials.« less

Allotropic control: How certain fluorinated carbonate electrolytes protect aluminum current collectors by promoting the formation of insoluble coordination polymers

DOE PAGES

Shkrob, Ilya A.; Pupek, Krzysztof Z.; Abraham, Daniel P.

2016-07-28

Here, there is a strong incentive for increasing the operation voltage of Li-ion cells above 4.5 V in order to increase the density of stored energy. Aluminum is an inexpensive, lightweight metal that is commonly used as a positive electrode current collector in these cells. Imide LiX salts, such as lithium bis(trifluoromethylsulfonyl)imide (X = TFSI), and lithium bis(fluorosulfonyl)imide (X = FSI), are chemically stable on the energized lithiated transition metal oxide electrodes, but their presence in the electrolyte causes rapid anodic dissolution and pitting of Al current collectors at potentials exceeding 4.0 V versus Li/Li +. For LiBF 4 andmore » LiPF 6, the release of HF near the energized surfaces passivates the exposed Al metal, inhibiting this pitting corrosion, but it also causes the gradual degradation of the cathode active material, negating this important advantage. Here we report that in certain electrolytes containing fluorinated carbonate solvents and LiX salts, the threshold voltage for safe operation of Al current collectors can be increased to 5.5 V versus Li/Li +. Interestingly, the most efficient solvent also facilitates the formation of an insoluble gel when AlX 3 is introduced into this solvent. We suggest that this solvent promotes the aggregation of coordination polymers of AlX 3 at the exposed Al surface that isolate this surface from the electrolyte, thereby preventing further Al dissolution and corrosion. Other examples of Al collector protection may also involve this mechanism. Our study suggests that such “allotropic control” could be a way of widening the operation window of Li-ion cells without electrode deterioration, Al current collector corrosion, and electrolyte breakdown.« less

Experience with soluble neutron poisons for criticality control at ICPP

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, R.E.; Mortimer, S.R.

1978-01-01

Soluble neutron poisons assure criticality control in two of the headend fuel reprocessing systems at the Idaho Chemical Processing Plant. Soluble poisons have been used successfully since 1964 and will be employed in the projected new headend processes. The use of soluble poisons (1) greatly increases the process output (2) allows versatility in the size of fuel assemblies processed and (3) allows the practical reprocessing of some fuels. The safety limit for all fluids entering the U-Zr alloy dissolver is 3.6 g/liter boron. To allow for possible deviations in the measurement systems and drift between analytical sampling periods, the standardmore » practice is to use 3.85 g/liter boron as the lower limit. This dissolver has had 4000 successful hours of operation using soluble poisons. The electrolytic dissolution process depends on soluble gadolinium for criticality safety. This system is used to process high enriched uranium clad in stainless steel. Electrolytic dissolution takes advantage of the anodic corrosion that occurs when a large electrical current is passed through the fuel elements in a corrosive environment. Three control methods are used on each headend system. First, the poison is mixed according to standard operating procedures and the measurements are affirmed by the operator's supervisor. Second, the poisoned solution is stirred, sampled, analyzed, and the analysis reported while still in the mix tank. Finally, a Nuclear Poison Detection System (NPDS) must show an acceptable poison concentration before the solution can be transferred. The major disadvantage of using soluble poisons is the need for very sophisticated control systems and procedures, which require extensive checkout. The need for a poisoned primary heating and cooling system means a secondary system is needed as well. Experience has shown, however, that production enhancement more than makes up for the problems.« less

Allotropic control: How certain fluorinated carbonate electrolytes protect aluminum current collectors by promoting the formation of insoluble coordination polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shkrob, Ilya A.; Pupek, Krzysztof Z.; Abraham, Daniel P.

Here, there is a strong incentive for increasing the operation voltage of Li-ion cells above 4.5 V in order to increase the density of stored energy. Aluminum is an inexpensive, lightweight metal that is commonly used as a positive electrode current collector in these cells. Imide LiX salts, such as lithium bis(trifluoromethylsulfonyl)imide (X = TFSI), and lithium bis(fluorosulfonyl)imide (X = FSI), are chemically stable on the energized lithiated transition metal oxide electrodes, but their presence in the electrolyte causes rapid anodic dissolution and pitting of Al current collectors at potentials exceeding 4.0 V versus Li/Li +. For LiBF 4 andmore » LiPF 6, the release of HF near the energized surfaces passivates the exposed Al metal, inhibiting this pitting corrosion, but it also causes the gradual degradation of the cathode active material, negating this important advantage. Here we report that in certain electrolytes containing fluorinated carbonate solvents and LiX salts, the threshold voltage for safe operation of Al current collectors can be increased to 5.5 V versus Li/Li +. Interestingly, the most efficient solvent also facilitates the formation of an insoluble gel when AlX 3 is introduced into this solvent. We suggest that this solvent promotes the aggregation of coordination polymers of AlX 3 at the exposed Al surface that isolate this surface from the electrolyte, thereby preventing further Al dissolution and corrosion. Other examples of Al collector protection may also involve this mechanism. Our study suggests that such “allotropic control” could be a way of widening the operation window of Li-ion cells without electrode deterioration, Al current collector corrosion, and electrolyte breakdown.« less

Beyond Yolk–Shell Nanoparticles: Fe 3 O 4 @Fe 3 C Core@Shell Nanoparticles as Yolks and Carbon Nanospindles as Shells for Efficient Lithium Ion Storage

DOE PAGES

Zhang, Jianan; Wang, Kaixi; Xu, Qun; ...

2015-02-25

In order to well address the problems of large volume change and dissolution of Fe 3O 4 nanomaterials during Li + intercalation/extraction, herein we demonstrate a one-step in situ nanospace-confined pyrolysis strategy for robust yolk–shell nanospindles with very sufficient internal void space (VSIVS) for high-rate and long-term lithium ion batteries (LIBs), in which an Fe 3O 4@Fe 3C core@shell nanoparticle is well confined in the compartment of a hollow carbon nanospindle. This structure can not only introduce VSIVS to accommodate volume change of Fe 3O 4 but also afford a dual shell of Fe 3C and carbon to restrict Femore » 3O 4 dissolution, thus providing dual roles for greatly improving the capacity retention. Consequently, Fe 3O 4@Fe 3C–C yolk–shell nanospindles deliver a high reversible capacity of 1128.3 mAh g –1 at even 500 mA g –1, excellent high rate capacity (604.8 mAh g –1 at 2000 mA g –1), and prolonged cycling life (maintaining 1120.2 mAh g –1 at 500 mA g –1 for 100 cycles) for LIBs, which are much better than those of Fe 3O 4@C core@shell nanospindles and Fe 3O 4 nanoparticles. The present Fe 3O 4@Fe 3C–C yolk–shell nanospindles are the most efficient Fe 3O 4-based anode materials ever reported for LIBs.« less

Ohmic resistance affects microbial community and ...

EPA Pesticide Factsheets

Multi-anode microbial electrochemical cells (MXCs) are considered as one of the most promising configurations for scale-up of MXCs, but fundamental understanding of anode kinetics governing current density is limited in the MXCs. In this study we first assessed microbial community and electrochemical kinetic parameters for biofilms on individual anodes in a multi-anode MXC to better comprehend anode fundamentals. Microbial community analysis using 16S rRNA illumine sequencing showed that Geobactor genus, one of the most kinetically efficient anode-respiring bacteria (ARB), was abundant (87%) only on the biofilm anode closest to a reference electrode in which current density was the highest among four anodes. In comparison, Geobacter populations were less than 11% for other three anodes more distant from the reference electrode, generating small current density. Half-saturation anode potential (EKA) was the lowest at -0.251 to -0.242 V (vs. standard hydrogen electrode) for the closest anode, while EKA was as high as -0.134 V for the farthest anode. Our study clearly proves that ohmic resistance changes anode potential which mainly causes different biofilm communities on individual anodes and consequently influences anode kinetics. This study explored the use of multiple anodes in microelectrochemical cells and the microbial community on these anodes, as a function of the efficiency in producing hydrogen peroxide.

Anode sheath transition in an anodic arc for synthesis of nanomaterials

NASA Astrophysics Data System (ADS)

Nemchinsky, V. A.; Raitses, Y.

2016-06-01

The arc discharge with ablating anode or so-called anodic arc is widely used for synthesis of nanomaterials, including carbon nanotubes and fullerens, metal nanoparticles etc. We present the model of this arc, which confirms the existence of the two different modes of the arc operation with two different anode sheath regimes, namely, with negative anode sheath and with positive anode sheath. It was previously suggested that these regimes are associated with two different anode ablating modes—low ablation mode with constant ablation rate and the enhanced ablation mode (Fetterman et al 2008 Carbon 46 1322). The transition of the arc operation from low ablation mode to high ablation mode is determined by the current density at the anode. The model can be used to self-consistently determine the distribution of the electric field, electron density and electron temperature in the near-anode region of the arc discharge. Simulations of the carbon arc predict that for low arc ablating modes, the current is driven mainly by the electron diffusion to the anode. For positive anode sheath, the anode voltage is close to the ionization potential of anode material, while for negative anode sheath, the anode voltage is an order of magnitude smaller. It is also shown that the near-anode plasma, is far from the ionization equilibrium.

The effects of stacking sequence and thermal cycling on the flexural properties of laminate composites of aluminium-epoxy/basalt-glass fibres

NASA Astrophysics Data System (ADS)

Abdollahi Azghan, Mehdi; Eslami-Farsani, Reza

2018-02-01

The current study aimed at investigating the effects of different stacking sequences and thermal cycling on the flexural properties of fibre metal laminates (FMLs). FMLs were composed of two aluminium alloy 2024-T3 sheets and epoxy polymer-matrix composites that have four layers of basalt and/or glass fibres with five different stacking sequences. For FML samples the thermal cycle time was about 6 min for temperature cycles from 25 °C to 115 °C. Flexural properties of samples evaluated after 55 thermal cycles and compared to non-exposed samples. Surface modification of aluminium performed by electrochemical treatment (anodizing) method and aluminium surfaces have been examined by scanning electron microscopy (SEM). Also, the flexural failure mechanisms investigated by the optical microscope study of fractured surfaces. SEM images indicated that the porosity of the aluminium surface increased after anodizing process. The findings of the present study showed that flexural modulus were maximum for basalt fibres based FML, minimum for glass fibres based FML while basalt/glass fibres based FML lies between them. Due to change in the failure mechanism of basalt/glass fibres based FMLs that have glass fibres at outer layer of the polymer composite, the flexural strength of this FML is lower than glass and basalt fibres based FML. After thermal cycling, due to the good thermal properties of basalt fibres, flexural properties of basalt fibres based FML structures decreased less than other composites.

Method for Making a Fuel Cell from a Solid Oxide Monolithic Framework

NASA Technical Reports Server (NTRS)

Sofie, Stephen W. (Inventor); Cable, Thomas L. (Inventor)

2014-01-01

The invention is a novel solid oxide fuel cell (SOFC) stack comprising individual bi-electrode supported fuel cells in which a thin electrolyte is supported between electrodes of essentially equal thickness. Individual cell units are made from graded pore ceramic tape that has been created by the freeze cast method followed by freeze drying. Each piece of graded pore tape later becomes a graded pore electrode scaffold that subsequent to sintering, is made into either an anode or a cathode by means of appropriate solution and thermal treatment means. Each cell unit is assembled by depositing of a thin coating of ion conducting ceramic material upon the side of each of two pieces of tape surface having the smallest pore openings, and then mating the coated surfaces to create an unsintered electrode scaffold pair sandwiching an electrolyte layer. The opposing major outer exposed surfaces of each cell unit is given a thin coating of electrically conductive ceramic, and multiple cell units are stacked, or built up by stacking of individual cell layers, to create an unsintered fuel cell stack. Ceramic or glass edge seals are installed to create flow channels for fuel and air. The cell stack with edge sealants is then sintered into a ceramic monolithic framework. Said solution and thermal treatments means convert the electrode scaffolds into anodes and cathodes. The thin layers of electrically conductive ceramic become the interconnects in the assembled stack.

Advanced Materials Enabled by Atomic Layer Deposition for High Energy Density Rechargeable Batteries

NASA Astrophysics Data System (ADS)

Chen, Lin

In order to meet the ever increasing energy needs of society and realize the US Department of Energy (DOE)'s target for energy storage, acquiring a fundamental understanding of the chemical mechanisms in batteries for direct guidance and searching novel advanced materials with high energy density are critical. To realize rechargeable batteries with superior energy density, great cathodes and excellent anodes are required. LiMn2O4 (LMO) has been considered as a simpler surrogate for high energy cathode materials like NMC. Previous studies demonstrated that Al2O3 coatings prepared by atomic layer deposition (ALD) improved the capacity of LMO cathodes. This improvement was attributed to a reduction in surface area and diminished Mn dissolution. However, here we propose a different mechanism for ALD Al 2O3 on LMO based on in-situ and ex-situ investigations coupled with density functional theory calculations. We discovered that Al2O 3 not only coats the LMO, but also dopes the LMO surface with Al leading to changes in the Mn oxidation state. Different thicknesses of Al2O 3 were deposited on nonstoichiometric LiMn2O4 for electrochemical measurements. The LMO treated with one cycle of ALD Al2O3 (1xAl 2O3 LMO) to produce a sub-monolayer coating yielded a remarkable initial capacity, 16.4% higher than its uncoated LMO counterpart in full cells. The stability of 1xAl2O3 LMO is also much better as a result of stabilized defects with Al species. Furthermore, 4xAl 2O3 LMO demonstrates remarkable capacity retention. Stoichiometric LiMn2O4 was also evaluated with similar improved performance achieved. All superior results, accomplished by great stability and reduced Mn dissolution, is thanks to the synergetic effects of Al-doping and ALD Al2O 3 coating. Turning our attention to the anode, we again utilized aluminum oxide ALD to form conformal films on lithium. We elaborately designed and studied, for the first time, the growth mechanism during Al2O3 ALD on lithium metal in-situ quart crystal microbalance (QCM) measurements and found larger growth than expected during the initial cycles. Besides, we discovered that electrolytes show much enhanced wettability on Li with Al2O3 coating, leading to uniform and dense solid electrolyte interphase formation as well as less electrolyte required for battery operations. Also, we achieved more than 2 times longer cycling life with protected Li and obtained Coulombic efficiencies as high as ˜98% at a practical current rate of 1 mA/cm2, compared to bare Li. More significantly, when the electrolyte volume is limited (10 muL and 5 muL), the cycling life is about 4 times longer. X-ray photoelectron spectroscopy (XPS) for electrodes after cycles and in-situ transmission electron microscopy (TEM) demonstrate that most of lithium is deposited beneath the film. The more uniform Al2O3 coated lithium after cycling observed by scanning electron microscopy (SEM) verifies that ALD Al2O 3 is exceptionally effective to prevent lithium dendrite formation. These results demonstrate that ALD Al2O3 coatings offer a promising route towards energy storage devices that utilize lithium metal anodes, such as Li-S batteries.

Synthesis of NiO nanotubes for use as negative electrodes in lithium ion batteries

NASA Astrophysics Data System (ADS)

Needham, S. A.; Wang, G. X.; Liu, H. K.

Nickel oxide (NiO) nanotubes have been produced for the first time via a template processing method. The synthesis involved a two step chemical reaction in which nickel hydroxide (Ni(OH) 2) nanotubes were firstly formed within the walls of an anodic aluminium oxide (AAO) template. The template was then dissolved away using concentrated NaOH, and the freed nanotubes were converted to NiO by heat treatment in air at 350 °C. Individual nanotubes measured 60 μm in length with a 200 nm outer diameter and a wall thickness of 20-30 nm. The NiO nanotube powder was used in Li-ion cells for assessment of the lithium storage ability. Preliminary testing indicates that the cells demonstrate controlled and sustainable lithium diffusion after the formation of an SEI. Reversible capacities in the 300 mAh g -1 range were typical.

Theoretical investigations of plasma processes in the ion bombardment thruster

NASA Technical Reports Server (NTRS)

Wilhelm, H. E.

1975-01-01

A physical model for a thruster discharge was developed, consisting of a spatially diverging plasma sustained electrically between a small ring cathode and a larger ring anode in a cylindrical chamber with an axial magnetic field. The associated boundary-value problem for the coupled partial differential equations with mixed boundary conditions, which describe the electric potential and the plasma velocity fields, was solved in closed form. By means of quantum-mechanical perturbation theory, a formula for the number S(E) of atoms sputtered on the average by an ion of energy E was derived from first principles. The boundary-value problem describing the diffusion of the sputtered atoms through the surrounding rarefied electron-ion plasma to the system surfaces of ion propulsion systems was formulated and treated analytically. It is shown that outer boundary-value problems of this type lead to a complex integral equation, which requires numerical resolution.

Synthesis of Various Metal/TiO2 Core/shell Nanorod Arrays

NASA Astrophysics Data System (ADS)

Zhu, Wei; Wang, Guan-zhong; Hong, Xun; Shen, Xiao-shuang

2011-02-01

We present a general approach to fabricate metal/TiO2 core/shell nanorod structures by two-step electrodeposition. Firstly, TiO2 nanotubes with uniform wall thickness are prepared in anodic aluminum oxide (AAO) membranes by electrodeposition. The wall thickness of the nanotubes could be easily controlled by modulating the deposition time, and their outer diameter and length are only limited by the channel diameter and the thickness of the AAO membranes, respectively. The nanotubes' tops prepared by this method are open, while the bottoms are connected directly with the Au film at the back of the AAO membranes. Secondly, Pd, Cu, and Fe elements are filled into the TiO2 nanotubes to form core/shell structures. The core/shell nanorods prepared by this two-step process are high density and free-standing, and their length is dependent on the deposition time.

The development and test of a deformable diffraction grating for a stigmatic EUV spectroheliometer

NASA Technical Reports Server (NTRS)

Timothy, J. Gethyn; Walker, A. B. C., Jr.; Morgan, J. S.; Huber, M. C. E.; Tondello, G.

1992-01-01

The objectives were to address currently unanswered fundamental questions concerning the fine scale structure of the chromosphere, transition region, and corona. The unique characteristics of the spectroheliometer was used in combination with plasma diagnostic techniques to study the temperature, density, and velocity structures of specific features in the solar outer atmosphere. A unified understanding was sought of the interplay between the time dependent geometry of the magnetic field structure and the associated flows of mass and energy, the key to which lies in the smallest spatial scales that are unobservable with current EUV instruments. Toroidal diffraction gratings were fabricated and tested by a new technique using an elastically deformable substrate. The toroidal diffraction gratings was procured and tested to be used for the evaluation of the Multi-Anode Microchannel Array (MAMA) detector systems for the Solar Ultraviolet Measurements of Emitted Radiation (SUMER) and UV Coronagraph Spectrometer (UVCS) instruments on the SOHO mission.

Preliminary Experimental Measurements for a Gallium Electromagnetic (GEM) Thruster

NASA Technical Reports Server (NTRS)

Thomas, Robert E.; Burton, Rodney L.; Glumac, Nick G.; Polzin, Kurt A.

2007-01-01

A low-energy gallium plasma source is used to perform a spatially and temporally broad spectroscopic survey in the 220-520 nm range. Neutral, singly, and doubly ionized gallium are present in a 20 J, 1.8 kA (peak) arc discharge operating with a central cathode. When the polarity of the inner electrode is reversed the discharge current and arc voltage waveforms remain similar. Utilizing a central anode configuration, multiple Ga lines are absent in the 270-340 nm range. In addition, neutral and singly ionized Fe spectral lines are present, indicating erosion of the outer electrode. With graphite present on the insulator to facilitate breakdown, line emission from the gallium species is further reduced and while emissions from singly and doubly ionized carbon atoms and molecular carbon (C2) radicals are observed. These data indicate that a significant fraction of energy is shifted from the gallium and deposited into the various carbon species.

Anodic Behaviour of High Nitrogen-Bearing Steel in PEMFC Environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, H.; Turner, J. A.

2008-02-01

High nitrogen-bearing stainless steels, AISI Type 201 and AL219, were investigated in simulated polymer electrolyte membrane fuel cell (PEMFC) environments to assess the use of these materials in fuel cell bipolar plate applications. Both steels exhibit better corrosion behavior than 316L steel in the same environments. Type 201 steel shows similar but lower interfacial contact resistance (ICR) than 316L, while AL219 steel shows higher ICR than 316L. X-ray photoelectron spectroscopy (XPS) analysis shows that the air-formed films on Type 201 and AL219 are composed of iron oxides, chromium oxide, and manganese oxide. Iron oxides dominate the composition of the air-formedmore » film, specially the outer layer. Chromium oxide dominates passive films. Surface film thicknesses were estimated. The results suggest that high nitrogen-bearing stainless steels are promising materials for PEMFC bipolar plates.« less

Optimization of chemical displacement deposition of copper on porous silicon.

PubMed

Bandarenka, Hanna; Redko, Sergey; Nenzi, Paolo; Balucani, Marco; Bondarenko, Vitaly

2012-11-01

Copper (II) sulfate was used as a source of copper to achieve uniform distribution of Cu particles deposited on porous silicon. Layers of the porous silicon were formed by electrochemical anodization of Si wafers in a mixture of HF, C3H7OH and deionized water. The well-known chemical displacement technique was modified to grow the copper particles of specific sizes. SEM and XRD analysis revealed that the outer surface of the porous silicon was covered with copper particles of the crystal orientation inherited from the planes of porous silicon skeleton. The copper crystals were found to have the cubic face centering elementary cell. In addition, the traces of Cu2O cubic primitive crystalline phases were identified. The dimensions of Cu particles were determined by the Feret's analysis of the SEM images. The sizes of the particles varied widely from a few to hundreds of nanometers. A phenomenological model of copper deposition was proposed.

Electrolytic/fuel cell bundles and systems including a current collector in communication with an electrode thereof

DOEpatents

Hawkes, Grant L.; Herring, James S.; Stoots, Carl M.; O& #x27; Brien, James E.

2013-03-05

Electrolytic/fuel cell bundles and systems including such bundles include an electrically conductive current collector in communication with an anode or a cathode of each of a plurality of cells. A cross-sectional area of the current collector may vary in a direction generally parallel to a general direction of current flow through the current collector. The current collector may include a porous monolithic structure. At least one cell of the plurality of cells may include a current collector that surrounds an outer electrode of the cell and has at least six substantially planar exterior surfaces. The planar surfaces may extend along a length of the cell, and may abut against a substantially planar surface of a current collector of an adjacent cell. Methods for generating electricity and for performing electrolysis include flowing current through a conductive current collector having a varying cross-sectional area.

Selective growth of palladium and titanium dioxide nanostructures inside carbon nanotube membranes

PubMed Central

2012-01-01

Hybrid nanostructured arrays based on carbon nanotubes (CNT) and palladium or titanium dioxide materials have been synthesized using self-supported and silicon-supported anodized aluminum oxide (AAO) as nanoporous template. It is well demonstrated that carbon nanotubes can be grown using these membranes and hydrocarbon precursors that decompose at temperatures closer to 600°C without the use of a metal catalyst. In this process, carbonic fragments condensate to form stacked graphitic sheets, which adopt the shape of the pores, yielding from these moulds' multi-walled carbon nanotubes. After this process, the ends of the tubes remain open and accessible to other substances, whereas the outer walls are protected by the alumina. Taking advantage of this fact, we have performed the synthesis of palladium and titanium dioxide nanostructures selectively inside carbon nanotubes using these CNT-AAO membranes as nanoreactors. PMID:22731888

Ab initio study of radiation effects on the Li4Ti5O12 electrode used in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Samin, Adib; Kurth, Michael; Cao, Lei

2015-04-01

Lithium-ion batteries are currently in wide use owing to their high energy density and enhanced capabilities. Li4Ti5O12 is a promising anode material for lithium-ion batteries because of its advantageous properties. Lithium-ion batteries could be exposed to radiation occurring in various conditions such as during outer space exploration and nuclear accidents. In this study, we apply density functional theory to explore the effect of radiation damage on this electrode and, ultimately, on the performance of the battery. It was found that radiation could affect the structural stability of the material. Furthermore, the electrode was shown to undergo a transition from insulator to metal, following the defects due to radiation. In addition, the effect of radiation on the intercalation potential was found to be highly dependent on the nature of the defect induced.

Expression of DNAJB12 or DNAJB14 Causes Coordinate Invasion of the Nucleus by Membranes Associated with a Novel Nuclear Pore Structure

PubMed Central

Goodwin, Edward C.; Motamedi, Nasim; Lipovsky, Alex; Fernández-Busnadiego, Rubén; DiMaio, Daniel

2014-01-01

DNAJB12 and DNAJB14 are transmembrane proteins in the endoplasmic reticulum (ER) that serve as co-chaperones for Hsc70/Hsp70 heat shock proteins. We demonstrate that over-expression of DNAJB12 or DNAJB14 causes the formation of elaborate membranous structures within cell nuclei, which we designate DJANGOS for DNAJ-associated nuclear globular structures. DJANGOS contain DNAJB12, DNAJB14, Hsc70 and markers of the ER lumen and ER and nuclear membranes. Strikingly, they are evenly distributed underneath the nuclear envelope and are of uniform size in any one nucleus. DJANGOS are composed primarily of single-walled membrane tubes and sheets that connect to the nuclear envelope via a unique configuration of membranes, in which the nuclear pore complex appears anchored exclusively to the outer nuclear membrane, allowing both the inner and outer nuclear membranes to flow past the circumference of the nuclear pore complex into the nucleus. DJANGOS break down rapidly during cell division and reform synchronously in the daughter cell nuclei, demonstrating that they are dynamic structures that undergo coordinate formation and dissolution. Genetic studies showed that the chaperone activity of DNAJ/Hsc70 is required for the formation of DJANGOS. Further analysis of these structures will provide insight into nuclear pore formation and function, activities of molecular chaperones, and mechanisms that maintain membrane identity. PMID:24732912

Mechanisms of anode power deposition in a low pressure free burning arc

NASA Technical Reports Server (NTRS)

Soulas, George C.; Myers, Roger M.

1994-01-01

Anode power deposition is a dominant power loss mechanism for arc jets and MPD thrusters. In this study, a free burning arc experiment was operated at pressures and current densities similar to those in arc jets and MPD thrusters in an attempt to identify the physics controlling this loss mechanism. Use of a free burning arc allowed for the isolation of independent variables controlling anode power deposition and provided a convenient and flexible way to cover a broad range of currents, anode surface pressures, and applied magnetic field strengths and orientations using an argon gas. Test results showed that anode power deposition decreased with increasing anode surface pressure up to 6.7 Pa (0.05 torr) and then became insensitive to pressure. Anode power increased with increasing arc current while the electron number density near the anode surface increased linearity. Anode power also increased with increasing applied magnetic field strength due to an increasing anode fall voltage. Applied magnetic field orientation had an effect only at high currents and low anode surface pressures, where anode power decreased when applied field lines intercepted the anode surface. The results demonstrated that anode power deposition was dominated by the current carrying electrons and that the anode fall voltage was the largest contributor. Furthermore, the results showed that anode power deposition can be reduced by operating at increased anode pressures, reduced arc currents, and applied magnetic field strengths and with magnetic field lines intercepting the anode.

A Seafloor Microbial Biome Hosted within Incipient Ferromanganese Crusts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Templeton, Alexis S.; Knowles, A. S.; Eldridge, D. L.

2009-11-15

Unsedimented volcanic rocks exposed on the seafloor at ridge systems and Seamounts host complex, abundant and diverse microbial communities that are relatively cosmopolitan in distribution (Lysnes, Thorseth et al. 2004; Mason, Stingl et al. 2007; Santelli, Orcutt et al. 2008). The most commonly held hypothesis is that the energy released by the hydration, dissolution and oxidative alteration of volcanic glasses in seawater drives the formation of an ocean crust biosphere (Thorseth, Furnes et al. 1992; Fisk, Giovannoni et al. 1998; Furnes and Staudigel 1999). The combined thermodynamically favorable weathering reactions could theoretically support anywhere from 105 to 109 cells/gram ofmore » rock depending upon the metabolisms utilized and cellular growth rates and turnover (Bach and Edwards 2003; Santelli, Orcutt et al. 2008). Yet microbially-mediated basalt alteration and energy conservation has not been directly demonstrated on the seafloor. By using synchrotron-based x-ray microprobe mapping, x-ray absorption spectroscopy and high-resolution scanning and transmission electron microscopy observations of young volcanic glasses recovered from the outer flanks of Loihi Seamount, we intended to identify the initial rates and mechanisms of microbial basalt colonization and bioalteration. Instead, here we show that microbial biofilms are intimately associated with ferromanganese crusts precipitating onto basalt surfaces from cold seawater. Thus we hypothesize that microbial communities colonizing seafloor rocks are established and sustained by external inputs of potential energy sources, such as dissolved and particulate Fe(II), Mn(II) and organic matter, rather than rock dissolution.« less

Growth behavior of anodic oxide formed by aluminum anodizing in glutaric and its derivative acid electrolytes

NASA Astrophysics Data System (ADS)

Nakajima, Daiki; Kikuchi, Tatsuya; Natsui, Shungo; Suzuki, Ryosuke O.

2014-12-01

The growth behavior of anodic oxide films formed via anodizing in glutaric and its derivative acid solutions was investigated based on the acid dissociation constants of electrolytes. High-purity aluminum foils were anodized in glutaric, ketoglutaric, and acetonedicarboxylic acid solutions under various electrochemical conditions. A thin barrier anodic oxide film grew uniformly on the aluminum substrate by glutaric acid anodizing, and further anodizing caused the film to breakdown due to a high electric field. In contrast, an anodic porous alumina film with a submicrometer-scale cell diameter was successfully formed by ketoglutaric acid anodizing at 293 K. However, the increase and decrease in the temperature of the ketoglutaric acid resulted in non-uniform oxide growth and localized pitting corrosion of the aluminum substrate. An anodic porous alumina film could also be fabricated by acetonedicarboxylic acid anodizing due to the relatively low dissociation constants associated with the acid. Acid dissociation constants are an important factor for the fabrication of anodic porous alumina films.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mehdi, Beata L.; Qian, Jiangfeng; Nasybulin, Eduard

Lithium (Li)-ion batteries are currently used for a wide variety of portable electronic devices, electric vehicles and renewable energy applications. In addition, extensive worldwide research efforts are now being devoted to more advanced “beyond Li-ion” battery chemistries - such as lithium-sulfur (Li-S) and lithium-air (Li-O2) - in which the carbon anode is replaced with Li metal. However, the practical application of Li metal anode systems has been highly problematic. The main challenges involve controlling the formation of a solid-electrolyte interphase (SEI) layer and the suppression of Li dendrite growth during the charge/discharge process (achieving “dendrite-free” cycling). The SEI layer formationmore » continuously consumes the electrolyte components creating highly resistive layer, which leads to the rapid decrease of cycling performance and degradation of the Li anode. The growth of Li metal dendrites at the anode contributes to rapid capacity fading (the presence of “dead Li” created during the discharge leads to an increased overpotential) and, in the case of continuous growth, leads to internal short circuits and extreme safety issues. Here we demonstrate the application of an operando electrochemical scanning transmission electron microscopy (ec-(S)TEM) cell to study the SEI layer formation and the initial stages of Li dendrite growth - the goal is to develop a mechanism for mitigating the degradation processes and increasing safety. Bright field (BF) STEM images in Figure 1 A-C show Li metal deposition and dissolution processes at the interface between the Pt working electrode and the lithium hexafluorophosphate (LiPF6) in propylene carbonate (PC) electrolyte during three charge/discharge cycles. A contrast reversal caused by Li metal being lighter/less dense than surrounding electrolyte (Li appears brighter than the background in BF STEM images) allows Li to be uniquely identified from the other components in the system - the only solid material that is less dense than the electrolyte is Li metal. Using these images, we can precisely quantify the total volume of Li deposition, the thickness of the SEI layer (observed as a ring of positive contrast around the electrode) and alloy formation due to Li+ ion insertion during each cycle. Furthermore, at the end of each discharge cycle we can quantify the presence of “dead Li” detached from the Pt electrode, thereby demonstrating the degree of irreversibility (and degradation of Pt electrode) associated with insertion/removal of Li+during this process with direct correlation to electrochemical performance. Such analyses provide significant insights into Li metal dendrite growth, which is critical to understand the complex interfacial reactions needed to be controlled for future Li-based and next generation energy storage systems.« less

Anode power deposition in quasi-steady MPD arcs. [accelerator anode heat flux measurement

NASA Technical Reports Server (NTRS)

Saber, A. J.; Jahn, R. G.

1973-01-01

The power deposited in the anode of a quasi-steady MPD accelerator has been measured directly by thermocouples attached to the inside surface of a shell anode which provide a local measurement of anode heat flux. The results over a range of arc currents from 5.5 to 44 kiloamperes and argon mass flows from 1 g/sec to 48 g/sec show that the fraction of the total input power deposited in the anode decreases drastically from 50% at an arc power of 200 kW to 10% at 20 MW, and that anode power is not uniformly deposited in the anode. A theoretical model of the anode heat transfer, including effects of anode work function, electron thermal energy, and anode sheath, can be brought into reasonable agreement with the measurements, provided the effective range of the conduction electrons from within the discharge plasma to the anode surface is properly acknowledged.

Wet-chemical dissolution of TRISO-coated simulated high-temperature-reactor fuel particles

NASA Astrophysics Data System (ADS)

Skolo, K. P.; Jacobs, P.; Venter, J. H.; Klopper, W.; Crouse, P. L.

2012-01-01

Chemical etching with different mixtures of acidic solutions has been investigated to disintegrate the two outermost coatings from tri-structural isotropic coated particles containing zirconia kernels, which are used in simulated particles instead of uranium dioxide. A scanning electron microscope (SEM) was used to study the morphology of the particles after the first etching step as well as at different stages of the second etching step. SEM examination shows that the outer carbon layer can be readily removed with a CrO 3-HNO 3/H 2SO 4 solution. This finding was verified by energy dispersive spectroscopy (EDS) analysis. Etching of the silicon carbide layer in a hydrofluoric-nitric solution yielded partial removal of the coating and localized attack of the underlying coating layers. The SEM results provide evidence that the etching of the silicon carbide layer is strongly influenced by its microstructure.

How the novel integration of electrolysis in tidal flow constructed wetlands intensifies nutrient removal and odor control.

PubMed

Ju, Xinxin; Wu, Shubiao; Huang, Xu; Zhang, Yansheng; Dong, Renjie

2014-10-01

Intensified nutrient removal and odor control in a novel electrolysis-integrated tidal flow constructed wetland were evaluated. The average removal efficiencies of COD and NH4(+)-N were above 85% and 80% in the two experimental wetlands at influent COD concentration of 300 mg/L and ammonium nitrogen concentration of 60 mg/L regardless of electrolysis integration. Effluent nitrate concentration decreased from 2.5mg/L to 0.5mg/L with the reduction in current intensity from 1.5 mA/cm(2) to 0.57 mA/cm(2). This result reveals the important role of current intensity in nitrogen transformation. Owing to the ferrous and ferric iron coagulant formed through the electro-dissolution of the iron anode, electrolysis integration not only exerted a positive effect on phosphorus removal but also effectively inhibited sulfide accumulation for odor control. Although electrolysis operation enhanced nutrient removal and promoted the emission of CH4, no significant difference was observed in the microbial communities and abundance of the two experimental wetlands. Copyright © 2014 Elsevier Ltd. All rights reserved.

Microstructural characterization of the cycling behavior of electrodeposited manganese oxide supercapacitors using 3D electron tomography

NASA Astrophysics Data System (ADS)

Dalili, N.; Clark, M. P.; Davari, E.; Ivey, D. G.

2016-10-01

Manganese oxide has been investigated extensively as an electrochemical capacitor or supercapacitor electrode material. Manganese oxide is inexpensive to fabricate and exhibits relatively high capacitance values, i.e., in excess of 200 F g-1 in many cases; the actual value depends very much on the fabrication method and test conditions. The cycling behavior of Mn oxide, fabricated using anodic electrodeposition, is investigated using slice and view techniques, via a dual scanning electron microscope (SEM) and focused ion beam (FIB) instrument to generate three-dimensional (3D) images, coupled with electrochemical characterization. The initial as-fabricated electrode has a rod-like appearance, with a fine-scale, sheet-like morphology within the rods. The rod-like structure remains after cycling, but there are significant morphological changes. These include partial dissolution of Mn oxide followed by redeposition of Mn oxide in regions close to the substrate. The redeposited material has a finer morphology than the original as-fabricated Mn oxide. The Mn oxide coverage is also better near the substrate. These effects result in an increase in the specific capacitance.

Preparation of anti-adhesion surfaces on aluminium substrates of rubber plastic moulds using a coupling method of liquid plasma and electrochemical machining

NASA Astrophysics Data System (ADS)

Meng, Jianbing; Dong, Xiaojuan; Wei, Xiuting; Yin, Zhanmin

2014-03-01

Hard anti-adhesion surfaces, with low roughness and wear resistance, on aluminium substrates of rubber plastic moulds were fabricated via a new coupling method of liquid plasma and electrochemical machining. With the aid of liquid plasma thermal polishing and electrochemical anodic dissolution, micro/nano-scale binary structures were prepared as the base of the anti-adhesion surfaces. The anti-adhesion behaviours of the resulting aluminium surfaces were analysed by a surface roughness measuring instrument, a scanning electron microscope (SEM), a Fourier-transform infrared spectrophotometer (FTIR), an X-ray diffractometer (XRD), an optical contact angle meter, a digital Vickers micro-hardness (Hv) tester, and electronic universal testing. The results show that, after the liquid plasma and electrochemical machining, micro/nano-scale binary structures composed of micro-scale pits and nano-scale elongated boss structures were present on the sample surfaces. As a result, the anti-adhesion surfaces fabricated by the above coupling method have good anti-adhesion properties, better wear resistance and lower roughness.

Effective Trapping of Lithium Polysulfides Using a Functionalized Carbon Nanotube-Coated Separator for Lithium-Sulfur Cells with Enhanced Cycling Stability.

PubMed

Ponraj, Rubha; Kannan, Aravindaraj G; Ahn, Jun Hwan; Lee, Jae Hee; Kang, Joonhee; Han, Byungchan; Kim, Dong-Won

2017-11-08

The critical issues that hinder the practical applications of lithium-sulfur batteries, such as dissolution and migration of lithium polysulfides, poor electronic conductivity of sulfur and its discharge products, and low loading of sulfur, have been addressed by designing a functional separator modified using hydroxyl-functionalized carbon nanotubes (CNTOH). Density functional theory calculations and experimental results demonstrate that the hydroxyl groups in the CNTOH provoked strong interaction with lithium polysulfides and resulted in effective trapping of lithium polysulfides within the sulfur cathode side. The reduction in migration of lithium polysulfides to the lithium anode resulted in enhanced stability of the lithium electrode. The conductive nature of CNTOH also aided to efficiently reutilize the adsorbed reaction intermediates for subsequent cycling. As a result, the lithium-sulfur cell assembled with a functional separator exhibited a high initial discharge capacity of 1056 mAh g -1 (corresponding to an areal capacity of 3.2 mAh cm -2 ) with a capacity fading rate of 0.11% per cycle over 400 cycles at 0.5 C rate.

Environmental resistance of oxide tags fabricated on 304L stainless steel via nanosecond pulsed laser irradiation

DOE PAGES

Lawrence, Samantha Kay; Adams, David P.; Bahr, David F.; ...

2015-11-14

Nanosecond pulsed laser irradiation was used to fabricate colored, mechanically robust oxide “tags” on 304L stainless steel. Immersion in simulated seawater solution, salt fog exposure, and anodic polarization in a 3.5% NaCl solution were employed to evaluate the environmental resistance of these oxide tags. Single layer oxides outside a narrow thickness range (~ 100–150 nm) are susceptible to dissolution in chloride containing environments. The 304L substrates immediately beneath the oxides corrode severely—attributed to Cr-depletion in the melt zone during laser processing. For the first time, multilayered oxides were fabricated with pulsed laser irradiation in an effort to expand the protectivemore » thickness range while also increasing the variety of film colors attainable in this range. Layered films grown using a laser scan rate of 475 mm/s are more resistant to both localized and general corrosion than oxides fabricated at 550 mm/s. Furthermore, in the absence of pre-processing to mitigate Cr-depletion, layered films can enhance environmental stability of the system.« less

Preparation of anti-adhesion surfaces on aluminium substrates of rubber plastic moulds using a coupling method of liquid plasma and electrochemical machining

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meng, Jianbing, E-mail: jianbingmeng@126.com; Dong, Xiaojuan; Wei, Xiuting

Hard anti-adhesion surfaces, with low roughness and wear resistance, on aluminium substrates of rubber plastic moulds were fabricated via a new coupling method of liquid plasma and electrochemical machining. With the aid of liquid plasma thermal polishing and electrochemical anodic dissolution, micro/nano-scale binary structures were prepared as the base of the anti-adhesion surfaces. The anti-adhesion behaviours of the resulting aluminium surfaces were analysed by a surface roughness measuring instrument, a scanning electron microscope (SEM), a Fourier-transform infrared spectrophotometer (FTIR), an X-ray diffractometer (XRD), an optical contact angle meter, a digital Vickers micro-hardness (Hv) tester, and electronic universal testing. The resultsmore » show that, after the liquid plasma and electrochemical machining, micro/nano-scale binary structures composed of micro-scale pits and nano-scale elongated boss structures were present on the sample surfaces. As a result, the anti-adhesion surfaces fabricated by the above coupling method have good anti-adhesion properties, better wear resistance and lower roughness.« less

Titanium deposition from ionic liquids - appropriate choice of electrolyte and precursor.

PubMed

Berger, Claudia A; Arkhipova, Maria; Farkas, Attila; Maas, Gerhard; Jacob, Timo

2016-02-14

In this study titanium isopropoxide was dissolved in 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (BMITFSI) and further in a custom-made guanidinium-based ionic liquid (N11N11NpipGuaTFSI). Electrochemical investigations were carried out by means of cyclic voltammetry (CV) and the initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). For BMITFSI we found one large cathodic reduction peak at a potential of -1.2 V vs. Pt, corresponding to the growth of monoatomic high islands. The obtained deposit was identified as elemental titanium by Auger Electron Spectroscopy (AES). Furthermore, we found a corresponding anodic peak at -0.3 V vs. Pt, which is associated with the dissolution of the islands. This observation leads to the assumption that titanium deposition from the imidazolium-based room-temperature ionic liquid (RTIL) proceeds in a one-step electron transfer. In contrast, for the guanidinium-based RTIL we found several peaks during titanium reduction and oxidation, which indicates a multi-step electron transfer in this alternative electrolyte.

Silver-dendrimer nanocomposites as oligonucleotide labels for electrochemical stripping detection of DNA hybridization.

PubMed

Jin, Xin; Zhou, Ling; Zhu, Bo; Jiang, Xue; Zhu, Ningning

2018-06-01

Silver-dendrimer nanocomposites were synthesized and used as oligonucleotide labels for electrochemical stripping detection of DNA hybridization. The synthesized silver-dendrimer nanocomposites were characterized by UV-vis spectrophotometry, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Ratios of silver/dendrimer were optimized in order to obtain stable nanocomposites with maximal silver loading in the interior of a polymeric shell. The silver-dendrimer nanocomposites were attached to sequence-known DNA probes specific to colitoxin, and used to detect probe hybridization by dissolution of the silver nanoparticles in the interior of dendrimer in a diluted nitric acid, followed by measurement of Ag + ions by anodic stripping voltammetry (ASV). Use of differential pulse voltammetry for the stripping step, along with optimization of the ASV conditions, enabled a detection limit of 0.78 pM. The present strategy, in combination with dendrimer-encapsulated copper labeled oligonucleotides probe reported previously, could potentially be used to detect single or multiple DNA targets in one sample. Copyright © 2018 Elsevier B.V. All rights reserved.

A Preliminary Study on the Synthesis and Characterization of Multilayered Ag/Co Magnetic Nanowires Fabricated via the Electrodeposition Method

PubMed Central

Peng, Cheng-Hsiung; Wu, Tsung-Yung; Hwang, Chyi-Ching

2013-01-01

A single-bath electrodeposition method was developed to integrate multilayer Ag/Co nanowires with a commercial anodic alumina oxide (AAO) template with a pore diameter of 100–200 nm. An electrolyte system containing silver nitride and cobalt sulfide was studied using cyclic voltammetry, and the electrodeposition rate was varied to optimize the electrodeposition conditions. A constant stepwise potential and a variable cation ratio of [Co2+]/[Ag+] were used during electrodeposition. After the dissolution of the template in aqueous NaOH solution, multilayered Ag/Co nanowires were obtained with a composition of [Co]/[Ag80Co20], as identified by XRD and TEM, when [Co2+]/[Ag+] = 150. By annealing at 200°C for 1 h, uniformly structured (Co99.57/Ag100) nanowires were obtained. Compared with pure Co nanowires, the magnetic hysteresis loops showed a greater magnetic anisotropy for (Co99.57/Ag100) nanowires than for pure Co nanowires, corresponding to a change in the easy axis upon magnetization. PMID:24072985

Influence of Pb 2+ ions in the H 2 oxidation on Pt catalyzed hydrogen diffusion anodes in sulfuric acid: presence of oscillatory phenomena

NASA Astrophysics Data System (ADS)

Expósito, E.; Sánchez-Sánchez, C. M.; Solla-Gullón, J.; Montiel, V.

The influence of Pb 2+ ions in sulfuric acid medium on the behavior of a platinum catalyzed hydrogen diffusion electrode (HDE) in a filter press reactor has been studied. A voltammetric study of the H 2 oxidation reaction on a polyoriented platinum electrode and a platinum rotating disk electrode (RDE) in presence of lead ions in solution has also been carried out. Potential oscillations were found in galvanostatic experiments of H 2 oxidation using a HDE catalyzed with platinum when Pb 2+ ions are present in solution. This oscillatory phenomenon was also observed when hydrogen oxidation was carried out in presence of Pb 2+ ions using a platinum RDE. The oscillatory behavior observed has been attributed to an adsorption-oxidation-desorption process of lead on the platinum surface. Due to the low solubility of Pb 2+ in sulfuric acid, at high values of coverage, lead is oxidised to insoluble lead sulfate that blocks the Pt surface. The coupling of the dissolution of lead sulfate and the Pb electrochemical adsorption-oxidation processes cause the oscillatory phenomenon.

Manufacturing of Dysprosium-Iron Alloys by Electrolysis in Fluoride-Based Electrolytes: Oxide Solubility Determinations

NASA Astrophysics Data System (ADS)

Martinez, Ana Maria; Støre, Anne; Osen, Karen Sende

2018-04-01

Electrolytic production of light rare earth elements and alloys takes place in a fluoride-based electrolyte using rare earth oxides as raw material. The optimization of this method, mainly in terms of the energy efficiency and environmental impact control, is rather challenging. Anode effects, evolution of fluorine-containing compounds, and side cathode reactions could largely be minimized by a good control of the amount of rare earth oxide species dissolved in the fluoride-based electrolyte and their dissolution rate. The oxide content of the fluoride melts REF3-LiF (RE = Nd, Dy) at different compositions and temperatures were experimentally determined by carbothermal analysis of melt samples. The highest solubility values of oxide species, added as Dy2O3 and Dy2(CO3)3, were obtained to be of ca. 3 wt pct (expressed as Dy2O3) in the case of the equimolar DyF3-LiF melt at 1323 K (1050 °C). The oxide saturation values increased with the amount of REF3 present in the molten bath and the working temperature.

Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yadav, Gautam G.; Gallaway, Joshua W.; Turney, Damon E.

2017-03-06

Manganese dioxide cathodes are inexpensive and have high theoretical capacity (based on two electrons) of 617 mAh g-1, making them attractive for low-cost, energy-dense batteries. They are used in non-rechargeable batteries with anodes like zinc. Only ~10% of the theoretical capacity is currently accessible in rechargeable alkaline systems. Attempts to access the full capacity using additives have been unsuccessful. We report a class of Bi-birnessite (a layered manganese oxide polymorph mixed with bismuth oxide (Bi2O3)) cathodes intercalated with Cu2+ that deliver near-full two-electron capacity reversibly for >6,000 cycles. The key to rechargeability lies in exploiting the redox potentials of Cumore » to reversibly intercalate into the Bi-birnessite-layered structure during its dissolution and precipitation process for stabilizing and enhancing its charge transfer characteristics. This process holds promise for other applications like catalysis and intercalation of metal ions into layered structures. A large prismatic rechargeable Zn-birnessite cell delivering ~140 Wh l-1 is shown.« less

Enhanced ablation of small anodes in a carbon nanotube arc discharge

NASA Astrophysics Data System (ADS)

Raitses, Yevgeny; Fetterman, Abraham; Keidar, Michael

2008-11-01

An atmospheric pressure helium arc discharge is used for carbon nanotube synthesis. The arc discharge operates in an anodic mode with the ablating anode made from a graphite material. For such conditions, models predict the electron-repelling (negative) anode sheath. In the present experiments, the anode ablation rate is investigated as a function of the anode diameter. It is found that anomalously high ablation occurs for small anode diameters (< 0.4 cm). This result is explained by the formation of an electron-attracting (positive) anode sheath leading to increased power losses on small anodes as compared to larger anodes [1]. The suggested mechanism for the positive anode sheath formation is plasma convergence. The increased ablation rate due to this positive sheath could imply a greater yield of carbon nanotube production. [1] A. J. Fetterman, Y. Raitses and M. Keidar, Carbon (2008).

Automated Dissolution for Enteric-Coated Aspirin Tablets: A Case Study for Method Transfer to a RoboDis II.

PubMed

Ibrahim, Sarah A; Martini, Luigi

2014-08-01

Dissolution method transfer is a complicated yet common process in the pharmaceutical industry. With increased pharmaceutical product manufacturing and dissolution acceptance requirements, dissolution testing has become one of the most labor-intensive quality control testing methods. There is an increased trend for automation in dissolution testing, particularly for large pharmaceutical companies to reduce variability and increase personnel efficiency. There is no official guideline for dissolution testing method transfer from a manual, semi-automated, to automated dissolution tester. In this study, a manual multipoint dissolution testing procedure for an enteric-coated aspirin tablet was transferred effectively and reproducibly to a fully automated dissolution testing device, RoboDis II. Enteric-coated aspirin samples were used as a model formulation to assess the feasibility and accuracy of media pH change during continuous automated dissolution testing. Several RoboDis II parameters were evaluated to ensure the integrity and equivalency of dissolution method transfer from a manual dissolution tester. This current study provides a systematic outline for the transfer of the manual dissolution testing protocol to an automated dissolution tester. This study further supports that automated dissolution testers compliant with regulatory requirements and similar to manual dissolution testers facilitate method transfer. © 2014 Society for Laboratory Automation and Screening.

Effects of anodizing parameters and heat treatment on nanotopographical features, bioactivity, and cell culture response of additively manufactured porous titanium.

PubMed

Amin Yavari, S; Chai, Y C; Böttger, A J; Wauthle, R; Schrooten, J; Weinans, H; Zadpoor, A A

2015-06-01

Anodizing could be used for bio-functionalization of the surfaces of titanium alloys. In this study, we use anodizing for creating nanotubes on the surface of porous titanium alloy bone substitutes manufactured using selective laser melting. Different sets of anodizing parameters (voltage: 10 or 20V anodizing time: 30min to 3h) are used for anodizing porous titanium structures that were later heat treated at 500°C. The nanotopographical features are examined using electron microscopy while the bioactivity of anodized surfaces is measured using immersion tests in the simulated body fluid (SBF). Moreover, the effects of anodizing and heat treatment on the performance of one representative anodized porous titanium structures are evaluated using in vitro cell culture assays using human periosteum-derived cells (hPDCs). It has been shown that while anodizing with different anodizing parameters results in very different nanotopographical features, i.e. nanotubes in the range of 20 to 55nm, anodized surfaces have limited apatite-forming ability regardless of the applied anodizing parameters. The results of in vitro cell culture show that both anodizing, and thus generation of regular nanotopographical feature, and heat treatment improve the cell culture response of porous titanium. In particular, cell proliferation measured using metabolic activity and DNA content was improved for anodized and heat treated as well as for anodized but not heat-treated specimens. Heat treatment additionally improved the cell attachment of porous titanium surfaces and upregulated expression of osteogenic markers. Anodized but not heat-treated specimens showed some limited signs of upregulated expression of osteogenic markers. In conclusion, while varying the anodizing parameters creates different nanotube structure, it does not improve apatite-forming ability of porous titanium. However, both anodizing and heat treatment at 500°C improve the cell culture response of porous titanium. Copyright © 2015 Elsevier B.V. All rights reserved.

Investigation of the short argon arc with hot anode. I. Numerical simulations of non-equilibrium effects in the near-electrode regions

NASA Astrophysics Data System (ADS)

Khrabry, A.; Kaganovich, I. D.; Nemchinsky, V.; Khodak, A.

2018-01-01

The atmospheric pressure arcs have recently found application in the production of nanoparticles. The distinguishing features of such arcs are small length and hot ablating anode characterized by intensive electron emission and radiation from its surface. We performed a one-dimensional modeling of argon arc, which shows that near-electrode effects of thermal and ionization non-equilibrium play an important role in the operation of a short arc, because the non-equilibrium regions are up to several millimeters long and are comparable to the arc length. The near-anode region is typically longer than the near-cathode region and its length depends more strongly on the current density. The model was extensively verified and validated against previous simulation results and experimental data. The Volt-Ampere characteristic (VAC) of the near-anode region depends on the anode cooling mechanism. The anode voltage is negative. In the case of strong anode cooling (water-cooled anode) when the anode is cold, temperature and plasma density gradients increase with current density, resulting in a decrease of the anode voltage (the absolute value increases). Falling VAC of the near-anode region suggests the arc constriction near the anode. Without anode cooling, the anode temperature increases significantly with the current density, leading to a drastic increase in the thermionic emission current from the anode. Correspondingly, the anode voltage increases to suppress the emission, and the opposite trend in the VAC is observed. The results of simulations were found to be independent of sheath model used: collisional (fluid) or collisionless model gave the same plasma profiles for both near-anode and near-cathode regions.

Investigation of the short argon arc with hot anode. I. Numerical simulations of non-equilibrium effects in the near-electrode regions

DOE PAGES

Khrabry, A.; Kaganovich, I. D.; Nemchinsky, V.; ...

2018-01-22

The atmospheric pressure arcs have recently found application in the production of nanoparticles. The distinguishing features of such arcs are small length and hot ablating anode characterized by intensive electron emission and radiation from its surface. We performed a one-dimensional modeling of argon arc, which shows that near-electrode effects of thermal and ionization non-equilibrium play an important role in the operation of a short arc, because the non-equilibrium regions are up to several millimeters long and are comparable to the arc length. The near-anode region is typically longer than the near-cathode region and its length depends more strongly on themore » current density. The model was extensively verified and validated against previous simulation results and experimental data. The Volt-Ampere characteristic (VAC) of the near-anode region depends on the anode cooling mechanism. The anode voltage is negative. In the case of strong anode cooling (water-cooled anode) when the anode is cold, temperature and plasma density gradients increase with current density, resulting in a decrease of the anode voltage (the absolute value increases). Falling VAC of the near-anode region suggests the arc constriction near the anode. Without anode cooling, the anode temperature increases significantly with the current density, leading to a drastic increase in the thermionic emission current from the anode. Correspondingly, the anode voltage increases to suppress the emission, and the opposite trend in the VAC is observed. Here, the results of simulations were found to be independent of sheath model used: collisional (fluid) or collisionless model gave the same plasma profiles for both near-anode and near-cathode regions.« less

Investigation of the short argon arc with hot anode. I. Numerical simulations of non-equilibrium effects in the near-electrode regions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khrabry, A.; Kaganovich, I. D.; Nemchinsky, V.

The atmospheric pressure arcs have recently found application in the production of nanoparticles. The distinguishing features of such arcs are small length and hot ablating anode characterized by intensive electron emission and radiation from its surface. We performed a one-dimensional modeling of argon arc, which shows that near-electrode effects of thermal and ionization non-equilibrium play an important role in the operation of a short arc, because the non-equilibrium regions are up to several millimeters long and are comparable to the arc length. The near-anode region is typically longer than the near-cathode region and its length depends more strongly on themore » current density. The model was extensively verified and validated against previous simulation results and experimental data. The Volt-Ampere characteristic (VAC) of the near-anode region depends on the anode cooling mechanism. The anode voltage is negative. In the case of strong anode cooling (water-cooled anode) when the anode is cold, temperature and plasma density gradients increase with current density, resulting in a decrease of the anode voltage (the absolute value increases). Falling VAC of the near-anode region suggests the arc constriction near the anode. Without anode cooling, the anode temperature increases significantly with the current density, leading to a drastic increase in the thermionic emission current from the anode. Correspondingly, the anode voltage increases to suppress the emission, and the opposite trend in the VAC is observed. Here, the results of simulations were found to be independent of sheath model used: collisional (fluid) or collisionless model gave the same plasma profiles for both near-anode and near-cathode regions.« less

Protective lithium ion conducting ceramic coating for lithium metal anodes and associate method

DOEpatents

Bates, John B.

1994-01-01

A battery structure including a cathode, a lithium metal anode and an electrolyte disposed between the lithium anode and the cathode utilizes a thin-film layer of lithium phosphorus oxynitride overlying so as to coat the lithium anode and thereby separate the lithium anode from the electrolyte. If desired, a preliminary layer of lithium nitride may be coated upon the lithium anode before the lithium phosphorous oxynitride is, in turn, coated upon the lithium anode so that the separation of the anode and the electrolyte is further enhanced. By coating the lithium anode with this material lay-up, the life of the battery is lengthened and the performance of the battery is enhanced.

Anode power in quasisteady magnetoplasmadynamic accelerators

NASA Technical Reports Server (NTRS)

Saber, A. J.; Jahn, R. G.

1978-01-01

Anode heat flux in a quasi-steady MPD accelerator has been measured directly and locally by thermocouples attached to the inside surface of a shell anode. These measurements show that over a range of arc current from 5.5 to 44 kA, and argon mass flow from 1 to 48 g/s, the fraction of the total arc power deposited in the anode decreases from 50% at 200 kW to 10% at 20 MW. A theoretical model of the anode heat transfer asserts that energy exchange between electrons and heavy particles in the plasma near the anode occurs over distances greater than the anode sheath thickness, and hence the usual anode fall voltage, electron temperature, and work function contributions to the anode heat flux are supplemented by a contribution from the interelectrode potential. Calculations of anode heat flux using the measured current density, plasma potential, and electron temperature in the plasma adjacent to the anode agree with the direct measurements and indicate that the decrease in anode power fraction at higher arc powers can be attributed to the smaller mean free paths in the interelectrode plasma.

Methods for solid electrolyte interphase formation and anode pre-lithiation of lithium ion capacitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raman, Santhanam; Xi, Xiaomei; Ye, Xiang-Rong

A method of pre-doping an anode of an energy storage device can include immersing the anode and a dopant source in an electrolyte, and coupling a substantially constant current between the anode and the dopant source. A method of pre-doping an anode of an energy storage device can include immersing the anode and a dopant source in an electrolyte, and coupling a substantially constant voltage across the anode and the dopant source. An energy storage device can include an anode having a lithium ion pre-doping level of about 60% to about 90%.

Aluminum low temperature smelting cell metal collection

DOEpatents

Beck, Theodore R.; Brown, Craig W.

2002-07-16

A method of producing aluminum in an electrolytic cell containing alumina dissolved in an electrolyte. The method comprises the steps of providing a molten salt electrolyte in an electrolytic cell having an anodic liner for containing the electrolyte, the liner having an anodic bottom and walls including at least one end wall extending upwardly from the anodic bottom, the anodic liner being substantially inert with respect to the molten electrolyte. A plurality of non-consumable anodes is provided and disposed vertically in the electrolyte. A plurality of cathodes is disposed vertically in the electrolyte in alternating relationship with the anodes. The anodes are electrically connected to the anodic liner. An electric current is passed through the anodic liner to the anodes, through the electrolyte to the cathodes, and aluminum is deposited on said cathodes. Oxygen bubbles are generated at the anodes and the anodic liner, the bubbles stirring the electrolyte. Molten aluminum is collected from the cathodes into a tubular member positioned underneath the cathodes. The tubular member is in liquid communication with each cathode to collect the molten aluminum therefrom while excluding electrolyte. Molten aluminum is delivered through the tubular member to a molten aluminum reservoir located substantially opposite the anodes and cathodes. The molten aluminum is collected from the cathodes and delivered to the reservoir while avoiding contact of the molten aluminum with the anodic bottom.

Does the dose-solubility ratio affect the mean dissolution time of drugs?

PubMed

Lánský, P; Weiss, M

1999-09-01

To present a new model for describing drug dissolution. On the basis of the new model to characterize the dissolution profile by the distribution function of the random dissolution time of a drug molecule, which generalizes the classical first order model. Instead of assuming a constant fractional dissolution rate, as in the classical model, it is considered that the fractional dissolution rate is a decreasing function of the dissolved amount controlled by the dose-solubility ratio. The differential equation derived from this assumption is solved and the distribution measures (half-dissolution time, mean dissolution time, relative dispersion of the dissolution time, dissolution time density, and fractional dissolution rate) are calculated. Finally, instead of monotonically decreasing the fractional dissolution rate, a generalization resulting in zero dissolution rate at time origin is introduced. The behavior of the model is divided into two regions defined by q, the ratio of the dose to the solubility level: q < 1 (complete dissolution of the dose, dissolution time) and q > 1 (saturation of the solution, saturation time). The singular case q = 1 is also treated and in this situation the mean as well as the relative dispersion of the dissolution time increase to infinity. The model was successfully fitted to data (1). This empirical model is descriptive without detailed physical reasoning behind its derivation. According to the model, the mean dissolution time is affected by the dose-solubility ratio. Although this prediction appears to be in accordance with preliminary application, further validation based on more suitable experimental data is required.

Growth behavior of anodic porous alumina formed in malic acid solution

NASA Astrophysics Data System (ADS)

Kikuchi, Tatsuya; Yamamoto, Tsuyoshi; Suzuki, Ryosuke O.

2013-11-01

The growth behavior of anodic porous alumina formed on aluminum by anodizing in malic acid solutions was investigated. High-purity aluminum plates were electropolished in CH3COOH/HClO4 solutions and then anodized in 0.5 M malic acid solutions at 293 K and constant cell voltages of 200-350 V. The anodic porous alumina grew on the aluminum substrate at voltages of 200-250 V, and a black, burned oxide film was formed at higher voltages. The nanopores of the anodic oxide were only formed at grain boundaries of the aluminum substrate during the initial stage of anodizing, and then the growth region extended to the entire aluminum surface as the anodizing time increased. The anodic porous alumina with several defects was formed by anodizing in malic acid solution at 250 V, and oxide cells were approximately 300-800 nm in diameter.

Effects of Bacillus subtilis endospore surface reactivity on the rate of forsterite dissolution

NASA Astrophysics Data System (ADS)

Harrold, Z.; Gorman-Lewis, D.

2013-12-01

Primary mineral dissolution products, such as silica (Si), calcium (Ca) and magnesium (Mg), play an important role in numerous biologic and geochemical cycles including microbial metabolism, plant growth and secondary mineral precipitation. The flux of these and other dissolution products into the environment is largely controlled by the rate of primary silicate mineral dissolution. Bacteria, a ubiquitous component in water-rock systems, are known to facilitate mineral dissolution and may play a substantial role in determining the overall flux of dissolution products into the environment. Bacterial cell walls are complex and highly reactive organic surfaces that can affect mineral dissolution rates directly through microbe-mineral adsorption or indirectly by complexing dissolution products. The effect of bacterial surface adsorption on chemical weathering rates may even outweigh the influence of active processes in environments where a high proportion of cells are metabolically dormant or cell metabolism is slow. Complications associated with eliminating or accounting for ongoing metabolic processes in long-term dissolution studies have made it challenging to isolate the influence of cell wall interactions on mineral dissolution rates. We utilized Bacillus subtilis endospores, a robust and metabolically dormant cell type, to isolate and quantify the effects of bacterial surface reactivity on forsterite (Mg2SiO4) dissolution rates. We measured the influence of both direct and indirect microbe-mineral interactions on forsterite dissolution. Indirect pathways were isolated using dialysis tubing to prevent mineral-microbe contact while allowing free exchange of dissolved mineral products and endospore-ion adsorption. Homogenous experimental assays allowed both direct microbe-mineral and indirect microbe-ion interactions to affect forsterite dissolution rates. Dissolution rates were calculated based on silica concentrations and zero-order dissolution kinetics. Additional analyses including Mg concentrations, microprobe and BET analyses support mineral dissolution rate calculations and stoichiometry considerations. All experimental assays containing endospores show increased forsterite dissolution rates relative to abiotic controls. Forsterite dissolution rates increased by approximately one order of magnitude in dialysis bound, biotic experiments relative to abiotic assays. Homogenous biotic assays exhibited a more complex dissolution rate profile that changes over time. All microbially mediated forsterite dissolution rates returned to abiotic control rates after 10 to 15 days of incubation. This shift in dissolution rate likely corresponds to maximum endospore surface adsorption capacity. The Bacillus subtilis endospore surface serves as a first-order proxy for studying the effect of metabolizing microbe surfaces on silicate dissolution rates. Comparisons with published abiotic, microbial, and organic acid mediated forsterite dissolution rates will provide insight on the importance of bacterial surfaces in primary mineral dissolution processes.

[Isolation and identification of electrochemically active microorganism from micro-aerobic environment].

PubMed

Wu, Song; Xiao, Yong; Zheng, Zhi-Yong; Zheng, Yue; Yang, Zhao-Hui; Zhao, Feng

2014-10-01

Extracellular electron transfer of electrochemically active microorganism plays vital role in biogeochemical cycling of metals and carbon and in biosynthesis of bioenergy. Compared to anaerobic anode, micro-aerobic anode captures more energy from microbial fuel cell. However, most of previous researches focused on functioning bacteria in anaerobic anode, functioning bacteria in micro-aerobic anode was rarely studied. Herein, we used the traditional aerobic screening technology to isolate functioning bacteria from a micro-aerobic anode. Three pure cultures Aeromonas sp. WS-XY2, Citrobacter sp. WS-XY3 and Bacterium strain WS-XY4 were obtained. WS-XY2 and WS-XY3 were belonged to Proteobacteria, whereas WS-XY4 was possibly a new species. Cyclic voltammetry and chronoamperometry analysis demonstrated all of them showed the electrochemical activity by direct extracellular electron transfer, and micro-aerobic anode could select bacteria that have similar electrochemical activity to proliferate on the anode. We further conclude that functioning bacteria in micro-aerobic anode are more efficient than that of anaerobic anode may be the reason that micro-aerobic anode has better performance than anaerobic anode. Therefore, a thorough study of functioning bacteria in micro-aerobic anode will significantly promote the energy recovery from microbial fuel cell.

Structural changes of anodic layer on titanium in sulfate solution as a function of anodization duration in constant current mode

NASA Astrophysics Data System (ADS)

Komiya, Shinji; Sakamoto, Kouta; Ohtsu, Naofumi

2014-03-01

The present study investigated the effect of anodization time, in constant current mode, on the anodic oxide layer formed on titanium (Ti). Anodization of the Ti substrate was　carried out in a 0.1 M (NH4)2SO4 aqueous solution with reaction times of various durations, after which the characteristics and photocatalytic activity were investigated in detail. The TiO2 layer fabricated in a short duration exhibited comparatively flat surface morphology and an anatase-type crystal structure. This layer acted as a photocatalyst only under ultraviolet light (UV) illumination. Upon prolonging the anodization, the layer structure changed drastically. The surface morphology became rough, and the crystal structure changed to rutile-type TiO2. Furthermore, the layer showed photocatalytic activity both under UV and visible light illumination. Further anodization increased the amount of methylene blue (MB) adsorbed on the surface, but did not cause additional change to the structure of the anodic layer. The surface morphology and crystal structure of the anodic layer were predominantly controlled by the anodization time; thus, the anodization time is an important parameter for controlling the characteristics of the anodic layer.

A novel determination of calcite dissolution kinetics in seawater

NASA Astrophysics Data System (ADS)

Subhas, Adam V.; Rollins, Nick E.; Berelson, William M.; Dong, Sijia; Erez, Jonathan; Adkins, Jess F.

2015-12-01

We present a novel determination of the dissolution kinetics of inorganic calcite in seawater. We dissolved 13 C -labeled calcite in unlabeled seawater, and traced the evolving δ13 C composition of the fluid over time to establish dissolution rates. This method provides sensitive determinations of dissolution rate, which we couple with tight constraints on both seawater saturation state and surface area of the dissolving minerals. We have determined dissolution rates for two different abiotic calcite materials and three different grain sizes. Near-equilibrium dissolution rates are highly nonlinear, and are well normalized by geometric surface area, giving an empirical dissolution rate dependence on saturation state (Ω) of: This result substantiates the non-linear response of calcite dissolution to undersaturation. The bulk dissolution rate constant calculated here is in excellent agreement with those determined in far from equilibrium and dilute solution experiments. Plots of dissolution versus undersaturation indicates the presence of at least two dissolution mechanisms, implying a criticality in the calcite-seawater system. Finally, our new rate determination has implications for modeling of pelagic and seafloor dissolution. Nonlinear dissolution kinetics in a simple 1-D lysocline model indicate a possible transition from kinetic to diffusive control with increasing water depth, and also confirm the importance of respiration-driven dissolution in setting the shape of the calcite lysocline.

Synthesis of self-organized TiO{sub 2} nanotube arrays: Microstructural, stereoscopic, and topographic studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Quiroz, Heiddy P., E-mail: hpquirozg@unal.edu.co; Dussan, A., E-mail: adussanc@unal.edu.co

2016-08-07

In this work, titanium dioxide nanotubes were prepared by using titanium foils via electrochemical anodization in ethylene glycol solutions containing different amounts of water and fluoride in the ranges of 1%–3% and 0.15%–0.5%, respectively, to determine their effects on morphology, optical, and crystalline structure properties. Annealing processes were performed on all samples in the range between 273 and 723 K. Morphology and structure properties of the samples were studied by scanning electron microscopy, X-ray diffraction (XRD), and transmission electron microscopy. Titanium dioxide (TiO{sub 2}) nanotubes, through anodization method, are strongly influenced by conditions, like fluoride concentration and applied voltages. Tube lengthsmore » between 2 and 7 μm were obtained, exhibiting different diameters and wall thicknesses. When alternating voltage was applied, the outer surface of the nanotubes exhibited evenly spaced ring-shaped regions, while smooth tubes were observed when constant voltage was applied. Reflection peaks, corresponding to Brookite, Anatase, and Rutile, of TiO{sub 2} phases, were observed from the XRD pattern. These phases were corroborated via μXRD measurements, and the Ti{sub 3}O{sub 5} phase was also observed in detail. Absorption coefficient (α), optical band gap (Eg), and extinction coefficient (ε) of TiO{sub 2} nanotubes were calculated by transmittance spectra in the UV–Vis range. Strong absorption was noted in the UV region from reflectance and absorbance measurements. A correlation between synthesis parameters and physical properties is presented.« less

Implosion dynamics of a megampere wire-array Z-pinch with an inner low-density foam shell at the Angara-5-1 facility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aleksandrov, V. V.; Bolkhovitinov, E. A.; Volkov, G. S., E-mail: volkov@triniti.ru

The implosion dynamics of a pinch with a highly inhomogeneous initial axial distribution of the load mass was studied experimentally. A cascade array consisting of a double nested tungsten wire array and a coaxial inner cylindrical shell located symmetrically with respect to the high-voltage electrodes was used as a load of the Angara-5-1 high-current generator. The cylindrical foam shell was half as long as the cathode− anode gap, and its diameter was equal to the diameter of the inner wire array. It is shown experimentally that two stages are typical of the implosion dynamics of such a load: the formationmore » of two separate pinches formed as a result of implosion of the wire array near the cathode and anode and the subsequent implosion of the central part of the load containing the cylindrical foam shell. The conditions are determined at which the implosion of the central part of the pinch with the foam cylinder is preceded by intense irradiation of the foam with the soft X-ray (SXR) emission generated by the near-electrode pinches and converting it into the plasma state. Using such a load, which models the main elements of the scheme of a dynamic hohlraum for inertial confinement fusion, it is possible to increase the efficiency of interaction between the outer accelerated plasma sheath and the inner foam shell by preionizing the foam with the SXR emission of the near-electrode pinches.« less

A 200 W Hall thruster with hollow indented anode

NASA Astrophysics Data System (ADS)

Ding, Yongjie; Sun, Hezhi; Wei, Liqiu; Li, Peng; Su, Hongbo; Peng, Wuji; Yu, Daren

2017-10-01

A hollow indented anode is proposed for increasing the neutral gas density in a discharge channel, in order to improve the performance of the thruster. The experimental results show that a hollow indented anode structure can effectively improve the performance, compared to a hollow straight anode under similar operating conditions, in terms of thrust, propellant utilization, ionization rate, and anode efficiency. Furthermore, simulations show that the indented anode can effectively increase the neutral gas density in a discharge channel and on the centerline of the channel, compared to a hollow straight anode. In addition, it can increase the ionization rate in the channel and the pre-ionization in the anode. Therefore, the hollow indented anode could be considered as an important design idea for improving thruster performance.

Performance of Zinc Anodes for Cathodic Protection of Reinforced Concrete Bridges

DOE Office of Scientific and Technical Information (OSTI.GOV)

Covino, Bernard S. Jr.; Cramer, Stephen D.; Bullard, Sophie J.

2002-03-01

Operation of thermal spray zinc (Zn) anodes for cathodic protection (CP) of reinforced concrete structures was investigated in laboratory and field studies conducted by the Albany Research Center (ARC) in collaboration with the Oregon Department of Transportation. The purposes of the research presented in this report were: evaluate the need for preheating concrete to improve the adhesion of the anode; estimate the service life of thermal spray Zn CP anodes; determine the optimum thickness for Zn CP anodes; characterize the anode-concrete interfacial chemistry; and correlate field and laboratory results. Laboratory studies involved accelerated electrochemical aging of thermal sprayed Zn anodesmore » on concrete slabs, some of which were periodically wetted while others were unwetted. Concrete used in the slabs contained either 1.2 or 3 kg NaCl /m3 (2 or 5 lbs NaCl /yd3) as part of the concrete mix design. The Zn anodes were applied to the slabs using the twin wire arc-spray technique. Half of the slabs were preheated to 120-160 C (250-320 F) to improve the initial Zn anode bond strength and the other half were not. Accelerated aging was done at a current density of 0.032 A/m2 (3 mA/ft2), 15 times that used on Oregon DOT Coastal bridges, i.e, . 0.0022 A/m2 (0.2 mA/ft2) Cores from the Cape Creek Bridge (OR), the Richmond San Rafael Bridge (CA), and the East Camino Underpass (CA) were used to study the anode-concrete interfacial chemistry, to relate the chemistry to electrochemical age at the time of sampling, and to compare the chemistry of the field anodes to the chemistry of anodes from the laboratory studies. Cores from a CALTRANS study of a silane sealant used prior to the application of the Zn anodes and cores with galvanized rebar from the Longbird Bridge (Bermuda) were also studied. Aged laboratory and field anodes were characterized by measuring some or all of the following parameters: thickness, bond strength, anode-concrete interfacial chemistry, bulk chemistry, anode resistance, circuit resistance, electrochemical age, and air and water permeability. Models are presented for the operation of periodically-wetted and unwetted thermal spray Zn anodes from the initial energizing of the anode to the end of its service life. The models were developed in terms of bond strength, circuit resistance, anode-concrete interfacial chemistry, electrochemical age, and anode condition. The most significant results of the research are: (1) preheating concrete surfaces prior to coating with Zn is unnecessary; (2) anodes generally fail due to loss of bond strength rather than Zn consumption; (3) Unwetted anodes fail more quickly than periodically-wetted anodes; (4) 0.47-0.60 mm (12-15 mil) anode thickness is adequate for most Oregon DOT coastal impressed current CP (ICCP) installations; (5) based on bond strength, thermal spray Zn ICCP anode service life is approximately 27 years at 0.0022 A/m2 (0.2 mA/ft2); (6) anode reaction products alter the anode-concrete interface by rejecting Ca from the cement paste, by replacing it with Zn, and by the accumulation of a Zn mineral layer that includes chloride and sulfur compounds; (7) CP system circuit resistance provides an effective means for monitoring the condition of Zn ICCP anodes as they age.« less

Ni-SDC cermet anode for medium-temperature solid oxide fuel cell with lanthanum gallate electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Xinge; Ohara, Satoshi; Maric, Radenka; Mukai, Kazuo; Fukui, Takehisa; Yoshida, Hiroyuki; Nishimura, Masayoshi; Inagaki, Toru; Miura, Kazuhiro

The polarization properties and microstructure of Ni-SDC (samaria-doped ceria) cermet anodes prepared from spray pyrolysis (SP) composite powder, and element interface diffusion between the anode and a La 0.9Sr 0.1Ga 0.8Mg 0.2O 3- δ (LSGM) electrolyte are investigated as a function of anode sintering temperature. The anode sintered at 1250°C displays minimum anode polarization (with anode ohmic loss), while the anode prepared at 1300°C has the best electrochemical overpotential, viz., 27 mV at 300 mA cm -2 operating at 800°C. The anode ohmic loss gradually increases with increase in the sintering temperature at levels below 1300°C, and sharply increases at 1350°C. Electron micrographs show a clear grain growth at sintering temperatures higher than 1300°C. The anode microstructure appears to be optimized at 1300°C, in which nickel particles form a network with well-connected SDC particles finely distributed over the surfaces of the nickel particles. The anode sintered at 1350°C has severe grain growth and an apparent interface diffusion of nickel from the anode to the electrolyte. The nickel interface diffusion is assumed to be the main reason for the increment in ohmic loss, and the resulting loss in anode performance. The findings suggest that sintering Ni-SDC composite powder near 1250°C is the best method to prepare the anode on a LSGM electrolyte.

Position-sensitive proportional counter with low-resistance metal-wire anode

DOEpatents

Kopp, Manfred K.

1980-01-01

A position-sensitive proportional counter circuit is provided which allows the use of a conventional (low-resistance, metal-wire anode) proportional counter for spatial resolution of an ionizing event along the anode of the counter. A pair of specially designed active-capacitance preamplifiers are used to terminate the anode ends wherein the anode is treated as an RC line. The preamplifiers act as stabilized active capacitance loads and each is composed of a series-feedback, low-noise amplifier, a unity-gain, shunt-feedback amplifier whose output is connected through a feedback capacitor to the series-feedback amplifier input. The stabilized capacitance loading of the anode allows distributed RC-line position encoding and subsequent time difference decoding by sensing the difference in rise times of pulses at the anode ends where the difference is primarily in response to the distributed capacitance along the anode. This allows the use of lower resistance wire anodes for spatial radiation detection which simplifies the counter construction and handling of the anodes, and stabilizes the anode resistivity at high count rates (>10.sup.6 counts/sec).

Geochemistry of shallow ground water in coastal plain environments in the southeastern United States: Implications for aquifer susceptibility

USGS Publications Warehouse

Tesoriero, A.J.; Spruill, T.B.; Eimers, J.L.

2004-01-01

Ground-water chemistry data from coastal plain environments have been examined to determine the geochemical conditions and processes that occur in these areas and assess their implications for aquifer susceptibility. Two distinct geochemical environments were studied to represent a range of conditions: an inner coastal plain setting having more well-drained soils and lower organic carbon (C) content and an outer coastal plain environment that has more poorly drained soils and high organic C content. Higher concentrations of most major ions and dissolved inorganic and organic C in the outer coastal plain setting indicate a greater degree of mineral dissolution and organic matter oxidation. Accordingly, outer coastal plain waters are more reducing than inner coastal plain waters. Low dissolved oxygen (O2) and nitrate (NO 3-) concentrations and high iron (Fe) concentrations indicate that ferric iron (Fe (III)) is an important electron acceptor in this setting, while dissolved O2 is the most common terminal electron acceptor in the inner coastal plain setting. The presence of a wide range of redox conditions in the shallow aquifer system examined here underscores the importance of providing a detailed geochemical characterization of ground water when assessing the intrinsic susceptibility of coastal plain settings. The greater prevalence of aerobic conditions in the inner coastal plain setting makes this region more susceptible to contamination by constituents that are more stable under these conditions and is consistent with the significantly (p<0.05) higher concentrations of NO3- found in this setting. Herbicides and their transformation products were frequently detected (36% of wells sampled), however concentrations were typically low (<0.1 ??g/L). Shallow water table depths often found in coastal plain settings may result in an increased risk of the detection of pesticides (e.g., alachlor) that degrade rapidly in the unsaturated zone.

Geochemistry of host rocks in the Howards Pass district, Yukon-Northwest Territories, Canada: implications for sedimentary environments of Zn-Pb and phosphate mineralization

USGS Publications Warehouse

Slack, John F.; Falck, Hendrik; Kelley, Karen D.; Xue, Gabriel G.

2017-01-01

Detailed lithogeochemical data are reported here on early Paleozoic sedimentary rocks that host the large Howards Pass stratiform Zn-Pb deposits in Yukon-Northwest Territories. Redox-sensitive trace elements (Mo, Re, V, U) and Ce anomalies in members of the Duo Lake Formation record significant environmental changes. During the deposition of lower footwall units (Pyritic siliceous and Calcareous mudstone members), bottom waters were anoxic and sulphidic, respectively; these members formed in a marginal basin that may have become increasingly restricted with time. Relative to lower members, a major environmental change is proposed for deposition of the overlying Lower cherty mudstone member, which contains phosphorite beds up to ∼0.8 m thick in the upper part, near the base of the Zn-Pb deposits. The presence of these beds, together with models for modern phosphorite formation, suggests P input from an upwelling system and phosphorite deposition in an upper slope or outer shelf setting. The overlying Active mudstone member contains stratabound to stratiform Zn-Pb deposits within black mudstone and gray calcareous mudstone. Data for unmineralized black mudstone in this member indicate deposition under diverse redox conditions from suboxic to sulphidic. Especially distinctive in this member are uniformly low ratios of light to heavy rare earth elements that are unique within the Duo Lake Formation, attributed here to the dissolution of sedimentary apatite by downward-percolating acidic metalliferous brines. Strata that overlie the Active member (Upper siliceous mudstone member) consist mainly of black mudstone with thin (0.5–1.5 cm) laminae of fine-grained apatite, recording continued deposition on an upper slope or outer shelf under predominantly suboxic bottom waters. Results of this study suggest that exploration for similar stratiform sediment-hosted Zn-Pb deposits should include the outer parts of ancient continental margins, especially at and near stratigraphic transitions from marginal basin facies to overlying slope or shelf facies.

Simulation results of influence of constricted arc column on anode deformation and melting pool swirl in vacuum arcs with AMF contacts

NASA Astrophysics Data System (ADS)

Wang, Lijun; Zhang, Xiao; Huang, Xiaolong; Jia, Shenli

2017-11-01

In the process of vacuum arc breaking, the energy injected into the anode will cause anode melting, evaporation, and deformation, resulting in the formation of the anode melting pool. The anode activities have great influence on the arc behavior. When the arc current is large enough, even the influence of axial magnetic field is considered, the arc column still is in contraction state, which means the arc burns only on a part of the electrode. In this paper, the model of anode melting pool deformation and rotation is used, and the model includes anode melting and solidification module, magneto-hydro-dynamic module of the anode melting pool, the volume of fraction method, and the current continuity equation. In this paper, the diffuse arc area is selected as 100%, 75%, and 50%, respectively. The anode temperature and deformation, the anode melting layer thickness, and the rotational velocity of the anode melting pool are obtained. The results show that when the current is at 17.5 kA (rms) and the diffuse arc area is 100%, the anode's maximum temperature is 1477 K and the crater depth is 0.83 mm. But when the diffuse arc areas are 75% and 50%, the anode's maximum temperatures reach 1500 K and 1761 K, and the crater depths reach 1.2 mm and 3 mm, respectively. Arc contraction will lead to more serious anode deformation. A similar result is obtained when the simulation current is 12.5 kA. Under the similar situation, the simulation results in the crater depth, the residual melt layer thickness, the rotational speed of the melting pool, and the maximum temperature of the anode at current zero are in good agreement with the experimental results.

Corrosion Prevention of Steel Reinforcement in 7.5% NaCl Solution using Pure Magnesium Anode

NASA Astrophysics Data System (ADS)

Iyer Murthy, Yogesh; Gandhi, Sumit; Kumar, Abhishek

2018-03-01

The current work investigates the performance of pure Magnesium on corrosion prevention of steel reinforcements by way of sacrificial anoding. Two set of six steel reinforcements were tested for half-cell potential, weight loss, anode efficiency and tensile strength for each of the sacrificial anodes in a high chloride atmosphere of 7.5% NaCl in tap water. Significant reduction in weight of anode was observed during the initial 12 days. The reduction in weight of steel reinforcements tied with anodes was found to be negligible, while that of reinforcements without anodes was significantly higher. Five distinct zones of corrosion were observed during the test. The tensile strength of steel cathodically protected by Mg alloy anodes was found less affected. It could be concluded that pure Mg anode provides an effective way of corrosion mitigation.

Movable anode x-ray source with enhanced anode cooling

DOEpatents

Bird, C.R.; Rockett, P.D.

1987-08-04

An x-ray source is disclosed having a cathode and a disc-shaped anode with a peripheral surface at constant radius from the anode axis opposed to the cathode. The anode has stub axle sections rotatably carried in heat conducting bearing plates which are mounted by thermoelectric coolers to bellows which normally bias the bearing plates to a retracted position spaced from opposing anode side faces. The bellows cooperate with the x-ray source mounting structure for forming closed passages for heat transport fluid. Flow of such fluid under pressure expands the bellows and brings the bearing plates into heat conducting contact with the anode side faces. A worm gear is mounted on a shaft and engages serrations in the anode periphery for rotating the anode when flow of coolant is terminated between x-ray emission events. 5 figs.

Movable anode x-ray source with enhanced anode cooling

DOEpatents

Bird, Charles R.; Rockett, Paul D.

1987-01-01

An x-ray source having a cathode and a disc-shaped anode with a peripheral surface at constant radius from the anode axis opposed to the cathode. The anode has stub axle sections rotatably carried in heat conducting bearing plates which are mounted by thermoelectric coolers to bellows which normally bias the bearing plates to a retracted position spaced from opposing anode side faces. The bellows cooperate with the x-ray source mounting structure for forming closed passages for heat transport fluid. Flow of such fluid under pressure expands the bellows and brings the bearing plates into heat conducting contact with the anode side faces. A worm gear is mounted on a shaft and engages serrations in the anode periphery for rotating the anode when flow of coolant is terminated between x-ray emission events.

FLUORINE CELL ANODE ASSEMBLY

DOEpatents

Cable, R.E.; Goode, W.B. Jr.; Henderson, W.K.; Montillon, G.H.

1962-06-26

An improved anode assembly is deslgned for use in electrolytlc cells ln the productlon of hydrogen and fluorlne from a moIten electrolyte. The anode assembly comprises a copper post, a copper hanger supported by the post, a plurality of carbon anode members, and bolt means for clamplng half of the anode members to one slde of the hanger and for clamplng the other half of the anode members to the other slde of the hanger. The heads of the clamplng bolts are recessed withln the anode members and carbon plugs are inserted ln the recesses above the bolt heads to protect the boIts agalnst corroslon. A copper washer is provided under the head of each clamplng boIt such that the anode members can be tightly clamped to the hanger with a resultant low anode jolnt resistance. (AEC)

Influence of anodization parameters on the volume expansion of anodic aluminum oxide formed in mixed solution of phosphoric and oxalic acids

NASA Astrophysics Data System (ADS)

Kao, Tzung-Ta; Chang, Yao-Chung

2014-01-01

The growth of anodic alumina oxide was conducted in the mixed solution of phosphoric and oxalic acids. The influence of anodizing voltage, electrolyte temperature, and concentration of phosphoric and oxalic acids on the volume expansion of anodic aluminum oxide has been investigated. Either anodizing parameter is chosen to its full extent of range that allows the anodization process to be conducted without electric breakdown and to explore the highest possible volume expansion factor. The volume expansion factors were found to vary between 1.25 and 1.9 depending on the anodizing parameters. The variation is explained in connection with electric field, ion transport number, temperature effect, concentration, and activity of acids. The formation of anodic porous alumina at anodizing voltage 160 V in 1.1 M phosphoric acid mixed with 0.14 M oxalic acid at 2 °C showed the peak volume expansion factor of 1.9 and the corresponding moderate growth rate of 168 nm/min.

High-speed MCP anodes for high time resolution low-energy charged particle spectrometers

NASA Astrophysics Data System (ADS)

Saito, Yoshifumi; Yokota, Shoichiro; Asamura, Kazushi; Krieger, Amanda

2017-02-01

The time resolution of low-energy charged particle measurements is becoming higher and higher. In order to realize high time resolution measurements, a 1-D circular delay line anode has been developed as a high-speed microchannel plate (MCP) anode. The maximum count rate of the 1-D circular delay line anode is around 1 × 107/s/360°, which is much higher than the widely used resistive anode, whose maximum count rate is around 1 × 106/s/360°. In order to achieve much higher speeds, an MCP anode with application-specific integrated circuit (ASIC) has been developed. We have decided to adopt an anode configuration in which a discrete anode is formed on a ceramic substrate, and a bare ASIC chip is installed on the back of the ceramic. It has been found that the anode can detect at a high count rate of 2 × 108/s/360°. Developments in both delay line and discrete anodes, as well as readout electronics, will be reviewed.

Discriminative Dissolution Method for Benzoyl Metronidazole Oral Suspension.

PubMed

da Silva, Aline Santos; da Rosa Silva, Carlos Eduardo; Paula, Fávero Reisdorfer; da Silva, Fabiana Ernestina Barcellos

2016-06-01

A dissolution method for benzoyl metronidazole (BMZ) oral suspensions was developed and validated using a high-performance liquid chromatography (HPLC) method. After determination of sink conditions, dissolution profiles were evaluated using different dissolution media and agitation speeds. The sample insertion mode in dissolution media was also evaluated. The best conditions were obtained using a paddle, 50 rpm stirring speed, simulated gastric fluid (without pepsin) as the dissolution medium, and sample insertion by a syringe. These conditions were suitable for providing sink conditions and discriminatory power between different formulations. Through the tested conditions, the results can be considered specific, linear, precise, accurate, and robust. The dissolution profiles of five samples were compared using the similarity factor (f 2) and dissolution efficiency. The dissolution kinetics were evaluated and described by the Weibull model. Whereas there is no monograph for this pharmaceutical formulation, the dissolution method proposed can be considered suitable for quality control and dissolution profile comparison of different commercial formulations.

Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Harrison, Anna L.; Eisenhauer, Anton; Dietzel, Martin

2017-12-01

In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 - δ88/86Srfluid = -0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = -0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7-8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr isotopes as environmental proxies in aquatic environments.

Stainless steel anodes for alkaline water electrolysis and methods of making

DOEpatents

Soloveichik, Grigorii Lev

2014-01-21

The corrosion resistance of stainless steel anodes for use in alkaline water electrolysis was increased by immersion of the stainless steel anode into a caustic solution prior to electrolysis. Also disclosed herein are electrolyzers employing the so-treated stainless steel anodes. The pre-treatment process provides a stainless steel anode that has a higher corrosion resistance than an untreated stainless steel anode of the same composition.

The plant cell wall in the feeding sites of cyst nematodes.

PubMed

Bohlmann, Holger; Sobczak, Miroslaw

2014-01-01

Plant parasitic cyst nematodes (genera Heterodera and Globodera) are serious pests for many crops. They enter the host roots as migratory second stage juveniles (J2) and migrate intracellularly toward the vascular cylinder using their stylet and a set of cell wall degrading enzymes produced in the pharyngeal glands. They select an initial syncytial cell (ISC) within the vascular cylinder or inner cortex layers to induce the formation of a multicellular feeding site called a syncytium, which is the only source of nutrients for the parasite during its entire life. A syncytium can consist of more than hundred cells whose protoplasts are fused together through local cell wall dissolutions. While the nematode produces a cocktail of cell wall degrading and modifying enzymes during migration through the root, the cell wall degradations occurring during syncytium development are due to the plants own cell wall modifying and degrading proteins. The outer syncytial cell wall thickens to withstand the increasing osmotic pressure inside the syncytium. Furthermore, pronounced cell wall ingrowths can be formed on the outer syncytial wall at the interface with xylem vessels. They increase the surface of the symplast-apoplast interface, thus enhancing nutrient uptake into the syncytium. Processes of cell wall degradation, synthesis and modification in the syncytium are facilitated by a variety of plant proteins and enzymes including expansins, glucanases, pectate lyases and cellulose synthases, which are produced inside the syncytium or in cells surrounding the syncytium.

Properties of a new type Al/Pb-0.3%Ag alloy composite anode for zinc electrowinning

NASA Astrophysics Data System (ADS)

Yang, Hai-tao; Liu, Huan-rong; Zhang, Yong-chun; Chen, Bu-ming; Guo, Zhong-cheng; Xu, Rui-dong

2013-10-01

An Al/Pb-0.3%Ag alloy composite anode was produced via composite casting. Its electrocatalytic activity for the oxygen evolution reaction and corrosion resistance was evaluated by anodic polarization curves and accelerated corrosion test, respectively. The microscopic morphologies of the anode section and anodic oxidation layer during accelerated corrosion test were obtained by scanning electron microscopy. It is found that the composite anode (hard anodizing) displays a more compact interfacial combination and a better adhesive strength than plating tin. Compared with industrial Pb-0.3%Ag anodes, the oxygen evolution overpotentials of Al/Pb-0.3%Ag alloy (hard anodizing) and Al/Pb-0.3%Ag alloy (plating tin) at 500 A·m-2 were lower by 57 and 14 mV, respectively. Furthermore, the corrosion rates of Pb-0.3%Ag alloy, Al/Pb-0.3%Ag alloy (hard anodizing), and Al/Pb-0.3%Ag alloy (plating tin) were 13.977, 9.487, and 11.824 g·m-2·h-1, respectively, in accelerated corrosion test for 8 h at 2000 A·m-2. The anodic oxidation layer of Al/Pb-0.3%Ag alloy (hard anodizing) is more compact than Pb-0.3%Ag alloy and Al/Pb-0.3%Ag alloy (plating tin) after the test.

Application of Dst Interpretation Results by Log - Log Method in the Pore Space Type Estimation for the Upper Jurassic Carbonate Reservoir Rocks of the Carpathian Foredeep Basement / Interpretacja Testów Wykonywanych Rurowymi Próbnikami Złoża - Rpz w Skałach Węglanowych Górnej Jury Podłoża Zapadliska Przedkarpackiego

NASA Astrophysics Data System (ADS)

Dubiel, Stanisław; Zubrzycki, Adam; Rybicki, Czesław; Maruta, Michał

2012-11-01

In the south part of the Carpathian Foredeep basement, between Bochnia and Ropczyce, the Upper Jurassic (Oxfordian, Kimmeridian and Tithonian) carbonate complex plays important role as a hydrocarbon bearing formation. It consists of shallow marine carbonates deposited in environments of the outer carbonate ramp as reef limestones (dolomites), microbial - sponge or coral biostromes and marly or micrite limestones as well. The inner pore space system of these rocks was affected by different diagenetic processes as calcite cementation, dissolution, dolomitization and most probably by tectonic fracturing as well. These phenomena have modified pore space systems within limestone / dolomite series forming more or less developed reservoir zones (horizons). According to the interpretation of DST results (analysis of pressure build up curves by log - log method) for 11 intervals (marked out previously by well logging due to porosity increase readings) within the Upper Jurassic formation 3 types of pore/fracture space systems were distinguished: - type I - fracture - vuggy porosity system in which fractures connecting voids and vugs within organogenic carbonates are of great importance for medium flow; - type II - vuggy - fracture porosity system where a pore space consists of weak connected voids and intergranular/intercrystalline pores with minor influence of fractures; - type III - cavern porosity system in which a secondary porosity is developed due to dolomitization and cement/grain dissolution processes.

Formulation, in vitro evaluation and study of variables on tri-layered gastro-retentive delivery system of diltiazem HCl.

PubMed

Raut Desai, Shilpa; Rohera, Bhagwan D

2014-03-01

Tri-layered floating tablets using only one grade of polyethylene oxide (PEO) would enable easy manufacturing, reproducibility and controlled release for highly soluble drugs. To evaluate the potential of PEO as a sole polymer for the controlled release and to study the effect of formulation variables on release and gastric retention of highly soluble Diltiazem hydrochloride (DTZ). Tablets were compressed with middle layer consisting of drug and polymer while outer layers consisted of polymer with sodium bicarbonate. Design of formulation to obtain 12 h, zero-order release and rapid floatation was done by varying the grades, quantity of PEO and sodium bicarbonate. Dissolution data were fitted in drug release models and swelling/erosion studies were undertaken to verify the drug release mechanism. Effect of formulation variables and tablet surface morphology using scanning electron microscopy were studied. The optimized formula passed the criteria of USP dissolution test I and exhibited floating lag-time of 3-4 min. Drug release was faster from low molecular weight (MW) PEO as compared to high MW. With an increase in the amount of sodium bicarbonate, faster buoyancy was achieved due to the increased CO2 gas formation. Drug release followed zero-order and gave a good fit to the Korsmeyer-Peppas model, which suggested that drug release was due to diffusion through polymer swelling. Zero-order, controlled release profile with the desired buoyancy can be achieved by using optimum formula quantities of sodium bicarbonate and polymer. The tri-layered system shows promising delivery of DTZ, and possibly other water-soluble drugs.

[Dissolution behavior of Fuzi Lizhong pill based on simultaneous determination of two components in Glycyrrhizae Radix et Rhizoma].

PubMed

Jiang, Mao-Yuan; Zhang, Zhen; Shi, Jin-Feng; Zhang, Jin-Ming; Fu, Chao-Mei; Lin, Xia; Liu, Yu-Mei

2018-03-01

To preliminarily investigate the dissolution behavior of Fuzi Lizhong pill, provide the basis for its quality control and lay foundation for in vivo dissolution behavior by determining the dissolution rate of liquiritin and glycyrrhizic acid. High-performance liquid chromatography (HPLC) method for simultaneous content determination of the two active ingredients of liquiritin and glycyrrhizic acid in Fuzi Lizhong pill was established; The dissolution amount of these two active ingredients in fifteen batches of Fuzi Lizhong pill from five manufacturers was obtained at different time points, and then the cumulative dissolution rate was calculated and cumulative dissolution curve was drawn. The similarity of cumulative dissolution curve of different batches was evaluated based on the same factory, and the similarity of cumulative dissolution curve of different factories was evaluated based on the same active ingredients. The dissolution model of Fuzi Lizhong pill based on two kinds of active ingredients was established by fitting with the dissolution data. The best dissolution medium was 0.25% sodium lauryl sulfate. The dissolution behavior of liquiritin and glycyrrhizic acid in Fuzi Lizhong pill was basically the same and sustained release in 48 h. Three batches of the factories (factory 2, factory 3, factory 4 and factory 5) appeared to be similar in dissolution behavior, indicating similarity in dissolution behavior in most factories. Two of the three batches from factory 1 appeared to be not similar in dissolution behavior of liquiritin and glycyrrhizic acid. The dissolution data of the effective ingredients from different factories were same in fitting, and Weibull model was the best model in these batches. Fuzi Lizhong pill in 15 batches from 5 factories showed sustained release in 48 h, proving obviously slow releasing characteristics "pill is lenitive and keeps a long-time efficacy". The generally good dissolution behavior also suggested that quality of different batches from most factories was stable. The dissolution behavior of liquiritin and glycyrrhizic acid in different factories was different, suggesting that the source of medicinal materials and preparation technology parameters in five factories were different. Copyright© by the Chinese Pharmaceutical Association.

Optimization of Dissolution Compartments in a Biorelevant Dissolution Apparatus Golem v2, Supported by Multivariate Analysis.

PubMed

Stupák, Ivan; Pavloková, Sylvie; Vysloužil, Jakub; Dohnal, Jiří; Čulen, Martin

2017-11-23

Biorelevant dissolution instruments represent an important tool for pharmaceutical research and development. These instruments are designed to simulate the dissolution of drug formulations in conditions most closely mimicking the gastrointestinal tract. In this work, we focused on the optimization of dissolution compartments/vessels for an updated version of the biorelevant dissolution apparatus-Golem v2. We designed eight compartments of uniform size but different inner geometry. The dissolution performance of the compartments was tested using immediate release caffeine tablets and evaluated by standard statistical methods and principal component analysis. Based on two phases of dissolution testing (using 250 and 100 mL of dissolution medium), we selected two compartment types yielding the highest measurement reproducibility. We also confirmed a statistically ssignificant effect of agitation rate and dissolution volume on the extent of drug dissolved and measurement reproducibility.

Corrosion inhibition by inorganic cationic inhibitors on the high strength alumunium alloy, 2024-T3

NASA Astrophysics Data System (ADS)

Chilukuri, Anusha

The toxicity and carcinogenic nature of chromates has led to the investigation of environmentally friendly compounds that offer good corrosion resistance to AA 2024-T3. Among the candidate inhibitors are rare earth metal cationic (REM) and zinc compounds, which have received much of attention over the past two decades. A comparative study on the corrosion inhibition caused by rare earth metal cations, Ce3+, Pr3+, La3+ and Zn2+ cations on the alloy was done. Cathodic polarization showed that these inhibitor ions suppress the oxygen reduction reaction (ORR) to varying extents with Zn2+ providing the best inhibition. Pr3+ exhibited windows of concentration (100-300 ppm) in which the corrosion rate is minimum; similar to the Ce3+ cation. Scanning Electron Microscopy (SEM) studies showed that the mechanism of inhibition of the Pr3+ ion is also similar to that of the Ce3+ ion. Potentiodynamic polarization experiments after 30 min immersion time showed greatest suppression of oxygen reduction reaction in neutral chloride solutions (pH 7), which reached a maximum at a Zn2+ ion concentration of 5 mM. Anodic polarization experiments after 30 min immersion time, showed no anodic inhibition by the inhibitor in any concentration (0.1 mM - 10 mM) and at any pH. However, anodic polarization of samples immersed after longer immersion times (upto 4 days) in mildly acidic Zn2+ (pH 4) solutions showed significant reduction in anodic kinetics indicating that zinc also acts as a “slow anodic inhibitor”. In contrast to the polarization experiments, coupons exposed to inhibited acidic solutions at pH 4 showed complete suppression of dissolution of Al2CuMg particles compared to zinc-free solutions in the SEM studies. Samples exposed in pH 4 Zn2+-bearing solution exhibited highest polarization resistance which was also observed to increase with time. In deaerated solutions, the inhibition by Zn2+ at pH 4 is not observed as strongly. The ability to make the interfacial electrolyte alkaline is retarded in the absence of oxygen. As a result precipitation of Zn oxides and hydroxides was suppressed. Impedance in decarbonated chloride solutions showed that the absence of CO 2 reduces inhibition by Zn2+ at pH 4. The carbonate protective layer formed in aerated solutions is essential for providing better protection of the substrate at pH 4. Inhibitor cations were exchanged into insoluble ion-exchanging sodium bentonites and incorporated as pigments in organic coatings applied to AA 2024-T3 substrates. XRD of the pigments ensured ion exchange and UV-visible spectroscopy was used to characterize inhibitor ion release from the bentonites. Salt spray exposure tests on scribed panels were preformed and results were compared to those from SrCrO4 pigmented coatings. Zn-exchanged bentonite pigmented coatings showed better performance compared to the other exchanged bentonites when incorporated into epoxy coatings with total impedance magnitude in the same order as SrCrO4. PVB (Polyvinyl Butyral) coatings containing Zn bentonite, however, did not show superior behaviour in the impedance response due to less or no water uptake. Salt spray exposures for a period of 336 h, showed that Zn bentonite incorporated into PVB suppressed blistering compared to the neat PVB and other pigmented bentonites.

40 CFR 63.842 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... section as follows: Anode bake cycle means the period during which the regularly repeated sequence of loading, preheating, firing, cooling, and removing anodes from all sections within an anode bake furnace occurs one time. Anode bake furnace means an oven in which the formed green anodes are baked for use in a...

40 CFR 63.842 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... section as follows: Anode bake cycle means the period during which the regularly repeated sequence of loading, preheating, firing, cooling, and removing anodes from all sections within an anode bake furnace occurs one time. Anode bake furnace means an oven in which the formed green anodes are baked for use in a...

40 CFR 63.842 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... section as follows: Anode bake cycle means the period during which the regularly repeated sequence of loading, preheating, firing, cooling, and removing anodes from all sections within an anode bake furnace occurs one time. Anode bake furnace means an oven in which the formed green anodes are baked for use in a...

40 CFR 63.842 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... section as follows: Anode bake cycle means the period during which the regularly repeated sequence of loading, preheating, firing, cooling, and removing anodes from all sections within an anode bake furnace occurs one time. Anode bake furnace means an oven in which the formed green anodes are baked for use in a...

40 CFR 63.842 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... section as follows: Anode bake cycle means the period during which the regularly repeated sequence of loading, preheating, firing, cooling, and removing anodes from all sections within an anode bake furnace occurs one time. Anode bake furnace means an oven in which the formed green anodes are baked for use in a...

Effect of anode oxide films on glow discharge spatial structure

NASA Astrophysics Data System (ADS)

Gulamov, E. N.; Islamov, R. S.; Zabelin, Alexandre M.

1994-04-01

A self-consistent calculation of voltage fall on the anode film as a function of its resistance has been performed in the presence of anode current spots under elevated-pressure glow discharge in nitrogen and N2:He equals 1:1 mixture. It has been shown that resistance of anode oxide films in industrial lasers with continuous copper anode can reach the values when total suppression of anode current structures takes place.

Electrolytic Cell For Production Of Aluminum Employing Planar Anodes.

DOEpatents

Barnett, Robert J.; Mezner, Michael B.; Bradford, Donald R

2004-10-05

A method of producing aluminum in an electrolytic cell containing alumina dissolved in an electrolyte, the method comprising providing a molten salt electrolyte having alumina dissolved therein in an electrolytic cell. A plurality of anodes and cathodes having planar surfaces are disposed in a generally vertical orientation in the electrolyte, the anodes and cathodes arranged in alternating or interleaving relationship to provide anode planar surfaces disposed opposite cathode planar surfaces, the anode comprised of carbon. Electric current is passed through anodes and through the electrolyte to the cathodes depositing aluminum at the cathodes and forming carbon containing gas at the anodes.

Electrohydrodynamically patterned colloidal crystals

NASA Technical Reports Server (NTRS)

Hayward, Ryan C. (Inventor); Poon, Hak F. (Inventor); Xiao, Yi (Inventor); Saville, Dudley A. (Inventor); Aksay, Ilhan A. (Inventor)

2003-01-01

A method for assembling patterned crystalline arrays of colloidal particles using ultraviolet illumination of an optically-sensitive semiconducting anode while using the anode to apply an electronic field to the colloidal particles. The ultraviolet illumination increases current density, and consequently, the flow of the colloidal particles. As a result, colloidal particles can be caused to migrate from non-illuminated areas of the anode to illuminated areas of the anode. Selective illumination of the anode can also be used to permanently affix colloidal crystals to illuminated areas of the anode while not affixing them to non-illuminated areas of the anode.

A new, bright and hard aluminum surface produced by anodization

NASA Astrophysics Data System (ADS)

Hou, Fengyan; Hu, Bo; Tay, See Leng; Wang, Yuxin; Xiong, Chao; Gao, Wei

2017-07-01

Anodized aluminum (Al) and Al alloys have a wide range of applications. However, certain anodized finishings have relatively low hardness, dull appearance and/or poor corrosion resistance, which limited their applications. In this research, Al was first electropolished in a phosphoric acid-based solution, then anodized in a sulfuric acid-based solution under controlled processing parameters. The anodized specimen was then sealed by two-step sealing method. A systematic study including microstructure, surface morphology, hardness and corrosion resistance of these anodized films has been conducted. Results show that the hardness of this new anodized film was increased by a factor of 10 compared with the pure Al metal. Salt spray corrosion testing also demonstrated the greatly improved corrosion resistance. Unlike the traditional hard anodized Al which presents a dull-colored surface, this newly developed anodized Al alloy possesses a very bright and shiny surface with good hardness and corrosion resistance.

[Effect of the initial anode potential on electricity generation in microbial fuel cell].

PubMed

Fan, Ming-Zhi; Liang, Peng; Cao, Xiao-Xin; Huang, Xia

2008-01-01

The initial anode potential of the microbial fuel cell (MFC) was changed by additional circuit in the anode chamber, and the influence of the initial anode potential on the electricigens was studied. When the initial anode potential was 350 mV (vs Hg/Hg2 Cl2), the growth of microorganisms was much slower than that of the microorganisms which grew on the anode with an initial potential of -200 mV or 200 mV (vs Hg/Hg2 Cl2). After stable electricity generation, the anode resistances of the three MFCs, which had initial anode potentials of 350 mV, 200 mV and -200 mV respectively, were 71 Omega, 43 Omega and 80 Omega. The community structures in MFCs, before and after the electricity generation, were also studied by denaturing gradient gel electrophoresis (DGGE). Clostridium sticklandii, Pseudomonas mendocina and Paenibacillus taejonensis were the three most enriched strains on the anode.

Thermal investigation of an electrical high-current arc with porous gas-cooled anode

NASA Technical Reports Server (NTRS)

Eckert, E. R. G.; Schoeck, P. A.; Winter, E. R. F.

1984-01-01

The following guantities were measured on a high-intensity electric arc with tungsten cathode and transpiration-cooled graphite anode burning in argon: electric current and voltage, cooling gas flow rate (argon), surface temperature of the anode and of the anode holder, and temperature profile in three cross-sections of the arc are column. The last mentioned values were obtained from spectroscopic photographs. From the measured quantities, the following values were calculated: the heat flux into the anode surface, the heat loss of the anode by radiation and conduction, and the heat which was regeneratively transported by the cooling gas back into the arc space. Heat balances for the anode were also obtained. The anode losses (which are approximately 80% of the total arc power for free burning arcs) were reduced by transpiration cooling to 20%. The physical processes of the energy transfer from the arc to the anode are discussed qualitatively.

Fuel cell system shutdown with anode pressure control

DOEpatents

Clingerman, Bruce J.; Doan, Tien M.; Keskula, Donald H.

2002-01-01

A venting methodology and pressure sensing and vent valving arrangement for monitoring anode bypass valve operating during the normal shutdown of a fuel cell apparatus of the type used in vehicle propulsion systems. During a normal shutdown routine, the pressure differential between the anode inlet and anode outlet is monitored in real time in a period corresponding to the normal closing speed of the anode bypass valve and the pressure differential at the end of the closing cycle of the anode bypass valve is compared to the pressure differential at the beginning of the closing cycle. If the difference in pressure differential at the beginning and end of the anode bypass closing cycle indicates that the anode bypass valve has not properly closed, a system controller switches from a normal shutdown mode to a rapid shutdown mode in which the anode inlet is instantaneously vented by rapid vents.

Improvement of corrosion resistance of NiTi sputtered thin films by anodization

NASA Astrophysics Data System (ADS)

Bayat, N.; Sanjabi, S.; Barber, Z. H.

2011-08-01

Anodization of sputtered NiTi thin films has been studied in 1 M acetic acid at 23 °C for different voltages from 2 to 10 V. The morphology and cross-sectional structures of the untreated and anodized surfaces were investigated by field emission scanning electron microscopy (FE-SEM). The results show that increasing anodization voltage leads to film surface roughening and unevenness. It can be seen that the thickness of the anodized layer formed on the NiTi surface is in the nanometer range. The corrosion resistance of anodized thin films was studied by potentiodynamic scan (PDS) and impedance spectroscopy (EIS) techniques in Hank's solution at 310 K (37 °C). It was shown that the corrosion resistance of the anodized film surface improved with increasing voltage to 6 V. Anodization of austenitic sputtered NiTi thin films has also been studied, in the same anodizing conditions, at 4 V. Comparison of anodized sputtered NiTi thin films with anodized austenitic shape memory films illustrate that the former are more corrosion resistant than the latter after 1 h immersion in Hank's solution, which is attributed to the higher grain boundary density to quickly form a stable and protective passive film.

Effect of TiO2 Addition on Grain Growth, Anodic Bubble Evolution and Anodic Overvoltage of NiFe2O4-Based Composite Inert Anodes

NASA Astrophysics Data System (ADS)

Wang, Bin; Du, Jinjing; Liu, Yihan; Fang, Zhao; Hu, Ping

2017-11-01

A two-step powder compaction and sintering process was employed to fabricate TiO2-doped NiFe2O4 ceramic-based inert anodes. Grain growth during isothermal sintering was analyzed using Brook grain growth model. The bubble behavior of NiFe2O4 ceramic-based inert anodes was investigated in a two-compartment see-through quartz cell for aluminum electrolysis process. Anodic overvoltage and potential decay curves of the inert anodes were measured by using the steady state and current interruption technique. The results showed that the kinetic index of grain growth decreased with an increase in temperature. The average activation energy of grain growth for 1.0 wt.% TiO2-doped NiFe2O4 ceramic samples with a sintering temperature range from 1373 to 1673 K dropped from 675.30 to 183.47 kJ/mol. The diameter size of bubbles before releasing from the bottom surface of the anodes was reduced with increasing the current density, and the larger average releasing bubble size for carbon anode at the same current density could be obtained, which was compared to the NiFe2O4 inert anodes. Besides, the cell voltage of carbon anodes fluctuated much more violently under the same experimental conditions. After adding small amount of TiO2, a minor reduction in anodic overvoltage of NiFe2O4-based anodes can be observed.