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.

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

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.

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.

An analysis of variable dissolution rates of sacrificial zinc anodes: a case study of the Hamble estuary, UK.

PubMed

Rees, Aldous B; Gallagher, Anthony; Comber, Sean; Wright, Laurence A

2017-09-01

Sacrificial anodes are intrinsic to the protection of boats and marine structures by preventing the corrosion of metals higher up the galvanic scale through their preferential breakdown. The dissolution of anodes directly inputs component metals into local receiving waters, with variable rates of dissolution evident in coastal and estuarine environments. With recent changes to the Environmental Quality Standard (EQS), the load for zinc in estuaries such as the Hamble, UK, which has a large amount of recreational craft, now exceeds the zinc standard of 7.9 μg/l. A survey of boat owners determined corrosion rates and estimated zinc loading at between 6.95 and 7.11 t/year. The research confirms the variable anode corrosion within the Hamble and highlighted a lack of awareness of anode technology among boat owners. Monitoring and investigation discounted metal structures and subterranean power cables as being responsible for these variations but instead linked accelerated dissolution to marina power supplies and estuarine salinity variations.

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.

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.

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.

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.

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

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.

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.

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.

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

Electrochemical Dissolution of Tungsten Carbide in NaCl-KCl-Na2WO4 Molten Salt

NASA Astrophysics Data System (ADS)

Zhang, Liwen; Nie, Zuoren; Xi, Xiaoli; Ma, Liwen; Xiao, Xiangjun; Li, Ming

2018-02-01

Tungsten carbide was utilized as anode to extract tungsten in a NaCl-KCl-Na2WO4 molten salt, and the electrochemical dissolution was investigated. Although the molten salt electrochemical method is a short process method of tungsten extraction from tungsten carbide in one step, the dissolution efficiency and current efficiency are quite low. In order to improve the dissolution rate and current efficiency, the sodium tungstate was added as the active substance. The dissolution rate, the anode current efficiency, and the cathode current efficiency were calculated with different contents of sodium tungstate addition. The anodes prior to and following the reaction, as well as the product, were analyzed through X-ray diffraction, scanning electron microscopy, and energy dispersive spectrometry. The results demonstrated that the sodium tungstate could improve the dissolution rate and the current efficiency, due to the addition of sodium tungstate decreasing the charge transfer resistance in the electrolysis system. Due to the fact that the addition of sodium tungstate could remove the carbon during electrolysis, pure tungsten powders with 100 nm diameter were obtained when the content of sodium tungstate was 1.0 pct.

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.

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.

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.

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.

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.

Effect of the microstructure of Ti-5Mo on the anodic dissolution in H/sub 2/SO/sub 4/

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

Kim, Y.J.; Oriani, R.A.

1987-04-01

The effect of microstructure of the Ti-5Mo alloy on its anodic dissolution rate in sulfuric acid solution at various temperatures has been investigated. TiMo alloys exhibit a region of increased dissolution rate in the vicinity of +0.20 V (saturated calomel electrode (SCE)) in 10% H/sub 2/SO/sub 4/, the same potential region in which pure Mo exhibits a large anodic dissolution rate. Aging of Ti-5Mo at 350 C was found to lead to the formation of ..omega.. phase. Heat treatment caused larger passive currents in 10% H/sub 2/SO/sub 4/, but the critical passivation potentials and corrosion potentials were not significantly affected.more » Molybdenum was enriched in the oxide formed on aged Ti-5Mo at +0.23 V (SCE), in comparison with the Mo concentration found in the oxide on as-received Ti-5Mo.« less

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.

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.

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.

Preventing the dissolution of lithium polysulfides in lithium-sulfur cells by using Nafion-coated cathodes.

PubMed

Oh, Soo Jung; Lee, Jun Kyu; Yoon, Woo Young

2014-09-01

The principal drawback of lithium-sulfur batteries is the dissolution of long-chain lithium polysulfides into the electrolyte, which limits cycling performance. To overcome this problem, we focused on the development of a novel cathode as well as anode material and designed Nafion-coated NiCrAl/S as a cathode and lithium powder as an anode. Nafion-coated NiCrAl/S cathode was synthesized using a two-step dip-coating technique. The lithium-powder anode was used instead of a lithium-foil anode to prohibit dendrite growth and to improve on the electrochemical behaviors. The cells showed an initial discharge capacity of about 900 mA g(-1) and a final discharge capacity of 772 mA g(-1) after 100 cycles at 0.1 C-rate. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) demonstrate that using the Nafion-coated NiCrAl/S cathode can suppress the dissolution of long-chain lithium polysulfides. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

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

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.

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.

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.

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.

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.

The recovery of zinc from hot galvanizing slag in an anion-exchange membrane electrolysis reactor.

PubMed

Ren, Xiulian; Wei, Qifeng; Hu, Surong; Wei, Sijie

2010-09-15

This paper reports the optimization of the process parameters for recovery of zinc from hot galvanizing slag in an anion-exchange membrane electrolysis reactor. The experiments were carried out in an ammoniacal ammonium chloride system. The influence of composition of electrolytes, pH, stirring rate, current density and temperature, on cathodic current efficiency, specific power consumption and anodic dissolution of Zn were investigated. The results indicate that the cathode current efficiency increases and the hydrogen evolution decreased with increasing the cathode current density. The partial current for electrodeposition of Zn has liner relationship with omega(1/2) (omega: rotation rate). The highest current efficiency for dissolving zinc was obtained when NH(4)Cl concentration was 53.46 g L(-1) and the anodic dissolution of zinc was determined by mass transfer rate at stirring rate 0-300 r min(-1). Increase in temperature benefits to improve CE and dissolution of Zn, and reduce cell voltage. Initial pH of electrolytes plays an important role in the deposition and anodic dissolution of Zn. The results of single factor experiment show that about 50% energy consumption was saved for electrodeposition of Zn in the anion-exchange membrane electrolysis reactor. Copyright 2010 Elsevier B.V. All rights reserved.

Fabrication of porous anodic alumina using normal anodization and pulse anodization

NASA Astrophysics Data System (ADS)

Chin, I. K.; Yam, F. K.; Hassan, Z.

2015-05-01

This article reports on the fabrication of porous anodic alumina (PAA) by two-step anodizing the low purity commercial aluminum sheets at room temperature. Different variations of the second-step anodization were conducted: normal anodization (NA) with direct current potential difference; pulse anodization (PA) alternate between potential differences of 10 V and 0 V; hybrid pulse anodization (HPA) alternate between potential differences of 10 V and -2 V. The method influenced the film homogeneity of the PAA and the most homogeneous structure was obtained via PA. The morphological properties are further elucidated using measured current-transient profiles. The absent of current rise profile in PA indicates the anodization temperature and dissolution of the PAA structure were greatly reduced by alternating potential differences.

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.

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.

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.

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.

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

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.

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

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

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.

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.

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

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.

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.

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.

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.

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.

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

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

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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.

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

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.

[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.

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

Bone Cell–materials Interactions and Ni Ion Release of Anodized Equiatomic NiTi Alloy

PubMed Central

Bernard, Sheldon A.; Balla, Vamsi Krishna; Davies, Neal M.; Bose, Susmita; Bandyopadhyay, Amit

2011-01-01

Laser processed NiTi alloy was anodized for different durations in H2SO4 electrolyte with varying pH to create biocompatible surfaces with low Ni ion release as well as bioactive surfaces to enhance biocompatibility and bone cell-materials interactions. The anodized surfaces were assessed for their in vitro cell-materials interactions using human fetal osteoblast (hFOB) cells for 3, 7 and 11 days, and Ni ion release up to 8 weeks in simulated body fluids. The results were correlated with surface morphologies of anodized surfaces characterized using field-emission scanning electron microscopy (FESEM). The results show that the anodization creates a surface with nano/micro roughness depending on anodization conditions. The hydrophilicity of NiTi surface was found to improve after anodization due to lower contact angles in cell media, which dropped from 32° to < 5°. The improved wettability of anodized surfaces is further corroborated by their high surface energy comparable to that of cp Ti. Relatively high surface energy, especially polar component, and nano/micro surface features of anodized surfaces significantly increased the number of living cells and their adherence and growth on these surfaces. Finally, a significant drop in Ni ion release from 268 ± 11 to 136 ± 15 ppb was observed for NiTi surfaces after anodization. This work indicates that anodization of NiTi alloy has a positive influence on the surface energy and surface morphology, which in turn improve bone cell-materials interactions and reduce Ni ion release in vitro. PMID:21232641

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.

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.

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

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.

Bone cell-materials interactions and Ni ion release of anodized equiatomic NiTi alloy.

PubMed

Bernard, Sheldon A; Balla, Vamsi Krishna; Davies, Neal M; Bose, Susmita; Bandyopadhyay, Amit

2011-04-01

A laser processed NiTi alloy was anodized for different times in H(2)SO(4) electrolyte with varying pH to create biocompatible surfaces with low Ni ion release as well as bioactive surfaces to enhance biocompatibility and bone cell-material interactions. The anodized surfaces were assessed for their in vitro cell-material interactions using human fetal osteoblast (hFOB) cells for 3, 7 and 11 days, and Ni ion release up to 8 weeks in simulated body fluids. The results were correlated with the surface morphologies of anodized surfaces characterized using field-emission scanning electron microscopy (FESEM). The results show that anodization creates a surface with nano/micro-roughness depending on the anodization conditions. The hydrophilicity of the NiTi surface was found to improve after anodization, as shown by the lower contact angles in cell medium, which dropped from 32° to <5°. The improved wettability of anodized surfaces is further corroborated by their high surface energy, comparable with that of commercially pure Ti. Relatively high surface energies, especially the polar component, and nano/micro surface features of anodized surfaces significantly increased the number of living cells and their adherence and growth on these surfaces. Finally, a significant drop in Ni ion release from 268±11 to 136±15 ppb was observed for NiTi surfaces after anodization. This work indicates that anodization of a NiTi alloy has a positive influence on the surface energy and surface morphology, which in turn improves bone cell-material interactions and reduces Ni ion release in vitro. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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.

Fabrication of the micro/nano-structure superhydrophobic surface on aluminum alloy by sulfuric acid anodizing and polypropylene coating.

PubMed

Wu, Ruomei; Liang, Shuquan; Liu, Jun; Pan, Anqiang; Yu, Y; Tang, Yan

2013-03-01

The preparation of the superhydrophobic surface on aluminum alloy by anodizing and polypropylene (PP) coating was reported. Both the different anodizing process and different PP coatings of aluminum alloy were investigated. The effects of different anodizing conditions, such as electrolyte concentration, anodization time and current on the superhydrophobic surface were discussed. By PP coating after anodizing, a good superhydrophobic surface was facilely fabricated. The optimum conditions for anodizing were determined by orthogonal experiments. After the aluminium-alloy was grinded with 600# sandpaper, pretreated by 73 g/L hydrochloric acid solution at 1 min, when the concentration of sulfuric acid was 180 g/L, the concentration of oxalic acid was 5 g/L, the concentration of potassium dichromate was 10 g/L, the concentration of chloride sodium was 50 g/L and 63 g/L of glycerol, anodization time was 20 min, and anodization current was 1.2 A/dm2, anodization temperature was 30-35 degrees C, the best micro-nanostructure aluminum alloy films was obtained. On the other hand, the PP with different concentrations was used to the PP with different concentrations was used to coat the aluminum alloy surface after anodizing. The results showed that the best superhydrophobicity was achieved by coating PP, and the duration of the superhydrophobic surface was improved by modifying the coat the aluminum alloy surface after anodizing. The results showed that the best superhydrophobicity was surface with high concentration PP. The morphologies of micro/nano-structure superhydrophobic surface were further confirmed by scanning electron microscope (SEM). The material of PP with the low surface free energy combined with the micro/nano-structures of the surface resulted in the superhydrophobicity of the aluminum alloy surface.

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

Surface characteristics, corrosion and bioactivity of chemically treated biomedical grade NiTi alloy.

PubMed

Chembath, Manju; Balaraju, J N; Sujata, M

2015-11-01

The surface of NiTi alloy was chemically modified using acidified ferric chloride solution and the characteristics of the alloy surface were studied from the view point of application as a bioimplant. Chemically treated NiTi was also subjected to post treatments by annealing at 400°C and passivation in nitric acid. The surface of NiTi alloy after chemical treatment developed a nanogrid structure with a combination of one dimensional channel and two dimensional network-like patterns. From SEM studies, it was found that the undulations formed after chemical treatment remained unaffected after annealing, while after passivation process the undulated surface was filled with oxides of titanium. XPS analysis revealed that the surface of passivated sample was enriched with oxides of titanium, predominantly TiO2. The influence of post treatment on the corrosion resistance of chemically treated NiTi alloy was monitored using Potentiodynamic Polarization and Electrochemical Impedance Spectroscopy (EIS) in Phosphate Buffered Saline (PBS) solution. In the chemically treated condition, NiTi alloy exhibited poor corrosion resistance due to the instability of the surface. On the other hand, the breakdown potential (0.8V) obtained was highest for the passivated samples compared to other surface treated samples. During anodic polarization, chemically treated samples displayed dissolution phenomenon which was predominantly activation controlled. But after annealing and passivation processes, the behavior of anodic polarization was typical of a diffusion controlled process which confirmed the enhanced passivity of the post treated surfaces. The total resistance, including the porous and barrier layer, was in the range of mega ohms for passivated surfaces, which could be attributed to the decrease in surface nickel content and formation of compact titanium oxide. The passivated sample displayed good bioactivity in terms of hydroxyapatite growth, noticed after 14days immersion in Hanks' solution. Copyright © 2015 Elsevier B.V. All rights reserved.

Surface States and Effective Surface Area on Photoluminescent P-Type Porous Silicon

NASA Technical Reports Server (NTRS)

Weisz, S. Z.; Porras, A. Ramirez; Resto, O.; Goldstein, Y.; Many, A.; Savir, E.

1997-01-01

The present study is motivated by the possibility of utilizing porous silicon for spectral sensors. Pulse measurements on the porous-Si/electrolyte system are employed to determine the surface effective area and the surface-state density at various stages of the anodization process used to produce the porous material. Such measurements were combined with studies of the photoluminescence spectra. These spectra were found to shift progressively to the blue as a function of anodization time. The luminescence intensity increases initially with anodization time, reaches a maximum and then decreases with further anodization. The surface state density, on the other hand, increases with anodization time from an initial value of about 2 x 10(exp 12)/sq cm surface to about 1013 sq cm for the anodized surface. This value is attained already after -2 min anodization and upon further anodization remains fairly constant. In parallel, the effective surface area increases by a factor of 10-30. This behavior is markedly different from the one observed previously for n-type porous Si.

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.

Superhydrophobic NiTi shape memory alloy surfaces fabricated by anodization and surface mechanical attrition treatment

NASA Astrophysics Data System (ADS)

Ou, Shih-Fu; Wang, Kuang-Kuo; Hsu, Yen-Chi

2017-12-01

This paper describes the fabrication of superhydrophobic NiTi shape memory alloy (SMA) surfaces using an environmentally friendly method based on an economical anodizing process. Perfluorooctyltriethoxysilane was used to reduce the surface energy of the anodized surfaces. The wettability, morphology, composition, and microstructure of the surfaces were investigated by scanning electron microscopy, transmission electron microscopy, and x-ray photoelectron spectroscopy. The surface of the treated NiTi SMA exhibited superhydrophobicity, with a water contact angle of 150.6° and sliding angle of 8°. The anodic film on the NiTi SMA comprised of TiO2 and NiO, as well as traces of TiCl3. In addition, before the NiTi SMA was anodized, it underwent a surface mechanical attrition treatment to grain-refine its surface. This method efficiently enhanced the growth rate of the anodic oxide film, and improved the hydrophobic uniformity of the anodized NiTi-SMA-surface.

Anodization: a promising nano-modification technique of titanium implants for orthopedic applications.

PubMed

Yao, Chang; Webster, Thomas J

2006-01-01

Anodization is a well-established surface modification technique that produces protective oxide layers on valve metals such as titanium. Many studies have used anodization to produce micro-porous titanium oxide films on implant surfaces for orthopedic applications. An additional hydrothermal treatment has also been used in conjunction with anodization to deposit hydroxyapatite on titanium surfaces; this is in contrast to using traditional plasma spray deposition techniques. Recently, the ability to create nanometer surface structures (e.g., nano-tubular) via anodization of titanium implants in fluorine solutions have intrigued investigators to fabricate nano-scale surface features that mimic the natural bone environment. This paper will present an overview of anodization techniques used to produce micro-porous titanium oxide structures and nano-tubular oxide structures, subsequent properties of these anodized titanium surfaces, and ultimately their in vitro as well as in vivo biological responses pertinent for orthopedic applications. Lastly, this review will emphasize why anodized titanium structures that have nanometer surface features enhance bone forming cell functions.

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.

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.

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.

Fabrication of the superhydrophobic surface on aluminum alloy by anodizing and polymeric coating

NASA Astrophysics Data System (ADS)

Liu, Wenyong; Luo, Yuting; Sun, Linyu; Wu, Ruomei; Jiang, Haiyun; Liu, Yuejun

2013-01-01

We reported the preparation of the superhydrophobic surface on aluminum alloy via anodizing and polymeric coating. Both the different anodizing processes and different polymeric coatings of aluminum alloy were investigated. The effects of different anodizing conditions, such as electrolyte concentration, anodization time and current on the superhydrophobic surface were discussed. The results showed that a good superhydrophobic surface was facilely fabricated by polypropylene (PP) coating after anodizing. The optimum conditions for anodizing were determined by orthogonal experiments. When the concentration of oxalic acid was 10 g/L, the concentration of NaCl was 1.25 g/L, anodization time was 40 min, and anodization current was 0.4 A, the best superhydrophobic surface on aluminum alloy with the contact angle (CA) of 162° and the sliding angle of 2° was obtained. On the other hand, the different polymeric coatings, such as polystyrene (PS), polypropylene (PP) and polypropylene grafting maleic anhydride (PP-g-MAH) were used to coat the aluminum alloy surface after anodizing. The results showed that the superhydrophobicity was most excellent by coating PP, while the duration of the hydrophobic surface was poor. By modifying the surface with the silane coupling agent before PP coating, the duration of the superhydrophobic surface was improved. The morphologies of the superhydrophobic surface were further confirmed by optical microscope (OM) and scanning electron microscope (SEM). Combined with the material of PP with the low surface free energy, the micro/nano-structures of the surface resulted in the superhydrophobicity of the aluminum alloy surface.

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.

Mirror-finished superhydrophobic aluminum surfaces modified by anodic alumina nanofibers and self-assembled monolayers

NASA Astrophysics Data System (ADS)

Nakajima, Daiki; Kikuchi, Tatsuya; Natsui, Shungo; Suzuki, Ryosuke O.

2018-05-01

We demonstrate mirror-finished superhydrophobic aluminum surfaces fabricated via the formation of anodic alumina nanofibers and subsequent modification with self-assembled monolayers (SAMs). High-density anodic alumina nanofibers were formed on the aluminum surface via anodizing in a pyrophosphoric acid solution. The alumina nanofibers became tangled and bundled by further anodizing at low temperature because of their own weight, and the aluminum surface was completely covered by the long falling nanofibers. The nanofiber-covered aluminum surface exhibited superhydrophilic behavior, with a contact angle measuring less than 10°. As the nanofiber-covered aluminum surface was modified with n-alkylphosphonic acid SAMs, the water contact angle drastically shifted to superhydrophobicity, measuring more than 150°. The contact angle increased with the applied voltage during pyrophosphoric acid anodizing, the anodizing time, and the number of carbon atoms contained in the SAM molecules modified on the alumina nanofibers. By optimizing the anodizing and SAM-modification conditions, superhydrophobic behavior could be achieved with only a brief pyrophosphoric acid anodizing period of 3 min and subsequent simple immersion in SAM solutions. The superhydrophobic aluminum surface exhibited a high reflectance, measuring approximately 99% across most of the visible spectrum, similar to that of an electropolished aluminum surface. Therefore, our mirror-finished superhydrophobic aluminum surface based on anodic alumina nanofibers and SAMs can be used as a reflective mirror in various optical applications such as concentrated solar power systems.

Aluminum reduction cell electrode

DOEpatents

Payne, J.R.

1983-09-20

The invention is directed to an anode-cathode structure for an electrolytic cell for the reduction of alumina wherein the structure is comprised of a carbon anode assembly which straddles a wedge-shaped refractory hard metal cathode assembly having steeply sloped cathodic surfaces, each cathodic surface being paired in essentially parallel planar relationship with an anode surface. The anode-cathode structure not only takes into account the structural weakness of refractory hard metal materials but also permits the changing of the RHM assembly during operation of the cell. Further, the anode-cathode structure enhances the removal of anode gas from the interpolar gap between the anode and cathode surfaces. 10 figs.

Aluminum reduction cell electrode

DOEpatents

Payne, John R.

1983-09-20

The invention is directed to an anode-cathode structure for an electrolytic cell for the reduction of alumina wherein the structure is comprised of a carbon anode assembly which straddles a wedge-shaped refractory hard metal cathode assembly having steeply sloped cathodic surfaces, each cathodic surface being paired in essentially parallel planar relationship with an anode surface. The anode-cathode structure not only takes into account the structural weakness of refractory hard metal materials but also permits the changing of the RHM assembly during operation of the cell. Further, the anode-cathode structure enhances the removal of anode gas from the interpolar gap between the anode and cathode surfaces.

Histomorphometric and histologic evaluation of titanium-zirconium (aTiZr) implants with anodized surfaces.

PubMed

Sharma, Ajay; McQuillan, A James; Shibata, Yo; Sharma, Lavanya A; Waddell, John Neil; Duncan, Warwick John

2016-05-01

The choice of implant surface has a significant influence on osseointegration. Modification of TiZr surface by anodization is reported to have the potential to modulate the osteoblast cell behaviour favouring more rapid bone formation. The aim of this study is to investigate the effect of anodizing the surface of TiZr discs with respect to osseointegration after four weeks implantation in sheep femurs. Titanium (Ti) and TiZr discs were anodized in an electrolyte containing DL-α-glycerophosphate and calcium acetate at 300 V. The surface characteristics were analyzed by scanning electron microscopy, electron dispersive spectroscopy, atomic force microscopy and goniometry. Forty implant discs with thickness of 1.5 and 10 mm diameter (10 of each-titanium, titanium-zirconium, anodized titanium and anodized titanium-zirconium) were placed in the femoral condyles of 10 sheep. Histomorphometric and histologic analysis were performed 4 weeks after implantation. The anodized implants displayed hydrophilic, porous, nano-to-micrometer scale roughened surfaces. Energy dispersive spectroscopy analysis revealed calcium and phosphorous incorporation into the surface of both titanium and titanium-zirconium after anodization. Histologically there was new bone apposition on all implanted discs, slightly more pronounced on anodised discs. The percentage bone-to-implant contact measurements of anodized implants were higher than machined/unmodified implants but there was no significant difference between the two groups with anodized surfaces (P > 0.05, n = 10). The present histomorphometric and histological findings confirm that surface modification of titanium-zirconium by anodization is similar to anodised titanium enhances early osseointegration compared to machined implant surfaces.

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.

Anodized aluminum on LDEF

NASA Technical Reports Server (NTRS)

Golden, Johnny L.

1993-01-01

A compilation of reported analyses and results obtained for anodized aluminum flown on the Long Duration Exposure Facility (LDEF) was prepared. Chromic acid, sulfuric acid, and dyed sulfuric acid anodized surfaces were exposed to the space environment. The vast majority of the anodized surface on LDEF was chromic acid anodize because of its selection as a thermal control coating for use on the spacecraft primary structure, trays, tray clamps, and space end thermal covers. Reports indicate that the chromic acid anodize was stable in solar absorptance and thermal emittance, but that contamination effects caused increases in absorptance on surfaces exposed to low atomic oxygen fluences. There were some discrepancies, however, in that some chromic acid anodized specimens exhibited significant increases in absorptance. Sulfuric acid anodized surfaces also appeared stable, although very little surface area was available for evaluation. One type of dyed sulfuric acid anodize was assessed as an optical baffle coating and was observed to have improved infrared absorptance characteristics with exposure on LDEF.

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.

Coherent anti-Stokes Raman Scattering (CARS) Microscopy Visualizes Pharmaceutical Tablets During Dissolution

PubMed Central

Fussell, Andrew L.; Kleinebudde, Peter; Herek, Jennifer; Strachan, Clare J.; Offerhaus, Herman L.

2014-01-01

Traditional pharmaceutical dissolution tests determine the amount of drug dissolved over time by measuring drug content in the dissolution medium. This method provides little direct information about what is happening on the surface of the dissolving tablet. As the tablet surface composition and structure can change during dissolution, it is essential to monitor it during dissolution testing. In this work coherent anti-Stokes Raman scattering microscopy is used to image the surface of tablets during dissolution while UV absorption spectroscopy is simultaneously providing inline analysis of dissolved drug concentration for tablets containing a 50% mixture of theophylline anhydrate and ethyl cellulose. The measurements showed that in situ CARS microscopy is capable of imaging selectively theophylline in the presence of ethyl cellulose. Additionally, the theophylline anhydrate converted to theophylline monohydrate during dissolution, with needle-shaped crystals growing on the tablet surface during dissolution. The conversion of theophylline anhydrate to monohydrate, combined with reduced exposure of the drug to the flowing dissolution medium resulted in decreased dissolution rates. Our results show that in situ CARS microscopy combined with inline UV absorption spectroscopy is capable of monitoring pharmaceutical tablet dissolution and correlating surface changes with changes in dissolution rate. PMID:25045833

Superhydrophilicity of a nanofiber-covered aluminum surface fabricated via pyrophosphoric acid anodizing

NASA Astrophysics Data System (ADS)

Nakajima, Daiki; Kikuchi, Tatsuya; Natsui, Shungo; Suzuki, Ryosuke O.

2016-12-01

A superhydrophilic aluminum surface covered by numerous alumina nanofibers was fabricated via pyrophosphoric acid anodizing. High-density anodic alumina nanofibers grow on the bottom of a honeycomb oxide via anodizing in concentrated pyrophosphoric acid. The water contact angle on the nanofiber-covered aluminum surface decreased with time after a 4 μL droplet was placed on the surface, and a superhydrophilic behavior with a contact angle measuring 2.2° was observed within 2 s; this contact angle is considerably lower than those observed for electropolished and porous alumina-covered aluminum surfaces. There was no dependence of the superhydrophilicity on the density of alumina nanofibers fabricated via different constant voltage anodizing conditions. The superhydrophilic property of the surface covered by anodic alumina nanofibers was maintained during an exposure test for 359 h. The quick-drying and snow-sliding behaviors of the superhydrophilic aluminum covered with anodic alumina nanofibers were demonstrated.

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.

Anodizing of High Electrically Stressed Components

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

Flores, P.; Henderson, D. J.; Good, D. E.

2013-06-01

Anodizing creates an aluminum oxide coating that penetrates into the surface as well as builds above the surface of aluminum creating a very hard ceramic-type coating with good dielectric properties. Over time and use, the electrical carrying components (or spools in this case) experience electrical breakdown, yielding undesirable x-ray dosages or failure. The spool is located in the high vacuum region of a rod pinch diode section of an x-ray producing machine. Machine operators have recorded decreases in x-ray dosages over numerous shots using the reusable spool component, and re-anodizing the interior surface of the spool does not provide themore » expected improvement. A machine operation subject matter expert coated the anodized surface with diffusion pump oil to eliminate electrical breakdown as a temporary fix. It is known that an anodized surface is very porous, and it is because of this porosity that the surface may trap air that becomes a catalyst for electrical breakdown. In this paper we present a solution of mitigating electrical breakdown by oiling. We will also present results of surface anodizing improvements achieved by surface finish preparation and surface sealing. We conclude that oiling the anodized surface and using anodized hot dip sealing processes will have similar results.« less

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.

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.

Investigation of the mechanical and chemical characteristics of nanotubular and nano-pitted anodic films on grade 2 titanium dental implant materials.

PubMed

Weszl, Miklós; Tóth, Krisztián László; Kientzl, Imre; Nagy, Péter; Pammer, Dávid; Pelyhe, Liza; Vrana, Nihal E; Scharnweber, Dieter; Wolf-Brandstetter, Cornelia; Joób F, Árpád; Bognár, Eszter

2017-09-01

The objective of this study was to investigate the reproducibility, mechanical integrity, surface characteristics and corrosion behavior of nanotubular (NT) titanium oxide arrays in comparison with a novel nano-pitted (NP) anodic film. Surface treatment processes were developed to grow homogenous NT and NP anodic films on the surface of grade 2 titanium discs and dental implants. The effect of process parameters on the surface characteristics and reproducibility of the anodic films was investigated and optimized. The mechanical integrity of the NT and NP anodic films were investigated by scanning electron microscopy, surface roughness measurement, scratch resistance and screwing tests, while the chemical and physicochemical properties were investigated in corrosion tests, contact angle measurement and X-ray photoelectron spectroscopy (XPS). The growth of NT anodic films was highly affected by process parameters, especially by temperature, and they were apt to corrosion and exfoliation. In contrast, the anodic growth of NP film showed high reproducibility even on the surface of 3-dimensional screw dental implants and they did not show signs of corrosion and exfoliation. The underlying reason of the difference in the tendency for exfoliation of the NT and NP anodic films is unclear; however the XPS analysis revealed fluorine dopants in a magnitude larger concentration on NT anodic film than on NP surface, which was identified as a possible causative. Concerning other surface characteristics that are supposed to affect the biological behavior of titanium implants, surface roughness values were found to be similar, whereas considerable differences were revealed in the wettability of the NT and NP anodic films. Our findings suggest that the applicability of NT anodic films on the surface of titanium bone implants may be limited because of mechanical considerations. In contrast, it is worth to consider the applicability of nano-pitted anodic films over nanotubular arrays for the enhancement of the biological properties of titanium implants. Copyright © 2017 Elsevier B.V. All rights reserved.

Assessment of Surface Area Characteristics of Dental Implants with Gradual Bioactive Surface Treatment

NASA Astrophysics Data System (ADS)

Czan, Andrej; Babík, Ondrej; Miklos, Matej; Záušková, Lucia; Mezencevová, Viktória

2017-10-01

Since most of the implant surface is in direct contact with bone tissue, shape and integrity of said surface has great influence on successful osseointegration. Among other characteristics that predetermine titanium of different grades of pureness as ideal biomaterial, titanium shows high mechanical strength making precise miniature machining increasingly difficult. Current titanium-based implants are often anodized due to colour coding. This anodized layer has important functional properties for right usage and also bio-compatibility of dental implants. Physical method of anodizing and usage of anodizing mediums has a significant influence on the surface quality and itself functionality. However, basic requirement of the dental implant with satisfactory properties is quality of machined surface before anodizing. Roughness, for example, is factor affecting of time length of anodizing operation and so whole productivity. The paper is focused on monitoring of surface and area characteristics, such as roughness or surface integrity after different cutting conditions of miniature machining of dental implants and their impact on suitability for creation of satisfactory anodized layer with the correct biocompatible functional properties.

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.

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.

Synthesis and characterization of hybrid micro/nano-structured NiTi surfaces by a combination of etching and anodizing

NASA Astrophysics Data System (ADS)

Huan, Z.; Fratila-Apachitei, L. E.; Apachitei, I.; Duszczyk, J.

2014-02-01

The purpose of this study was to generate hybrid micro/nano-structures on biomedical nickel-titanium alloy (NiTi). To achieve this, NiTi surfaces were firstly electrochemically etched and then anodized in fluoride-containing electrolyte. With the etching process, the NiTi surface was micro-roughened through the formation of micropits uniformly distributed over the entire surface. Following the subsequent anodizing process, self-organized nanotube structures enriched in TiO2 could be superimposed on the etched surface under specific conditions. Furthermore, the anodizing treatment significantly reduced water contact angles and increased the surface free energy compared to the surfaces prior to anodizing. The results of this study show for the first time that it is possible to create hybrid micro/nano-structures on biomedical NiTi alloys by combining electrochemical etching and anodizing under controlled conditions. These novel structures are expected to significantly enhance the surface biofunctionality of the material when compared to conventional implant devices with either micro- or nano-structured surfaces.

Synthesis and characterization of hybrid micro/nano-structured NiTi surfaces by a combination of etching and anodizing.

PubMed

Huan, Z; Fratila-Apachitei, L E; Apachitei, I; Duszczyk, J

2014-02-07

The purpose of this study was to generate hybrid micro/nano-structures on biomedical nickel-titanium alloy (NiTi). To achieve this, NiTi surfaces were firstly electrochemically etched and then anodized in fluoride-containing electrolyte. With the etching process, the NiTi surface was micro-roughened through the formation of micropits uniformly distributed over the entire surface. Following the subsequent anodizing process, self-organized nanotube structures enriched in TiO2 could be superimposed on the etched surface under specific conditions. Furthermore, the anodizing treatment significantly reduced water contact angles and increased the surface free energy compared to the surfaces prior to anodizing. The results of this study show for the first time that it is possible to create hybrid micro/nano-structures on biomedical NiTi alloys by combining electrochemical etching and anodizing under controlled conditions. These novel structures are expected to significantly enhance the surface biofunctionality of the material when compared to conventional implant devices with either micro- or nano-structured surfaces.

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.

Internal passivation of Al-based microchannel devices by electrochemical anodization

NASA Astrophysics Data System (ADS)

Hymel, Paul J.; Guan, D. S.; Mu, Yang; Meng, W. J.; Meng, Andrew C.

2015-02-01

Metal-based microchannel devices have wide-ranging applications. We report here a method to electrochemically anodize the internal surfaces of Al microchannels, with the purpose of forming a uniform and dense anodic aluminum oxide (AAO) layer on microchannel internal surfaces for chemical passivation and corrosion resistance. A pulsed electrolyte flow was utilized to emulate conventional anodization processes while replenishing depleted ionic species within Al microtubes and microchannels. After anodization, the AAO film was sealed in hot water to close the nanopores. Focused ion beam (FIB) sectioning, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) were utilized to characterize the AAO morphology and composition. Potentiodynamic polarization corrosion testing of anodized Al microtube half-sections in a NaCl solution showed an order of magnitude decrease in anodic corrosion current when compared to an unanodized tube. The surface passivation process was repeated for Al-based microchannel heat exchangers. A corrosion testing method based on the anodization process showed higher resistance to ion transport through the anodized specimens than unanodized specimens, thus verifying the internal anodization and sealing process as a viable method for surface passivation of Al microchannel devices.

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

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.

Comparison of sulfuric and oxalic acid anodizing for preparation of thermal control coatings for spacecraft

NASA Technical Reports Server (NTRS)

Le, Huong G.; Watcher, John M.; Smith, Charles A.

1988-01-01

The development of thermal control surfaces, which maintain stable solar absorptivity and infrared emissivity over long periods, is challenging due to severe conditions in low-Earth orbit (LEO). Some candidate coatings are second-surface silver-coated Teflon; second-surface, silvered optical solar reflectors made of glass or quartz; and anodized aluminum. Sulfuric acid anodized and oxalic acid anodized aluminum was evaluated under simulated LEO conditions. Oxalic acid anodizing shows promise of greater stability in LEO over long missions, such as the 30 years planned for the Space Station. However, sulfuric acid anodizing shows lower solar absorptivity.

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.

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

Determination of the dissolution slowness surface by study of etched shapes I. Morphology of the dissolution slowness surface and theoretical etched shapes

NASA Astrophysics Data System (ADS)

Leblois, T.; Tellier, C. R.

1992-07-01

We propose a theoretical model for the anisotropic etching of crystals, in order to be applied in the micromachining. The originality of the model is due to the introduction of dissolution tensors to express the representative surface of the dissolution slowness. The knowledge of the equation of the slowness surface allows us to determine the trajectories of all the elements which compose the starting surface. It is then possible to construct the final etched shape by numerical simulation. Several examples are given in this paper which show that the final etched shapes are correlated to the extrema of the dissolution slowness. Since the slowness surface must be determined from experiments, emphasis is placed on difficulties encountered when we correlate theory to experiments. Nous avons modélisé le processus de dissolution anisotrope des cristaux en vue d'une application à la simulation des formes obtenues par photolithogravure chimique. La principale originalité de ce modèle tient à l'introduction de tenseurs de dissolution pour exprimer la surface représentative de la lenteur de dissolution. La connaissance de l'équation de la lenteur de dissolution permet de calculer les trajectoires des différents éléments constituant la surface de départ puis de reconstituer par simulation la forme dissoute. Les simulations démontrent que les formes limites des cristaux dissous sont corrélées aux extrema de la lenteur de dissolution. La détermination de la surface de la lenteur se faisant à partir de mesures expérimetales, nous nous sommes efforcés de montrer toutes les difficultés attachées à cette analyse.

Surface characterization of anodized zirconium for biomedical applications

NASA Astrophysics Data System (ADS)

Sanchez, A. Gomez; Schreiner, W.; Duffó, G.; Ceré, S.

2011-05-01

Mechanical properties and corrosion resistance of zirconium make this material suitable for biomedical implants. Its good in vivo performance is mainly due to the presence of a protective oxide layer that minimizes corrosion rate, diminishes the amount of metallic ions released to the biological media and facilitates the osseointegration process. Since the implant surface is the region in contact with living tissues, the characteristics of the surface film are of great interest. Surface modification is a route to enhance both biocompatibility and corrosion resistance of permanent implant materials. Anodizing is presented as an interesting process to modify metal surfaces with good reproducibility and independence of the geometry. In this work the surface of zirconium before and after anodizing in 1 mol/L phosphoric acid solution at a fixed potential between 3 and 30 V, was characterized by means of several surface techniques. It was found that during anodization the surface oxide grows with an inhomogeneous coverage on zirconium surface, modifying the topography. The incorporation of P from the electrolyte to the surface oxide during the anodizing process changes the surface chemistry. After 30 days of immersion in Simulated Body Fluid (SBF) solution, Ca-P rich compounds were present on anodized zirconium.

Li 2S Film Formation on Lithium Anode Surface of Li–S batteries

DOE PAGES

Liu, Zhixiao; Bertolini, Samuel; Balbuena, Perla B.; ...

2016-02-02

The precipitation of lithium sulfide (Li 2S) on the Li metal anode surface adversely impacts the performance of lithium–sulfur (Li–S) batteries. In this work, a first-principles approach including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations is employed to theoretically elucidate the Li 2S/Li metal surface interactions and the nucleation and growth of a Li 2S film on the anode surface due to long-chain polysulfide decomposition during battery operation. DFT analyses of the energetic properties and electronic structures demonstrate that a single molecule adsorption on Li surface releases energy forming chemical bonds between the S atoms andmore » Li atoms from the anode surface. Reaction pathways of the Li 2S film formation on Li metal surfaces are investigated based on DFT calculations. It is found that a distorted Li 2S (111) plane forms on a Li(110) surface and a perfect Li 2S (111) plane forms on a Li(111) surface. The total energy of the system decreases along the reaction pathway; hence Li 2S film formation on the Li anode surface is thermodynamically favorable. Finally, the calculated difference charge density of the Li 2S film/Li surface suggests that the precipitated film would interact with the Li anode via strong chemical bonds. AIMD simulations reveal the role of the anode surface structure and the origin of the Li 2S formation via decomposition of Li 2S 8 polysulfide species formed at the cathode side and dissolved in the electrolyte medium in which they travel to the anode side during battery cycling.« less

Li 2S Film Formation on Lithium Anode Surface of Li–S batteries

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

Liu, Zhixiao; Bertolini, Samuel; Balbuena, Perla B.

The precipitation of lithium sulfide (Li 2S) on the Li metal anode surface adversely impacts the performance of lithium–sulfur (Li–S) batteries. In this work, a first-principles approach including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations is employed to theoretically elucidate the Li 2S/Li metal surface interactions and the nucleation and growth of a Li 2S film on the anode surface due to long-chain polysulfide decomposition during battery operation. DFT analyses of the energetic properties and electronic structures demonstrate that a single molecule adsorption on Li surface releases energy forming chemical bonds between the S atoms andmore » Li atoms from the anode surface. Reaction pathways of the Li 2S film formation on Li metal surfaces are investigated based on DFT calculations. It is found that a distorted Li 2S (111) plane forms on a Li(110) surface and a perfect Li 2S (111) plane forms on a Li(111) surface. The total energy of the system decreases along the reaction pathway; hence Li 2S film formation on the Li anode surface is thermodynamically favorable. Finally, the calculated difference charge density of the Li 2S film/Li surface suggests that the precipitated film would interact with the Li anode via strong chemical bonds. AIMD simulations reveal the role of the anode surface structure and the origin of the Li 2S formation via decomposition of Li 2S 8 polysulfide species formed at the cathode side and dissolved in the electrolyte medium in which they travel to the anode side during battery cycling.« less

Li2S Film Formation on Lithium Anode Surface of Li-S batteries.

PubMed

Liu, Zhixiao; Bertolini, Samuel; Balbuena, Perla B; Mukherjee, Partha P

2016-02-01

The precipitation of lithium sulfide (Li2S) on the Li metal anode surface adversely impacts the performance of lithium-sulfur (Li-S) batteries. In this study, a first-principles approach including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations is employed to theoretically elucidate the Li2S/Li metal surface interactions and the nucleation and growth of a Li2S film on the anode surface due to long-chain polysulfide decomposition during battery operation. DFT analyses of the energetic properties and electronic structures demonstrate that a single molecule adsorption on Li surface releases energy forming chemical bonds between the S atoms and Li atoms from the anode surface. Reaction pathways of the Li2S film formation on Li metal surfaces are investigated based on DFT calculations. It is found that a distorted Li2S (111) plane forms on a Li(110) surface and a perfect Li2S (111) plane forms on a Li(111) surface. The total energy of the system decreases along the reaction pathway; hence Li2S film formation on the Li anode surface is thermodynamically favorable. The calculated difference charge density of the Li2S film/Li surface suggests that the precipitated film would interact with the Li anode via strong chemical bonds. AIMD simulations reveal the role of the anode surface structure and the origin of the Li2S formation via decomposition of Li2S8 polysulfide species formed at the cathode side and dissolved in the electrolyte medium in which they travel to the anode side during battery cycling.

Optimal condition for fabricating superhydrophobic Aluminum surfaces with controlled anodizing processes

NASA Astrophysics Data System (ADS)

Saffari, Hamid; Sohrabi, Beheshteh; Noori, Mohammad Reza; Bahrami, Hamid Reza Talesh

2018-03-01

A single step anodizing process is used to produce micro-nano structures on Aluminum (1050) substrates with sulfuric acid as electrolyte. Therefore, surface energy of the anodized layer is reduced using stearic acid modification. Undoubtedly, effects of different parameters including anodizing time, electrical current, and type and concentration of electrolyte on the final contact angle are systemically studied and optimized. Results show that anodizing current of 0.41 A, electrolyte (sulfuric acid) concentration of 15 wt.% and anodizing time of 90 min are optimal conditions which give contact angle as high as 159.2° and sliding angle lower than 5°. Moreover, the study reveals that adding oxalic acid to the sulfuric acid cannot enhance superhydrophobicity of the samples. Also, scanning electron microscopy images of samples show that irregular (bird's nest) structures present on the surface instead of high-ordered honeycomb structures expecting from normal anodizing process. Additionally, X-ray diffraction analysis of the samples shows that only amorphous structures present on the surface. The Brunauer-Emmett-Teller (BET) specific surface area of the anodized layer is 2.55 m2 g-1 in optimal condition. Ultimately, the surface keeps its hydrophobicity in air and deionized water (DIW) after one week and 12 weeks, respectively.

Insight into Flufenamic Acid Cocrystal Dissolution in the Presence of a Polymer in Solution: from Single Crystal to Powder Dissolution.

PubMed

Guo, Minshan; Wang, Ke; Qiao, Ning; Fábián, László; Sadiq, Ghazala; Li, Mingzhong

2017-12-04

Effects of three polymers, polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), and copolymer of vinylpyrrolidone/vinyl acetate (PVP-VA), on the dissolution behavior of the cocrystals of flufenamic acid with theophylline (FFA-TP CO) and nicotinamide (FFA-NIC CO) were investigated at multiple length scales. At the molecular level, the interactions of crystal surfaces with a polymer were analyzed by observing etching pattern changes using atomic force microscopy. At the macroscopic scale, dissolution rates of particular faces of a single crystal were determined by measurement of the physical retreat velocities of the faces using optical light microscopy. In the bulk experiments, the FFA concentration in a dissolution medium in the absence or presence of a polymer was measured under both sink and nonsink conditions. It has been found that the dissolution mechanisms of FFA-TP CO are controlled by the defect sites of the crystal surface and by precipitation of the parent drug FFA as individual crystals in the bulk fluid. In contrast, the dissolution mechanisms of FFA-NIC CO are controlled by surface layer removal and by a surface precipitation mechanism, where the parent drug FFA precipitates directly onto the surface of the dissolving cocrystals. Through controlling the dissolution environment by predissolving a polymer, PVP or PVP-VA, which can interact with the crystal surface to alter its dissolution properties, improved solubility, and dissolution rates of FFA-TP CO and FFA-NIC CO have been demonstrated.

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

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.

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

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

Advances in aluminum anodizing

NASA Technical Reports Server (NTRS)

Dale, K. H.

1969-01-01

White anodize is applied to aluminum alloy surfaces by specific surface preparation, anodizing, pigmentation, and sealing techniques. The development techniques resulted in alloys, which are used in space vehicles, with good reflectance values and excellent corrosive resistance.

Dissolution of minerals with rough surfaces

NASA Astrophysics Data System (ADS)

de Assis, Thiago A.; Aarão Reis, Fábio D. A.

2018-05-01

We study dissolution of minerals with initial rough surfaces using kinetic Monte Carlo simulations and a scaling approach. We consider a simple cubic lattice structure, a thermally activated rate of detachment of a molecule (site), and rough surface configurations produced by fractional Brownian motion algorithm. First we revisit the problem of dissolution of initial flat surfaces, in which the dissolution rate rF reaches an approximately constant value at short times and is controlled by detachment of step edge sites. For initial rough surfaces, the dissolution rate r at short times is much larger than rF ; after dissolution of some hundreds of molecular layers, r decreases by some orders of magnitude across several time decades. Meanwhile, the surface evolves through configurations of decreasing energy, beginning with dissolution of isolated sites, then formation of terraces with disordered boundaries, their growth, and final smoothing. A crossover time to a smooth configuration is defined when r = 1.5rF ; the surface retreat at the crossover is approximately 3 times the initial roughness and is temperature-independent, while the crossover time is proportional to the initial roughness and is controlled by step-edge site detachment. The initial dissolution process is described by the so-called rough rates, which are measured for fixed ratios between the surface retreat and the initial roughness. The temperature dependence of the rough rates indicates control by kink site detachment; in general, it suggests that rough rates are controlled by the weakest microscopic bonds during the nucleation and formation of the lowest energy configurations of the crystalline surface. Our results are related to recent laboratory studies which show enhanced dissolution in polished calcite surfaces. In the application to calcite dissolution in alkaline environment, the minimal values of recently measured dissolution rate spectra give rF ∼10-9 mol/(m2 s), and the calculated rate laws of our model give rough rates in the range 10-6 -10-5 mol/(m2 s). This estimate is consistent with the range of calcite dissolution rates obtained in a recent work after treatment of literature data, which suggests the universal control of kink site dissolution in short term laboratory works. The weak effects of lattice size on our results also suggest that smoothing of mineral grain surfaces across geological times may be a microscopic explanation for the difference of chemical weathering rate of silicate minerals in laboratory and in the environment.

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.

Dissolution of cinnabar (HgS) in the presence of natural organic matter

USGS Publications Warehouse

Waples, J.S.; Nagy, K.L.; Aiken, G.R.; Ryan, J.N.

2005-01-01

Cinnabar (HgS) dissolution rates were measured in the presence of 12 different natural dissolved organic matter (DOM) isolates including humic, fulvic, and hydrophobic acid fractions. Initial dissolution rates varied by 1.3 orders of magnitude, from 2.31 ?? 10-13 to 7.16 ?? 10-12 mol Hg (mg C)-1 m-2 s-1. Rates correlate positively with three DOM characteristics: specific ultraviolet absorbance (R2 = 0.88), aromaticity (R2 = 0.80), and molecular weight (R2 = 0.76). Three experimental observations demonstrate that dissolution was controlled by the interaction of DOM with the cinnabar surface: (1) linear rates of Hg release with time, (2) significantly reduced rates when DOM was physically separated from the surface by dialysis membranes, and (3) rates that approached constant values at a specific ratio of DOM concentration to cinnabar surface area, suggesting a maximum surface coverage by dissolution-reactive DOM. Dissolution rates for the hydrophobic acid fractions correlate negatively with sorbed DOM concentrations, indicating the presence of a DOM component that reduced the surface area of cinnabar that can be dissolved. When two hydrophobic acid isolates that enhanced dissolution to different extents were mixed equally, a 20% reduction in rate occurred compared to the rate with the more dissolution-enhancing isolate alone. Rates in the presence of the more dissolution-enhancing isolate were reduced by as much as 60% when cinnabar was prereacted with the isolate that enhanced dissolution to a lesser extent. The data, taken together, imply that the property of DOM that enhances cinnabar dissolution is distinct from the property that causes it to sorb irreversibly to the cinnabar surface. Copyright ?? 2005 Elsevier Ltd.

Morphological evolution of dissolving feldspar particles with anisotropic surface kinetics and implications for dissolution rate normalization and grain size dependence: A kinetic modeling study

NASA Astrophysics Data System (ADS)

Zhang, Li; Lüttge, Andreas

2009-11-01

With previous two-dimensional (2D) simulations based on surface-specific feldspar dissolution succeeding in relating the macroscopic feldspar kinetics to the molecular-scale surface reactions of Si and Al atoms ( Zhang and Lüttge, 2008, 2009), we extended our modeling effort to three-dimensional (3D) feldspar particle dissolution simulations. Bearing on the same theoretical basis, the 3D feldspar particle dissolution simulations have verified the anisotropic surface kinetics observed in the 2D surface-specific simulations. The combined effect of saturation state, pH, and temperature on the surface kinetics anisotropy has been subsequently evaluated, found offering diverse options for morphological evolution of dissolving feldspar nanoparticles with varying grain sizes and starting shapes. Among the three primary faces on the simulated feldspar surface, the (1 0 0) face has the biggest dissolution rate across an extensively wide saturation state range and thus acquires a higher percentage of the surface area upon dissolution. The slowest dissolution occurs to either (0 0 1) or (0 1 0) faces depending on the bond energies of Si-(O)-Si ( ΦSi-O-Si/ kT) and Al-(O)-Si ( ΦAl-O-Si/ kT). When the ratio of ΦSi-O-Si/ kT to ΦAl-O-Si/ kT changes from 6:3 to 7:5, the dissolution rates of three primary faces change from the trend of (1 0 0) > (0 1 0) > (0 0 1) to the trend of (1 0 0) > (0 0 1) > (0 1 0). The rate difference between faces becomes more distinct and accordingly edge rounding becomes more significant. Feldspar nanoparticles also experience an increasing degree of edge rounding from far-from-equilibrium to close-to-equilibrium. Furthermore, we assessed the connection between the continuous morphological modification and the variation in the bulk dissolution rate during the dissolution of a single feldspar particle. Different normalization treatments equivalent to the commonly used mass, cube assumption, sphere assumption, geometric surface area, and reactive surface area normalizations have been used to normalize the bulk dissolution rate. For each of the treatments, time consistence and grain size dependence of the normalized dissolution rate have been evaluated and the results revealed significant dependences on the magnitude of surface kinetic anisotropy under differing environmental conditions. In general, the normalized dissolution rates are strongly dependent on grain size. Time-consistent normalization treatment varies with the investigated condition. The modeling results suggest that the sphere-, cube-, and BET-normalized dissolution rates are appropriate under the far-from-equilibrium conditions at low pH where these normalizations are time-consistent and are slightly dependent on grain size.

Surface chemistry of a hydrogenated mesoporous p-type silicon

NASA Astrophysics Data System (ADS)

Media, El-Mahdi; Outemzabet, Ratiba

2017-02-01

The finality of this work is devoted to the grafting of organic molecules on hydrogen passivated mesoporous silicon surfaces. The study would aid in the development for the formation of organic monolayers on silicon surface to be exploited for different applications such as the realisation of biosensors and medical devices. The basic material is silicon which has been first investigated by FTIR at atomistic plane during the anodic forward and backward polarization (i.e. "go" and "return"). For this study, we applied a numerical program based on least squares method to infrared absorbance spectra obtained by an in situ attenuated total reflection on p-type silicon in diluted HF electrolyte. Our numerical treatment is based on the fitting of the different bands of IR absorbance into Gaussians corresponding to the different modes of vibration of molecular groups such as siloxanes and hydrides. An adjustment of these absorbance bands is done systematically. The areas under the fitted bands permit one to follow the intensity of the different modes of vibration that exist during the anodic forward and backward polarization in order to compare the reversibility of the phenomenon of the anodic dissolution of silicon. It permits also to follow the evolution between the hydrogen silicon termination at forward and backward scanning applied potential. Finally a comparison between the states of the initial and final surface was carried out. We confirm the presence of clearly four and three distinct vibration modes of siloxanes/hydroxide, SiOx, and hydrides, SiHx, respectively. The results show clearly that the adsorbed species found in the final stage after an electrochemical treatment consist of surface hydrogen and they show also that the surface morphology is different compared to the starting one, which is considered as reference. It is clear that the H-terminated of porous silicon surface is hydrophobic in nature. The hydrophobic character of this surface makes difficult the grafting of a probe which serves to get other molecules; where from the necessity of the presence of a hydrophilic surface on the porous silicon surface. This will facilitate the penetration and the grafting of the molecules probes. So to improve the penetration and the grafting of the organic molecules or the immobilization of the probes on the hydrogenated mesoporous silicon surfaces under wet chemical conditions an intermediate step is required. In this second study, we use the following procedure. After the porosification of the silicon by electrochemical anodisation, the porous SiH layer returns a hydrophobic surface. This stage is a starting point of multistep scheme for the surface modification. The next step is the thermal hydrosilylation in order to have an acidic surface. The acidic surface was then modified by the chains of Poly(ethylene glycol) (PEG) which is a highly investigated polymer for the covalent modification of biological macromolecules and surfaces. The grafting of PEG returns a hydrophilic surface confirmed by the IR results.

Etching of semiconductor cubic crystals: Determination of the dissolution slowness surfaces

NASA Astrophysics Data System (ADS)

Tellier, C. R.

1990-03-01

Equations of the representative surface of dissolution slowness for cubic crystals are determined in the framework of a tensorial approach of the orientation-dependent etching process. The independent dissolution constants are deduced from symmetry considerations. Using previous data on the chemical etching of germanium and gallium arsenide crystals, some possible polar diagrams of the dissolution slowness are proposed. A numerical and graphical simulation method is used to obtain the derived dissolution shapes. The influence of extrema in the dissolution slowness on the successive dissolution shapes is also examined. A graphical construction of limiting shapes of etched crystals appears possible using the tensorial representation of the dissolution slowness.

Anode initiated surface flashover switch

DOEpatents

Brainard, John P.; Koss, Robert J.

2003-04-29

A high voltage surface flashover switch has a pair of electrodes spaced by an insulator. A high voltage is applied to an anode, which is smaller than the opposing, grounded, cathode. When a controllable source of electrons near the cathode is energized, the electrons are attracted to the anode where they reflect to the insulator and initiate anode to cathode breakdown.

Fabrication of anodic aluminium oxide templates on curved surfaces.

PubMed

Yin, Aijun; Guico, Rodney S; Xu, Jimmy

2007-01-24

Aluminium anodization provides a simple and inexpensive way to obtain nanoporous templates with uniform and controllable pore diameters and periods over a wide range. Moreover, one of the interesting possibilities afforded by the anodization process is that the anodization can take place on arbitrary surfaces, such as curved surfaces, which has not yet been well studied or applied in nanofabrication. In this paper, we characterize the anodization of Al films on silicon substrates with a curved top surface. The structures of the resultant anodic aluminium oxide (AAO) films are examined by scanning electron microscopy. Unique features including cessation, bending, and branching of pore channels are observed in the curved area. Possible growth mechanisms are proposed, which can also contribute to the understanding of the self-organization mechanism in the formation of porous AAO membranes. The new structures may open new opportunities in optical, electronic and electrochemical applications.

Formic acid fuel cells and catalysts

DOEpatents

Masel, Richard I.; Larsen, Robert; Ha, Su Yun

2010-06-22

An exemplary fuel cell of the invention includes a formic acid fuel solution in communication with an anode (12, 134), an oxidizer in communication with a cathode (16, 135) electrically linked to the anode, and an anode catalyst that includes Pd. An exemplary formic acid fuel cell membrane electrode assembly (130) includes a proton-conducting membrane (131) having opposing first (132) and second surfaces (133), a cathode catalyst on the second membrane surface, and an anode catalyst including Pd on the first surface.

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.

[Corrosion resistant properties of different anodized microtopographies on titanium surfaces].

PubMed

Fangjun, Huo; Li, Xie; Xingye, Tong; Yueting, Wang; Weihua, Guo; Weidong, Tian

2015-12-01

To investigate the corrosion resistant properties of titanium samples prepared by anodic oxidation with different surface morphologies. Pure titanium substrates were treated by anodic oxidation to obtain porous titanium films in micron, submicron, and micron-submicron scales. The surface morphologies, coating cross-sectional morphologies, crystalline structures, and surface roughness of these samples were characterized. Electrochemical technique was used to measure the corrosion potential (Ecorr), current density of corrosion (Icorr), and polarization resistance (Rp) of these samples in a simulated body fluid. Pure titanium could be modified to exhibit different surface morphologies by the anodic oxidation technique. The Tafel curve results showed that the technique can improve the corrosion resistance of pure titanium. Furthermore, the corrosion resistance varied with different surface morphologies. The submicron porous surface sample demonstrated the best corrosion resistance, with maximal Ecorr and Rp and minimal Icorr. Anodic oxidation technology can improve the corrosion resistance of pure titanium in a simulated body fluid. The submicron porous surface sample exhibited the best corrosion resistance because of its small surface area and thick barrier layer.

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.

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

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.

Combinatorial localized dissolution analysis: Application to acid-induced dissolution of dental enamel and the effect of surface treatments.

PubMed

Parker, Alexander S; Al Botros, Rehab; Kinnear, Sophie L; Snowden, Michael E; McKelvey, Kim; Ashcroft, Alexander T; Carvell, Mel; Joiner, Andrew; Peruffo, Massimo; Philpotts, Carol; Unwin, Patrick R

2016-08-15

A combination of scanning electrochemical cell microscopy (SECCM) and atomic force microscopy (AFM) is used to quantitatively study the acid-induced dissolution of dental enamel. A micron-scale liquid meniscus formed at the end of a dual barrelled pipette, which constitutes the SECCM probe, is brought into contact with the enamel surface for a defined period. Dissolution occurs at the interface of the meniscus and the enamel surface, under conditions of well-defined mass transport, creating etch pits that are then analysed via AFM. This technique is applied to bovine dental enamel, and the effect of various treatments of the enamel surface on acid dissolution (1mM HNO3) is studied. The treatments investigated are zinc ions, fluoride ions and the two combined. A finite element method (FEM) simulation of SECCM mass transport and interfacial reactivity, allows the intrinsic rate constant for acid-induced dissolution to be quantitatively determined. The dissolution of enamel, in terms of Ca(2+) flux ( [Formula: see text] ), is first order with respect to the interfacial proton concentration and given by the following rate law: [Formula: see text] , with k0=0.099±0.008cms(-1). Treating the enamel with either fluoride or zinc ions slows the dissolution rate, although in this model system the partly protective barrier only extends around 10-20nm into the enamel surface, so that after a period of a few seconds dissolution of modified surfaces tends towards that of native enamel. A combination of both treatments exhibits the greatest protection to the enamel surface, but the effect is again transient. Copyright © 2016 Elsevier Inc. All rights reserved.

Dissolution of solid dosage form. II. Equations for the dissolution of nondisintegrating tablet under the sink condition.

PubMed

Yonezawa, Y; Shirakura, K; Otsuka, A; Sunada, H

1991-03-01

An equation for dissolution from the whole surface of a nondisintegrating single component tablet under the sink condition was derived. Also, equations for several dissolution manners of the tablet under the sink condition were derived in the postulation of the dominant dissolution rate constant which determines the dissolution manner. The applicability or validity of these equations were examined by the dissolution measurements with nondisintegrating single component tablets. About one-tenth the amount of the amount needed to saturate the solution was used to prepare a tablet, and dissolution measurements were carried out with the tablet whose flat or side surface was masked with an adhesive tape in accordance with the conditions for derivation of equations. Among the derived equations, dissolution from the whole surface of a tablet was expressed by a form similar to the cube root law equation for particles. Hence, a single component tablet compressed by the use of a suitable amount was thought to behave like a single crystal. Also, equations derived for several dissolution manners were thought to be applicable for the dissolution of a nonspherical particle and crystal concerning the crystal's habit and its dissolution property, and the extended applicability was examined by converting the crystal into a simplified or idealized form, i.e., rectangle or plate.

Surface characterization in composite and titanium bonding: Carbon fiber surface treatments for improved adhesion to thermoplastic polymers

NASA Technical Reports Server (NTRS)

Devilbiss, T. A.; Wightman, J. P.

1987-01-01

The effect of anodization in NaOH, H2SO4, and amine salts on the surface chemistry of carbon fibers was examined by X-ray photoelectron spectroscopy (XPS). The surfaces of carbon fibers after anodization in NaOH and H2SO4 were examined by scanning transmission electron microscopy (STEM), angular dependent XPS, UV absorption spectroscopy of the anodization bath, secondary ion mass spectrometry, and polar/dispersive surface energy analysis. Hercules AS-4, Dexter Hysol XAS, and Union Carbide T-300 fibers were examined by STEM, angular dependent XPS, and breaking strength measurement before and after commercial surface treatment. Oxygen and nitrogen were added to the fiber surfaces by anodization in amine salts. Analysis of the plasmon peak in the carbon 1s signal indicated that H2SO4 anodization affected the morphological structure of the carbon fiber surface. The work of adhesion of carbon fibers to thermoplastic resins was calculated using the geometric mean relationship. A correlation was observed between the dispersive component of the work of adhesion and the interfacial adhesion.

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.

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.

In situ dissolution analysis of pharmaceutical dosage forms using coherent anti-Stokes Raman scattering (CARS) microscopy

NASA Astrophysics Data System (ADS)

Fussell, A. L.; Garbacik, E. T.; Löbmann, K.; Offerhaus, H. L.; Kleinebudde, P.; Strachan, C. J.

2014-02-01

A custom-built intrinsic flow-through dissolution setup was developed and incorporated into a home-built CARS microscope consisting of a synchronously pumped optical parametric oscillator (OPO) and an inverted microscope with a 20X/0.5NA objective. CARS dissolution images (512×512 pixels) were collected every 1.12s for the duration of the dissolution experiment. Hyperspectral CARS images were obtained pre- and postdissolution by rapidly imaging while sweeping the wavelength of the OPO in discrete steps so that each frame in the data stack corresponds to a vibrational frequency. An image-processing routine projects this hyperspectral data into a single image wherein each compound appears with a unique color. Dissolution was conducted using theophylline and cimetidine-naproxen co-amorphous mixture. After 15 minutes of theophylline dissolution, hyperspectral imaging showed a conversion of theophylline anhydrate to the monohydrate, confirmed by a peak shift in the CARS spectra. CARS dissolution images showed that monohydrate crystal growth began immediately and reached a maximum with complete surface coverage at about 300s. This result correlated with the UV dissolution data where surface crystal growth on theophylline compacts resulted in a rapidly reducing dissolution rate during the first 300s. Co-amorphous cimetidinenaproxen didn't appear to crystallize during dissolution. We observed solid-state conversions on the compact's surface in situ during dissolution. Hyperspectral CARS imaging allowed visual discrimination between the solid-state forms on the compact's surface. In the case of theophylline we were able to correlate the solid-state change with a change in dissolution rate.

Anodic behavior of uranium in AlCl3-1-ethyl-3-methyl-imidazolium chloride ionic liquid

NASA Astrophysics Data System (ADS)

Jiang, Yidong; Luo, Lizhu; Wang, Shaofei; Bin, Ren; Zhang, Guikai; Wang, Xiaolin

2018-01-01

The oxidation state of metals unambiguously affects its anodic behavior in ionic liquid. We systematically investigated the anodic behavior of uranium with different surface oxidation states by electrochemical measurements, spectroscopic methods and surface analysis techniques. In the anodic process, metal uranium can be oxidized to U3+. The corresponding products accumulated on the metal/ILs interface will form a viscous layer. The anodic behavior of uranium is also strongly dependent upon the surface oxide states including thickness and homogeneity of the oxide film. With an increase in the thickness of oxide film, it will be breached at potentials in excess of a critical value. A uniform oxide on uranium surface can be breached evenly, and then the underlying metal starts to dissolve forming a viscous layer which can facilitate uniformly stripping of oxide, thus giving an oxide-free surface. Otherwise, a nonuniform oxide can result in a severe pitted surface with residue oxygen.

Final Report: Rational Design of Anode Surface Chemistry in Microbial Fuel Cells for Improved Exoelectrogen Attachment and Electron Transfer

DTIC Science & Technology

2015-12-21

SECURITY CLASSIFICATION OF: The overall goal of this project is to determine how electrode surface chemistry can be rationally designed to decrease...2015 Approved for Public Release; Distribution Unlimited Final Report: Rational Design of Anode Surface Chemistry in Microbial Fuel Cells for...ABSTRACT Final Report: Rational Design of Anode Surface Chemistry in Microbial Fuel Cells for Improved Exoelectrogen Attachment and Electron Transfer

Cathodic Corrosion at the Bismuth-Ionic Liquid Electrolyte Interface under Conditions for CO 2 Reduction

DOE PAGES

Medina Ramos, Jonnathan; Zhang, Weiwei; Yoon, Kichul; ...

2018-03-08

Bismuth electrodes undergo distinctive electrochemically induced structural changes in nonaqueous imidazolium ([Im])(+))-based ionic liquid solutions under cathodic polarization. In situ X-ray reflectivity (XR) studies have been undertaken to probe well-ordered Bi (001) films which originally contain a native Bi 2O 3 layer. This oxide layer gets reduced to Bi(0)during the first cyclic voltammetry (CV) scan in acetonitrile solutions containing 1-butyl-3-methylimidazolium ([BMIM](+)) electrolytes. Approximately 60% of the Bi (001) Bragg peak reflectivity is lost during a potential sweep between -1.5 and -1.9 V vs Ag/AgCI due to a similar to 4-10% thinning and a similar to 40% decrease in lateral sizemore » of Bi (001) domains, which are mostly reversed during the anodic scan. Repeated potential cycling enhances the thinning and roughening of the films, suggesting that partial dissolution of Bi ensues during negative polarization. The mechanism of this behavior is understood through molecular dynamics simulations using ReaxFF and density functional theory (DFT) calculations. Both approaches indicate that [Im] + cations bind to the metal surface more strongly than tetrabutylammonium (TBA +) as the potential and the charge on the Bi surface become more negative. ReaxFF simulations predict a higher degree of disorder for a negatively charged Bi (001) slab in the presence of the [Im](+)cations and substantial migration of Bi atoms from the surface. DFT simulations show the formation of Bi center dot center dot center dot[Im] + complexes that lead to the dissolution of Bi atoms from step edges on the Bi (001) surface at potentials between -1.65 and -1.95 V. Bi desorption from a flat terrace requires a potential of approximately -2.25 V. Together, these results suggest the formation of a Bi center dot center dot center dot[Im] + complex through partial cathodic corrosion of the Bi film under conditions (potential and electrolyte composition) that favor the catalytic reduction of CO 2 .« less

Cathodic Corrosion at the Bismuth-Ionic Liquid Electrolyte Interface under Conditions for CO 2 Reduction

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

Medina Ramos, Jonnathan; Zhang, Weiwei; Yoon, Kichul

Bismuth electrodes undergo distinctive electrochemically induced structural changes in nonaqueous imidazolium ([Im])(+))-based ionic liquid solutions under cathodic polarization. In situ X-ray reflectivity (XR) studies have been undertaken to probe well-ordered Bi (001) films which originally contain a native Bi 2O 3 layer. This oxide layer gets reduced to Bi(0)during the first cyclic voltammetry (CV) scan in acetonitrile solutions containing 1-butyl-3-methylimidazolium ([BMIM](+)) electrolytes. Approximately 60% of the Bi (001) Bragg peak reflectivity is lost during a potential sweep between -1.5 and -1.9 V vs Ag/AgCI due to a similar to 4-10% thinning and a similar to 40% decrease in lateral sizemore » of Bi (001) domains, which are mostly reversed during the anodic scan. Repeated potential cycling enhances the thinning and roughening of the films, suggesting that partial dissolution of Bi ensues during negative polarization. The mechanism of this behavior is understood through molecular dynamics simulations using ReaxFF and density functional theory (DFT) calculations. Both approaches indicate that [Im] + cations bind to the metal surface more strongly than tetrabutylammonium (TBA +) as the potential and the charge on the Bi surface become more negative. ReaxFF simulations predict a higher degree of disorder for a negatively charged Bi (001) slab in the presence of the [Im](+)cations and substantial migration of Bi atoms from the surface. DFT simulations show the formation of Bi center dot center dot center dot[Im] + complexes that lead to the dissolution of Bi atoms from step edges on the Bi (001) surface at potentials between -1.65 and -1.95 V. Bi desorption from a flat terrace requires a potential of approximately -2.25 V. Together, these results suggest the formation of a Bi center dot center dot center dot[Im] + complex through partial cathodic corrosion of the Bi film under conditions (potential and electrolyte composition) that favor the catalytic reduction of CO 2 .« less

Design and fabrication of Ni nanowires having periodically hollow nanostructures

NASA Astrophysics Data System (ADS)

Sada, Takao; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2014-09-01

We propose a concept for the design and fabrication of metal nanowires having periodically hollow nanostructures inside the pores of an anodic aluminum oxide (AAO) membrane using a sacrificial metal. In this study, nickel (Ni) and silver (Ag) were used as the base metal and the sacrificial metal, respectively. Alternating an applied potential between -0.4 and -1.0 V provided alternatively deposited Ni and Ag segments in a Ni-Ag `barcode' nanowire with a diameter of 18 or 35 nm. After etching away the Ag segments, we fabricated Ni nanowires with nanopores of 12 +/- 5.3 nm. Such nanostructure formation is explained by the formation of a Ni shell layer over the surface of the Ag segments due to the strong affinity of Ni2+ for the interior surfaces of AAO. The Ni shell layer allows the Ni segments to remain even after dissolution of the Ag segments. Because the electroplating conditions can be easily controlled, we could carefully adjust the size and pitch of the periodically hollow nanospaces. We also describe a method for the fabrication of Ni nanorods by forming an Ag shell instead of a Ni shell on the Ni-Ag barcode nanowire, in which the interior of the AAO surfaces was modified with a compound bearing a thiol group prior to electroplating.We propose a concept for the design and fabrication of metal nanowires having periodically hollow nanostructures inside the pores of an anodic aluminum oxide (AAO) membrane using a sacrificial metal. In this study, nickel (Ni) and silver (Ag) were used as the base metal and the sacrificial metal, respectively. Alternating an applied potential between -0.4 and -1.0 V provided alternatively deposited Ni and Ag segments in a Ni-Ag `barcode' nanowire with a diameter of 18 or 35 nm. After etching away the Ag segments, we fabricated Ni nanowires with nanopores of 12 +/- 5.3 nm. Such nanostructure formation is explained by the formation of a Ni shell layer over the surface of the Ag segments due to the strong affinity of Ni2+ for the interior surfaces of AAO. The Ni shell layer allows the Ni segments to remain even after dissolution of the Ag segments. Because the electroplating conditions can be easily controlled, we could carefully adjust the size and pitch of the periodically hollow nanospaces. We also describe a method for the fabrication of Ni nanorods by forming an Ag shell instead of a Ni shell on the Ni-Ag barcode nanowire, in which the interior of the AAO surfaces was modified with a compound bearing a thiol group prior to electroplating. Electronic supplementary information (ESI) available: Information on the current profile during pulsed-electroplating, the histogram for the Ni and nanopores, and STEM images of obtained nanowires. See DOI: 10.1039/c4nr02625j

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.

Hierarchically ordered self-lubricating superhydrophobic anodized aluminum surfaces with enhanced corrosion resistance.

PubMed

Vengatesh, Panneerselvam; Kulandainathan, Manickam Anbu

2015-01-28

Herein, we report a facile method for the fabrication of self-lubricating superhydrophobic hierarchical anodic aluminum oxide (AAO) surfaces with improved corrosion protection, which is greatly anticipated to have a high impact in catalysis, aerospace, and the shipping industries. This method involves chemical grafting of as-formed AAO using low surface free energy molecules like long chain saturated fatty acids, perfluorinated fatty acid (perfluorooctadecanoic acid, PFODA), and perfluorosulfonicacid-polytetrafluoroethylene copolymer. The pre and post treatment processes in the anodization of aluminum (Al) play a vital role in the grafting of fatty acids. Wettability and surface free energy were analyzed using a contact angle meter and achieved 161.5° for PFODA grafted anodized aluminum (PFODA-Al). This study was also aimed at evaluating the surface for corrosion resistance by Tafel polarization and self-lubricating properties by tribological studies using a pin-on-disc tribometer. The collective results showed that chemically grafted AAO nanostructures exhibit high corrosion resistance toward seawater and low frictional coefficient due to low surface energy and self-lubricating property of fatty acids covalently linked to anodized Al surfaces.

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.

Surface Modification of Porous Titanium Granules for Improving Bioactivity.

PubMed

Karaji, Zahra Gorgin; Houshmand, Behzad; Faghihi, Shahab

The highly porous titanium granules are currently being used as bone substitute material and for bone tissue augmentation. However, they suffer from weak bone bonding ability. The aim of this study was to create a nanostructured surface oxide layer on irregularly shaped titanium granules to improve their bioactivity. This could be achieved using optimized electrochemical anodic oxidation (anodizing) and heat treatment processes. The anodizing process was done in an ethylene glycol-based electrolyte at an optimized condition of 60 V for 3 hours. The anodized granules were subsequently annealed at 450°C for 1 hour. Scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDS), and x-ray diffraction (XRD) were used to characterize the surface structure and morphology of the granules. The in vitro bioactivity of the samples was evaluated by immersion of specimens in simulated body fluid (SBF) for 1, 2, and 3 weeks. The human osteoblastic sarcoma cell line, MG63, was used to evaluate cell viability on the samples using dimethylthiazol-diphenyl tetrazolium bromide (MTT) assay. The results demonstrated the formation of amorphous nanostructured titanium oxide after anodizing, which transformed to crystalline anatase and rutile phases upon heat treatment. After immersion in SBF, spherical aggregates of amorphous calcium phosphate were formed on the surface of the anodized sample, which turned into crystalline hydroxyapatite on the surface of the anodized annealed sample. No cytotoxicity was detected among the samples. It is suggested that anodic oxidation followed by heat treatment could be used as an effective surface treatment procedure to improve bioactivity of titanium granules implemented for bone tissue repair and augmentation.

Enhanced in vitro biological activity generated by surface characteristics of anodically oxidized titanium--the contribution of the oxidation effect.

PubMed

Wurihan; Yamada, A; Suzuki, D; Shibata, Y; Kamijo, R; Miyazaki, T

2015-05-20

Anodically oxidized titanium surfaces, prepared by spark discharge, have micro-submicron surface topography and nano-scale surface chemistry, such as hydrophilic functional groups or hydroxyl radicals in parallel. The complexity of the surface characteristics makes it difficult to draw a clear conclusion as to which surface characteristic, of anodically oxidized titanium, is critical in each biological event. This study examined the in vitro biological changes, induced by various surface characteristics of anodically oxidized titanium with, or without, release of hydroxyl radicals onto the surface. Anodically oxidized titanium enhanced the expression of genes associated with differentiating osteoblasts and increased the degree of matrix mineralization by these cells in vitro. The phenotypes of cells on the anodically oxidized titanium were the same with, or without, release of hydroxyl radicals. However, the nanomechanical properties of this in vitro mineralized tissue were significantly enhanced on surfaces, with release of hydroxyl radicals by oxidation effects. In addition, the mineralized tissue, produced in the presence of bone morphogenetic protein-2 on bare titanium, had significantly weaker nanomechanical properties, despite there being higher osteogenic gene expression levels. We show that enhanced osteogenic cell differentiation on modified titanium is not a sufficient indicator of enhanced in vitro mineralization. This is based on the inferior mechanical properties of mineralized tissues, without either being cultured on a titanium surface with release of hydroxyl radicals, or being supplemented with lysyl oxidase family members.

Evaluation of correlation between dissolution rates of loxoprofen tablets and their surface morphology observed by scanning electron microscope and atomic force microscope.

PubMed

Yoshikawa, Shinichi; Murata, Ryo; Shida, Shigenari; Uwai, Koji; Suzuki, Tsuneyoshi; Katsumata, Shunji; Takeshita, Mitsuhiro

2010-01-01

We observed the surface morphological structures of 60 mg tablets of Loxonin, Loxot, and Lobu using scanning electron microscope (SEM) and atomic force microscope (AFM) to evaluate the dissolution rates. We found a significant difference among the initial dissolution rates of the three kinds of loxoprofen sodium tablets. Petal forms of different sizes were commonly observed on the surface of the Loxonin and Loxot tablets in which loxoprofen sodium was confirmed by measuring the energy-dispersible X-ray (EDX) spectrum of NaKalpha using SEM. However, a petal form was not observed on the surface of the Lobu tablet, indicating differences among the drug production processes. Surface area and particle size of the principal ingredient in tablets are important factors for dissolution rate. The mean size of the smallest fine particles constituting each tablet was also determined with AFM. There was a correlation between the initial dissolution rate and the mean size of the smallest particles in each tablet. Visualizing tablet surface morphology using SEM and AFM provides information on the drug production processes and initial dissolution rate, and is associated with the time course of pharmacological activities after tablet administration.

Does the stepwave model predict mica dissolution kinetics?

NASA Astrophysics Data System (ADS)

Kurganskaya, Inna; Arvidson, Rolf S.; Fischer, Cornelius; Luttge, Andreas

2012-11-01

The micas are a unique class of minerals because of their layered structure. A frequent question arising in mica dissolution studies is whether this layered structure radically changes the dissolution mechanism. We address this question here, using data from VSI and AFM experiments involving muscovite to evaluate crystallographic controls on mica dissolution. These data provide insight into the dissolution process, and reveal important links to patterns of dissolution observed in framework minerals. Under our experimental conditions (pH 9.4, 155 °C), the minimal global rate of normal surface retreat observed in VSI data was 1.42 × 10-10 mol/m2/s (σ = 27%) while the local rate observed at deep etch pits reached 416 × 10-10 mol/m2/s (σ = 49%). Complementary AFM data clearly show crystallographic control of mica dissolution, both in terms of step advance and the geometric influence of interlayer rotation (stacking periodicity). These observations indicate that basal/edge surface area ratios are highly variable and change continuously over the course of reaction, thus obviating their utility as characteristic parameters defining mica reactivity. Instead, these observations of overall dissolution rate and the influence of screw dislocations illustrate the link between atomic step movement and overall dissolution rate defined by surface retreat normal to the mica surface. Considered in light of similar observations available elsewhere in the literature, these relationships provide support for application of the stepwave model to mica dissolution kinetics. This approach provides a basic mechanistic link between the dissolution kinetics of phyllosilicates, framework silicates, and related minerals, and suggests a resolution to the general problem of mica reactivity.

Anodized Steel Electrodes for Supercapacitors.

PubMed

Sagu, Jagdeep S; Wijayantha, K G Upul; Bohm, Mallika; Bohm, Siva; Kumar Rout, Tapan

2016-03-09

Steel was anodized in 10 M NaOH to enhance its surface texture and internal surface area for application as an electrode in supercapacitors. A mechanism was proposed for the anodization process. Field-emission gun scanning electron microscopy (FEGSEM) studies of anodized steel revealed that it contains a highly porous sponge like structure ideal for supercapacitor electrodes. X-ray photoelectron spectroscopy (XPS) measurements showed that the surface of the anodized steel was Fe2O3, whereas X-ray diffraction (XRD) measurements indicated that the bulk remained as metallic Fe. The supercapacitor performance of the anodized steel was tested in 1 M NaOH and a capacitance of 18 mF cm(-2) was obtained. Cyclic voltammetry measurements showed that there was a large psueudocapacitive contribution which was due to oxidation of Fe to Fe(OH)2 and then further oxidation to FeOOH, and the respective reduction of these species back to metallic Fe. These redox processes were found to be remarkably reversible as the electrode showed no loss in capacitance after 10000 cycles. The results demonstrate that anodization of steel is a suitable method to produce high-surface-area electrodes for supercapacitors with excellent cycling lifetime.

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.

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

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.

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

Dissolution process analysis using model-free Noyes-Whitney integral equation.

PubMed

Hattori, Yusuke; Haruna, Yoshimasa; Otsuka, Makoto

2013-02-01

Drug dissolution process of solid dosages is theoretically described by Noyes-Whitney-Nernst equation. However, the analysis of the process is demonstrated assuming some models. Normally, the model-dependent methods are idealized and require some limitations. In this study, Noyes-Whitney integral equation was proposed and applied to represent the drug dissolution profiles of a solid formulation via the non-linear least squares (NLLS) method. The integral equation is a model-free formula involving the dissolution rate constant as a parameter. In the present study, several solid formulations were prepared via changing the blending time of magnesium stearate (MgSt) with theophylline monohydrate, α-lactose monohydrate, and crystalline cellulose. The formula could excellently represent the dissolution profile, and thereby the rate constant and specific surface area could be obtained by NLLS method. Since the long time blending coated the particle surface with MgSt, it was found that the water permeation was disturbed by its layer dissociating into disintegrant particles. In the end, the solid formulations were not disintegrated; however, the specific surface area gradually increased during the process of dissolution. The X-ray CT observation supported this result and demonstrated that the rough surface was dominant as compared to dissolution, and thus, specific surface area of the solid formulation gradually increased. Copyright © 2012 Elsevier B.V. All rights reserved.

Study on the fabrication of back surface reflectors in nano-crystalline silicon thin-film solar cells by using random texturing aluminum anodization

NASA Astrophysics Data System (ADS)

Shin, Kang Sik; Jang, Eunseok; Cho, Jun-Sik; Yoo, Jinsu; Park, Joo Hyung; Byungsung, O.

2015-09-01

In recent decades, researchers have improved the efficiency of amorphous silicon solar cells in many ways. One of the easiest and most practical methods to improve solar-cell efficiency is adopting a back surface reflector (BSR) as the bottom layer or as the substrate. The BSR reflects the incident light back to the absorber layer in a solar cell, thus elongating the light path and causing the so-called "light trapping effect". The elongation of the light path in certain wavelength ranges can be enhanced with the proper scale of BSR surface structure or morphology. An aluminum substrate with a surface modified by aluminum anodizing is used to improve the optical properties for applications in amorphous silicon solar cells as a BSR in this research due to the high reflectivity and the low material cost. The solar cells with a BSR were formed and analyzed by using the following procedures: First, the surface of the aluminum substrate was degreased by using acetone, ethanol and distilled water, and it was chemically polished in a dilute alkali solution. After the cleaning process, the aluminum surface's morphology was modified by using a controlled anodization in a dilute acid solution to form oxide on the surface. The oxidized film was etched off by using an alkali solution to leave an aluminum surface with randomly-ordered dimple-patterns of approximately one micrometer in size. The anodizing conditions and the anodized aluminum surfaces after the oxide layer had been removed were systematically investigated according to the applied voltage. Finally, amorphous silicon solar cells were deposited on a modified aluminum plate by using dc magnetron sputtering. The surfaces of the anodized aluminum were observed by using field-emission scanning electron microscopy. The total and the diffuse reflectances of the surface-modified aluminum sheets were measured by using UV spectroscopy. We observed that the diffuse reflectances increased with increasing anodizing voltage. The properties of the solar cells on anodized aluminum substrates were analyzed by using a solar simulator.

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

Sun, Ying-Sui; Yang, Wei-En; Zhang, Lan

In nasal reconstruction, the response of cells to titanium (Ti) implants is mainly determined by surface features of the implant. In a pilot study, the authors applied electrochemical anodization to Ti surfaces in an alkaline solution to create a network of nanoscale surface structures. This nanonetwork was intended to enhance the responses of primary human nasal epithelial cell (HNEpC) to the Ti surface. In this study, the authors then treated the anodized, nanonetwork-structured Ti surface using nitrogen plasma immersion ion implantation (NPIII) in order to further improve the HNEpC response to the Ti surface. Subsequently, surface characterization was performed tomore » elucidate morphology, roughness, wettability, and chemistry of specimens. Cytotoxicity, blood, and HNEpC responses were also evaluated. Our results demonstrate that NPIII treatment led to the formation of a noncytotoxic TiN-containing thin film (thickness <100 nm) on the electrochemically anodized Ti surface with a nanonetwork-structure. NPIII treatment was shown to improve blood clotting and the adhesion of platelets to the anodized Ti surface as well as the adhesion and proliferation of hNEpC. This research spreads our understanding of the fact that a TiN-containing thin film, produced using NPIII treatment, could be used to improve blood and HNEpC responses to anodized, nanonetwork-structured Ti surfaces in nasal implant applications.« less

Optical and electrical properties of porous silicon layer formed on the textured surface by electrochemical etching

NASA Astrophysics Data System (ADS)

Weiying, Ou; Lei, Zhao; Hongwei, Diao; Jun, Zhang; Wenjing, Wang

2011-05-01

Porous silicon (PS) layers were formed on textured crystalline silicon by electrochemical etching in HF-based electrolyte. Optical and electrical properties of the TMAH textured surfaces with PS formation are studied. Moreover, the influences of the initial structures and the anodizing time on the optical and electrical properties of the surfaces after PS formation are investigated. The results show that the TMAH textured surfaces with PS formation present a dramatic decrease in reflectance. The longer the anodizing time is, the lower the reflectance. Moreover, an initial surface with bigger pyramids achieved lower reflectance in a short wavelength range. A minimum reflectance of 3.86% at 460 nm is achieved for a short anodizing time of 2 min. Furthermore, the reflectance spectrum of the sample, which was etched in 3 vol.% TMAH for 25 min and then anodized for 20 min, is extremely flat and lies between 3.67% and 6.15% in the wavelength range from 400 to 1040 nm. In addition, for a short anodizing time, a slight increase in the effective carrier lifetime is observed. Our results indicate that PS layers formed on a TMAH textured surface for a short anodization treatment can be used as both broadband antireflection coatings and passivation layers for the application in solar cells.

Modelling of crater formation on anode surface by high-current vacuum arcs

NASA Astrophysics Data System (ADS)

Tian, Yunbo; Wang, Zhenxing; Jiang, Yanjun; Ma, Hui; Liu, Zhiyuan; Geng, Yingsan; Wang, Jianhua; Nordlund, Kai; Djurabekova, Flyura

2016-11-01

Anode melting and crater formation significantly affect interruption of high-current vacuum arcs. The primary objective of this paper is to theoretically investigate the mechanism of anode surface crater formation, caused by the combined effect of surface heating during the vacuum arc and pressure exerted on the molten surface by ions and electrons from the arc plasma. A model of fluid flow and heat transfer in the arc anode is developed and combined with a magnetohydrodynamics model of the vacuum arc plasma. Crater formation is observed in simulation for a peak arcing current higher than 15 kA on 40 mm diam. Cu electrodes spaced 10 mm apart. The flow of liquid metal starts after 4 or 5 ms of arcing, and the maximum velocities are 0.95 m/s and 1.39 m/s for 20 kA and 25 kA arcs, respectively. This flow redistributes thermal energy, and the maximum temperature of the anode surface does not remain in the center. Moreover, the condition for the liquid droplet formation on the anode surfaces is developed. The solidification process after current zero is also analyzed. The solidification time has been found to be more than 3 ms after 25 kA arcing. The long solidification time and sharp features on crater rims induce Taylor cone formation.

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.

An Analysis of Mechanical Properties of Anodized Aluminum Film at High Stress

NASA Astrophysics Data System (ADS)

Zhao, Xixi; Wei, Guoying; Yu, Yundan; Guo, Yuemei; Zhang, Ao

2015-10-01

In this paper, a new environmental-friendly electrolyte containing sulfuric acid and tartaric acid has been used as the substitute of chromic acid for anodization. The work discussed the influence of anodizing voltages on the fatigue life of anodized Al 2024-T3 by performing fatigue tests with 0.1 stress ratio (R) at 320 MPa. Meanwhile the fatigue cycles to failure, yield strength, tensile strength and fracture surface of anodic films at different conditions were investigated. The results showed that the fatigue life of anodized and sealed specimens reduced a lot compared to aluminum alloy, which can be attributed to the crack sites initiated at the oxide layer. The fracture surface analyses also revealed that the number of crack initiation sites enlarged with the increase of anodizing voltage.

Modifying Surface Chemistry of Metal Oxides for Boosting Dissolution Kinetics in Water by Liquid Cell Electron Microscopy.

PubMed

Lu, Yue; Geng, Jiguo; Wang, Kuan; Zhang, Wei; Ding, Wenqiang; Zhang, Zhenhua; Xie, Shaohua; Dai, Hongxing; Chen, Fu-Rong; Sui, Manling

2017-08-22

Dissolution of metal oxides is fundamentally important for understanding mineral evolution and micromachining oxide functional materials. In general, dissolution of metal oxides is a slow and inefficient chemical reaction. Here, by introducing oxygen deficiencies to modify the surface chemistry of oxides, we can boost the dissolution kinetics of metal oxides in water, as in situ demonstrated in a liquid environmental transmission electron microscope (LETEM). The dissolution rate constant significantly increases by 16-19 orders of magnitude, equivalent to a reduction of 0.97-1.11 eV in activation energy, as compared with the normal dissolution in acid. It is evidenced from the high-resolution TEM imaging, electron energy loss spectra, and first-principle calculations where the dissolution route of metal oxides is dynamically changed by local interoperability between altered water chemistry and surface oxygen deficiencies via electron radiolysis. This discovery inspires the development of a highly efficient electron lithography method for metal oxide films in ecofriendly water, which offers an advanced technique for nanodevice fabrication.

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

Bi-functional anodic TiO2 oxide: Nanotubes for wettability control and barrier oxide for uniform coloring

NASA Astrophysics Data System (ADS)

Kim, Sunkyu; Jung, Minkyeong; Kim, Moonsu; Choi, Jinsub

2017-06-01

A uniformly colored TiO2, on which the surface is functionalized with nanotubes to control wettability, was prepared by a two-step anodization; the first anodization was carried out to prepare nanotubes for a super-hydrophilic or -hydrophobic surface and the second anodization was performed to fabricate a thin film barrier oxide to ensure uniform coloring. The effect of the nanotubes on barrier oxide coloring was examined by spectrophotometry and UV-vis-IR spectroscopy. We found four different regimes governing the color changes in terms of anodization voltage, indicating that the color of the duplex TiO2 was primarily determined by the thickness of the barrier oxide layer formed during the second anodization step. The surface wettability, as confirmed by the water contact angle, revealed that the single barrier TiO2 yielded 74.6° ± 2.1, whereas the nanotubes on the barrier oxide imparted super-hydrophilic properties as a result of increasing surface roughness as well as imparting a higher hydrophobicity after organic acid treatment.

Electrochemical Performance Estimation of Anodized AZ31B Magnesium Alloy as Function of Change in the Current Density

NASA Astrophysics Data System (ADS)

Girón, L.; Aperador, W.; Tirado, L.; Franco, F.; Caicedo, J. C.

2017-08-01

The anodized AZ31B magnesium alloys were synthesized via electrodeposition processes. The aim of this work was to determine the electrochemical behavior of magnesium alloys by using anodized alloys as a protective coating. The anodized alloys were characterized by x-ray diffraction, exhibiting the crystallography orientation for Mg and MgO phases. The x-ray photoelectron spectroscopy was used to determine the chemical composition of anodized magnesium alloys. By using electrochemical impedance spectroscopy and Tafel curves, it was possible to estimate the electrochemical behavior of anodized AZ31B magnesium alloys in Hank's balanced salt solution (HBSS). Scanning electron microscopy was performed to analyze chemical changes and morphological surface changes on anodized Mg alloys due to the reaction in HBSS/anodized magnesium surface interface. Electrochemical behavior in HBSS indicates that the coatings may be a promising material for biomedical industry.

Methods of conditioning direct methanol fuel cells

DOEpatents

Rice, Cynthia; Ren, Xiaoming; Gottesfeld, Shimshon

2005-11-08

Methods for conditioning the membrane electrode assembly of a direct methanol fuel cell ("DMFC") are disclosed. In a first method, an electrical current of polarity opposite to that used in a functioning direct methanol fuel cell is passed through the anode surface of the membrane electrode assembly. In a second method, methanol is supplied to an anode surface of the membrane electrode assembly, allowed to cross over the polymer electrolyte membrane of the membrane electrode assembly to a cathode surface of the membrane electrode assembly, and an electrical current of polarity opposite to that in a functioning direct methanol fuel cell is drawn through the membrane electrode assembly, wherein methanol is oxidized at the cathode surface of the membrane electrode assembly while the catalyst on the anode surface is reduced. Surface oxides on the direct methanol fuel cell anode catalyst of the membrane electrode assembly are thereby reduced.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600 C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Process for producing a high emittance coating and resulting article

NASA Technical Reports Server (NTRS)

Le, Huong G. (Inventor); O'Brien, Dudley L. (Inventor)

1993-01-01

Process for anodizing aluminum or its alloys to obtain a surface particularly having high infrared emittance by anodizing an aluminum or aluminum alloy substrate surface in an aqueous sulfuric acid solution at elevated temperature and by a step-wise current density procedure, followed by sealing the resulting anodized surface. In a preferred embodiment the aluminum or aluminum alloy substrate is first alkaline cleaned and then chemically brightened in an acid bath The resulting cleaned substrate is anodized in a 15% by weight sulfuric acid bath maintained at a temperature of 30.degree. C. Anodizing is carried out by a step-wise current density procedure at 19 amperes per square ft. (ASF) for 20 minutes, 15 ASF for 20 minutes and 10 ASF for 20 minutes. After anodizing the sample is sealed by immersion in water at 200.degree. F. and then air dried. The resulting coating has a high infrared emissivity of about 0.92 and a solar absorptivity of about 0.2, for a 5657 aluminum alloy, and a relatively thick anodic coating of about 1 mil.

Improving dissolution and oral bioavailability of pranlukast hemihydrate by particle surface modification with surfactants and homogenization

PubMed Central

Ha, Eun-Sol; Baek, In-hwan; Yoo, Jin-Wook; Jung, Yunjin; Kim, Min-Soo

2015-01-01

The present study was carried out to develop an oral formulation of pranlukast hemihydrate with improved dissolution and oral bioavailability using a surface-modified microparticle. Based on solubility measurements, surface-modified pranlukast hemihydrate microparticles were manufactured using the spray-drying method with hydroxypropylmethyl cellulose, sucrose laurate, and water and without the use of an organic solvent. The hydrophilicity of the surface-modified pranlukast hemihydrate microparticle increased, leading to enhanced dissolution and oral bioavailability of pranlukast hemihydrate without a change in crystallinity. The surface-modified microparticles with an hydroxypropylmethyl cellulose/sucrose laurate ratio of 1:2 showed rapid dissolution of up to 85% within 30 minutes in dissolution medium (pH 6.8) and oral bioavailability higher than that of the commercial product, with approximately 2.5-fold and 3.9-fold increases in area under the curve (AUC0→12 h) and peak plasma concentration, respectively. Therefore, the surface-modified microparticle is an effective oral drug delivery system for the poorly water-soluble therapeutic pranlukast hemihydrate. PMID:26150699

Microscopic modeling of confined crystal growth and dissolution.

PubMed

Høgberget, Jørgen; Røyne, Anja; Dysthe, Dag K; Jettestuen, Espen

2016-08-01

We extend the (1+1)-dimensional fluid solid-on-solid (SOS) model to include a confining flat surface opposite to the SOS surface subject to a constant load. This load is balanced by a repulsive surface-surface interaction given by an ansatz which agrees with known analytical solutions in the limit of two separated flat surfaces. Mechanical equilibrium is imposed at all times by repositioning the confining surface. By the use of kinetic Monte Carlo (KMC) we calculate how the equilibrium concentration (deposition rate) depends on the applied load, and find it to reproduce analytical thermodynamics independent of the parameters of the interaction ansatz. We also study the dependency between the surface roughness and the saturation level as we vary the surface tension, and expand on previous analyses of the asymmetry between growth and dissolution by parametrizing the linear growth rate constant for growth and dissolution separately. We find the presence of a confining surface to affect the speed of growth and dissolution equally.

Microscopic modeling of confined crystal growth and dissolution

NASA Astrophysics Data System (ADS)

Høgberget, Jørgen; Røyne, Anja; Dysthe, Dag K.; Jettestuen, Espen

2016-08-01

We extend the (1+1)-dimensional fluid solid-on-solid (SOS) model to include a confining flat surface opposite to the SOS surface subject to a constant load. This load is balanced by a repulsive surface-surface interaction given by an ansatz which agrees with known analytical solutions in the limit of two separated flat surfaces. Mechanical equilibrium is imposed at all times by repositioning the confining surface. By the use of kinetic Monte Carlo (KMC) we calculate how the equilibrium concentration (deposition rate) depends on the applied load, and find it to reproduce analytical thermodynamics independent of the parameters of the interaction ansatz. We also study the dependency between the surface roughness and the saturation level as we vary the surface tension, and expand on previous analyses of the asymmetry between growth and dissolution by parametrizing the linear growth rate constant for growth and dissolution separately. We find the presence of a confining surface to affect the speed of growth and dissolution equally.

Calcite dissolution rate spectra measured by in situ digital holographic microscopy.

PubMed

Brand, Alexander S; Feng, Pan; Bullard, Jeffrey W

2017-09-01

Digital holographic microscopy in reflection mode is used to track in situ , real-time nanoscale topography evolution of cleaved (104) calcite surfaces exposed to flowing or static deionized water. The method captures full-field holograms of the surface at frame rates of up to 12.5 s -1 . Numerical reconstruction provides 3D surface topography with vertical resolution of a few nanometers and enables measurement of time-dependent local dissolution fluxes. A statistical distribution, or spectrum, of dissolution rates is generated by sampling multiple area domains on multiple crystals. The data show, as has been demonstrated by Fischer et al. (2012), that dissolution is most fully described by a rate spectrum, although the modal dissolution rate agrees well with published mean dissolution rates ( e.g. , 0.1 µmol m -2 s -1 to 0.3 µmol m -2 s -1 ). Rhombohedral etch pits and other morphological features resulting from rapid local dissolution appear at different times and are heterogeneously distributed across the surface and through the depth. This makes the distribution in rates measured on a single crystal dependent both on the sample observation field size and on time, even at nominally constant undersaturation. Statistical analysis of the inherent noise in the DHM measurements indicates that the technique is robust and that it likely can be applied to quantify and interpret rate spectra for the dissolution or growth of other minerals.

Calcite dissolution rate spectra measured by in situ digital holographic microscopy

NASA Astrophysics Data System (ADS)

Brand, Alexander S.; Feng, Pan; Bullard, Jeffrey W.

2017-09-01

Digital holographic microscopy in reflection mode is used to track in situ, real-time nanoscale topography evolution of cleaved (104) calcite surfaces exposed to flowing or static deionized water. The method captures full-field holograms of the surface at frame rates of up to 12.5 s-1. Numerical reconstruction provides 3D surface topography with vertical resolution of a few nanometers and enables measurement of time-dependent local dissolution fluxes. A statistical distribution, or spectrum, of dissolution rates is generated by sampling multiple area domains on multiple crystals. The data show, as has been demonstrated by Fischer et al. (2012), that dissolution is most fully described by a rate spectrum, although the modal dissolution rate agrees well with published mean dissolution rates (e.g., 0.1 μmol m-2 s-1 to 0.3 μmol m-2 s-1). Rhombohedral etch pits and other morphological features resulting from rapid local dissolution appear at different times and are heterogeneously distributed across the surface and through the depth. This makes the distribution in rates measured on a single crystal dependent both on the sample observation field size and on time, even at nominally constant undersaturation. Statistical analysis of the inherent noise in the DHM measurements indicates that the technique is robust and that it likely can be applied to quantify and interpret rate spectra for the dissolution or growth of other minerals.

Dissolution of explosive compounds TNT, RDX, and HMX under continuous flow conditions.

PubMed

Wang, Chao; Fuller, Mark E; Schaefer, Charles; Caplan, Jeffrey L; Jin, Yan

2012-05-30

2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) are common contaminants around active military firing ranges. Dissolution of these compounds is usually the first step prior to their spreading in subsurface environments. Nevertheless, dissolution of individual TNT, RDX, and HMX under continuous flow conditions has not been well investigated. This study applied spectral confocal microscopy to observe and quantify the dissolution of TNT, RDX, and HMX (<100 μm crystals) in micromodel channels. Dissolution models were developed to describe the changes of their radii, surface areas, volumes, and specific surface areas as a function of time. Results indicated that a model incorporating a resistance term that accounts for the surface area in direct contact with the channel surfaces (and hence, was not exposed to the flowing water) described the dissolution processes well. The model without the resistance term, however, could not capture the observed data at the late stage of TNT dissolution. The model-fitted mass transfer coefficients were in agreement with the previous reports. The study highlights the importance of including the resistance term in the dissolution model and illustrates the utility of the newly developed spectral imaging method for quantification of mass transfer of TNT, RDX, and HMX. Copyright © 2012 Elsevier B.V. All rights reserved.

Ti/IrO2/SnO2 anode for electrochemical degradation of chlorpyrifos in water: optimization and degradation performances

NASA Astrophysics Data System (ADS)

Pathiraja, G. C.; Wijesingha, M. S.; Nanayakkara, N.

2017-05-01

Chlorpyrifos, a widely used organophosphate pesticide which can be found in surface water bodies, is harmful for human body. Thus, treating water contaminated with chlorpyrifos is important. In our previous studies, novel Ti/IrO2-SnO2 anode was successfully developed for electrochemical degradation of chlorpyrifos in chloride free water. In this study, optimization of previously developed Ti/IrO2-SnO2 anode for mineralization of chlorpyrifos was successfully performed through response surface methodology. During the optimization study, two-level factorial design was used to determine the optimal coating solutions concentration for developing the Ti/IrO2-SnO2 anode. Cyclic voltammetry and open circuit potential were performed to investigate the electrochemically active surface area and stability of these anodes. The response surface and contour plots show that 0.3 M of [Ir] and 7.5 mM of [Sn] coated electrode has both highest anodic charge and stability. Scanning Electron Microscopic (SEM) images show the evidence of having both compact and porous regions in the surface of the thin film, resulting larger surface area. Within 6 h, the best result for mineralization (55.56%) of chlorpyrifos was obtained with 0.3 M of [Ir] and 7.5 mM of [Sn] coated anode using Total organic Carbon (TOC) analyzer. Therefore, the optimum coating concentration was found as 0.3 M of [Ir] and 7.5 mM of [Sn]. It would require an energy consumption of 6 kWhm-3.

Stirring effect on kaolinite dissolution rate

NASA Astrophysics Data System (ADS)

Metz, Volker; Ganor, Jiwchar

2001-10-01

Experiments were carried out measuring kaolinite dissolution rates using stirred and nonstirred flow-through reactors at pHs 2 to 4 and temperatures of 25°C, 50°C, and 70°C. The results show an increase of kaolinite dissolution rate with increasing stirring speed. The stirring effect is reversible, i.e., as the stirring slows down the dissolution rate decreases. The effect of stirring speed on kaolinite dissolution rate is higher at 25°C than at 50°C and 70°C and at pH 4 than at pHs 2 and 3. It is suggested that fine kaolinite particles are formed as a result of stirring-induced spalling or abrasion of kaolinite. These very fine particles have an increased ratio of reactive surface area to specific surface area, which results in enhancement of kaolinite dissolution rate. A balance between production and dissolution of the fine particles explains both the reversibility and the temperature and pH dependence of the stirring effect. Since the stirring effect on kaolinite dissolution rate varies with temperature and pH, measurement of kinetic parameters such as activation energy may be influenced by stirring. Therefore, standard use of nonagitated reaction vessels for kinetic experiments of mineral dissolution and precipitation is recommended, at least for slow reactions that are surface controlled.

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 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.

Rapid temperature increase near the anode and cathode in the afterglow of a pulsed positive streamer discharge

NASA Astrophysics Data System (ADS)

Ono, Ryo

2018-06-01

The spatiotemporal evolution of the temperature in the afterglow of point-to-plane, pulsed positive streamer discharge was measured near the anode tip and cathode surface using laser-induced predissociation fluorescence of OH radicals. The temperature exhibited a rapid increase and displayed a steep spatial gradient after a discharge pulse. The rate of temperature rise reached 84 K μs‑1 at mm, where z represents the distance from the anode tip. The temperature rise was much faster than in the middle of the gap; it was only 2.8 K μs‑1 at mm. The temperature reached 1700 K near the anode tip at s and 1500 K near the cathode surface at s, where t represents the postdischarge time. The spatial gradient reached 1280 K mm‑1 near the anode tip at s. The mechanism responsible for the rapid temperature increase was discussed, including rapid heating of the gas in the early postdischarge phase (s), and vibration-to-translation energy transfer in the later postdischarge phase (s). The high temperatures near the anode tip and cathode surface are particularly important for the ignition of combustible mixtures and for surface treatments, including solid-surface treatments, water treatments, and plasma medicine using pulsed streamer discharges.

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

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.

Calcium phosphates deposited on titanium electrode surface--part 1: Effect of the electrode polarity and oxide film on the deposited materials.

PubMed

Okawa, Seigo; Watanabe, Kouichi; Kanatani, Mitsugu

2013-01-01

We report experimental results about the effect of polarity of electrode and anodized titanium oxide film on the deposited materials by electrolysis of an acidic calcium phosphate solution. Mirror-polished titanium and anodized titanium were used as anode or cathode, and a Pt plate was used as a counter electrode. The load voltage was held constant at 20 VDC. No deposited materials were found on the anode surface. On the other hand, dicalcium phosphate dihydrate (DCPD) was deposited on the cathode surface at the beginning of the electrolysis. After the electrolysis time 600 s, the non-stoichiometric hydroxyapatite (HAp) with several hundred nanometers was formed on the specimen surface. Based on X-ray photoelectron spectroscopy data, the anodized oxide film contained both P(5+) and P(3+) ions. This characteristic of the oxide film and the electrolysis conditions were related to the behavior of the deposition of ultra fine HAp with high crystallinity.

Revisiting classical silicate dissolution rate laws under hydrothermal conditions

NASA Astrophysics Data System (ADS)

Pollet-Villard, Marion; Daval, Damien; Saldi, Giuseppe; Knauss, Kevin; Wild, Bastien; Fritz, Bertrand

2015-04-01

In the context of geothermal energy, the relative intensities of primary mineral leaching and secondary mineral precipitation can affect porosity and permeability of the reservoir, thereby influencing its hydraulic performance and the efficiency of the geothermal power station. That is why the prediction of reaction kinetics of fluid/rock interactions represents a critical issue in this context. Moreover, in several geothermal systems such as the one of Soultz-sous-Forêts (Alsace, France), the circulation of aqueous fluids induces only modest modifications of their chemical composition. Therefore, fluid-rock interactions take place at close-to-equilibrium conditions, where the rate-affinity relations are poorly known and intensively debated [1]. To describe more precisely the dissolution processes, our strategy consists in investigating the dissolution of the main cleavages of K-spar minerals (one of the prevalent primary minerals in the reservoir of Soultz-sous-Forêts geothermal system) over a wide range of Gibbs free energy (ΔG) conditions. The aims are to decipher the impact of crystallographic orientation and microstructural surface modifications on the dissolution kinetics and to propose a relation between K-spar dissolution rate and ΔG. Our experimental work relies on a coupled approach which combines classical experiments of K-spar dissolution monitored by aqueous chemical analyses (ICP-AES) and innovative techniques of nm- to μm-scale characterization of solid surface (SEM, AFM, VSI) [2]. Our results confirm that K-spar dissolution is an anisotropic process: we measure a tenfold factor between the slowest and the fastest-dissolving surfaces. Moreover, the formation of etch pits on surfaces during their alteration has been evidenced on all of the different faces that have been studied. This complex evolution of the surface topography casts doubt of the relevance of a surface model based on shrinking particles and represents a possible cause of an apparent modification of silicate dissolution rate over time. In addition, we evidenced that the relation between K-spar dissolution rate and ΔG depends on the crystallographic orientation of the altered surface, and differs from the transition state theory currently implemented into geochemical codes. Importantly, this theoretical curve overestimates the dissolution rates measured in close-to-equilibrium conditions. Taken together, the new findings show promise as a means for improving the accuracy of geochemical simulations. [1] Schott, J., Pokrovsky, O. S., and Oelkers, E. H., 2009. The Link Between Mineral Dissolution/Precipitation Kinetics and Solution Chemistry. Rev Mineral Geochem 70, 207-258. [2] Daval, D., Hellmann, R., Saldi, G. D., Wirth, R., and Knauss, K. G., 2013. Linking nm-scale measurements of the anisotropy of silicate surface reactivity to macroscopic dissolution rate laws: New insights based on diopside. Geochim Cosmochim Acta 107, 121-134.

Use of glancing angle X-ray powder diffractometry to depth-profile phase transformations during dissolution of indomethacin and theophylline tablets.

PubMed

Debnath, Smita; Predecki, Paul; Suryanarayanan, Raj

2004-01-01

The purpose of this study was (i) to develop glancing angle x-ray powder diffractometry (XRD) as a method for profiling phase transformations as a function of tablet depth; and (ii) to apply this technique to (a) study indomethacin crystallization during dissolution of partially amorphous indomethacin tablets and to (b) profile anhydrate --> hydrate transformations during dissolution of theophylline tablets. The intrinsic dissolution rates of indomethacin and theophylline were determined after different pharmaceutical processing steps. Phase transformations during dissolution were evaluated by various techniques. Transformation in the bulk and on the tablet surface was characterized by conventional XRD and scanning electron microscopy, respectively. Glancing angle XRD enabled us to profile these transformations as a function of depth from the tablet surface. Pharmaceutical processing resulted in a decrease in crystallinity of both indomethacin and theophylline. When placed in contact with the dissolution medium, while indomethacin recrystallized, theophylline anhydrate rapidly converted to theophylline monohydrate. Due to intimate contact with the dissolution medium, drug transformation occurred to a greater extent at or near the tablet surface. Glancing angle XRD enabled us to depth profile the extent of phase transformations as a function of the distance from the tablet surface. The processed sample (both indomethacin and theophylline) transformed more rapidly than did the corresponding unprocessed drug. Several challenges associated with the glancing angle technique, that is, the effects of sorbed water, phase transformations during the experimental timescale, and the influence of phase transformation on penetration depth, were addressed. Increased solubility, and consequently dissolution rate, is one of the potential advantages of metastable phases. This advantage is negated if, during dissolution, the metastable to stable transformation rate > dissolution rate. Glancing angle XRD enabled us to quantify and thereby profile phase transformations as a function of compact depth. The technique has potential utility in monitoring surface reactions, both chemical decomposition and physical transformations, in pharmaceutical systems.

Single-step direct fabrication of pillar-on-pore hybrid nanostructures in anodizing aluminum for superior superhydrophobic efficiency.

PubMed

Jeong, Chanyoung; Choi, Chang-Hwan

2012-02-01

Conventional electrochemical anodizing processes of metals such as aluminum typically produce planar and homogeneous nanopore structures. If hydrophobically treated, such 2D planar and interconnected pore structures typically result in lower contact angle and larger contact angle hysteresis than 3D disconnected pillar structures and, hence, exhibit inferior superhydrophobic efficiency. In this study, we demonstrate for the first time that the anodizing parameters can be engineered to design novel pillar-on-pore (POP) hybrid nanostructures directly in a simple one-step fabrication process so that superior surface superhydrophobicity can also be realized effectively from the electrochemical anodization process. On the basis of the characteristic of forming a self-ordered porous morphology in a hexagonal array, the modulation of anodizing voltage and duration enabled the formulation of the hybrid-type nanostructures having controlled pillar morphology on top of a porous layer in both mild and hard anodization modes. The hybrid nanostructures of the anodized metal oxide layer initially enhanced the surface hydrophilicity significantly (i.e., superhydrophilic). However, after a hydrophobic monolayer coating, such hybrid nanostructures then showed superior superhydrophobic nonwetting properties not attainable by the plain nanoporous surfaces produced by conventional anodization conditions. The well-regulated anodization process suggests that electrochemical anodizing can expand its usefulness and efficacy to render various metallic substrates with great superhydrophilicity or -hydrophobicity by directly realizing pillar-like structures on top of a self-ordered nanoporous array through a simple one-step fabrication procedure.

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.

Design and fabrication of Ni nanowires having periodically hollow nanostructures.

PubMed

Sada, Takao; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2014-10-07

We propose a concept for the design and fabrication of metal nanowires having periodically hollow nanostructures inside the pores of an anodic aluminum oxide (AAO) membrane using a sacrificial metal. In this study, nickel (Ni) and silver (Ag) were used as the base metal and the sacrificial metal, respectively. Alternating an applied potential between -0.4 and -1.0 V provided alternatively deposited Ni and Ag segments in a Ni-Ag 'barcode' nanowire with a diameter of 18 or 35 nm. After etching away the Ag segments, we fabricated Ni nanowires with nanopores of 12 ± 5.3 nm. Such nanostructure formation is explained by the formation of a Ni shell layer over the surface of the Ag segments due to the strong affinity of Ni(2+) for the interior surfaces of AAO. The Ni shell layer allows the Ni segments to remain even after dissolution of the Ag segments. Because the electroplating conditions can be easily controlled, we could carefully adjust the size and pitch of the periodically hollow nanospaces. We also describe a method for the fabrication of Ni nanorods by forming an Ag shell instead of a Ni shell on the Ni-Ag barcode nanowire, in which the interior of the AAO surfaces was modified with a compound bearing a thiol group prior to electroplating.

Theoretical Analysis of Drug Dissolution: I. Solubility and Intrinsic Dissolution Rate.

PubMed

Shekunov, Boris; Montgomery, Eda Ross

2016-09-01

The first-principles approach presented in this work combines surface kinetics and convective diffusion modeling applied to compounds with pH-dependent solubility and in different dissolution media. This analysis is based on experimental data available for approximately 100 compounds of pharmaceutical interest. Overall, there is a linear relationship between the drug solubility and intrinsic dissolution rate expressed through the total kinetic coefficient of dissolution and dimensionless numbers defining the mass transfer regime. The contribution of surface kinetics appears to be significant constituting on average ∼20% resistance to the dissolution flux in the compendial rotating disk apparatus at 100 rpm. The surface kinetics contribution becomes more dominant under conditions of fast laminar or turbulent flows or in cases when the surface kinetic coefficient may decrease as a function of solution composition or pH. Limitations of the well-known convective diffusion equation for rotating disk by Levich are examined using direct computational modeling with simultaneous dissociation and acid-base reactions in which intrinsic dissolution rate is strongly dependent on pH profile and solution ionic strength. It is shown that concept of diffusion boundary layer does not strictly apply for reacting/interacting species and that thin-film diffusion models cannot be used quantitatively in general case. Copyright © 2016. Published by Elsevier Inc.

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.

Enhanced methanol utilization in direct methanol fuel cell

DOEpatents

Ren, Xiaoming; Gottesfeld, Shimshon

2001-10-02

The fuel utilization of a direct methanol fuel cell is enhanced for improved cell efficiency. Distribution plates at the anode and cathode of the fuel cell are configured to distribute reactants vertically and laterally uniformly over a catalyzed membrane surface of the fuel cell. A conductive sheet between the anode distribution plate and the anodic membrane surface forms a mass transport barrier to the methanol fuel that is large relative to a mass transport barrier for a gaseous hydrogen fuel cell. In a preferred embodiment, the distribution plate is a perforated corrugated sheet. The mass transport barrier may be conveniently increased by increasing the thickness of an anode conductive sheet adjacent the membrane surface of the fuel cell.

Nanocomposite protective coatings for battery anodes

DOEpatents

Lemmon, John P; Xiao, Jie; Liu, Jun

2014-01-21

Modified surfaces on metal anodes for batteries can help resist formation of malfunction-inducing surface defects. The modification can include application of a protective nanocomposite coating that can inhibit formation of surface defects. such as dendrites, on the anode during charge/discharge cycles. For example, for anodes having a metal (M'), the protective coating can be characterized by products of chemical or electrochemical dissociation of a nanocomposite containing a polymer and an exfoliated compound (M.sub.a'M.sub.b''X.sub.c). The metal, M', comprises Li, Na, or Zn. The exfoliated compound comprises M' among lamella of M.sub.b''X.sub.c, wherein M'' is Fe, Mo, Ta, W, or V, and X is S, O, or Se.

Surface Modification of Titanium Using Anodization to Enhance Antimicrobial Properties and Osseointegration

NASA Astrophysics Data System (ADS)

Jain, Sakshi

Titanium and its alloys are frequently used in dental and orthopedic implants because they have good mechanical strength, chemical stability and biocompatibility. These properties can be further improved by surface treatments such as anodization that are able to grow thicker and produce crystalline oxide layers with controlled morphological and physico-chemical properties. Both anatase (A) and rutile (R) crystalline phases of titanium oxide have been shown to promote bioactivity and antimicrobial effects. In a previous study in our laboratories, four electrolyte mixtures were optimized to produce anodized layers on commercially pure titanium consisting of specific anatase and rutile oxide ratios at an endpoint forming voltage of 180 V. In the present study, changes that occurred in the anodized layers with increasing forming voltage including crystallinity, thickness, surface morphology, surface roughness, surface chemistry, fractal dimension, shear strength, and corrosion resistance were determined for each of these electrolytes. The results showed the crystallinity, thickness, surface pore sizes, and surface roughness increased with increasing forming voltage. Incorporation of phosphorus into the anodized layers was shown in phosphoric acid containing electrolytes at higher forming voltages. Decreases in corrosion resistance were also shown at higher forming voltages in each electrolyte due to increased pore interconnectivity within the anodized layers. In addition, the apatite inducing ability of anodized layers in SBF was examined for selected forming voltages in each electrolyte. Anodization in phosphoric acid containing electrolytes was shown to be more favorable for apatite formation. The streptococcal and MRSA bacterial attachment before and after UV treatments was determined for selected forming voltages in each electrolyte. Additionally, the killing efficacy after 10-minute pre-irradiation with UVA or UVC treatments was determined. UVA treatments showed trends of at least a 20% reduction in bacterial attachment regardless of the crystallinity within the oxide for S. sanguinis. The anodized layer with an approximately equal distribution of anatase and rutile phases showed bacterial killing efficacy over 50% for S. sanguinis and over 80% for MRSA after UVA or UVC treatments. Finally, two forming voltage sample groups in two of the electrolytes were examined for MC3T3E-1 cell attachment, proliferation, and differentiation. Total intracellular protein content, alkaline phosphatase (ALP) activity, osteocalcin (OCN) activity, and cellular mineralization were investigated for different time periods up to 21 days. All sample groups showed suitable cellular proliferation, differentiation, and maturation but those anodized in the phosphoric acid containing electrolyte showed delayed proliferation and early differentiation and maturation. Also, anodized samples containing at least 50% anatase were shown to produce higher osteoblast mineralization compared to majority rutile phase anodized layers.

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.

An interferometric study of the dissolution kinetics of anorthite: The role of reactive surface area

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

Luettge, A.; Bolton, E.W.; Lasaga, A.C.

1999-07-01

An optical interferometry system has been used to study the dynamics of the dissolution of anorthite (010) cleavage surfaces. With this technique, it is possible to measure directly the surface retreat of alumino-silicates as a function of time and thereby the dissolution rate using a new application of interferometry. The dissolution experiments are carried out in a flow-through cell system with a near endmember anorthite (An{sub 98}) from Miyake-Jima, Tokyo, Japan, Perchloric acid solutions (pH 3) were used at a constant temperature of 25 C. After having measured the topography of the original pristine anorthite surface, measurements of the surfacemore » normal retreat were taken after 48,84,120, and 168 hrs of run duration at 15 different regions on the surface. An internal-reference technique allows absolute measurements of the changes in surface height for the very first time. From these measurements, an average bulk rate for dissolution of the (010) anorthite surface is calculated to be 5.7 x 10{sup {minus}13} [moles/cm{sub 2}/sec]. Finally, their directly determined bulk rate for the (010) face is compared with the bulk rates calculated from the rate law obtained from powder experiments and using the BET or total surface area.« less

Surface treatments for aluminium alloys

NASA Astrophysics Data System (ADS)

Ardelean, M.; Lascău, S.; Ardelean, E.; Josan, A.

2018-01-01

Typically, in contact with the atmosphere, the aluminium surface is covered with an aluminium oxide layer, with a thickness of less than 1-2μm. Due to its low thickness, high porosity and low mechanical strength, this layer does not protect the metal from corrosion. Anodizing for protective and decorative purposes is the most common method of superficial oxidation processes and is carried out through anodic oxidation. The oxide films, resulted from anodizing, are porous, have a thickness of 20-50μm, and are heat-resistant, stable to water vapour and other corrosion agents. Hard anodizing complies with the same obtains principles as well as decorative and protective anodization. The difference is in that hard anodizing is achieved at low temperatures and high intensity of electric current. In the paper are presented the results of decorative and hard anodization for specimens made from several aluminium alloys in terms of the appearance of the specimens and of the thickness of the anodized.

Sodium hydroxide anodization of Ti-Al-4V adherends

NASA Technical Reports Server (NTRS)

Filbey, Jennifer A.; Wightman, J. P.; Progar, D. J.

1987-01-01

The use of sodium hydroxide anodization (SHA) for Ti-6Al-4V adherends is examined. The SHA surface is evaluated using SEM, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The SHA procedures of Kennedy et al. (1983) were employed in this experiment. The photomicrographs of the SHA (sandblasted) and PSHA (sandblasted and pickled) oxide surface reveal that the two surfaces differ. The PSHA is patchy and similar to a chromic acid anodization surface and the porosity of the PSHA is more uniform than the SHA surface. The compositions of the surfaces are studied. It is noted that SHA is an effective pretreatment for Ti-6Al-4V adherends.

Dissolution of Biogenic and Synthetic UO2 under Varied Reducing Conditions

PubMed Central

ULRICH, KAI – UWE; SINGH, ABHAS; SCHOFIELD, ELEANOR J.; BARGAR, JOHN R.; VEERAMANI, HARISH; SHARP, JONATHAN O.; LATMANI, RIZLAN BERNIER -; GIAMMAR, DANIEL E.

2008-01-01

The chemical stability of biogenic UO2, a nanoparticulate product of environmental bioremediation, may be impacted by the particles’ surface free energy, structural defects, and compositional variability in analogy to abiotic UO2+x (0 ≤ x ≤ 0.25). This study quantifies and compares intrinsic solubility and dissolution rate constants of biogenic nano-UO2 and synthetic bulk UO2.00, taking molecular-scale structure into account. Rates were determined under anoxic conditions as a function of pH and dissolved inorganic carbon in continuous-flow experiments. The dissolution rates of biogenic and synthetic UO2 solids were lowest at near neutral pH and increased with decreasing pH. Similar surface area-normalized rates of biogenic and synthetic UO2 suggest comparable reactive surface site densities. This finding is consistent with the identified structural homology of biogenic UO2 and stoichiometric UO2.00. Compared to carbonate-free anoxic conditions, dissolved inorganic carbon accelerated the dissolution rate of biogenic UO2 by 3 orders of magnitude. This phenomenon suggests continuous surface oxidation of U(IV) to U(VI), with detachment of U(VI) as the rate-determining step in dissolution. Although reducing conditions were maintained throughout the experiments, the UO2 surface can be oxidized by water and radiogenic oxidants. Even in anoxic aquifers, UO2 dissolution may be controlled by surface U(VI) rather than U(IV) phases. PMID:18754482

The dissolution of calcite in CO2-saturated solutions at 25°C and 1 atmosphere total pressure

USGS Publications Warehouse

Plummer, Niel; Wigley, T.M.L.

1976-01-01

The dissolution of Iceland spar in CO2-saturated solutions at 25°C and 1 atm total pressure has been followed by measurement of pH as a function of time. Surface concentrations of reactant and product species have been calculated from bulk fluid data using mass transport theory and a model that accounts for homogeneous reactions in the bulk fluid. The surface concentrations are found to be close to bulk solution values. This indicates that calcite dissolution under the experimental conditions is controlled by the kinetics of surface reaction. The rate of calcite dissolution follows an empirical second order relation with respect to calcium and hydrogen ion from near the initial condition (pH 3.91) to approximately pH 5.9. Beyond pH 5.9 the rate of surface reaction is greatly reduced and higher reaction orders are observed. Calculations show that the rate of calcite dissolution in natural environments may be influenced by both transport and surface-reaction processes. In the absence of inhibition, relatively short times should be sufficient to establish equilibrium.

Numerical ages of Holocene tributary debris fans inferred from dissolution pitting on carbonate boulders in the Grand Canyon of Arizona

USGS Publications Warehouse

Hereford, R.; Thompson, K.S.; Burke, K.J.

1998-01-01

Carbonate boulders transported down steep tributary channels by debris flow came to rest on Holocene debris fans beside the Colorado River in Grand Canyon National Park. Weakly acidic rainfall and the metabolic activity of blue-green algae have produced roughly hemispheric dissolution pits as much as 2-cm deep on the initially smooth surfaces of the boulders. The average depth of dissolution pits increases with relative age of fan surfaces. The deepening rate averages 2.4 mm/1000 yr (standard error = 0.2 mm/1000 yr), as calculated from several radiometrically dated surfaces and an archeological structure. This linear rate, which appears constant over at least the past 3000 yr, is consistent with field relations limiting the maximum age of the fans and with the physical chemistry of limestone dissolution. Dissolution-pit measurements (n = 6973) were made on 617 boulders on 71 fan surfaces at the 26 largest debris fans in Grand Canyon. Among these fan surfaces, the average pit depth ranges from 1.2 to 17.4 mm, and the resulting pit dissolution ages range from 500 to 7300 cal yr B.P. Most (75%) surfaces are younger than 3000 yr, probably because of removal of older debris fans by the Colorado River. Many of the ages are close to 800, 1600, 2300, 3100, or 4300 cal yr B.P. If not the result of differential preservation of fan surfaces, this clustering implies periods of heightened debris-flow activity and increased precipitation.

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.

Mitigation of Sulfur Poisoning of Ni/Zirconia SOFC Anodes by Antimony and Tin

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

Marina, Olga A.; Coyle, Christopher A.; Engelhard, Mark H.

2011-02-28

Surface Ni/Sb and Ni/Sb alloys were found to efficiently minimize the negative effects of sulfur on the performance of Ni/zirconia anode-supported solid oxide fuel cells (SOFC). Prior to operating on fuel gas containing low concentrations of H2S, the nickel/zirconia anodes were briefly exposed to antimony or tin vapor, which only slightly affected the SOFC performance. During the subsequent exposures to 1 and 5 ppm H2S, increases in anodic polarization losses were minimal compared to those observed for the standard nickel/zirconia anodes. Post-test XPS analyses showed that Sb and Sn tended to segregate to the surface of Ni particles, and furthermore » confirmed a significant reduction of adsorbed sulfur on the Ni surface in Ni/Sn and Ni/Sb samples compared to the Ni. The effect may be the result of weaker sulfur adsorption on bimetallic surfaces, adsorption site competition between sulfur and Sb or Sn on Ni, or other factors. The use of dilute binary alloys of Ni-Sb or Ni-Sn in the place of Ni, or brief exposure to Sb or Sn vapor, may be effective means to counteract the effects of sulfur poisoning in SOFC anodes and Ni catalysts. Other advantages, including suppression of coking or tailoring the anode composition for the internal reforming, are also expected.« less

Etching Behavior of Aluminum Alloy Extrusions

NASA Astrophysics Data System (ADS)

Zhu, Hanliang

2014-11-01

The etching treatment is an important process step in influencing the surface quality of anodized aluminum alloy extrusions. The aim of etching is to produce a homogeneously matte surface. However, in the etching process, further surface imperfections can be generated on the extrusion surface due to uneven materials loss from different microstructural components. These surface imperfections formed prior to anodizing can significantly influence the surface quality of the final anodized extrusion products. In this article, various factors that influence the materials loss during alkaline etching of aluminum alloy extrusions are investigated. The influencing variables considered include etching process parameters, Fe-rich particles, Mg-Si precipitates, and extrusion profiles. This study provides a basis for improving the surface quality in industrial extrusion products by optimizing various process parameters.

Masking of aluminum surface against anodizing

NASA Technical Reports Server (NTRS)

Crawford, G. B.; Thompson, R. E.

1969-01-01

Masking material and a thickening agent preserve limited unanodized areas when aluminum surfaces are anodized with chromic acid. For protection of large areas it combines well with a certain self-adhesive plastic tape.

Effect of surface anodization on stability of orthodontic microimplant

PubMed Central

Karmarker, Sanket; Yu, Wonjae

2012-01-01

Objective To determine the effect of surface anodization on the interfacial strength between an orthodontic microimplant (MI) and the rabbit tibial bone, particularly in the initial phase after placement. Methods A total of 36 MIs were driven into the tibias of 3 mature rabbits by using the self-drilling method and then removed after 6 weeks. Half the MIs were as-machined (n = 18; machined group), while the remaining had anodized surfaces (n = 18; anodized group). The peak insertion torque (PIT) and the peak removal torque (PRT) values were measured for the 2 groups of MIs. These values were then used to calculate the interfacial shear strength between the MI and cortical bone. Results There were no statistical differences in terms of PIT between the 2 groups. However, mean PRT was significantly greater for the anodized implants (3.79 ± 1.39 Ncm) than for the machined ones (2.05 ± 1.07 Ncm) (p < 0.01). The interfacial strengths, converted from PRT, were calculated at 10.6 MPa and 5.74 MPa for the anodized and machined group implants, respectively. Conclusions Anodization of orthodontic MIs may enhance their early-phase retention capability, thereby ensuring a more reliable source of absolute anchorage. PMID:23112925

Electrochemical surface modification of carbon mesh anode to improve the performance of air-cathode microbial fuel cells.

PubMed

Luo, Jianmei; Chi, Meiling; Wang, Hongyu; He, Huanhuan; Zhou, Minghua

2013-12-01

A convenient and promising alternative to surface modification of carbon mesh anode was fulfilled by electrochemical oxidation in the electrolyte of nitric acid or ammonium nitrate at ambient temperature. It was confirmed that such an anode modification method was low cost and effective not only in improving the efficiency of power generation in microbial fuel cells (MFCs) for synthetic wastewater treatment, but also helping to reduce the period for MFCs start-up. The MFCs with anode modification in electrolyte of nitric acid performed the best, achieving a Coulombic efficiency enhancement of 71 %. As characterized, the electrochemical modification resulted in the decrease of the anode potential and internal resistance but the increase of current response and nitrogen-containing and oxygen-containing functional groups on the carbon surface, which might contribute to the enhancement on the performances of MFCs.

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.

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.

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.

Pitting corrosion of titanium. Interim report, June-December 1993

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

Casillas, N.; Charlebois, S.J.; Smyrl, W.H.

1994-01-20

The breakdown of native and anodically-grown oxide films on Ti electrodes is investigated by scanning electrochemical microscopy (SECM), video microscopy, transmission electron microscopy and voltammetry. SECM is used to demonstrate that the oxidation of Br- on Ti occurs at microscopic surface sites (10 - 50 micrometer diameter, 30 sites/sq cm) that are randomly positioned across the oxide surface. After determining the position of the active sites for Br- oxidation, breakdown of the oxide is initiated by increasing the electrode potential to more positive values. Direct correspondence is observed between the location of the electroactive sites and corrosion pits, indicating thatmore » oxide breakdown is associated with a localized site of high electrical conductivity. The potential at which pitting is observed in voltammetric experiments is found to be proportional to the average oxide thickness, for values ranging between 20 and 100 A, indicating that breakdown is determined either by the magnitude of the electric field within the oxide or by the interfacial potential at the oxide/Br- solution interface. Pitting occurs at significantly lower potentials in Br- solutions than in C 1- solutions, suggesting a strong chemical interaction between the TiO2 surface and Br-. A mechanism of oxide breakdown is proposed that is based on the potential-dependent chemical dissolution of the oxide at microscopic surface sites.« less

Ni and Cr addition to alloy waste forms to reduce radionuclide environmental releases

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

Olson, L.

2016-10-11

Reference alloy waste forms (RAW) were fabricated and underwent hybrid corrosion/immersion testing to parameterize the ANL analytical oxidative-dissolution model to enable the calculation of fractional release rates and to determine the effectiveness of Ni and Cr trim additions in reducing release rates of radionuclide surrogates. Figure 1 shows the prototypical multiphase microstructure of the alloys with each phase type contributing about equally to the exposed surface area. The waste forms tested at SRNL were variations of the RAW-6 formulation that uses HT9 as the main alloy component, and are meant to enable evaluation of the impact of Ni and Crmore » trim additions on the release rates of actinides and Tc-99. The test solutions were deaerated alkaline and acidic brines, ranging in pH 3 to pH 10, representing potential repositories with those conditions. The testing approach consisted of 4 major steps; 1) bare surface corrosion measurements at pH values of 3, 5, 8, and 10, 2) hybrid potentiostatic hold/exposure measurements at pH 3, 3) measurement of radionuclide concentrations and relations to anodic current from potentiostatic holds, and 4) identification of corroding phases using SEM/EDS of electrodes.« less

Acoustic activation of water-in-oil microemulsions for controlled salt dissolution.

PubMed

Baxamusa, Salmaan; Ehrmann, Paul; Ong, Jemi

2018-06-18

The dynamic nature of the oil-water interface allows for sequestration of material within the dispersed domains of a microemulsion. Microstructural changes should therefore change the dissolution rate of a solid surface in a microemulsion. We hypothesize that microstructural changes due to formulation and cavitation in an acoustic field will enable control over solid dissolution rates. Water-in-oil microemulsions were formulated using cyclohexane, water, Triton X-100, and hexanol. The microstructure and solvation properties of Winsor Type IV formulations were characterized. Dissolution rates of KH 2 PO 4 (KDP), were measured. A kinetic analysis isolated the effect of the microstructure, and rate enhancements due to cavitation effects on the microstructure were characterized by measuring dissolution rates in an ultrasonic field. Dispersed aqueous domains of 2-6 nm radius dissolve a solid block of KDP at 0-10 nm/min. Dissolution rate is governed not by the domain-surface collision frequency but rather by a dissolution probability per domain-surface encounter. Higher probabilities are correlated with larger domains. Rapid and reversible dissolution rate increases of up to 270× were observed under ultrasonic conditions, with <20% of the increase due to bulk heating effects. The rest is attributed to cavitation-induced changes to the domain microstructure, providing a simple method for remotely activating and de-activating dissolution. Copyright © 2018 Elsevier Inc. All rights reserved.

Quantification of the resist dissolution process: an in situ analysis using high speed atomic force microscopy

NASA Astrophysics Data System (ADS)

Santillan, Julius Joseph; Shichiri, Motoharu; Itani, Toshiro

2016-03-01

This work focuses on the application of a high speed atomic force microscope (HS-AFM) for the in situ visualization / quantification of the resist dissolution process. This technique, as reported in the past, has provided useful pointers on the formation of resist patterns during dissolution. This paper discusses about an investigation made on the quantification of what we refer to as "dissolution unit size" or the basic units of patterning material dissolution. This was done through the establishment of an originally developed analysis method which extracts the difference between two succeeding temporal states of the material film surface (images) to indicate the amount of change occurring in the material film at a specific span of time. Preliminary experiments with actual patterning materials were done using a positive-tone EUV model resist composed only of polyhydroxystyrene (PHS)-based polymer with a molecular weight of 2,500 and a polydispersity index of 1.2. In the absence of a protecting group, the material was utilized at a 50nm film thickness with post application bake of 90°C/60s. The resulting film is soluble in the alkali-based developer even without exposure. Results have shown that the dissolution components (dissolution unit size) of the PHS-based material are not of fixed size. Instead, it was found that aside from one constantly dissolving unit size, another, much larger dissolution unit size trend also occurs during material dissolution. The presence of this larger dissolution unit size suggests an occurrence of "polymer clustering". Such polymer clustering was not significantly present during the initial stages of dissolution (near the original film surface) but becomes more persistently obvious after the dissolution process reaches a certain film thickness below the initial surface.

Processing Ti-25Ta-5Zr Bioalloy via Anodic Oxidation Procedure at High Voltage

NASA Astrophysics Data System (ADS)

Ionita, Daniela; Grecu, Mihaela; Dilea, Mirela; Cojocaru, Vasile Danut; Demetrescu, Ioana

2011-12-01

The current paper reports the processing of Ti-25Ta-5Zr bioalloy via anodic oxidation in NH4BF4 solution under constant potentiostatic conditions at high voltage to obtain more suitable properties for biomedical application. The maximum efficiency of the procedure is reached at highest applied voltage, when the corrosion rate in Hank's solution is decreased approxomately six times. The topography of the anodic layer has been studied using atomic force microscopy (AFM), and the results indicated that the anodic oxidation process increases the surface roughness. The AFM images indicated a different porosity for the anodized surfaces as well. After anodizing, the hydrophilic character of Ti-25Ta-5Zr samples has increased. A good correlation between corrosion rate obtained from potentiodynamic curves and corrosion rate from ions release analysis was obtained.

Preparation of Ti/IrO2 Anode with Low Iridium Content by Thermal Decomposition Process: Electrochemical removal of organic pollutants in water

NASA Astrophysics Data System (ADS)

Yaqub, Asim; Isa, Mohamed Hasnain; Ajab, Huma; Kutty, S. R. M.; Ezechi, Ezerie H.; Farooq, Robina

2018-04-01

In this study IrO2 (Iridium oxide) was coated onto a titanium plate anode from a dilute (50 mg/10 ml) IrCl3×H2O salt solution. Coating was done at high temperature (550∘C) using thermal decomposition. Surface morphology and characteristics of coated surface of Ti/IrO2 anode were examined by FESEM and XRD. The coated anode was applied for electrochemical removal of organic pollutants from synthetic water samples in 100 mL compartment of batch electrochemical cell. About 50% COD removal was obtained at anode prepared with low Ir content solution while 72% COD removal was obtained with anode prepared at high Ir content. Maximum COD removal was obtained at 10 mA/cm2 current density.

Long-term lithium-ion battery performance improvement via ultraviolet light treatment of the graphite anode

DOE PAGES

An, Seong Jin; Li, Jianlin; Sheng, Yangping; ...

2016-01-01

Effects of ultraviolet (UV) light on dried graphite anodes were investigated in terms of the cycle life of lithium ion batteries. The time variations for the UV treatment were 0 (no treatment), 20, 40, and 60 minutes. UV-light-treated graphite anodes were assembled for cycle life tests in pouch cells with pristine Li 1.02Ni 0.50Mn 0.29Co 0.19O 2 (NMC 532) cathodes. UV treatment for 40 minutes resulted in the highest capacity retention and the lowest resistance after the cycle life testing. X-ray photoelectron spectroscopy (XPS) and contact angle measurements on the graphite anodes showed changes in surface chemistry and wetting aftermore » the UV treatment. XPS also showed increases in solvent products and decreases in salt products on the SEI surface when UV-treated anodes were used. In conclusion, the thickness of the surface films and their compositions on the anodes and cathodes were also estimated using survey scans and snapshots from XPS depth profiles.« less

In situ fabrication of green reduced graphene-based biocompatible anode for efficient energy recycle.

PubMed

Cheng, Ying; Mallavarapu, Megharaj; Naidu, Ravi; Chen, Zuliang

2018-02-01

Improving the anode configuration to enhance biocompatibility and accelerate electron shuttling is critical for efficient energy recovery in microbial fuel cells (MFCs). In this paper, green reduced graphene nanocomposite was successfully coated using layer-by-layer assembly technique onto carbon brush anode. The modified anode achieved a 3.2-fold higher power density of 33.7 W m -3 at a current density of 69.4 A m -3 with a 75% shorter start period. As revealed in the characterization, the green synthesized nanocomposite film affords larger surface roughness for microbial colonization. Besides, gold nanoparticles, which anchored on graphene sheets, promise the relatively high electroactive sites and facilitate electron transfer from electricigens to the anode. The reduction-oxidation peaks in cyclic voltammograms indicated the mechanism of surface cytochromes facilitated current generation while the electrochemical impedance spectroscopy confirmed the enhanced electron transfer from surface cytochrome to electrode. The green synthesis process has the potential to generate a high performing anode in further applications of MFCs. Copyright © 2017 Elsevier Ltd. All rights reserved.

The morphological study of porous silicon formed by electrochemical anodization method

NASA Astrophysics Data System (ADS)

Suryana, R.; Sandi, D. K.; Nakatsuka, O.

2018-03-01

Due to its good physical and chemical properties, porous silicon (PSi) is very attractive to study. In this research, PSi has been fabricated on n-type Si (100) by the electrochemical anodization method. The electrolyte solution used was a mixture of HF (40%), ethanol (99%) and aquadest with volume ratio of 1:1:2, respectively. It was anodized on Si(100) surface at different current densities of 10 mA/cm2 and 20 mA/cm2 with the anodization time at each current density for 10 min, 20 min, and 30 min. The Scanning Electron Microscope (SEM) images showed that the PSi surfaces have inhomogeneous sized pores in the range of 95.00 nm–1.46 μm. The PSi layers with current density and anodization time of 10 mA/cm2 (10 min), 10mA/cm2 (20 min), and 20mA/cm2 (10 min) have spherical shaped pores while the others have some uncommon (cross sectional) shaped pores on surfaces. It is considered that the cross sectional shaped maybe caused by unstable the current during the electrochemical anodization process.

An upscaled rate law for magnesite dissolution in heterogeneous porous media

NASA Astrophysics Data System (ADS)

Wen, Hang; Li, Li

2017-08-01

Spatial heterogeneity in natural subsurface systems governs water fluxes and residence time in reactive zones and therefore determines effective rates of mineral dissolution. Extensive studies have documented mineral dissolution rates in natural systems, although a general rate law has remain elusive. Here we fill this gap by answering two questions: (1) how and to what extent does spatial heterogeneity affect water residence time and effectively-dissolving surface area? (2) what is the upscaled rate law that quantifies effective dissolution rates in natural, heterogeneous media? With data constraints from experimental work, 240 Monte-Carlo numerical experiments of magnesite dissolution within quartz matrix were run with spatial distributions characterized by a range of permeability variance σ2lnκ (0.5-6.0) and correlation length (2-50 cm). Although the total surface area and global residence time (τa) are the same in all experiments, the water fluxes through reactive magnesite zones varies between 0.7 and 72.8% of the total water fluxes. Highly heterogeneous media with large σ2lnκ and long λ divert water mostly into non-reactive preferential flow paths, therefore bypassing and minimizing flow in low permeability magnesite zones. As a result, the water residence time in magnesite zones (i.e., reactive residence time τa,r) is long and magnesite dissolution quickly reaches local equilibrium, which leads to small effective surface area and low dissolution rates. Magnesite dissolution rates in heterogeneous media vary from 2.7 to 100% of the rates in the equivalent homogeneous media, with effectively-dissolving surface area varying from 0.18 to 6.83 m2 (out of 51.71 m2 total magnesite surface area). Based on 240 numerical experiments and 45 column experiments, a general upscaled rate law in heterogeneous media, RMgCO3,ht =kAe,hm(1 - exp(-τa/τa,r))α, was derived to quantify effective dissolution rates. The dissolution rates in heterogeneous media are a function of the rate constants k being those measured under well-mixed conditions, effective surface area in equivalent homogeneous media Ae,hm, and the heterogeneity factor (1 - exp(-τa/τa,r))α. The heterogeneity factor quantify heterogeneity effects and depends on the relative magnitude of global residence time (τa) and reactive residence time (τa,r), as well as the shape factor α(= 5 σlnκ2) of the gamma distribution for reactive residence times. Exponential forms of rate laws have been used at the micro-scale describing direct interactions among water and mineral surface, and at the catchment scale describing weathering rates and concentration-discharge relationships. These observations highlight the key role of mineral-water contact time in determining dissolution rates at different scales. This work also emphasizes the importance of critical interfaces between reactive and non-reactive zones as determined by the details of spatial patterns and effective surface area as a scaling factor that quantifies dissolution rates in heterogeneous media across scales.

Effect of Processing Steps on the Mechanical Properties and Surface Appearance of 6063 Aluminium Extruded Products

PubMed Central

Asensio-Lozano, Juan; Suárez-Peña, Beatriz; Vander Voort, George F.

2014-01-01

6063 aluminum anodized extrusions may exhibit a common surface defect known as streaking, characterized by the formation of narrow bands with a surface gloss different from the surrounding material. The origin of this banding lies in the differential surface topography produced after etching during the anodizing stage, shown to be connected to certain microstructural characteristics. The present study has attempted to determine the origin of these defects and measure the mechanical properties in these zones, properties which were either barely acceptable or did not meet the specification’s requirements. Quantitative metallography and mechanical testing, both tensile and microhardness, were used for materials assessment at the different steps of the process of manufacturing 6063 anodized extrusions. The results of this research show that nonequilibrium solidification rates during billet casting could lead to the formation of coarse eutectic Mg2Si particles which have a deleterious effect on both mechanical properties and surface appearance in the anodized condition. However, differences in the size and density of the coarse Mg2Si particles have been found to exist in the streak profile compared to the surrounding zones. The study revealed the importance of these particles in explaining the origin of the marginal or sub-marginal properties and anodizing surface defects found. PMID:28788673

Effect of Processing Steps on the Mechanical Properties and Surface Appearance of 6063 Aluminium Extruded Products.

PubMed

Asensio-Lozano, Juan; Suárez-Peña, Beatriz; Vander Voort, George F

2014-05-30

6063 aluminum anodized extrusions may exhibit a common surface defect known as streaking, characterized by the formation of narrow bands with a surface gloss different from the surrounding material. The origin of this banding lies in the differential surface topography produced after etching during the anodizing stage, shown to be connected to certain microstructural characteristics. The present study has attempted to determine the origin of these defects and measure the mechanical properties in these zones, properties which were either barely acceptable or did not meet the specification's requirements. Quantitative metallography and mechanical testing, both tensile and microhardness, were used for materials assessment at the different steps of the process of manufacturing 6063 anodized extrusions. The results of this research show that nonequilibrium solidification rates during billet casting could lead to the formation of coarse eutectic Mg₂Si particles which have a deleterious effect on both mechanical properties and surface appearance in the anodized condition. However, differences in the size and density of the coarse Mg₂Si particles have been found to exist in the streak profile compared to the surrounding zones. The study revealed the importance of these particles in explaining the origin of the marginal or sub-marginal properties and anodizing surface defects found.

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.

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

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

Kinetics and mechanism of natural fluorapatite dissolution at 25 °C and pH from 3 to 12

NASA Astrophysics Data System (ADS)

Chaïrat, Claire; Schott, Jacques; Oelkers, Eric H.; Lartigue, Jean-Eric; Harouiya, Najatte

2007-12-01

The dissolution rates of natural fluorapatite (FAP), Ca 10(PO 4) 6F 2, were measured at 25 °C in mixed-flow reactors as a function of pH from 3.0 to 11.7, and aqueous calcium, phosphorus, and fluoride concentration. After an initial preferential Ca and/or F release, stoichiometric Ca, P, and F release was observed. Measured FAP dissolution rates decrease with increasing pH at 3 ⩽ pH ⩽ 7, FAP dissolution rates are pH independent at 7 ⩽ pH ⩽ 10, and FAP dissolution rates again decrease with increasing pH at pH ⩾ 10. Measured FAP dissolution rates are independent of aqueous Ca, P, and F concentration at pH ≈ 3 and pH ≈ 10. Apatite dissolution appears to be initiated by the relatively rapid removal from the near surface of F and the Ca located in the M1 sites, via proton for Ca exchange reactions. Dissolution rates are controlled by the destruction of this F and Ca depleted surface layer. The destruction of this layer is facilitated by the adsorption/penetration of protons into the surface at acidic conditions, and by surface hydration at neutral and basic conditions. Taking into account these two parallel mechanisms, measured fluorapatite forward dissolution rates can be accurately described using r+(molms)=6.61×10-6{aK}/{1+aK+aCa4aF1.4aOH0.6aH6K}+3.69×10-8[tbnd CaOH2+] where ai refers to the activity of the ith aqueous species, [tbnd CaOH2+] denotes the concentration of hydrated calcium sites at the surface of the leached layer (mol m -2), and Kex and Kads stand for the apparent stability constants of the Ca 2+/H + exchange and adsorption/penetration reactions, respectively.

Tin doped indium oxide anodes with artificially controlled nano-scale roughness using segregated Ag nanoparticles for organic solar cells

NASA Astrophysics Data System (ADS)

Kim, Hyo-Joong; Ko, Eun-Hye; Noh, Yong-Jin; Na, Seok-In; Kim, Han-Ki

2016-09-01

Nano-scale surface roughness in transparent ITO films was artificially formed by sputtering a mixed Ag and ITO layer and wet etching of segregated Ag nanoparticles from the surface of the ITO film. Effective removal of self-segregated Ag particles from the grain boundaries and surface of the crystalline ITO film led to a change in only the nano-scale surface morphology of ITO film without changes in the sheet resistance and optical transmittance. A nano-scale rough surface of the ITO film led to an increase in contact area between the hole transport layer and the ITO anode, and eventually increased the hole extraction efficiency in the organic solar cells (OSCs). The heterojunction OSCs fabricated on the ITO anode with a nano-scale surface roughness exhibited a higher power conversion efficiency of 3.320%, than that (2.938%) of OSCs made with the reference ITO/glass. The results here introduce a new method to improve the performance of OSCs by simply modifying the surface morphology of the ITO anodes.

Metal sponge for cryosorption pumping applications

DOEpatents

Myneni, Ganapati R.; Kneisel, Peter

1995-01-01

A system has been developed for adsorbing gases at high vacuum in a closed area. The system utilizes large surface clean anodized metal surfaces at low temperatures to adsorb the gases. The large surface clean anodized metal is referred to as a metal sponge. The metal sponge generates or maintains the high vacuum by increasing the available active cryosorbing surface area.

Fabrication of super slippery sheet-layered and porous anodic aluminium oxide surfaces and its anticorrosion property

NASA Astrophysics Data System (ADS)

Song, Tingting; Liu, Qi; Liu, Jingyuan; Yang, Wanlu; Chen, Rongrong; Jing, Xiaoyan; Takahashi, Kazunobu; Wang, Jun

2015-11-01

Inspired by natural plants such as Nepenthes pitcher plants, super slippery surfaces have been developed to improve the attributes of repellent surfaces. In this report, super slippery porous anodic aluminium oxide (AAO) surfaces have fabricated by a simple and reproducible method. Firstly, the aluminium substrates were treated by an anodic process producing micro-nano structured sheet-layered pores, and then immersed in Methyl Silicone Oil, Fluororalkylsilane (FAS) and DuPont Krytox, respectively, generating super slippery surfaces. Such a good material with excellent anti-corrosion property through a simple and repeatable method may be potential candidates for metallic application in anti-corrosion and extreme environment.

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.

Oxidative dissolution of silver nanoparticles: A new theoretical approach.

PubMed

Adamczyk, Zbigniew; Oćwieja, Magdalena; Mrowiec, Halina; Walas, Stanisław; Lupa, Dawid

2016-05-01

A general model of an oxidative dissolution of silver particle suspensions was developed that rigorously considers the bulk and surface solute transport. A two-step surface reaction scheme was proposed that comprises the formation of the silver oxide phase by direct oxidation and the acidic dissolution of this phase leading to silver ion release. By considering this, a complete set of equations is formulated describing oxygen and silver ion transport to and from particles' surfaces. These equations are solved in some limiting cases of nanoparticle dissolution in dilute suspensions. The obtained kinetic equations were used for the interpretation of experimental data pertinent to the dissolution kinetics of citrate-stabilized silver nanoparticles. In these kinetic measurements the role of pH and bulk suspension concentration was quantitatively evaluated by using the atomic absorption spectrometry (AAS). It was shown that the theoretical model adequately reflects the main features of the experimental results, especially the significant increase in the dissolution rate for lower pH. Also the presence of two kinetic regimes was quantitatively explained in terms of the decrease in the coverage of the fast dissolving oxide layer. The overall silver dissolution rate constants characterizing these two regimes were determined. Copyright © 2015 Elsevier Inc. All rights reserved.

Competitive interactions and controlled release of a natural antioxidant from halloysite nanotubes.

PubMed

Hári, József; Gyürki, Ádám; Sárközi, Márk; Földes, Enikő; Pukánszky, Béla

2016-01-15

Halloysite nanotubes used as potential carrier material for a controlled release stabilizer in polyethylene were thoroughly characterized with several techniques including the measurement of specific surface area, pore volume and surface energy. The high surface energy of the halloysite results in the strong bonding of the additive to the surface. Dissolution experiments carried out with eight different solvents for the determination of the effect of solvent characteristics on the amount of irreversibly bonded quercetin proved that adsorption and dissolution depend on competitive interactions prevailing in the system. Solvents with low polarity dissolve only surplus quercetin adsorbed in multilayers. Polyethylene is a very apolar polymer forming weak interactions with every substance; quercetin dissolves into it from the halloysite surface only above a critical surface coverage. Stabilization experiments confirmed that strong adhesion prevents dissolution and results in limited stabilization efficiency. At larger adsorbed amounts better stability and extended effect were measured indicating dissolution and controlled release. Copyright © 2015 Elsevier Inc. All rights reserved.

Mechanical properties of anodized coatings over molten aluminum alloy

DOE PAGES

Grillet, Anne M.; Gorby, Allen D.; Trujillo, Steven M.; ...

2007-10-22

A method to measure interfacial mechanical properties at high temperatures and in a controlled atmosphere has been developed to study anodized aluminum surface coatings at temperatures where the interior aluminum alloy is molten. This is the first time that the coating strength has been studied under these conditions. In this study, we have investigated the effects of ambient atmosphere, temperature, and surface finish on coating strength for samples of aluminum alloy 7075. Surprisingly, the effective Young's modulus or strength of the coating when tested in air was twice as high as when samples were tested in an inert nitrogen ormore » argon atmosphere. Additionally, the effective Young's modulus of the anodized coating increased with temperature in an air atmosphere but was independent of temperature in an inert atmosphere. The effect of surface finish was also examined. Sandblasting the surface prior to anodization was found to increase the strength of the anodized coating with the greatest enhancement noted for a nitrogen atmosphere. Lastly, machining marks were not found to significantly affect the strength.« less

Kinetics of gibbsite dissolution under low ionic strength conditions

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

Ganor, J.; Mogollon, J.L.; Lasaga, A.C.

1999-06-01

Experiments measuring synthetic gibbsite dissolution rates were carried out using both a stirred-flow-through reactor and a column reactor at 25 C, and pH range of 2.5--4.1. All experiments were conducted under far from equilibrium conditions ({Delta}G < {minus}1.1 kcal/mole). The experiments were performed with perchloric acid under relatively low (and variable) ionic strength conditions. An excellent agreement was found between the results of the well-mixed flow-through experiments and those of the (nonmixed) column experiments. This agreement shows that the gibbsite dissolution rate is independent of the stirring rate and therefore supports the conclusion of Bloom and Erich (1987) that gibbsitemore » dissolution reaction is surface controlled and not diffusion controlled. The Brunauer-Emmett-Teller (BET) surface area of the gibbsite increased during the flow-through experiments, while in the column experiments no significant change in surface area was observed. The significant differences in the BET surface area between the column experiments and the flow-through experiments, and the excellent agreement between the rates obtained by both methods, enable the authors to justify the substitution of the BET surface area for the reactive surface area. The dissolution rate of gibbsite varied as a function of the perchloric acid concentration. The authors interpret the gibbsite dissolution rate as a result of a combined effect of proton catalysis and perchlorate inhibition. Following the theoretical study of Ganor and Lasaga (1998) they propose specific reaction mechanisms for the gibbsite dissolution in the presence of perchloric acid. The mathematical predictions of two of these reaction mechanisms adequately describe the experimental data.« 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.

Engineering of Nanoscale Antifouling and Hydrophobic Surfaces on Naval Structural Steel HY-80 by Anodizing

DTIC Science & Technology

2015-06-01

examination of the morphologies of the nanoporous structures and the evaluation of the anodization parameters such as anodization potential, time... sponges , anemones, tunicates, and hydroids, whilst hard fouling comprises invertebrates such as barnacles, mussels, and tubeworms. The specific...of metals by making them more stable and highly resistant, but also to modify the surface by giving it a desired morphology . Ferrous alloys such as

Atomic force microscopy of atomic-scale ledges and etch pits formed during dissolution of quartz

NASA Technical Reports Server (NTRS)

Gratz, A. J.; Manne, S.; Hansma, P. K.

1991-01-01

The processes involved in the dissolution and growth of crystals are closely related. Atomic force microscopy (AFM) of faceted pits (called negative crystals) formed during quartz dissolution reveals subtle details of these underlying physical mechanisms for silicates. In imaging these surfaces, the AFM detected ledges less than 1 nm high that were spaced 10 to 90 nm apart. A dislocation pit, invisible to optical and scanning electron microscopy measurements and serving as a ledge source, was also imaged. These observations confirm the applicability of ledge-motion models to dissolution and growth of silicates; coupled with measurements of dissolution rate on facets, these methods provide a powerful tool for probing mineral surface kinetics.

Facile incorporation of hydroxyapatite onto an anodized Ti surface via a mussel inspired polydopamine coating

NASA Astrophysics Data System (ADS)

Zhe, Wang; Dong, Chaofang; Sefei, Yang; Dawei, Zhang; Kui, Xiao; Xiaogang, Li

2016-08-01

Inspired by the porous morphology of anodized Ti and the adhesive versatility of polydopamine (PDA), which can induce apatite mineralization, we fabricated a novel interface by coating a porous anodized TiO2 layer with PDA to rapidly immobilize HA on Ti-based substrates. It was found that the as-prepared PDA/anodized (HD) surface exhibited nanoscale roughness, which possessed an excellent ability to form apatite when immersed in 1.5× simulated body fluid (SBF), as observed by AFM and FE-SEM. The morphology and composition of each layer were further confirmed by XPS, XRD and FTIR. The corrosion resistance of the multilayer was investigated using potentiodynamic polarization curve and electrochemical impedance spectra (EIS) measurements in a 0.9 wt% NaCl solution, the results suggested that the HA/PDA/anodized (HDA) layer increased the corrosion resistance of pure Ti with higher corrosion potential and lower passive current, the surface wettability was also enhanced with the incorporation of HA. In vitro cellular assays showed that the HDA layer stimulated cell attachment and improved the alkaline phosphate (ALP) activity. Overall, the PDA/anodized treatment provided a viable method to quickly integrate HA, and the obtained HDA layer improved both corrosion resistance and biocompatibility of the Ti surface.

Fabrication of ultra thin anodic aluminium oxide membranes by low anodization voltages

NASA Astrophysics Data System (ADS)

Pastore, I.; Poplausks, R.; Apsite, I.; Pastare, I.; Lombardi, F.; Erts, D.

2011-06-01

Formation of ultrathin anodised aluminium oxide (AAO) membranes with high aspect ratio by Al anodization in sulphuric and oxalic acids at low potentials was investigated. Low anodization potentials ensure slow electrochemical reaction speeds and formation of AAO membranes with pore diameter and thickness below 20 nm and 70 nm respectively. Minimum time necessary for formation of continuous AAO membranes was determined. AAO membrane pore surface was covered with polymer Paraloid B72TM to transport it to the selected substrate. The fabricated ultra thin AAO membranes could be used to fabricate nanodot arrays on different surfaces.

Anodized aluminum on LDEF: A current status of measurements on chromic acid anodized aluminum

NASA Technical Reports Server (NTRS)

Golden, Johnny L.

1992-01-01

Chromic acid anodize was used as the exterior coating for aluminum surfaces on LDEF to provide passive thermal control. Chromic acid anodized aluminum was also used as test specimens in thermal control coatings experiments. The following is a compilation and analysis of the data obtained thus far.

Solutions for discharge chamber sputtering and anode deposit spalling in small mercury ion thrusters

NASA Technical Reports Server (NTRS)

Power, J. L.; Hiznay, D. J.

1975-01-01

Proposed solutions to the problems of sputter erosion and sputtered material spalling in the discharge chamber of small mercury ion thrusters are presented. The accelerated life test evaluated three such proposed solutions: (1) the use of tantalum as a single low sputter yield material for the exposed surfaces of the discharge chamber components subject to sputtering, (2) the use of a severely roughened anode surface to improve the adhesion of the sputter-deposited coating, and (3) the use of a wire cloth anode surface in order to limit the size of any coating flakes which might spall from it. Because of the promising results obtained in the accelerated life test with anode surfaces roughened by grit-blasting, experiments were carried out to optimize the grit-blasting procedure. The experimental results and an optimal grit-blasting procedure are presented.

Effect of anodic treatment on the electrocatalytic activity of superficial Raney nickel catalyst in cathodic hydrogen

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

Korovin, N.V.; Kozlova, N.I.; Kumenko, M.V.

This work is concerned with the effect of oxidation on the activity of Raney nickel catalyst in cathodic hydrogen evolution. The superficial Raney nickel catalyst (nickel SRC) was prepared by a previously described procedure. The surface of the nickel SRC was oxidized by applying an anodic sweep over the potential range from 0.25 to 1.00 V with a potential sweep rate of 1 mV/sec. The rate of cathodic hydrogen evolution increases after pretreatment of the surface of nickel SRC by application of an anodic pulse. A significant increase in the reaction rate most probably is due to oxygen adsorption onmore » the nickel SRC surface. The largest increase in the amount of weakly bound hydrogen corresponds to the most active electrode. Oxidation of the nickel surface by an anodic pulse causes both an acceleration and a retardation of the cathodic hydrogen evolution reaction.« less

High-absorptance high-emittance anodic coating

NASA Technical Reports Server (NTRS)

Le, Huong Giang (Inventor); Chesterfield, John L. (Inventor)

1998-01-01

A colored anodic coating for use on surfaces of substrates, e.g. aluminum substrates in which it is desirable to maintain a high solar absorptance (a) and a high infrared emittance (e), particularly in low earth orbit space environments. This anodic coating is preferably a dark colored coating, and even more preferably a black coating. This coating allows a touch temperature within an acceptable design range to preclude burning of an astronaut in case of contact, but also allows a solar radiation absorption in an amount such that an a/e ratio of unity is achieved. The coating of the invention comprises a first layer in the form of an acid anodized colored anodic layer for achieving a high solar absorptance and a second or high emittance layer in the form of a clear acid anodized layer for achieving a high emittance. The entire coating is quite thin, e.g. 1-2 mils and is quite stable in a hostile space environment of the type encountered in a low earth orbit. The coating is obtained by first creating the high emittance clear anodized coating on the metal surface followed by anodizing using a colored anodizing process.

High-absorptance high-emittance anodic coating

NASA Technical Reports Server (NTRS)

Le, Huong Giang (Inventor); Chesterfield, John L. (Inventor)

1999-01-01

A colored anodic coating for use on surfaces of substrates, e.g. aluminum substrates in which it is desirable to maintain a high solar absorptance (.alpha.) and a high infrared emittance (.epsilon.), particularly in low earth orbit space environments. This anodic coating is preferably a dark colored coating, and even more preferably a black coating. This coating allows a touch temperature within an acceptable design range to preclude burning of an astronaut in case of contact, but also allows a solar radiation absorption in an amount such that an .alpha./.epsilon. ratio of unity is achieved. The coating of the invention comprises a first layer in the form of an acid anodized colored anodic layer for achieving a high solar absorptance and a second or high emittance layer in the form of a clear acid anodized layer for achieving a high emittance. The entire coating is quite thin, e.g. 1-2 mils and is quite stable in a hostile space environment of the type encountered in a low earth orbit. The coating is obtained by first creating the high emittance clear anodized coating on the metal surface followed by anodizing using a colored anodizing process.

Aluminum surface corrosion and the mechanism of inhibitors using pH and metal ion selective imaging fiber bundles.

PubMed

Szunerits, Sabine; Walt, David R

2002-02-15

The localized corrosion behavior of a galvanic aluminum copper couple was investigated by in situ fluorescence imaging with a fiber-optic imaging sensor. Three different, but complementary methods were used for visualizing remote corrosion sites, mapping the topography of the metal surface, and measuring local chemical concentrations of H+, OH-, and Al3+. The first method is based on a pH-sensitive imaging fiber, where the fluorescent dye SNAFL was covalently attached to the fiber's distal end. Fluorescence images were acquired as a function of time at different areas of the galvanic couple. In a second method, the fluorescent dye morin was immobilized on the fiber-optic imaging sensor, which allowed the in situ localization of corrosion processes on pure aluminum to be visualized over time by monitoring the release of Al3+. The development of fluorescence on the aluminum surface defined the areas associated with the anodic dissolution of aluminum. We also investigated the inhibition of corrosion of pure aluminum by CeCl3 and 8-hydroxyquinoline. The decrease in current, the decrease in the number of active sites on the aluminum surface, and the faster surface passivation are all consistent indications that cerium chloride and 8-hydroxyquinoline inhibit corrosion effectively. From the number and extent of corrosion sites and the release of aluminum ions monitored with the fiber, it was shown that 8-hydroxyquinoline is a more effective inhibitor than cerium chloride.

In-life pteropod shell dissolution as an indicator of past ocean carbonate saturation

NASA Astrophysics Data System (ADS)

Wall-Palmer, Deborah; Smart, Christopher W.; Hart, Malcolm B.

2013-12-01

Recent concern over the effects of ocean acidification upon calcifying organisms has highlighted the aragonitic shelled thecosomatous pteropods as being at a high risk. Both in-situ and laboratory studies have shown that an increased dissolved CO2 concentration, leading to decreased water pH and low carbonate concentration, causes reduced calcification rates and enhanced dissolution in the shells of living pteropods. In fossil records unaffected by post-depositional dissolution, this in-life shell dissolution can be detected. Here we present the first evidence of variations of in-life pteropod shell dissolution due to variations in surface water carbonate concentration during the Late Pleistocene by analysing the surface layer of pteropod shells in marine sediment cores from the Caribbean Sea and Indian Ocean. In-life shell dissolution was determined by applying the Limacina Dissolution Index (LDX) to the sub-tropical pteropod Limacina inflata. Average shell size information shows that high in-life dissolution is accompanied by smaller shell sizes in L. inflata, which may indicate a reduction in calcification rate. Comparison of the LDX profile to Late Pleistocene Vostok atmospheric CO2 concentrations, shows that in-life pteropod dissolution is closely associated to variations in past ocean carbonate saturation. This study confirms the findings of laboratory studies, showing enhanced shell dissolution and reduced calcification in living pteropods when surface ocean carbonate concentrations were lower. Results also demonstrate that oceanic pH levels that were less acidic and changing less rapidly than those predicted for the 21st Century, negatively affected pteropods during the Late Pleistocene.

Accelerated life test of sputtering and anode deposit spalling in a small mercury ion thruster

NASA Technical Reports Server (NTRS)

Power, J. L.

1975-01-01

Tantalum and molybdenum sputtered from discharge chamber components during operation of a 5 centimeter diameter mercury ion thruster adhered much more strongly to coarsely grit blasted anode surfaces than to standard surfaces. Spalling of the sputtered coating did occur from a coarse screen anode surface but only in flakes less than a mesh unit long. The results were obtained in a 200 hour accelerated life test conducted at an elevated discharge potential of 64.6 volts. The test approximately reproduced the major sputter erosion and deposition effects that occur under normal operation but at approximately 75 times the normal rate. No discharge chamber component suffered sufficient erosion in the test to threaten its structural integrity or further serviceability. The test indicated that the use of tantalum-surfaced discharge chamber components in conjunction with a fine wire screen anode surface should cure the problems of sputter erosion and sputtered deposits spalling in long term operation of small mercury ion thrusters.

Improving Efficiency of Aluminium Sacrificial Anode Using Cold Work Process

NASA Astrophysics Data System (ADS)

Asmara, Y. P.; Siregar, J. P.; Tezara, C.; Ann, Chang Tai

2016-02-01

Aluminium is one of the preferred materials to be used as sacrificial anode for carbon steel protection. The efficiency of these can be low due to the formation of oxide layer which passivate the anodes. Currently, to improve its efficiency, there are efforts using a new technique called surface modifications. The objective of this research is to study corrosion mechanism of aluminium sacrificial anode which has been processed by cold work. The cold works are applied by reducing the thickness of aluminium sacrificial anodes at 20% and 40% of thickness reduction. The cathodic protection experiments were performed by immersion of aluminium connected to carbon steel cylinder in 3% NaCl solutions. Visual inspections using SEM had been conducted during the experiments and corrosion rate data were taken in every week for 8 weeks of immersion time. Corrosion rate data were measured using weight loss and linear polarization technique (LPR). From the results, it is observed that cold worked aluminium sacrificial anode have a better corrosion performance. It shows higher corrosion rate and lower corrosion potential. The anodes also provided a long functional for sacrificial anode before it stop working. From SEM investigation, it is shown that cold works have changed the microstructure of anodes which is suspected in increasing corrosion rate and cause de-passivate of the surface anodes.

A dynamic inert metal anode.

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

Hryn, J. N.

1998-11-09

A new concept for a stable anode for aluminum electrowinning is described. The anode consists of a cup-shaped metal alloy container filled with a molten salt that contains dissolved aluminum. The metal alloy can be any of a number of alloys, but it must contain aluminum as a secondary alloying metal. A possible alloy composition is copper with 5 to 15 weight percent aluminum. In the presence of oxygen, aluminum on the metal anode's exterior surface forms a continuous alumina film that is thick enough to protect the anode from chemical attack by cryolite during electrolysis and thin enough tomore » maintain electrical conductivity. However, the alumina film is soluble in cryolite, so it must be regenerated in situ. Film regeneration is achieved by the transport of aluminum metal from the anode's molten salt interior through the metal wall to the anode's exterior surface, where the transported aluminum oxidizes to alumina in the presence of evolving oxygen to maintain the protective alumina film. Periodic addition of aluminum metal to the anode's interior keeps the aluminum activity in the molten salt at the desired level. This concept for an inert anode is viable as long as the amount of aluminum produced at the cathode greatly exceeds the amount of aluminum required to maintain the anode's protective film.« less

Sequential pretreatment for cell disintegration of municipal sludge in a neutral Bio-electro-Fenton system.

PubMed

Yu, Qilin; Jin, Xiaochen; Zhang, Yaobin

2018-05-15

Sludge cell disruption was generally considered as the rate-limiting step for the anaerobic digestion of waste activated sludge (WAS). Advanced oxidation processes and bio-electro-chemical systems were recently reported to enhance the hydrolysis of WAS and sludge cell disruption, while the cell-breaking processes of these systems remain unclear yet. In this study, an innovative Bio-electro-Fenton system was developed to pretreat the WAS sequentially with cathode Fenton process and anode anaerobic digestion. Significant cell disruption and dissolution intracellular organics were founded after the treatment. X-ray photoelectron spectroscopy (XPS) analysis and fourier transform infrared spectroscopy (FT-IR) spectra indicated that Gram-negative bacteria were more sensitive to free radicals yielded in cathode to induce a chain reaction that destroyed the lipid-contained outer membrane, while Gram-positive bacteria with thick peptidoglycan layer were liable to be biologically decomposed in the anode. Compared with the oxidation of organic matters in the cathode Fenton, the secretion of enzyme increased in the anode which was beneficial to break down the complex matters (peptidoglycans) into simples that were available for anode oxidation by exoelectrogens. The results also showed a possible prospect for the application of this sequential pretreatment in bio-electro-Fenton systems to disrupt sludge cells and enhance the anaerobic digestion. Copyright © 2018 Elsevier Ltd. All rights reserved.

Minimizing Polysulfide Shuttle Effect in Lithium-Ion Sulfur Batteries by Anode Surface Passivation.

PubMed

Liu, Jian; Lu, Dongping; Zheng, Jianming; Yan, Pengfei; Wang, Biqiong; Sun, Xueliang; Shao, Yuyan; Wang, Chongmin; Xiao, Jie; Zhang, Ji-Guang; Liu, Jun

2018-06-25

Lithium-ion sulfur batteries use nonlithium materials as the anode for extended cycle life. However, polysulfide shuttle reactions still occur on the nonmetal anodes (such as graphite and Si), and result in undesirable low Coulombic efficiency. In this work, we used Al 2 O 3 layers coated by atomic layer deposition (ALD) technique to suppress the shuttle reactions. With the optimal thickness of 2 nm Al 2 O 3 coated on graphite anode, the Coulombic efficiency of the sulfur cathode was improved from 84% to 96% in the first cycle, and from 94% to 97% in the subsequent cycles. As a result, the discharge capacity of the sulfur cathode was increased to 550 mAh g -1 in the 100th cycle, as compared with 440 mAh g -1 when the pristine graphite anode was used. The Al 2 O 3 passivation layer minimizes the formation of insoluble sulfide (Li 2 S 2 , Li 2 S) on the surface of graphite anode and improves the efficiency and capacity retention of the graphite-sulfur batteries. The surface passivation strategy could also be used in other sulfur based battery systems (with Li, Si, and Sn anodes), to minimize side reactions and enable high-performance sulfur batteries.

Proton exchange membrane and electrode surface areas as factors that affect power generation in microbial fuel cells.

PubMed

Oh, Sang-Eun; Logan, Bruce E

2006-03-01

Power generation in microbial fuel cells (MFCs) is a function of the surface areas of the proton exchange membrane (PEM) and the cathode relative to that of the anode. To demonstrate this, the sizes of the anode and cathode were varied in two-chambered MFCs having PEMs with three different surface areas (A (PEM)=3.5, 6.2, or 30.6 cm(2)). For a fixed anode and cathode surface area (A (An)=A (Cat)=22.5 cm(2)), the power density normalized to the anode surface area increased with the PEM size in the order 45 mW/m(2) (A (PEM)=3.5 cm(2)), 68 mW/m(2) (A (PEM)=6.2 cm(2)), and 190 mW/m(2) (A (PEM)=30.6 cm(2)). PEM surface area was shown to limit power output when the surface area of the PEM was smaller than that of the electrodes due to an increase in internal resistance. When the relative cross sections of the PEM, anode, and cathode were scaled according to 2A (Cat)=A(PEM)=2A (An), the maximum power densities of the three different MFCs, based on the surface area of the PEM (A (PEM)=3.5, 6.2, or 30.6 cm(2)), were the same (168+/-4.53 mW/m(2)). Increasing the ionic strength and using ferricyanide at the cathode also increased power output.

Surface characteristics of anodized and hydrothermally treated titatnium with an increasing concentration of calcium ion

NASA Astrophysics Data System (ADS)

Park, Il Song; Bae, Tae Sung; Seol, Kyeong Won

2006-10-01

Titanium is widely used as an implant material due to its good mechanical properties and the excellent biocompatibility of the oxide film on the surface. To modify the unstable oxide surface of pure titanium, plasma electrolytic oxidation was applied in this study. The electrolyte used for anodizing was a mixture of GP (glycerophosphate disodium salt) and CA (calcium acetate). In addition, a hydrothermal treatment was performed to precipitate a calcium phosphate crystal on the titanium oxide layer for bioactivity. The effect of the CA concentration of the electrolyte on the surface of titanium was investigated, with CA concentrations at 0.1 M, 0.2 M, and 0.3 M. A high concentration of CA results in a low breakdown voltage; hence many large micropores were formed on the anodized surface. Moreover, the size of the HA crystals was more minute in proportion to the increasing concentration of CA. The crystal phase of titanium dioxide was mainly anatase, and a rutile phase was also observed. As the size and/or amount of HA crystals increased, the surface roughness increased. However, the surface roughness could be decreased by fully and uniformly covering the surface with HA crystals. The corrosion resistance in the saline solution was increased by anodic spark oxidation. In addition, it was slightly increased by a hydrothermal treatment. It is considered that a more stable and thicker titanium oxide layer is formed by anodic oxidation and a hydrothermal treatment.

Metal sponge for cryosorption pumping applications

DOEpatents

Myneni, G.R.; Kneisel, P.

1995-12-26

A system has been developed for adsorbing gases at high vacuum in a closed area. The system utilizes large surface clean anodized metal surfaces at low temperatures to adsorb the gases. The large surface clean anodized metal is referred to as a metal sponge. The metal sponge generates or maintains the high vacuum by increasing the available active cryosorbing surface area. 4 figs.

Dissolution of Calcite in the Twilight Zone: Bacterial Control of Dissolution of Sinking Planktonic Carbonates Is Unlikely

PubMed Central

Bissett, Andrew; Neu, Thomas R.; de Beer, Dirk

2011-01-01

We investigated the ability of bacterial communities to colonize and dissolve two biogenic carbonates (Foraminifera and oyster shells). Bacterial carbonate dissolution in the upper water column is postulated to be driven by metabolic activity of bacteria directly colonising carbonate surfaces and the subsequent development of acidic microenvironments. We employed a combination of microsensor measurements, scanning electron microscopy (SEM), confocal laser scanning microscopy (CLSM) and image analysis and molecular documentation of colonising bacteria to monitor microbial processes and document changes in shell surface topography. Bacterial communities rapidly colonised shell surfaces, forming dense biofilms with extracellular polymeric substance (EPS) deposits. Despite this, we found no evidence of bacterially mediated carbonate dissolution. Dissolution was not indicated by Ca2+ microprofiles, nor was changes in shell surface structure related to the presence of colonizing bacteria. Given the short time (days) settling carbonate material is actually in the twilight zone (500–1000 m), it is highly unlikely that microbial metabolic activity on directly colonised shells plays a significant role in dissolving settling carbonates in the shallow ocean. PMID:22102861

Dissolution of calcite in the twilight zone: bacterial control of dissolution of sinking planktonic carbonates is unlikely.

PubMed

Bissett, Andrew; Neu, Thomas R; Beer, Dirk de

2011-01-01

We investigated the ability of bacterial communities to colonize and dissolve two biogenic carbonates (Foraminifera and oyster shells). Bacterial carbonate dissolution in the upper water column is postulated to be driven by metabolic activity of bacteria directly colonising carbonate surfaces and the subsequent development of acidic microenvironments. We employed a combination of microsensor measurements, scanning electron microscopy (SEM), confocal laser scanning microscopy (CLSM) and image analysis and molecular documentation of colonising bacteria to monitor microbial processes and document changes in shell surface topography. Bacterial communities rapidly colonised shell surfaces, forming dense biofilms with extracellular polymeric substance (EPS) deposits. Despite this, we found no evidence of bacterially mediated carbonate dissolution. Dissolution was not indicated by Ca²⁺ microprofiles, nor was changes in shell surface structure related to the presence of colonizing bacteria. Given the short time (days) settling carbonate material is actually in the twilight zone (500-1000 m), it is highly unlikely that microbial metabolic activity on directly colonised shells plays a significant role in dissolving settling carbonates in the shallow ocean.

Thin film modeling of crystal dissolution and growth in confinement.

PubMed

Gagliardi, Luca; Pierre-Louis, Olivier

2018-01-01

We present a continuum model describing dissolution and growth of a crystal contact confined against a substrate. Diffusion and hydrodynamics in the liquid film separating the crystal and the substrate are modeled within the lubrication approximation. The model also accounts for the disjoining pressure and surface tension. Within this framework, we obtain evolution equations which govern the nonequilibrium dynamics of the crystal interface. Based on this model, we explore the problem of dissolution under an external load, known as pressure solution. We find that in steady state, diverging (power-law) crystal-surface repulsions lead to flat contacts with a monotonic increase of the dissolution rate as a function of the load. Forces induced by viscous dissipation then surpass those due to disjoining pressure at large enough loads. In contrast, finite repulsions (exponential) lead to sharp pointy contacts with a dissolution rate independent of the load and the liquid viscosity. Ultimately, in steady state, the crystal never touches the substrate when pressed against it. This result is independent from the nature of the crystal-surface interaction due to the combined effects of viscosity and surface tension.

Thin film modeling of crystal dissolution and growth in confinement

NASA Astrophysics Data System (ADS)

Gagliardi, Luca; Pierre-Louis, Olivier

2018-01-01

We present a continuum model describing dissolution and growth of a crystal contact confined against a substrate. Diffusion and hydrodynamics in the liquid film separating the crystal and the substrate are modeled within the lubrication approximation. The model also accounts for the disjoining pressure and surface tension. Within this framework, we obtain evolution equations which govern the nonequilibrium dynamics of the crystal interface. Based on this model, we explore the problem of dissolution under an external load, known as pressure solution. We find that in steady state, diverging (power-law) crystal-surface repulsions lead to flat contacts with a monotonic increase of the dissolution rate as a function of the load. Forces induced by viscous dissipation then surpass those due to disjoining pressure at large enough loads. In contrast, finite repulsions (exponential) lead to sharp pointy contacts with a dissolution rate independent of the load and the liquid viscosity. Ultimately, in steady state, the crystal never touches the substrate when pressed against it. This result is independent from the nature of the crystal-surface interaction due to the combined effects of viscosity and surface tension.

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.

Advantages of Oxide Films as Bases for Aluminum Pigmented Surface Coatings for Aluminum Alloys

NASA Technical Reports Server (NTRS)

Buzzard, R W; Mutchler, W H

1931-01-01

Both laboratory and weather-exposure corrosion tests showed conclusively that the protection afforded by aluminum pigmented spar varnish coatings applied to previously anodized aluminum surfaces was greatly superior to that afforded by the same coatings applied to surfaces which had simply been cleaned free from grease and not anodized.

Kinetics of brucite dissolution at 25°C in the presence of organic and inorganic ligands and divalent metals

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques; Castillo, Alain

2005-02-01

Brucite (Mg(OH) 2) dissolution rate was measured at 25°C in a mixed-flow reactor at various pH (5 to 11) and ionic strengths (0.01 to 0.03 M) as a function of the concentration of 15 organic and 5 inorganic ligands and 8 divalent metals. At neutral and weakly alkaline pH, the dissolution is promoted by the addition of the following ligands ranked by decreasing effectiveness: EDTA ≥ H 2PO 4- > catechol ≥ HCO 3- > ascorbate > citrate > oxalate > acetate ˜ lactate and it is inhibited by boric acid. At pH >10.5, it decreases in the presence of PO 43-, CO 32-, F -, oxine, salicylate, lactate, acetate, 4-hydroxybenzoate, SO 42- and B(OH) 4- with orthophosphate and borate being the strongest and the weakest inhibitor, respectively. Xylose (up to 0.1 M), glycine (up to 0.05 M), formate (up to 0.3 M) and fulvic and humic acids (up to 40 mg/L DOC) have no effect on brucite dissolution kinetics. Fluorine inhibits dissolution both in neutral and alkaline solutions. From F sorption experiments in batch and flow-through reactors and the analysis of reacted surfaces using X-ray Photoelectron Spectroscopy (XPS), it is shown that fluorine adsorption is followed by its incorporation in brucite lattice likely via isomorphic substitution with OH. The effect of eight divalent metals (Sr, Ba, Ca, Pb, Mn, Fe, Co and Ni) studied at pH 4.9 and 0.01 M concentration revealed brucite dissolution rates to be correlated with the water molecule exchange rates in the first hydration sphere of the corresponding cation. The effect of investigated ligands on brucite dissolution rate can be modelled within the framework of the surface coordination approach taking into account the adsorption of ligands on dissolution-active sites and the molecular structure of the surface complexes they form. The higher the value of the ligand sorption constant, the stronger will be its catalyzing or inhibiting effect. As for Fe and Al oxides, bi- or multidentate mononuclear surface complexes, that labilize Mg-O bonds and water coordination to Mg atoms at the surface, enhance brucite dissolution whereas bi- or polynuclear surface complexes tend to inhibit dissolution by bridging two or more metal centers and extending the cross-linking at the solid surface. Overall, results of this study demonstrate that very high concentrations of organic ligands (0.01-0.1 M) are necessary to enhance or inhibit brucite dissolution. As a result, the effect of extracellular organic products on the weathering rate of Mg-bearing minerals is expected to be weak.

Groundwater flow and its effect on salt dissolution in Gypsum Canyon watershed, Paradox Basin, southeast Utah, USA

NASA Astrophysics Data System (ADS)

Reitman, Nadine G.; Ge, Shemin; Mueller, Karl

2014-09-01

Groundwater flow is an important control on subsurface evaporite (salt) dissolution. Salt dissolution can drive faulting and associated subsidence on the land surface and increase salinity in groundwater. This study aims to understand the groundwater flow system of Gypsum Canyon watershed in the Paradox Basin, Utah, USA, and whether or not groundwater-driven dissolution affects surface deformation. The work characterizes the groundwater flow and solute transport systems of the watershed using a three-dimensional (3D) finite element flow and transport model, SUTRA. Spring samples were analyzed for stable isotopes of water and total dissolved solids. Spring water and hydraulic conductivity data provide constraints for model parameters. Model results indicate that regional groundwater flow is to the northwest towards the Colorado River, and shallow flow systems are influenced by topography. The low permeability obtained from laboratory tests is inconsistent with field observed discharges, supporting the notion that fracture permeability plays a significant role in controlling groundwater flow. Model output implies that groundwater-driven dissolution is small on average, and cannot account for volume changes in the evaporite deposits that could cause surface deformation, but it is speculated that dissolution may be highly localized and/or weaken evaporite deposits, and could lead to surface deformation over time.

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

Effects of anodic oxidation parameters on a modified titanium surface.

PubMed

Park, Il Song; Lee, Min Ho; Bae, Tae Sung; Seol, Kyeong Won

2008-02-01

Anodic oxidation is an electrochemical treatment that can be used to control the thickness of an oxide layer formed on a titanium surface. This procedure has the advantage of allowing the ions contained in an electrolyte to deposit onto the oxide layer. The characteristics of a layer treated with anodic oxidation can vary according to the type and concentration of the electrolytes as well as the processing variables used during anodic oxidation. In this study, the constant electrolyte for anodic oxidation was a mixed solution containing 0.02 M DL-alpha-glycerophosphate disodium salt and 0.2M calcium acetate. Anodic oxidation was carried out at different voltages, current densities, and duration of anodic oxidation. The results showed that the current density and variation in the duration of anodic oxidation did not have a large effect on the change in the characteristics of the layer. On the other hand, the size of the micropores was increased with increasing voltage of anodic oxidation, and anatase and rutile phases were found to co-exist in the porous titanium dioxide layer. In addition, the thickness of the oxide layer on titanium and the characteristic of corrosion resistance increased with increasing voltage. The MTT test showed that the cell viability was increased considerably as a result of anodic oxidation. The anodizing voltage is an important parameter that determines the characteristics of the anodic oxide layer of titanium. (c) 2007 Wiley Periodicals, Inc.

Chalcopyrite dissolution: Scanning photoelectron microscopy examination of the evolution of sulfur species with and without added iron or pyrite

NASA Astrophysics Data System (ADS)

Li, Yubiao; Qian, Gujie; Brown, Paul L.; Gerson, Andrea R.

2017-09-01

Dissolution and oxidation of sulfide minerals play key roles in both acid and metalliferous rock drainage and supergene enrichment. Surface speciation heterogeneity, critical to understanding mechanisms of mineral sulfide dissolution, has to date largely not been considered. To this end synchrotron scanning photoelectron microscopy (SPEM) was employed to examine freshly fractured and partially dissolved chalcopyrite (CuFeS2) surfaces (pH 1.0 HClO4 solution, redox potential 650 mV relative to a standard hydrogen electrode, 75 °C). S2- (bulk), S22- and Sn2- were found to be present on all samples at varying concentrations. Oxidation was observed to take place heterogeneously at the sub-micron scale. As compared to chalcopyrite partially dissolved for 5 days, extended dissolution to 10 days did not show appreciably enhanced oxidation of surface species; however surface roughness increased markedly due to the growth/overlap of oxidised sulfur species. On addition of 4 mM iron both S0 and SO42- were observed but not SO32-, indicating that the greater Fe3+ activity/concentration promotes heterogeneous sulfur oxidation. On contact of pyrite (FeS2) with chalcopyrite, significantly greater chalcopyrite surface oxidation was observed than for the other systems examined, with S0, SO32- and SO42- being identified heterogeneously across the surface. It is proposed that chalcopyrite oxidative dissolution is enhanced by increasing its cathodic area, e.g. contacting with pyrite, while increased Fe3+ activity/concentration also contributes to increased dissolution rates. The high degree of surface heterogeneity of these surface products indicates that these surfaces are not passivated by their formation. These results suggest that chalcopyrite dissolution will be accelerated when in contact with pyrite at solution redox potential intermediate between the rest potentials of chalcopyrite and pyrite (560 mV and 660 mV, respectively) and/or iron rich acidic waters with resulting enhanced formation of secondary sulfur containing species and release of copper and iron. This in turn suggests accelerated supergene formation and enhanced metalliferous drainage under these conditions.

Silicon Whisker and Carbon Nanofiber Composite Anode

NASA Technical Reports Server (NTRS)

Ma, Junqing (Inventor); Newman, Aron (Inventor); Lennhoff, John (Inventor)

2015-01-01

A carbon nanofiber can have a surface and include at least one crystalline whisker extending from the surface of the carbon nanofiber. A battery anode composition can be formed from a plurality of carbon nanofibers each including a plurality of crystalline whiskers.

Catalyst inks and method of application for direct methanol fuel cells

DOEpatents

Zelenay, Piotr; Davey, John; Ren, Xiaoming; Gottesfeld, Shimshon; Thomas, Sharon C.

2004-02-24

Inks are formulated for forming anode and cathode catalyst layers and applied to anode and cathode sides of a membrane for a direct methanol fuel cell. The inks comprise a Pt catalyst for the cathode and a Pt--Ru catalyst for the anode, purified water in an amount 4 to 20 times that of the catalyst by weight, and a perfluorosulfonic acid ionomer in an amount effective to provide an ionomer content in the anode and cathode surfaces of 20% to 80% by volume. The inks are prepared in a two-step process while cooling and agitating the solutions. The final solution is placed in a cooler and continuously agitated while spraying the solution over the anode or cathode surface of the membrane as determined by the catalyst content.

In situ detection of porosity initiation during aluminum thin film anodizing

NASA Astrophysics Data System (ADS)

Van Overmeere, Quentin; Nysten, Bernard; Proost, Joris

2009-02-01

High-resolution curvature measurements have been performed in situ during aluminum thin film anodizing in sulfuric acid. A well-defined transition in the rate of internal stress-induced curvature change is shown to allow for the accurate, real-time detection of porosity initiation. The validity of this in situ diagnostic tool was confirmed by a quantitative analysis of the spectral density distributions of the anodized surfaces. These were obtained by analyzing ex situ atomic force microscopy images of surfaces anodized for different times, and allowed to correlate the in situ detected transition in the rate of curvature change with the appearance of porosity.

Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals

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

Wang, Yifeng; Jove-Colon, Carlos F.; Kuhlman, Kristopher L.

2016-07-22

Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruentmore » dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). In conclusion, our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications.« less

Ferrihydrite dissolution by pyridine-2,6-bis(monothiocarboxylic acid) and hydrolysis products

NASA Astrophysics Data System (ADS)

Dhungana, Suraj; Anthony, Charles R.; Hersman, Larry E.

2007-12-01

Pyridine-2,6-bis(monothiocarboxylate) (pdtc), a metabolic product of microorganisms, including Pseudomonas putida and Pseudomonas stutzeri was investigated for its ability of dissolve Fe(III)(hydr)oxides at pH 7.5. Concentration dependent dissolution of ferrihydrite under anaerobic environment showed saturation of the dissolution rate at the higher concentration of pdtc. The surface controlled ferrihydrite dissolution rate was determined to be 1.2 × 10 -6 mol m -2 h -1. Anaerobic dissolution of ferrihydrite by pyridine-2,6-dicarboxylic acid or dipicolinic acid (dpa), a hydrolysis product of pdtc, was investigated to study the mechanism(s) involved in the pdtc facilitated ferrihydrite dissolution. These studies suggest that pdtc dissolved ferrihydrite using a reduction step, where dpa chelates the Fe reduced by a second hydrolysis product, H 2S. Dpa facilitated dissolution of ferrihydrite showed very small increase in the Fe dissolution when the concentration of external reductant, ascorbate, was doubled, suggesting the surface dynamics being dominated by the interactions between dpa and ferrihydrite. Greater than stoichiometric amounts of Fe were mobilized during dpa dissolution of ferrihydrite assisted by ascorbate and cysteine. This is attributed to the catalytic dissolution of Fe(III)(hydr)oxides by the in situ generated Fe(II) in the presence of a complex former, dpa.

What controls silicon isotope fractionation during dissolution of diatom opal?

NASA Astrophysics Data System (ADS)

Wetzel, F.; de Souza, G. F.; Reynolds, B. C.

2014-04-01

The silicon isotope composition of opal frustules from photosynthesising diatoms is a promising tool for studying past changes in the marine silicon cycle, and indirectly that of carbon. Dissolution of this opal may be accompanied by silicon isotope fractionation that could disturb the pristine silicon isotope composition of diatom opal acquired in the surface ocean. It has previously been shown that dissolution of fresh and sediment trap diatom opal in seawater does fractionate silicon isotopes. However, as the mechanism of silicon isotope fractionation remained elusive, it is uncertain whether opal dissolution in general is associated with silicon isotope fractionation considering that opal chemistry and surface properties are spatially and temporally (i.e. opal of different age) diverse. In this study we dissolved sediment core diatom opal in 5 mM NaOH and found that this process is not associated with significant silicon isotope fractionation. Since no variability of the isotope effect was observed over a wide range of dissolution rates, we can rule out the suggestion that back-reactions had a significant influence on the net isotope effect. Similarly, we did not observe an impact of temperature, specific surface area, or degree of undersaturation on silicon isotope partitioning during dissolution, such that these can most likely also be ruled out as controlling factors. We discuss the potential impacts of the chemical composition of the dissolution medium and age of diatom opal on silicon isotope fractionation during dissolution. It appears most likely that the controlling mechanism of silicon isotope fractionation during dissolution is related to the reactivity, or potentially, aluminium content of the opal. Such a dependency would imply that silicon isotope fractionation during dissolution of diatom opal is spatially and temporally variable. However, since the isotope effects during dissolution are small, the silicon isotope composition of diatom opal appears to be robust against dissolution in the deep sea sedimentary environment.

Surface breakdown igniter for mercury arc devices

DOEpatents

Bayless, John R.

1977-01-01

Surface breakdown igniter comprises a semiconductor of medium resistivity which has the arc device cathode as one electrode and has an igniter anode electrode so that when voltage is applied between the electrodes a spark is generated when electrical breakdown occurs over the surface of the semiconductor. The geometry of the igniter anode and cathode electrodes causes the igniter discharge to be forced away from the semiconductor surface.

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

In-situ study of the gas-phase composition and temperature of an intermediate-temperature solid oxide fuel cell anode surface fed by reformate natural gas

NASA Astrophysics Data System (ADS)

Santoni, F.; Silva Mosqueda, D. M.; Pumiglia, D.; Viceconti, E.; Conti, B.; Boigues Muñoz, C.; Bosio, B.; Ulgiati, S.; McPhail, S. J.

2017-12-01

An innovative experimental setup is used for in-depth and in-operando characterization of solid oxide fuel cell anodic processes. This work focuses on the heterogeneous reactions taking place on a 121 cm2 anode-supported cell (ASC) running with a H2, CH4, CO2, CO and steam gas mixture as a fuel, using an operating temperature of 923 K. The results have been obtained by analyzing the gas composition and temperature profiles along the anode surface in different conditions: open circuit voltage (OCV) and under two different current densities, 165 mA cm-2 and 330 mA cm-2, corresponding to 27% and 54% of fuel utilization, respectively. The gas composition and temperature analysis results are consistent, allowing to monitor the evolution of the principal chemical and electrochemical reactions along the anode surface. A possible competition between CO2 and H2O in methane internal reforming is shown under OCV condition and low current density values, leading to two different types of methane reforming: Steam Reforming and Dry Reforming. Under a current load of 40 A, the dominance of exothermic reactions leads to a more marked increase of temperature in the portion of the cell close to the inlet revealing that current density is not uniform along the anode surface.

The surface evolution of La0.4Sr0.6TiO3+δ anode in solid oxide fuel cells: Understanding the sulfur-promotion effect

NASA Astrophysics Data System (ADS)

Yan, Ning; Zanna, Sandrine; Klein, Lorena H.; Roushanafshar, Milad; Amirkhiz, Babak S.; Zeng, Yimin; Rothenberg, Gadi; Marcus, Philippe; Luo, Jing-Li

2017-03-01

The ideal solid oxide fuel cells (SOFCs) can be powered by readily available hydrocarbon fuels containing impurities. While this is commonly recognized as a key advantage of SOFC, it also, together with the elevated operating temperature, becomes the main barrier impeding the in-situ or operando investigations of the anode surface chemistry. Here, using a well-designed quenching experiment, we managed to characterize the near-surface structure of La0.4Sr0.6TiO3+δ (LST) anode in SOFCs fuelled by H2S-containing methane. This new method enabled us to clearly observe the surface amorphization and sulfidation of LST under simulated SOFC operating conditions. The ∼1 nm-thick two dimensional sulfur-adsorbed layer was on top of the disordered LST, containing -S, -SH and elemental sulfur species. In SOFC test, such "poisoned" anode showed increased performances: a ten-fold enhanced power density enhancement (up to 30 mW cm-2) and an improved open circuit voltage (from 0.69 V to 1.17 V). Moreover, its anodic polarization resistance in methane decreased to 21.53 Ω cm2, a difference of 95% compared with the sulfur-free anode. Control experiments confirmed that once the adsorbed sulfur species were removed electrochemically, methane conversion slowed down simultaneously till full stop.

Effects of anodic oxidation and hydrothermal treatment on surface characteristics and biocompatibility of Ti-30Nb-1Fe-1Hf alloy

NASA Astrophysics Data System (ADS)

Ou, Shih-Fu; Chou, Hsin-Hua; Lin, Chao-Sung; Shih, Ching-Jui; Wang, Kuang-Kuo; Pan, Yung-Ning

2012-06-01

Anodic oxidation followed by hydrothermal treatment has been widely applied for surface modification of titanium alloys to precipitate a crystalline hydroxyapatite (HA) layer in order to achieve improved osteoconduction. A majority of the studies in the literature imposed relatively high powers to enhance Ca and P in the anodic oxide film (AOF). However, high powers have been found to cause deterioration of the adhesive strength in one of the author's previous study. In this study, a new electrolyte comprising calcium acetate monohydrate (CA), β-glycerophosphate disodium pentahydrate (β-GP) and HA powder was developed, and the Ti-30Nb-1Fe-1Hf alloy was anodized in this HA-containing electrolyte to a relatively low voltage. Results show that the AOF anodized in the HA-containing electrolyte exhibits a better HA forming ability during hydrothermal treatment, attributing to the presence of HA powder in the electrolyte that effectively enhances both the Ca content and Ca/P ratio in the AOF. On the other hand, the adhesive strength was little affected due to the decrease in size of the craters residing in the AOF. With respect to the biological responses, not much difference in biocompatibility of the treated and untreated Ti-Nb surfaces was obtained. However, the anodized and hydrothermally treated surface promotes the attachment of cells.

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

Experimental study of brucite dissolution and precipitation in aqueous solutions: surface speciation and chemical affinity control

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques

2004-01-01

Dissolution and precipitation rates of brucite (Mg(OH) 2) were measured at 25°C in a mixed-flow reactor as a function of pH (2.5 to 12), ionic strength (10 -4 to 3 M), saturation index (-12 < log Ω < 0.4) and aqueous magnesium concentrations (10 -6 to 5·10 -4 M). Brucite surface charge and isoelectric point (pH IEP) were determined by surface titrations in a limited residence time reactor and electrophoretic measurements, respectively. The pH of zero charge and pH IEP were close to 11. A two-pK, one site surface speciation model which assumes a constant capacitance of the electric double layer (5 F/m 2) and lack of dependence on ionic strength predicts the dominance of >MgOH 2+ species at pH < 8 and their progressive replacement by >MgOH° and >MgO - as pH increases to 10-12. Rates are proportional to the square of >MgOH 2+ surface concentration at pH from 2.5 to 12. In accord with surface speciation predictions, dissolution rates do not depend on ionic strength at pH 6.5 to 11. Brucite dissolution and precipitation rates at close to equilibrium conditions obeyed TST-derived rate laws. At constant saturation indices, brucite precipitation rates were proportional to the square of >MgOH 2+ concentration. The following rate equation, consistent with transition state theory, describes brucite dissolution and precipitation kinetics over a wide range of solution composition and chemical affinity: R=k Mg+ · {>MgOH 2+} 2 · (1-Ω 2) where kMg+ is the dissolution rate constant, {> i} is surface species concentration (mol/m 2), and Ω is the solution saturation index with respect to brucite. Measurements of nonsteady state brucite dissolution rates, in response to cycling the pH from 12 to 2 (pH-jump experiments), indicate the important role of surface hydroxylation — that leads to the formation of Mg oxo or -hydroxo complexes — in the formation of dissolution-active sites. Replacement of water molecules by these oxygen donor complexes in the Mg coordination sphere has a labilizing effect on the dynamics of the remaining water molecules and thus increases reaction rates.

Anodizing color coded anodized Ti6Al4V medical devices for increasing bone cell functions

PubMed Central

Ross, Alexandra P; Webster, Thomas J

2013-01-01

Current titanium-based implants are often anodized in sulfuric acid (H2SO4) for color coding purposes. However, a crucial parameter in selecting the material for an orthopedic implant is the degree to which it will integrate into the surrounding bone. Loosening at the bone–implant interface can cause catastrophic failure when motion occurs between the implant and the surrounding bone. Recently, a different anodization process using hydrofluoric acid has been shown to increase bone growth on commercially pure titanium and titanium alloys through the creation of nanotubes. The objective of this study was to compare, for the first time, the influence of anodizing a titanium alloy medical device in sulfuric acid for color coding purposes, as is done in the orthopedic implant industry, followed by anodizing the device in hydrofluoric acid to implement nanotubes. Specifically, Ti6Al4V model implant samples were anodized first with sulfuric acid to create color-coding features, and then with hydrofluoric acid to implement surface features to enhance osteoblast functions. The material surfaces were characterized by visual inspection, scanning electron microscopy, contact angle measurements, and energy dispersive spectroscopy. Human osteoblasts were seeded onto the samples for a series of time points and were measured for adhesion and proliferation. After 1 and 2 weeks, the levels of alkaline phosphatase activity and calcium deposition were measured to assess the long-term differentiation of osteoblasts into the calcium depositing cells. The results showed that anodizing in hydrofluoric acid after anodizing in sulfuric acid partially retains color coding and creates unique surface features to increase osteoblast adhesion, proliferation, alkaline phosphatase activity, and calcium deposition. In this manner, this study provides a viable method to anodize an already color coded, anodized titanium alloy to potentially increase bone growth for numerous implant applications. PMID:23319862

Anodizing color coded anodized Ti6Al4V medical devices for increasing bone cell functions.

PubMed

Ross, Alexandra P; Webster, Thomas J

2013-01-01

Current titanium-based implants are often anodized in sulfuric acid (H(2)SO(4)) for color coding purposes. However, a crucial parameter in selecting the material for an orthopedic implant is the degree to which it will integrate into the surrounding bone. Loosening at the bone-implant interface can cause catastrophic failure when motion occurs between the implant and the surrounding bone. Recently, a different anodization process using hydrofluoric acid has been shown to increase bone growth on commercially pure titanium and titanium alloys through the creation of nanotubes. The objective of this study was to compare, for the first time, the influence of anodizing a titanium alloy medical device in sulfuric acid for color coding purposes, as is done in the orthopedic implant industry, followed by anodizing the device in hydrofluoric acid to implement nanotubes. Specifically, Ti6Al4V model implant samples were anodized first with sulfuric acid to create color-coding features, and then with hydrofluoric acid to implement surface features to enhance osteoblast functions. The material surfaces were characterized by visual inspection, scanning electron microscopy, contact angle measurements, and energy dispersive spectroscopy. Human osteoblasts were seeded onto the samples for a series of time points and were measured for adhesion and proliferation. After 1 and 2 weeks, the levels of alkaline phosphatase activity and calcium deposition were measured to assess the long-term differentiation of osteoblasts into the calcium depositing cells. The results showed that anodizing in hydrofluoric acid after anodizing in sulfuric acid partially retains color coding and creates unique surface features to increase osteoblast adhesion, proliferation, alkaline phosphatase activity, and calcium deposition. In this manner, this study provides a viable method to anodize an already color coded, anodized titanium alloy to potentially increase bone growth for numerous implant applications.

Supported plasma sputtering apparatus for high deposition rate over large area

DOEpatents

Moss, Ronald W.; McClanahan, Jr., Edwin D.; Laegreid, Nils

1977-01-01

A supported plasma sputtering apparatus is described having shaped electrical fields in the electron discharge region between the cathode and anode and the sputter region between the target and substrate while such regions are free of any externally applied magnetic field to provide a high deposition rate which is substantially uniform over a wide area. Plasma shaping electrodes separate from the anode and target shape the electrical fields in the electron discharge region and the sputter region to provide a high density plasma. The anode surrounds the target to cause substantially uniform sputtering over a large target area. In one embodiment the anode is in the form of an annular ring surrounding a flat target surface, such anode being provided with a ribbed upper surface which shields portions of the anode from exposure to sputtered material to maintain the electron discharge for a long stable operation. Several other embodiments accomplish the same result by using different anodes which either shield the anode from sputtered material, remove the sputtered coating on the anode by heating, or simultaneously mix sputtered metal from the auxiliary target with sputtered insulator from the main target so the resultant coating is conductive. A radio frequency potential alone or together with a D.C. potential, may be applied to the target for a greater sputtering rate.

Bioactivity of Ti-6Al-4V alloy implants treated with ibandronate after the formation of the nanotube TiO2 layer.

PubMed

Moon, So-Hee; Lee, Seung-Jae; Park, Il-Song; Lee, Min-Ho; Soh, Yun-Jo; Bae, Tae-Sung; Kim, Hyung-Seop

2012-11-01

Nanostructure surface of titanium implants treated with anodic oxidation, heat, and bisphosphonates, has been introduced to improve osseointegration of the implants. However, no information could be found about the efficiency of these approaches on Ti-6Al-4V alloy surfaces. This study examined the drug loading capacity of anodized nanotubular Ti-6Al-4V alloy surfaces in vitro as well as the bone response to surface immobilized bisphosphonates (BPs) on anodized nanotubular Ti-6Al-4V alloy surface in tibiae of rats. Ti-6Al-4V alloy titanium was divided into two groups: (1) control group (nontreated); (2) test group (anodized, heat-, and bisphosphonate-treated group). In vitro, amount of the drug released from the both groups' specimens was examined; all samples were 1 × 2 cm in size. In vivo, the 10 implants were placed inside of tibias of five rats. After 4 weeks, the bone response of the implants was evaluated using a removal torque test, and measuring bone contact and bone area. In addition, the surfaces of the extracted implants were observed by FE-SEM and EDS. In vitro, the drug loading capacity of the Ti-6Al-4V alloy surfaces was enhanced by anodizing surface modification. The values of the removal torque, bone contact, and bone area were significantly higher in the test group (p < 0.05). Furthermore, according to the EDS analysis, the amounts of Ca and P on the surface of the extracted implants were higher in the test group. Within the limits of this experiment, results of this research demonstrated that bisphosphonate-treated Ti-6Al-4V alloy implants with nanotubular surfaces have positive effects in bone-to-implant contact. Copyright © 2012 Wiley Periodicals, Inc.

Electrochemical anodizing treatment to enhance localized corrosion resistance of pure titanium.

PubMed

Prando, Davide; Brenna, Andrea; Bolzoni, Fabio M; Diamanti, Maria V; Pedeferri, Mariapia; Ormellese, Marco

2017-01-26

Titanium has outstanding corrosion resistance due to the thin protective oxide layer that is formed on its surface. Nevertheless, in harsh and severe environments, pure titanium may suffer localized corrosion. In those conditions, costly titanium alloys containing palladium, nickel and molybdenum are used. This purpose investigated how it is possible to control corrosion, at lower cost, by electrochemical surface treatment on pure titanium, increasing the thickness of the natural oxide layer. Anodic oxidation was performed on titanium by immersion in H2SO4 solution and applying voltages ranging from 10 to 80 V. Different anodic current densities were considered. Potentiodynamic tests in chloride- and fluoride-containing solutions were carried out on anodized titanium to determine the pitting potential. All tested anodizing treatments increased corrosion resistance of pure titanium, but never reached the performance of titanium alloys. The best corrosion behavior was obtained on titanium anodized at voltages lower than 40 V at 20 mA/cm2. Titanium samples anodized at low cell voltage were seen to give high corrosion resistance in chloride- and fluoride-containing solutions. Electrolyte bath and anodic current density have little effect on the corrosion behavior.

The anodic emitter effect and its inversion demonstrated by temperature measurements at doped and undoped tungsten electrodes

NASA Astrophysics Data System (ADS)

Hoebing, T.; Bergner, A.; Hermanns, P.; Mentel, J.; Awakowicz, P.

2016-04-01

The admixture of a small amount of emitter oxides, e.g. \\text{Th}{{\\text{O}}2} , \\text{L}{{\\text{a}}2}{{\\text{O}}3} or \\text{C}{{\\text{e}}2}{{\\text{O}}3} to tungsten generates the so-called emitter effect. It reduces the work function of tungsten cathodes, that are applied in high intensity discharge (HID) lamps. After leaving the electrode bulk and moving to the surface, a monolayer of Th, La, or Ce atoms is formed on the surface, which reduces the effective work function ϕ. Depending on the coverage of the electrode, the effective reduction in ϕ is subjected to the thermal desorption of the monolayer from the hot electrode surface. The thermal desorption of emitter atoms from the cathode is compensated not only by the supply from the interior of the electrode and by surface diffusion of the emitter material to its tip, but also to a large extent by a repatriation of the emitter ions from the plasma by the strong electric field in front of the cathode. Yet, an emitter ion current from the arc discharge to the anode may only be present, if the anode is cold enough to refrain from thermionic emission. Therefore, the ability of emitter oxides to reduce the temperature of tungsten anodes is only given for a moderate temperature so that the thermal desorption is low and an additional ion current is present in front of the anode. A higher electrode temperature leads to their evaporation and to an inversion of the emitter effect, which increases the temperature of the respective anodes in comparison with pure tungsten anodes. Within this article, the emitter effect of doped tungsten anodes and the transition to its inversion is investigated for thoriated, lanthanated, and ceriated tungsten electrodes by measurements of the electrode temperature in dependence on the discharge current. It is shown for a lanthanated and a ceriated anode that the emitter effect is sustained by an ion current at anode temperatures at which the thermal evaporation of emitter material is completed.

Titanium dental implant surfaces obtained by anodic spark deposition - From the past to the future.

PubMed

Kaluđerović, Milena R; Schreckenbach, Joachim P; Graf, Hans-Ludwig

2016-12-01

Commercial titanium-based dental implants are obtained applying various methods such as machining, acid etching, anodization, plasma spraying, grit blasting or combination techniques yielding materials with smooth or micro-roughened surfaces. Those techniques are used to optimize the surface properties and to maximize biocompatibility and bioactivity with bone tissue. Present review is focused on the material surfaces obtained by anodic spark deposition (ASD). From the early 1980s till present, the results of numerous studies have shown that anodically oxidized surfaces with different dopants express a positive effect on osteoblasts behavior in vitro and osseointegration in vivo. Those surfaces demonstrated a high biocompatibility and rapid osseointegration in clinical application. This paper provides an overview of the preparation of implant surfaces by employing ASD process. Moreover, reviewed are clinically used ASD implant surfaces (Ticer, TiUnite, Osstem, etc.). The electrolyte variations in ASD process and their influence on surface properties are given herein. Using different electrolytes, anode voltages and temperatures, the above fabrication process can yield various surface morphologies from smooth to rough, porous surfaces. Furthermore, ASD enables thickening of oxide layers and enrichment with different dopands from used electrolyte, which hinder release of potentially toxic titanium ions in surrounding tissue. Particularly exciting results were achieved by calcium and phosphorus doping of the oxide layer (Ticer, ZL Microdent; TiUnite, Nobel Biocare Holding AB) which significantly increased the osteocompatibility. Ticer, a dental implant with anodically oxidized surface and the first among similar materials employed in clinical practice, was found to promote fast osteoblast cell differentiation and mineralization processes. Moreover, Ticer accelerate the integration with the bone, increase the bone/implant contact and improve primary and secondary stability of the implants. Additionally, potential innovations in this field such as fabrication of nanotubes on the implant surfaces as well as novel approaches (e.g. coating with proteins, nanostructured topography; combining implant body and surface derived from titanium and zirconia) are elaborated in this review. Besides, biochemical aspects on implant surface cell/tissue interaction are summarized. From the clinical point of view implant surfaces fabricated by ASD technology possess fast and improved osseointegration, high healing rates and long term prognosis. Copyright © 2016 Elsevier B.V. All rights reserved.

Titania nanotubes with adjustable dimensions for drug reservoir sites and enhanced cell adhesion.

PubMed

Çalışkan, Nazlı; Bayram, Cem; Erdal, Ebru; Karahaliloğlu, Zeynep; Denkbaş, Emir Baki

2014-02-01

This study aims to generate a bactericidal agent releasing surface via nanotube layer on titanium metal and to investigate how aspect ratio of nanotubes affects drug elution time and cell proliferation. Titania nanotube layers were generated on metal surfaces by anodic oxidation at various voltage and time parameters. Gentamicin loading was carried out via simple pipetting and the samples were tested against S. aureus for the efficacy of the applied modification. Drug releasing time and cell proliferation were also tested in vitro. Titania nanotube layers with varying diameters and lengths were prepared after anodization and anodizing duration was found as the most effective parameter for amount of loaded drug and drug releasing time. Drug elution lasted up to 4 days after anodizing for 80 min of the samples, whereas release completed in 24 h when the samples were anodized for 20 min. All processed samples had bactericidal properties against S. aureus organism except unmodified titanium, which was also subjected to drug incorporation step. The anodization also enhanced water wettability and cell adhesion results. Anodic oxidation is an effective surface modification to enhance tissue-implant interactions and also resultant titania layer can act as a drug reservoir for the release of bactericidal agents. The use of implants as local drug eluting devices is promising but further in vivo testing is required. Copyright © 2013 Elsevier B.V. All rights reserved.

Preparation of bioactive titania films on titanium metal via anodic oxidation.

PubMed

Cui, X; Kim, H-M; Kawashita, M; Wang, L; Xiong, T; Kokubo, T; Nakamura, T

2009-01-01

To research the crystal structure and surface morphology of anodic films on titanium metal in different electrolytes under various electrochemical conditions and investigate the effect of the crystal structure of the oxide films on apatite-forming ability in simulated body fluid (SBF). Titanium oxide films were prepared using an anodic oxidation method on the surface of titanium metal in four different electrolytes: sulfuric acid, acetic acid, phosphoric acid and sodium sulfate solutions with different voltages for 1 min at room temperature. Anodic films that consisted of rutile and/or anatase phases with porous structures were formed on titanium metal after anodizing in H(2)SO(4) and Na(2)SO(4) electrolytes, while amorphous titania films were produced after anodizing in CH(3)COOH and H(3)PO(4) electrolytes. Titanium metal with the anatase and/or rutile crystal structure films showed excellent apatite-forming ability and produced a compact apatite layer covering all the surface of titanium after soaking in SBF for 7d, but titanium metal with amorphous titania layers was not able to induce apatite formation. The resultant apatite layer formed on titanium metal in SBF could enhance the bonding strength between living tissue and the implant. Anodic oxidation is believed to be an effective method for preparing bioactive titanium metal as an artificial bone substitute even under load-bearing conditions.

Replacing thermal sprayed zinc anodes on cathodically protected steel reinforced concrete bridges.

DOT National Transportation Integrated Search

2011-09-01

This research aimed to address questions underlying the replacement of arc-sprayed zinc anodes on cathodically protected steel reinforced concrete bridges and to develop a protocol to prepare the concrete surface for the new anode, through a combinat...

Replacing thermal sprayed zinc anodes on cathodically protected steel reinforced concrete bridges.

DOT National Transportation Integrated Search

2011-08-01

"This research aimed to address questions underlying the replacement of arc-sprayed zinc anodes on cathodically protected steel reinforced concrete bridges and to develop a protocol to prepare the concrete surface for the new anode, through a combina...

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.

Characterization and performance of anodic mixed culture biofilms in submersed microbial fuel cells.

PubMed

Saba, Beenish; Christy, Ann D; Yu, Zhongtang; Co, Anne C; Islam, Rafiq; Tuovinen, Olli H

2017-02-01

Microbial fuel cells (MFCs) were designed for laboratory scale experiments to study electroactive biofilms in anodic chambers. Anodic biofilms and current generation during biofilm growth were examined using single chambered MFCs submersed in algal catholyte. A culture of the marine green alga Nanochloropsis salina was used as a biocatholyte, and a rumen fluid microbiota was the anodic chamber inoculum. Electrical impedance spectroscopy was performed under varying external resistance once a week to identify mass transport limitations at the biofilm-electrolyte interface during the four-week experiment. The power generation increased from 249 to 461mWm -2 during the time course. Confocal laser scanning microscopy imaging showed that the depth of the bacterial biofilm on the anode was about 65μm. There were more viable bacteria on the biofilm surface and near the biofilm-electrolyte interface as compared to those close to the anode surface. The results suggest that biofilm growth on the anode creates a conductive layer, which can help overcome mass transport limitations in MFCs. Copyright © 2016 Elsevier B.V. All rights reserved.

Controlled surface oxidation of multi-layered graphene anode to increase hole injection efficiency in organic electronic devices

NASA Astrophysics Data System (ADS)

Han, Tae-Hee; Kwon, Sung-Joo; Seo, Hong-Kyu; Lee, Tae-Woo

2016-03-01

Ultraviolet ozone (UVO) surface treatment of graphene changes its sp2-hybridized carbons to sp3-bonded carbons, and introduces oxygen-containing components. Oxidized graphene has a finite energy band gap, so UVO modification of the surface of a four-layered graphene anode increases its surface ionization potential up to ∼5.2 eV and improves the hole injection efficiency (η) in organic electronic devices by reducing the energy barrier between the graphene anode and overlying organic layers. By controlling the conditions of the UVO treatment, the electrical properties of the graphene can be tuned to improve η. This controlled surface modification of the graphene will provide a way to achieve efficient and stable flexible displays and solid-state lighting.

Dissolution kinetics of a lunar glass simulant at 25 degrees C: the effect of pH and organic acids

NASA Technical Reports Server (NTRS)

Eick, M. J.; Grossl, P. R.; Golden, D. C.; Sparks, D. L.; Ming, D. W.

1996-01-01

The dissolution kinetics of a simulated lunar glass were examined at pH 3, 5, and 7. Additionally, the pH 7 experiments were conducted in the presence of citric and oxalic acid at concentrations of 2 and 20 mM. The organic acids were buffered at pH 7 to examine the effect of each molecule in their dissociated form. At pH 3, 5, and 7, the dissolution of the synthetic lunar glass was observed to proceed via a two-stage process. The first stage involved the parabolic release of Ca, Mg, Al, and Fe, and the linear release of Si. Dissolution was incongruent, creating a leached layer rich in Si and Ti which was verified by transmission electron microscopy (TEM). During the second stage the release of Ca, Mg, Al, and Fe was linear. A coupled diffusion/surface dissolution model was proposed for dissolution of the simulated lunar glass at pH 3, 5, and 7. During the first stage the initial release of mobile cations (i.e., Ca, Mg, Al, Fe) was limited by diffusion through the surface leached layer of the glass (parabolic release), while Si release was controlled by the hydrolysis of the Si-O-Al bonds at the glass surface (linear release). As dissolution continued, the mobile cations diffused from greater depths within the glass surface. A steady-state was then reached where the diffusion rate across the increased path lengths equalled the Si release rate from the surface. In the presence of the organic acids, the dissolution of the synthetic lunar glass proceeded by a one stage process. The release of Ca, Mg, Al, and Fe followed a parabolic relationship, while the release of Si was linear. The relative reactivity of the organic acids used in the experiments was citrate > oxalate. A thinner leached layer rich in Si/Ti, as compared to the pH experiments, was observed using TEM. Rate data suggest that the chemisorption of the organic anion to the surface silanol groups was responsible for enhanced dissolution in the presence of the organic acids. It is proposed that the increased rate of Si release is responsible for the one stage parabolic release of mobile cations and the relatively thin leached layer compared to experiments at pH 3 and 5.

Can accurate kinetic laws be created to describe chemical weathering?

NASA Astrophysics Data System (ADS)

Schott, Jacques; Oelkers, Eric H.; Bénézeth, Pascale; Goddéris, Yves; François, Louis

2012-11-01

Knowledge of the mechanisms and rates of mineral dissolution and growth, especially close to equilibrium, is essential for describing the temporal and spatial evolution of natural processes like weathering and its impact on CO2 budget and climate. The Surface Complexation approach (SC) combined with Transition State Theory (TST) provides an efficient framework for describing mineral dissolution over wide ranges of solution composition, chemical affinity, and temperature. There has been a large debate for several years, however, about the comparative merits of SC/TS versus classical growth theories for describing mineral dissolution and growth at near-to-equilibrium conditions. This study considers recent results obtained in our laboratory on oxides, hydroxides, silicates, and carbonates on near-equilibrium dissolution and growth via the combination of complementary microscopic and macroscopic techniques including hydrothermal atomic force microscopy, hydrogen-electrode concentration cell, mixed flow and batch reactors. Results show that the dissolution and precipitation of hydroxides, kaolinite, and hydromagnesite powders of relatively high BET surface area closely follow SC/TST rate laws with a linear dependence of both dissolution and growth rates on fluid saturation state (Ω) even at very close to equilibrium conditions (|ΔG| < 500 J/mol). This occurs because sufficient reactive sites (e.g. at kink, steps, and edges) are available at the exposed faces for dissolution and/or growth, allowing reactions to proceed via the direct and reversible detachment/attachment of reactants at the surface. In contrast, for magnesite and quartz, which have low surface areas, fewer active sites are available for growth and dissolution. Such minerals exhibit rates dependencies on Ω at near equilibrium conditions ranging from linear to highly non-linear functions of Ω, depending on the treatment of the crystals before the reaction. It follows that the form of the f(ΔG) function describing the growth and dissolution of minerals with low surface areas depends on the availability of reactive sites at the exposed faces and thus on the history of the mineral-fluid interaction and the hydrodynamic conditions under which the crystals are reacted. It is advocated that the crystal surface roughness could serve as a proxy of the density of reactive sites. The consequences of the different rate laws on the quantification of loess weathering along the Mississippi valley for the next one hundred years are examined.

Effects of NaCl, pH, and Potential on the Static Creep Behavior of AA1100

NASA Astrophysics Data System (ADS)

Wan, Quanhe; Quesnel, David J.

2013-03-01

The creep rates of AA1100 are measured during exposure to a variety of aggressive environments. NaCl solutions of various concentrations have no influence on the steady-state creep behavior, producing creep rates comparable to those measured in lab air at room temperature. However, after an initial incubation period of steady strain rate, a dramatic increase of strain rate is observed on exposure to HCl solutions and NaOH solutions, as well as during cathodic polarization of specimens in NaCl solutions. Creep strain produces a continuous deformation and elongation of the sample surface that is comparable to slow strain rates at crack tips thought to control the kinetics of crack growth during stress corrosion cracking (SCC). In this experiment, we separate the strain and surface deformation from the complex geometry of the crack tip to better understand the processes at work. Based on this concept, two possible explanations for the environmental influences on creep strain rates are discussed relating to the anodic dissolution of the free surface and hydrogen influences on deformation mechanisms. Consistencies of pH dependence between corrosion creep and SCC at low pH prove a creep-involved SCC mechanism, while the discrepancies between corrosion creep behavior and previous SCC results at high pH indicate a rate-limit step change in the crack propagation of the SCC process.

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

Yuan, Ke; De Andrade, Vincent; Feng, Zhange

The presence of impurity ions is known to significantly influence mineral surface morphology during crystal growth from aqueous solution, but knowledge on impurity ion-mineral interactions during dissolution under far-from equilibrium conditions remains limited. Here we show that calcite (CaCO 3) exhibits a rich array of dissolution features in the presence of Pb. During the initial stage, calcite exhibits non-classical surface features characterized as micro pyramids developed spontaneously in acidic Pb-bearing solutions. Subsequent pseudomorphic growth of cerussite (PbCO 3) was observed, where nucleation occurred entirely within a pore space created by dissolution at the calcite/substrate interface. Uneven growth rates yielded amore » cerussite shell made of lath- or dendritic-shaped crystals. The cerussite phase was separated from the calcite by pores of less than 200 nm under transmission X-ray microscopy, consistent with the interface-coupled dissolution-precipitation mechanism. These results show that impurity metal ions exert significant control over the microscale dissolution features found on mineral surfaces and provide new insights into interpreting and designing micro structures observed in naturally-occurring and synthetic carbonate minerals by dissolution. In addition, heterogeneous micro-environments created in transport limited reactions under pore spaces may lead to unusual growth forms during crystal nucleation and precipitation.« less

Dissolution of spherical cap CO2 bubbles attached to flat surfaces in air-saturated water

NASA Astrophysics Data System (ADS)

Peñas, Pablo; Parrales, Miguel A.; Rodriguez-Rodriguez, Javier

2014-11-01

Bubbles attached to flat surfaces immersed in quiescent liquid environments often display a spherical cap (SC) shape. Their dissolution is a phenomenon commonly observed experimentally. Modelling these bubbles as fully spherical may lead to an inaccurate estimate of the bubble dissolution rate. We develop a theoretical model for the diffusion-driven dissolution or growth of such multi-component SC gas bubbles under constant pressure and temperature conditions. Provided the contact angle of the bubble with the surface is large, the concentration gradients in the liquid may be approximated as spherically symmetric. The area available for mass transfer depends on the instantaneous bubble contact angle, whose dynamics is computed from the adhesion hysteresis model [Hong et al., Langmuir, vol. 27, 6890-6896 (2011)]. Numerical simulations and experimental measurements on the dissolution of SC CO2 bubbles immersed in air-saturated water support the validity of our model. We verify that contact line pinning slows down the dissolution rate, and the fact that any bubble immersed in a saturated gas-liquid solution eventually attains a final equilibrium size. Funded by the Spanish Ministry of Economy and Competitiveness through Grant DPI2011-28356-C03-0.

Hollow Nanostructured Anode Materials for Li-Ion Batteries

PubMed Central

2010-01-01

Hollow nanostructured anode materials lie at the heart of research relating to Li-ion batteries, which require high capacity, high rate capability, and high safety. The higher capacity and higher rate capability for hollow nanostructured anode materials than that for the bulk counterparts can be attributed to their higher surface area, shorter path length for Li+ transport, and more freedom for volume change, which can reduce the overpotential and allow better reaction kinetics at the electrode surface. In this article, we review recent research activities on hollow nanostructured anode materials for Li-ion batteries, including carbon materials, metals, metal oxides, and their hybrid materials. The major goal of this review is to highlight some recent progresses in using these hollow nanomaterials as anode materials to develop Li-ion batteries with high capacity, high rate capability, and excellent cycling stability. PMID:21076674

Graphite anode surface modification with controlled reduction of specific aryl diazonium salts for improved microbial fuel cells power output.

PubMed

Picot, Matthieu; Lapinsonnière, Laure; Rothballer, Michael; Barrière, Frédéric

2011-10-15

Graphite electrodes were modified with reduction of aryl diazonium salts and implemented as anodes in microbial fuel cells. First, reduction of 4-aminophenyl diazonium is considered using increased coulombic charge density from 16.5 to 200 mC/cm(2). This procedure introduced aryl amine functionalities at the surface which are neutral at neutral pH. These electrodes were implemented as anodes in "H" type microbial fuel cells inoculated with waste water, acetate as the substrate and using ferricyanide reduction at the cathode and a 1000 Ω external resistance. When the microbial anode had developed, the performances of the microbial fuel cells were measured under acetate saturation conditions and compared with those of control microbial fuel cells having an unmodified graphite anode. We found that the maximum power density of microbial fuel cell first increased as a function of the extent of modification, reaching an optimum after which it decreased for higher degree of surface modification, becoming even less performing than the control microbial fuel cell. Then, the effect of the introduction of charged groups at the surface was investigated at a low degree of surface modification. It was found that negatively charged groups at the surface (carboxylate) decreased microbial fuel cell power output while the introduction of positively charged groups doubled the power output. Scanning electron microscopy revealed that the microbial anode modified with positively charged groups was covered by a dense and homogeneous biofilm. Fluorescence in situ hybridization analyses showed that this biofilm consisted to a large extent of bacteria from the known electroactive Geobacter genus. In summary, the extent of modification of the anode was found to be critical for the microbial fuel cell performance. The nature of the chemical group introduced at the electrode surface was also found to significantly affect the performance of the microbial fuel cells. The method used for modification is easy to control and can be optimized and implemented for many carbon materials currently used in microbial fuel cells and other bioelectrochemical systems. Copyright © 2011 Elsevier B.V. All rights reserved.

Medium-chain-length poly-3-hydroxyalkanoates-carbon nanotubes composite anode enhances the performance of microbial fuel cell.

PubMed

Hindatu, Y; Annuar, M S M; Subramaniam, R; Gumel, A M

2017-06-01

Insufficient power generation from a microbial fuel cell (MFC) hampers its progress towards utility-scale development. Electrode modification with biopolymeric materials could potentially address this issue. In this study, medium-chain-length poly-3-hydroxyalkanoates (PHA)/carbon nanotubes (C) composite (CPHA) was successfully applied to modify the surface of carbon cloth (CC) anode in MFC. Characterization of the functional groups on the anodic surface and its morphology was carried out. The CC-CPHA composite anode recorded maximum power density of 254 mW/m 2 , which was 15-53% higher than the MFC operated with CC-C (214 mW/m 2 ) and pristine CC (119 mW/m 2 ) as the anode in a double-chambered MFC operated with Escherichia coli as the biocatalyst. Electrochemical impedance spectroscopy and cyclic voltammetry showed that power enhancement was attributed to better electron transfer capability by the bacteria for the MFC setup with CC-CPHA anode.

Possibility of High Phosphorus Pig Iron as Sacrificial Anode

NASA Astrophysics Data System (ADS)

Prasad, Nisheeth Kr.; Pathak, A. S.; Kundu, S.; Mondal, K.

2018-05-01

Cathodic protection is an effective method to control the corrosion of underground pipelines and submerged structures. In the present work, high phosphorus containing pig iron was utilized as sacrificial anode for cathodic protection of underground mild steel plates and the results were compared with that of a commercially pure magnesium sacrificial anode. Driving potential and current between the galvanically coupled sacrificial anodes and mild steel plates were continuously monitored in real time for one month. Microstructure and morphology of the corrosion products formed on the surface of pig iron, magnesium sacrificial anodes and mild steel plates were observed with the help of optical microscope and scanning electron microscopy, and phase identification were performed using x-ray diffraction, Raman spectroscopy and Fourier transform infrared spectroscopy. The distribution of phosphorus in the pig iron matrix and soluble rust formation on the surface of pig iron under buried condition were critical from the point of sacrificial effect, indicating the possible scientific reasons for high phosphorous pig iron to be used as sacrificial anode.

Surface modifications for carbon lithium intercalation anodes

DOEpatents

Tran, Tri D.; Kinoshita, Kimio

2000-01-01

A prefabricated carbon anode containing predetermined amounts of passivating film components is assembled into a lithium-ion rechargeable battery. The modified carbon anode enhances the reduction of the irreversible capacity loss during the first discharge of a cathode-loaded cell. The passivating film components, such as Li.sub.2 O and Li.sub.2 CO.sub.3, of a predetermined amount effective for optimal passivation of carbon, are incorporated into carbon anode materials to produce dry anodes that are essentially free of battery electrolyte prior to battery assembly.

Silicon-Based Anode and Method for Manufacturing the Same

NASA Technical Reports Server (NTRS)

Yushin, Gleb Nikolayevich (Inventor); Zdyrko, Bogdan (Inventor); Magasinski, Alexandre (Inventor); Luzinov, Igor (Inventor)

2017-01-01

A silicon-based anode comprising silicon, a carbon coating that coats the surface of the silicon, a polyvinyl acid that binds to at least a portion of the silicon, and vinylene carbonate that seals the interface between the silicon and the polyvinyl acid. Because of its properties, polyvinyl acid binders offer improved anode stability, tunable properties, and many other attractive attributes for silicon-based anodes, which enable the anode to withstand silicon cycles of expansion and contraction during charging and discharging.

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.

Conductive super-hydrophobic surfaces of polyaniline modified porous anodic alumina membranes.

PubMed

Chen, Xinhua; Chen, Guangming; Ma, Yongmei; Li, Xinhong; Jiang, Lei; Wang, Fosong

2006-03-01

A conductive polymer polyaniline (PANI) was employed to achieve surfaces of both super-hydrophobic and conductive on NaOH etched porous anodic alumina (PAA) membranes. The surfaces exhibit micro- and nanostructures. In the PANI modified PAA membrane, PANI is mainly emeraldine. After the membrane was immersed in HCl, the content of the protonated nitrogen increased, which increased the conductivity.

Evaluation of AA5052 alloy anode in alkaline electrolyte with organic rare-earth complex additives for aluminium-air batteries

NASA Astrophysics Data System (ADS)

Wang, Dapeng; Li, Heshun; Liu, Jie; Zhang, Daquan; Gao, Lixin; Tong, Lin

2015-10-01

Behaviours of the AA5052 aluminium alloy anode of the alkaline aluminium-air battery are studied by the hydrogen evolution test, the electrochemical measurements and the surface analysis method. The combination of amino-acid and rare earth as electrolyte additives effectively retards the self-corrosion of AA5052 aluminium alloy in 4 M NaOH solution. It shows that the combination of L-cysteine and cerium nitrate has a synergistic effect owing to the formation of a complex film on AA5052 alloy surface. The organic rare-earth complex can decrease the anodic polarisation, suppress the hydrogen evolution and increase the anodic utilization rate.

The use of ordered mixtures for improving the dissolution rate of low solubility compounds.

PubMed

Nyström, C; Westerberg, M

1986-03-01

The dissolution rate of micronized griseofulvin has been investigated, both for the agglomerated raw material and the material formulated as an ordered mixture, by means of the USP XX paddle method. During the experiments, which were performed at sink condition and constant temperature, the effects of adding a surfactant and of agitation were tested. The ordered mixture with sodium chloride gave a fast dissolution rate, practically independent of the test parameters. Micronized griseofulvin alone gave dissolution profiles that were improved by adding polysorbate 80 and by increased agitation, but the dissolution rates obtained were much lower than those for the ordered mixture. It was concluded that the rate limiting step in the dissolution of griseofulvin as the raw material is the penetration of the dissolution medium into the agglomerates. With an ordered mixture, these agglomerates were deaggregated during the mixing process, producing a system in which the entire external surface area of the primary particles was exposed to the dissolution medium. This conclusion was supported by calculation of the contact surface areas taking part in the dissolution process for the systems tested. The procedure developed in this study could be applied to preformulation work where a cohesive, low solubility drug of hydrophobic nature is to be formulated.

Facile method for preparing superoleophobic surfaces with hierarchical microcubic/nanowire structures

NASA Astrophysics Data System (ADS)

Kwak, Wonshik; Hwang, Woonbong

2016-02-01

To facilitate the fabrication of superoleophobic surfaces having hierarchical microcubic/nanowire structures (HMNS), even for low surface tension liquids including octane (surface tension = 21.1 mN m-1), and to understand the influences of surface structures on the oleophobicity, we developed a convenient method to achieve superoleophobic surfaces on aluminum substrates using chemical acid etching, anodization and fluorination treatment. The liquid repellency of the structured surface was validated through observable experimental results the contact and sliding angle measurements. The etching condition required to ensure high surface roughness was established, and an optimal anodizing condition was determined, as a critical parameter in building the superoleophobicity. The microcubic structures formed by acid etching are essential for achieving the formation of the hierarchical structure, and therefore, the nanowire structures formed by anodization lead to an enhancement of the superoleophobicity for low surface tension liquids. Under optimized morphology by microcubic/nanowire structures with fluorination treatment, the contact angle over 150° and the sliding angle less than 10° are achieved even for octane.

Steamed cake-derived 3D carbon foam with surface anchored carbon nanoparticles as freestanding anodes for high-performance microbial fuel cells.

PubMed

Yuan, Haoran; Dong, Ge; Li, Denian; Deng, Lifang; Cheng, Peng; Chen, Yong

2018-09-15

Anode design is highly significant for microbial fuel cells, since it simultaneously serves as the scaffold for electroactive microorganisms and as a medium for electron migration. In this study, a stiff 3D carbon foam with surface anchored nitrogen-containing carbon nanoparticles was facilely constructed via in-situ polyaniline coating of carbonized steamed cake prior to the carbonization process. The resultant product was determined to be an excellent freestanding anode that enabled the microbial fuel cell to deliver a maximum power density of up to 1307 mW/m 2 , which significantly outperformed its non-coated counterpart, the widely used commercial carbon felt. Further investigations revealed that the overall performance enhancement was associated with the open porosity, enlarged electroactive surface, increased biocompatibility, and decreased electric resistance of the anode scaffold. This promising anode material would offer a green and economical option for fabricating high-performance microbial fuel cell-based devices towards various ends. Copyright © 2018 Elsevier B.V. All rights reserved.

Controlling Morphological Parameters of Anodized Titania Nanotubes for Optimized Solar Energy Applications

PubMed Central

Haring, Andrew; Morris, Amanda; Hu, Michael

2012-01-01

Anodized TiO2 nanotubes have received much attention for their use in solar energy applications including water oxidation cells and hybrid solar cells [dye-sensitized solar cells (DSSCs) and bulk heterojuntion solar cells (BHJs)]. High surface area allows for increased dye-adsorption and photon absorption. Titania nanotubes grown by anodization of titanium in fluoride-containing electrolytes are aligned perpendicular to the substrate surface, reducing the electron diffusion path to the external circuit in solar cells. The nanotube morphology can be optimized for the various applications by adjusting the anodization parameters but the optimum crystallinity of the nanotube arrays remains to be realized. In addition to morphology and crystallinity, the method of device fabrication significantly affects photon and electron dynamics and its energy conversion efficiency. This paper provides the state-of-the-art knowledge to achieve experimental tailoring of morphological parameters including nanotube diameter, length, wall thickness, array surface smoothness, and annealing of nanotube arrays.

Effect of nanostructured titanium on anodization growth of self-organized TiO2 nanotubes

NASA Astrophysics Data System (ADS)

Zhang, Lan; Han, Yong

2010-02-01

To understand the effect of substrate microstructure on the formation of TiO2 nanotubes, anodic oxidizations of commercially pure titanium subjected to surface mechanical attrition treatment (SMATed-Ti) and unSMATed-Ti in a glycol solution containing NH4F and small amounts of water were investigated. The SMATed-Ti exhibit a nanocrystallized surface layer containing a high density of grain boundaries compared with unSMATed-Ti. The anodization results show that the formed TiO2 nanotube layer on the SMATed-Ti is much thicker than that on the unSMATed-Ti. It is indicated that nanocrystallized Ti is propitious to the growth of TiO2 nanotubes; grain boundaries and dislocations play the leading role in accelerating the reaction rate and ion diffusion coefficient during anodization. In addition, nanocrystallization of Ti does not change surface morphologies and phase components of the TiO2 nanotubes.

In situ nanoscale observations of gypsum dissolution by digital holographic microscopy.

PubMed

Feng, Pan; Brand, Alexander S; Chen, Lei; Bullard, Jeffrey W

2017-06-01

Recent topography measurements of gypsum dissolution have not reported the absolute dissolution rates, but instead focus on the rates of formation and growth of etch pits. In this study, the in situ absolute retreat rates of gypsum (010) cleavage surfaces at etch pits, at cleavage steps, and at apparently defect-free portions of the surface are measured in flowing water by reflection digital holographic microscopy. Observations made on randomly sampled fields of view on seven different cleavage surfaces reveal a range of local dissolution rates, the local rate being determined by the topographical features at which material is removed. Four characteristic types of topographical activity are observed: 1) smooth regions, free of etch pits or other noticeable defects, where dissolution rates are relatively low; 2) shallow, wide etch pits bounded by faceted walls which grow gradually at rates somewhat greater than in smooth regions; 3) narrow, deep etch pits which form and grow throughout the observation period at rates that exceed those at the shallow etch pits; and 4) relatively few, submicrometer cleavage steps which move in a wave-like manner and yield local dissolution fluxes that are about five times greater than at etch pits. Molar dissolution rates at all topographical features except submicrometer steps can be aggregated into a continuous, mildly bimodal distribution with a mean of 3.0 µmolm -2 s -1 and a standard deviation of 0.7 µmolm -2 s -1 .

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.

Fabrication of free standing anodic titanium oxide membranes with clean surface using recycling process.

PubMed

Meng, Xianhui; Lee, Tae-Young; Chen, Huiyu; Shin, Dong-Wook; Kwon, Kee-Won; Kwon, Sang Jik; Yoo, Ji-Beom

2010-07-01

Large area of self-organized, free standing anodic titanium oxide (ATO) nanotube membranes with clean surfaces were facilely prepared to desired lengths via electrochemical anodization of highly pure Ti sheets in an ethylene glycol electrolyte, with a small amount of NH4F and H2O at 50 V, followed by self-detachment of the ATO membrane from the Ti substrate using recycling processes. In the first anodization step, the nanowire oxide layer existed over the well-arranged ATO nanotube. After sufficiently rinsing with water, the whole ATO layer was removed from the Ti sheet by high pressure N2 gas, and a well-patterned dimple layer with a thickness of about 30 nm existed on the Ti substrate. By using these naturally formed nano-scale pits as templates, in the second and third anodization process, highly ordered, vertically aligned, and free standing ATO membranes with the anodic aluminum oxide (AAO)-like clean surface were obtained. The inter-pore distance and diameter was 154 +/- 2 nm and 91+/- 2 nm, the tube arrays lengths for 25 and 46 hours were 44 and 70 microm, respectively. The present study demonstrates a simple approach to producing high quality, length controllable, large area TiO2 membrane.

Relationships between structure and activity of carbon as a multifunctional support for electrocatalysts.

PubMed

Stevanović, Sanja I; Panić, Vladimir V; Dekanski, Aleksandar B; Tripković, Amalija V; Jovanović, Vladislava M

2012-07-14

We report on new insights into the relationships between structure and activity of glassy carbon (GC), as a model material for electrocatalyst support, during its anodization in acid solution. Our investigation strongly confirms the role of CFGs in promotion of Pt activity by the "spill-over" effect related to CO(ads) for methanol electrooxidation (MEO) on a carbon-supported Pt catalyst. Combined analysis of voltammetric and impedance behaviour as well as changes in GC surface morphology induced by intensification of anodizing conditions reveal an intrinsic influence of the carbon functionalization and the structure of a graphene oxide (GO) layer on the electrical and electrocatalytic properties of activated GC. Although GO continuously grows during anodization, it structurally changes from being a graphite inter-layer within graphite ribbons toward a continuous GO surface layer that deteriorates the native structure of GC. As a consequence of the increased distance between GO-spaced graphite layers, the GC conductivity decreases until the case of profound GO exfoliation under drastic anodizing conditions. This exposes the native, yet abundantly functionalized, GC texture. While GC capacitance continuously increases with intensification of anodizing conditions, the surface nano-roughness and GO resistance reach the highest values at modest anodizing conditions, and then decrease upon drastic anodization due to the onset of GO exfoliation. We found for the first time that the activity of a GC-supported Pt catalyst in MEO, as one of the promising half-reactions in polymer electrolyte fuel cells, strictly follows the changes in GC nano-roughness and GO-induced GC resistance. The highest GC/Pt MEO activity is reached when optimal distance between graphite layers and optimal degree of GC functionalization bring the highest amount of CFGs into intimate contact with the Pt surface. This confirms the promoting role of CFGs in MEO catalysis.

Variable-focus microscopy and UV surface dissolution imaging as complementary techniques in intrinsic dissolution rate determination.

PubMed

Ward, Adam; Walton, Karl; Box, Karl; Østergaard, Jesper; Gillie, Lisa J; Conway, Barbara R; Asare-Addo, Kofi

2017-09-15

This work reports a novel approach to the assessment of the surface properties of compacts used in Surface Dissolution Imaging (SDI). SDI is useful for determining intrinsic dissolution rate (IDR), an important parameter in early stage drug development. Surface topography, post-compaction and post-SDI run, have been measured using a non-contact, optical, three-dimensional microscope based on focus variation, the Alicona Infinite Focus Microscope, with the aim of correlating the IDRs to the surface properties. Ibuprofen (IBU) was used as a model poorly-soluble drug. DSC and XRD were used to monitor possible polymorphic changes that may have occurred post-compaction and post-SDI run. IBUs IDR decreased from 0.033mg/min/cm 2 to 0.022mg/min/cm 2 from 10 to 20min, respectively, during the experiment. XRD and DSC showed no form changes during the SDI run. The surface topography images showed that a distinct imprint was embossed on the surfaces of some compacts which could affect IDRs. Surface parameter values were associated with the SDI experiments which showed strong correlations with the IDR values. The variable-focus microscope can be used as a complimentary tool in the determination of IDR values from the SDI. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

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.

Preparation of ordered mesoporous and macroporous thermoplastic polyurethane surfaces for potential medical applications.

PubMed

Chennell, Philip; Feschet-Chassot, Emmanuelle; Sautou, Valérie; Mailhot-Jensen, Bénédicte

2018-05-01

Thermoplastic polyurethanes are widely used in medical devices. In order to limit some of their shortfalls, like microbial attachment, surfaces modifications can be required. In this work, a two-step replication method was used to create ordered macroporous and mesoporous thermoplastic polyurethane surfaces using anodic aluminum oxide as master template. The intermediate mould materials that were tested were polystyrene and a polyacrylate resin with inorganic filler. All obtained surfaces were characterized by scanning electron microscopy. The initial anodic aluminum oxide surfaces possessed macro or mesopores, function of anodization conditions. The intermediate mould structure correctly replicated the pattern, but the polystyrene surface structures (pillars) were less resistant than the polyacrylate resin ones. The thermoplastic polyurethane pattern possessed macropores or mesopores of about 130 nm or 46 nm diameter and of about 300 nm or 99 nm interpore distances, respectively, in accordance with the initial pattern. Thermoplastic polyurethanes pore depth was however less than initial anodic aluminum oxide pore depth, linked to an incomplete replication during intermediate mould preparation (60 to 90% depth replication). The correct replication of the original pattern confirms that this novel fabrication method is a promising route for surface patterning of thermoplastic polyurethanes that could be used for medical applications.

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.

Controlling initial biodegradation of magnesium by a biocompatible strontium phosphate conversion coating.

PubMed

Chen, X B; Nisbet, D R; Li, R W; Smith, P N; Abbott, T B; Easton, M A; Zhang, D-H; Birbilis, N

2014-03-01

A simple strontium phosphate (SrP) conversion coating process was developed to protect magnesium (Mg) from the initial degradation post-implantation. The coating morphology, deposition rate and resultant phases are all dependent on the processing temperature, which determines the protective ability for Mg in minimum essential medium (MEM). Coatings produced at 80 °C are primarily made up of strontium apatite (SrAp) with a granular surface, a high degree of crystallinity and the highest protective ability, which arises from retarding anodic dissolution of Mg in MEM. Following 14 days' immersion in MEM, the SrAp coating maintained its integrity with only a small fraction of the surface corroded. The post-degradation effect of uncoated Mg and Mg coated at 40 and 80 °C on the proliferation and differentiation of human mesenchymal stem cells was also studied, revealing that the SrP coatings are biocompatible and permit proliferation to a level similar to that of pure Mg. The present study suggests that the SrP conversion coating is a promising option for controlling the early rapid degradation rate, and hence hydrogen gas evolution, of Mg implants without adverse effects on surrounding cells and tissues. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Fuel cell anode configuration for CO tolerance

DOEpatents

Uribe, Francisco A.; Zawodzinski, Thomas A.

2004-11-16

A polymer electrolyte fuel cell (PEFC) is designed to operate on a reformate fuel stream containing oxygen and diluted hydrogen fuel with CO impurities. A polymer electrolyte membrane has an electrocatalytic surface formed from an electrocatalyst mixed with the polymer and bonded on an anode side of the membrane. An anode backing is formed of a porous electrically conductive material and has a first surface abutting the electrocatalytic surface and a second surface facing away from the membrane. The second surface has an oxidation catalyst layer effective to catalyze the oxidation of CO by oxygen present in the fuel stream where at least the layer of oxidation catalyst is formed of a non-precious metal oxidation catalyst selected from the group consisting of Cu, Fe, Co, Tb, W, Mo, Sn, and oxides thereof, and other metals having at least two low oxidation states.

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

Xu, Wu; Canfield, Nathan L.; Zhang, Ji-Guang

Methods for making composite anodes, such as macroporous composite anodes, are disclosed. Embodiments of the methods may include forming a tape from a slurry including a substrate metal precursor, an anode active material, a pore-forming agent, a binder, and a solvent. A laminated structure may be prepared from the tape and sintered to produce a porous structure, such as a macroporous structure. The macroporous structure may be heated to reduce a substrate metal precursor and/or anode active material. Macroporous composite anodes formed by some embodiments of the disclosed methods comprise a porous metal and an anode active material, wherein themore » anode active material is both externally and internally incorporated throughout and on the surface of the macroporous structure.« less

Aluminum anode for aluminum-air battery - Part II: Influence of In addition on the electrochemical characteristics of Al-Zn alloy in alkaline solution

NASA Astrophysics Data System (ADS)

Park, In-Jun; Choi, Seok-Ryul; Kim, Jung-Gu

2017-07-01

Effects of Zn and In additions on the aluminum anode for Al-air battery in alkaline solution are examined by the self-corrosion rate, cell voltage, current-voltage characteristics, anodic polarization, discharge performance and AC impedance measurements. The passivation behavior of Zn-added anode during anodic polarization decreases the discharge performance of Al-air battery. The addition of In to Al-Zn anode reduces the formation of Zn passivation film by repeated adsorption and desorption behavior of In ion onto anode surface. The attenuated Zn passive layer by In ion attack leads to the improvement of discharge performance of Al-air battery.

Patterned titania nanostructures produced by electrochemical anodization of titanium sheet

NASA Astrophysics Data System (ADS)

Dong, Junzhe; Ariyanti, Dessy; Gao, Wei; Niu, Zhenjiang; Weil, Emeline

2017-07-01

A two-step anodization method has been used to produce patterned arrays of TiO2 on the surface of Ti sheet. Hexagonal ripples were created on Ti substrate after removing the TiO2 layer produced by first-step anodization. The shallow concaves were served as an ideal position for the subsequent step anodization due to their low electrical resistance, resulting in novel hierarchical nanostructures with small pits inside the original ripples. The mechanism of morphology evolution during patterned anodization was studied through changing the anodizing voltages and duration time. This work provides a new idea for controlling nanostructures and thus tailoring the photocatalytic property and wettability of anodic TiO2.

Preparation of mesoporous titanium dioxide anode by a film- and pore-forming agent for the dye-sensitized solar cell

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

Hou, Wenjing; Xiao, Yaoming, E-mail: ymxiao@sxu.edu.cn; Han, Gaoyi, E-mail: han_gaoyis@sxu.edu.cn

2016-04-15

Highlights: • PVP is used as a film- and pore-forming agent to prepare the mesoporous TiO{sub 2} anode. • The TiO{sub 2} anode supplies high surface area for the dye adsorption. • The DSSC efficiency is strongly dependent on the pore properties of the TiO{sub 2} anode. • The DSSC efficiency with the TiO{sub 2} anode prepared by 20 wt% PVP reaches 8.39%. - Abstract: A novel mean of generating mesoporous titanium dioxide (TiO{sub 2}) anodes by employing polyvinylpyrrolidone (PVP) as the film- and pore-forming agent are proposed for dye-sensitized solar cells (DSSCs). The influences on the morphology and photovoltaicmore » performances of the TiO{sub 2} anodes are investigated by adjusting the PVP content in synthesizing the mesoporous TiO{sub 2} anodes. The photovoltaic conversion efficiency of the DSSC is found to be strongly dependent on the pore properties of the TiO{sub 2} anode. After the sintering process, the removal of the PVP leaves porously interconnected channel structures inside the TiO{sub 2} anode, supplying enhanced specific surface area for the dye adsorption as well as the efficient electron transmission. As a result, the TiO{sub 2} anode prepared by 20 wt% PVP presents the highest performances, based on which the DSSC achieves the highest conversion efficiency of 8.39%, approximately increased by 56.53% than that of the DSSC fabricated without PVP (5.36%).« less

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.

Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy

DOE PAGES

Horowitz, Yonatan; Han, Hui-Ling; Ralston, Walter T.; ...

2017-05-12

Fluorine-based additives have a tremendously beneficial effect on the performance of lithium-ion batteries, yet the origin of this phenomenon is unclear. This study shows that the formation of a solid-electrolyte interphase (SEI) on the anode surface in the first five charge/discharge cycles is affected by the stereochemistry of the electrolyte molecules on the anode surface starting at open-circuit potential (OCP). This study shows an anode-specific model system, the reduction of 1,2-diethoxy ethane with lithium bis(trifluoromethane)sulfonimide, as a salt on an amorphous silicon anode, and compares the electrochemical response and SEI formation to its fluorinated version, bis(2,2,2-trifluoroethoxy) ethane (BTFEOE), by summore » frequency generation (SFG) vibrational spectroscopy under reaction conditions. The SFG results suggest that the —CF 3 end-groups of the linear ether BTFEOE change their adsorption orientation on the a-Si surface at OCP, leading to a better protective layer. Finally, supporting evidence from ex situ scanning electron microscopy and X-ray photoelectron spectroscopy depth profiling measurements shows that the fluorinated ether, BTFEOE, yields a smooth SEI on the a-Si surface and enables lithium ions to intercalate deeper into the a-Si bulk.« less

Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy

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

Horowitz, Yonatan; Han, Hui-Ling; Ralston, Walter T.

Fluorine-based additives have a tremendously beneficial effect on the performance of lithium-ion batteries, yet the origin of this phenomenon is unclear. This study shows that the formation of a solid-electrolyte interphase (SEI) on the anode surface in the first five charge/discharge cycles is affected by the stereochemistry of the electrolyte molecules on the anode surface starting at open-circuit potential (OCP). This study shows an anode-specific model system, the reduction of 1,2-diethoxy ethane with lithium bis(trifluoromethane)sulfonimide, as a salt on an amorphous silicon anode, and compares the electrochemical response and SEI formation to its fluorinated version, bis(2,2,2-trifluoroethoxy) ethane (BTFEOE), by summore » frequency generation (SFG) vibrational spectroscopy under reaction conditions. The SFG results suggest that the —CF 3 end-groups of the linear ether BTFEOE change their adsorption orientation on the a-Si surface at OCP, leading to a better protective layer. Finally, supporting evidence from ex situ scanning electron microscopy and X-ray photoelectron spectroscopy depth profiling measurements shows that the fluorinated ether, BTFEOE, yields a smooth SEI on the a-Si surface and enables lithium ions to intercalate deeper into the a-Si bulk.« less

Nanopatterning of steel by one-step anodization for anti-adhesion of bacteria.

PubMed

Chen, Shiqiang; Li, Yuan; Cheng, Y Frank

2017-07-13

Surface nanopatterning of metals has been an effective technique for improved performance and functionalization. However, it is of great challenge to fabricate nanostructure on carbon steels despite their extensive use and urgent needs to maintain the performance reliability and durability. Here, we report a one-step anodization technique to nanopattern a carbon steel in 50 wt.% NaOH solution for highly effective anti-adhesion by sulphate reducing bacteria (SRB), i.e., Desulfovibrio desulfuricans subsp. desulfuricans (Beijerinck) Kluyver and van Niel. We characterize the morphology, structure, composition, and surface roughness of the nanostructured film formed on the steel as a function of anodizing potential. We quantify the surface hydrophobicity by contact angle measurements, and the SRB adhesion by fluorescent analysis. The optimal anodization potential of 2.0 V is determined for the best performance of anti-adhesion of SRB to the steel, resulting in a 23.5 times of reduction of SRB adhesion compared to bare steel. We discuss the mechanisms for the film formation on the steel during anodization, and the high-performance anti-adhesion of bacteria to nanopatterned steels. Our technique is simple, cost-effective and environment-friendly, providing a promising alternative for industry-scale surface nanopatterning of carbon steels for effective controlling of bacterial adhesion.

Anodized porous titanium coated with Ni-CeO2 deposits for enhancing surface toughness and wear resistance

NASA Astrophysics Data System (ADS)

Zhou, Xiaowei; Ouyang, Chun

2017-05-01

In order to make large improvements of surface toughness and wear resistance for pure titanium (Ti) substrate, anodic titanium oxide (ATO) surface with nanoporous structure was coated with the Ni-CeO2 nanocomposite coatings. Regarding TiO2 barrier layer on Ti surface to inhibit its electrochemical activity, pre-treatments were successively processed with anodizing, sensitizing, activating, and then followed by electroless Ni-P film to be acted as an activated layer for electroplating Ni-CeO2 deposits. The existing Pd atoms around ATO nanopores were expected as the heterogeneous nucleation sites for supporting the growing locations of electroless Ni-P film. The innovative of interface design using porous structure was introduced for bonding pinholes to achieve a metallurgical adhesion interface between Ti substrate and surface coatings. Besides the objectives of this work were to elucidate how effects by the adding CeO2 nanoparticles on modifying microstructures and wear mechanisms of Ni-CeO2 nanocomposite coatings. Many efforts of XRD, FE-SEM, TEM and Nanoindentation tests were devoted to comparing different wear behaviors of Ni-CeO2 coatings relative to pure nickel. Results indicated that uniform-distributed Ti nanopores with an average diameter size of ∼200 nm was achieved using the Phosphate-type anodizing solution at DC 150 V. A worn surface without fatigue cracks was observed for TAO surface coated with Ni-CeO2 deposits, showing the existing Ce-rich worn products to be acted as a solid lubricant phase for making a self-healing effect on de-lamination failures. More important, this finding will be the guidelines for Ce-rich precipitations to be expected as the strengthening phase in anodized porous of Ti, Al and Mg alloys for intensifying their surface properties.

Effect of alloying elements Al and Ca on corrosion resistance of plasma anodized Mg alloys

NASA Astrophysics Data System (ADS)

Anawati, Asoh, Hidetaka; Ono, Sachiko

2016-04-01

Plasma anodizing is a surface treatment used to form a ceramic-type oxide film on Mg alloys by the application of a high anodic voltage to create intense plasma near the metal surface. With proper selection of the process parameters, the technique can produce high quality oxide with superior adhesion, corrosion resistance, micro-hardness, wear resistance and strength. The effect of alloying element Al on plasma anodizing process of Mg alloys was studied by comparing the anodizing curves of pure Mg, AZ31, and AZ61 alloys while the effect of Ca were studied on AZ61 alloys containing 0, 1, and 2 wt% Ca. Anodizing was performed in 0.5 M Na3PO4 solution at a constant current density of 200 Am-2 at 25°C. Anodic oxide films with lava-like structure having mix composition of amorphous and crystal were formed on all of the alloys. The main crystal form of the oxide was Mg3(PO4)2 as analyzed by XRD. Alloying elements Al and Ca played role in modifying the plasma lifetime during anodization. Al tended to extend the strong plasma lifetime and therefore accelerated the film thickening. The effect of Ca on anodizing process was still unclear. The anodic film thickness and chemical composition were altered by the presence of Ca in the alloys. Electrochemical corrosion test in 0.9% NaCl solution showed that the corrosion behavior of the anodized specimens depend on the behavior of the substrate. Increasing Al and Ca content in the alloys tended to increase the corrosion resistance of the specimens. The corrosion resistance of the anodized specimens improved significantly about two orders of magnitude relative to the bare substrate.

U.sup.+4 generation in HTER

DOEpatents

Miller, William E [Naperville, IL; Gay, Eddie C [Park Forest, IL; Tomczuk, Zygmunt [Homer Glen, IL

2006-03-14

A improved device and process for recycling spent nuclear fuels, in particular uranium metal, that facilitates the refinement and recovery of uranium metal from spent metallic nuclear fuels. The electrorefiner device comprises two anodes in predetermined spatial relation to a cathode. The anodese have separate current and voltage controls. A much higher voltage than normal for the electrorefining process is applied to the second anode, thereby facilitating oxidization of uranium (III), U.sup.+, to uranium (IV), U.sup.+4. The current path from the second anode to the cathode is physically shorter than the similar current path from the second anode to the spent nuclear fuel contained in a first anode shaped as a basket. The resulting U.sup.+4 oxidizes and solubilizes rough uranium deposited on the surface of the cathode. A softer uranium metal surface is left on the cathode and is more readily removed by a scraper.

Investigation of anodic and chemical oxides grown on p-type InP with applications to surface passivation for n(+)-p solar cell fabrication

NASA Technical Reports Server (NTRS)

Faur, Maria; Faur, Mircea; Goradia, Manju; Goradia, Chandra; Jenkins, Phillip; Jayne, Douglas; Weinberg, Irving

1991-01-01

Most of the previously reported InP anodic oxides were grown on a n-type InP with applications to fabrication of MISFET structures and were described as a mixture of In2O3 and P2O5 stoichiometric compounds or nonstoichiometric phases which have properties similar to crystalline compounds In(OH)3, InPO4, and In(PO3)3. Details of the compositional change of the anodic oxides grown under different anodization conditions were previously reported. The use of P-rich oxides grown either by anodic or chemical oxidation are investigated for surface passivation of p-type InP and as a protective cap during junction formation by closed-ampoule sulfur diffusion. The investigation is based on but not limited to correlations between PL intensity and X-ray photoelectron spectroscopy (XPS) chemical composition data.

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.

Dissolution of Fe(III) (hydr) oxides by metal-EDTA complexes

NASA Astrophysics Data System (ADS)

Ngwack, Bernd; Sigg, Laura

1997-03-01

The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA CaEDTA ≫ PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced.

Electrolyte-induced surface transformation and transition-metal dissolution of fully delithiated LiNi 0.8Co 0.15Al 0.05O 2

DOE PAGES

Faenza, Nicholas V.; Lebens-Higgins, Zachary W.; Mukherjee, Pinaki; ...

2017-06-08

Here, enabling practical utilization of layered Rmore » $$\\bar{3}$$ m positive electrodes near full delithiation requires an enhanced understanding of the complex electrode–electrolyte interactions that often induce failure. Using Li[Ni 0.8Co 0.15Al 0.05]O 2 (NCA) as a model layered compound, the chemical and structural stability in a strenuous thermal and electrochemical environment was explored. Operando microcalorimetry and electrochemical impedance spectroscopy identified a fingerprint for a structural decomposition and transition-metal dissolution reaction that occurs on the positive electrode at full delithiation. Surface-sensitive characterization techniques, including X-ray absorption spectroscopy and high-resolution transmission electron microscopy, measured a structural and morphological transformation of the surface and subsurface regions of NCA. Despite the bulk structural integrity being maintained, NCA surface degradation at a high state of charge induces excessive transition-metal dissolution and significant positive electrode impedance development, resulting in a rapid decrease in electrochemical performance. Additionally, the impact of electrolyte salt, positive electrode surface area, and surface Li 2CO 3 content on the magnitude and character of the dissolution reaction was studied.« less

Electrolyte-Induced Surface Transformation and Transition-Metal Dissolution of Fully Delithiated LiNi0.8Co0.15Al0.05O2.

PubMed

Faenza, Nicholas V; Lebens-Higgins, Zachary W; Mukherjee, Pinaki; Sallis, Shawn; Pereira, Nathalie; Badway, Fadwa; Halajko, Anna; Ceder, Gerbrand; Cosandey, Frederic; Piper, Louis F J; Amatucci, Glenn G

2017-09-19

Enabling practical utilization of layered R3̅m positive electrodes near full delithiation requires an enhanced understanding of the complex electrode-electrolyte interactions that often induce failure. Using Li[Ni 0.8 Co 0.15 Al 0.05 ]O 2 (NCA) as a model layered compound, the chemical and structural stability in a strenuous thermal and electrochemical environment was explored. Operando microcalorimetry and electrochemical impedance spectroscopy identified a fingerprint for a structural decomposition and transition-metal dissolution reaction that occurs on the positive electrode at full delithiation. Surface-sensitive characterization techniques, including X-ray absorption spectroscopy and high-resolution transmission electron microscopy, measured a structural and morphological transformation of the surface and subsurface regions of NCA. Despite the bulk structural integrity being maintained, NCA surface degradation at a high state of charge induces excessive transition-metal dissolution and significant positive electrode impedance development, resulting in a rapid decrease in electrochemical performance. Additionally, the impact of electrolyte salt, positive electrode surface area, and surface Li 2 CO 3 content on the magnitude and character of the dissolution reaction was studied.

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.

On the dissolution properties of GaAs in Ga

NASA Technical Reports Server (NTRS)

Davidson, M. C.; Moynahan, A. H.

1977-01-01

The dissolution of GaAs in Ga was studied to determine the nature and cause of faceting effects. Ga was allowed to dissolve single crystalline faces under isothermal conditions. Of the crystalline planes with low number indices, only the (100) surface showed a direct correlation of dissolution sites to dislocations. The type of dissolution experienced depended on temperature, and there were three distinct types of behavior.

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.

One-Step Formation of WO3-Loaded TiO2 Nanotubes Composite Film for High Photocatalytic Performance

PubMed Central

Lee, Wai Hong; Lai, Chin Wei; Abd Hamid, Sharifah Bee

2015-01-01

High aspect ratio of WO3-loaded TiO2 nanotube arrays have been successfully synthesized using the electrochemical anodization method in an ethylene glycol electrolyte containing 0.5 wt% ammonium fluoride in a range of applied voltage of 10–40 V for 30 min. The novelty of this research works in the one-step formation of WO3-loaded TiO2 nanotube arrays composite film by using tungsten as the cathode material instead of the conventionally used platinum electrode. As compared with platinum, tungsten metal has lower stability, forming dissolved ions (W6+) in the electrolyte. The W6+ ions then move towards the titanium foil and form a coherent deposit on titanium foil. By controlling the oxidation rate and chemical dissolution rate of TiO2 during the electrochemical anodization, the nanotubular structure of TiO2 film could be achieved. In the present study, nanotube arrays were characterized using FESEM, EDAX, XRD, as well as Raman spectroscopy. Based on the results obtained, nanotube arrays with average pore diameter of up to 74 nm and length of 1.6 µm were produced. EDAX confirmed the presence of tungsten element within the nanotube arrays which varied in content from 1.06 at% to 3.29 at%. The photocatalytic activity of the nanotube arrays was then investigated using methyl orange degradation under TUV 96W UV-B Germicidal light irradiation. The nanotube with the highest aspect ratio, geometric surface area factor and at% of tungsten exhibited the highest photocatalytic activity due to more photo-induced electron-hole pairs generated by the larger surface area and because WO3 improves charge separation, reduces charge carrier recombination and increases charge carrier lifetime via accumulation of electrons and holes in the two different metal oxide semiconductor components.

Probing the molecular-level control of aluminosilicate dissolution: A sensitive solid-state NMR proxy for reactive surface area

NASA Astrophysics Data System (ADS)

Washton, Nancy M.; Brantley, Susan L.; Mueller, Karl T.

2008-12-01

For two suites of volcanic aluminosilicate glasses, the accessible and reactive sites for covalent attachment of the fluorine-containing (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS) probe molecule were measured by quantitative 19F nuclear magnetic resonance (NMR) spectroscopy. The first set of samples consists of six rhyolitic and dacitic glasses originating from volcanic activity in Iceland and one rhyolitic glass from the Bishop Tuff, CA. Due to differences in the reactive species present on the surfaces of these glasses, variations in the rate of acid-mediated dissolution (pH 4) for samples in this suite cannot be explained by variations in geometric or BET-measured surface area. In contrast, the rates scale directly with the surface density of TFS-reactive sites as measured by solid-state NMR. These data are consistent with the inference that the TFS-reactive M-OH species on the glass surface, which are known to be non-hydrogen-bonded Q 3 groups, represent loci accessible to and affected by proton-mediated dissolution. The second suite of samples, originating from a chronosequence in Kozushima, Japan, is comprised of four rhyolites that have been weathered for 1.1, 1.8, 26, and 52 ka. The number of TFS-reactive sites per gram increases with duration of weathering in the laboratory for the "Icelandic" samples and with duration of field weathering for both "Icelandic" and Japanese samples. One hypothesis is consistent with these and published modeling, laboratory, and field observations: over short timescales, dissolution is controlled by fast-dissolving sites, but over long timescales, dissolution is controlled by slower-dissolving sites, the surface density of which is proportional to the number of TFS-reactive Q 3 sites. These latter sites are not part of a hydrogen-bonded network on the surface of the glasses, and measurement of their surface site density allows predictions of trends in reactive surface area. The TFS treatment method, which is easily monitored by quantitative 19F solid-state NMR, therefore provides a chemically specific and quantifiable proxy to understand the nature of how sites on dissolving silicates control dissolution. Furthermore, 27Al NMR techniques are shown here to be useful in identifying clays on the glass surfaces, and these methods are therefore effective for quantifying concentrations of weathering impurities. Our interpretations offer a testable hypothesis for the mechanism of proton-promoted dissolution for low-iron aluminosilicate minerals and glasses and suggest that future investigations of reactive surfaces with high-sensitivity NMR techniques are warranted.

Water and oil wettability of anodized 6016 aluminum alloy surface

NASA Astrophysics Data System (ADS)

Rodrigues, S. P.; Alves, C. F. Almeida; Cavaleiro, A.; Carvalho, S.

2017-11-01

This paper reports on the control of wettability behaviour of a 6000 series aluminum (Al) alloy surface (Al6016-T4), which is widely used in the automotive and aerospace industries. In order to induce the surface micro-nanostructuring of the surface, a combination of prior mechanical polishing steps followed by anodization process with different conditions was used. The surface polishing with sandpaper grit size 1000 promoted aligned grooves on the surface leading to static water contact angle (WCA) of 91° and oil (α-bromonaphthalene) contact angle (OCA) of 32°, indicating a slightly hydrophobic and oleophilic character. H2SO4 and H3PO4 acid electrolytes were used to grow aluminum oxide layers (Al2O3) by anodization, working at 15 V/18° C and 100 V/0 °C, respectively, in one or two-steps configuration. Overall, the anodization results showed that the structured Al surfaces were hydrophilic and oleophilic-like with both WCA and OCA below 90°. The one-step configuration led to a dimple-shaped Al alloy surface with small diameter of around 31 nm, in case of H2SO4, and with larger diameters of around 223 nm in case of H3PO4. The larger dimples achieved with H3PO4 electrolyte allowed to reach a slight hydrophobic surface. The thicker porous Al oxide layers, produced by anodization in two-step configuration, revealed that the liquids can penetrate easily inside the non-ordered porous structures and, thus, the surface wettability tended to superhydrophilic and superoleophilic character (CA < 10°). These results indicate that the capillary-pressure balance model, described for wettability mechanisms of porous structures, was broken. Moreover, thicker oxide layers with narrow pores of about 29 nm diameter allowed to achieve WCA < OCA. This inversion in favour of the hydrophilic-oleophobic surface behaviour is of great interest either for lubrication of mechanical components or in water-oil separation process.

Electrochemical cell structure including an ionomeric barrier

DOEpatents

Lambert, Timothy N.; Hibbs, Michael

2017-06-20

An apparatus includes an electrochemical half-cell comprising: an electrolyte, an anode; and an ionomeric barrier positioned between the electrolyte and the anode. The anode may comprise a multi-electron vanadium phosphorous alloy, such as VP.sub.x, wherein x is 1-5. The electrochemical half-cell is configured to oxidize the vanadium and phosphorous alloy to release electrons. A method of mitigating corrosion in an electrochemical cell includes disposing an ionomeric barrier in a path of electrolyte or ion flow to an anode and mitigating anion accumulation on the surface of the anode.

Microhardness of anodic aluminum oxide formed in an alkaline electrolyte

NASA Astrophysics Data System (ADS)

Kanygina, O. N.; Filyak, M. M.

2017-04-01

The microhardness of anodic aluminum oxide formed by anodizing of aluminum sheet in electrolyte on the basis of sodium hydroxide has been determined experimentally. The microhardness of the hard film/soft substrate system has been estimated by three approaches: indentation geometry (length of diagonals) in film surfaces, the sum of the hardnesses of the film and the surface with allowance for the indentation surface area and geometry, and with allowance for the indentation depth. It is demonstrated that the approach accounting for the indentation depth makes it possible to eliminate the influence of the substrate. It is established that the microhardness of the films formed in alkaline electrolytes is comparable with that formed in acid electrolytes.

Investigation of the electrochemically active surface area and lithium diffusion in graphite anodes by a novel OsO4 staining method

NASA Astrophysics Data System (ADS)

Pfaffmann, Lukas; Birkenmaier, Claudia; Müller, Marcus; Bauer, Werner; Mitsch, Tim; Feinauer, Julian; Krämer, Yvonne; Scheiba, Frieder; Hintennach, Andreas; Schleid, Thomas; Schmidt, Volker; Ehrenberg, Helmut

2016-03-01

Negative electrodes of lithium-ion batteries generally consist of graphite-based active materials. In order to realize batteries with a high current density and therefore accelerated charging processes, the intercalation of lithium and the diffusion processes of these carbonaceous materials must be understood. In this paper, we visualized the electrochemical active surface area for three different anode materials using a novel OsO4 staining method in combination with scanning electron microscopy techniques. The diffusion behavior of these three anode materials is investigated by potentiostatic intermittent titration technique measurements. From those we determine the diffusion coefficient with and without consideration of the electrochemical active surface area.

Measurement of the surface charge accumulation using anodic aluminum oxide(AAO) structure in an inductively coupled plasma

NASA Astrophysics Data System (ADS)

Park, Ji-Hwan; Oh, Seung-Ju; Lee, Hyo-Chang; Kim, Yu-Sin; Kim, Young-Cheol; Kim, June Young; Ha, Chang-Seoung; Kwon, Soon-Ho; Lee, Jung-Joong; Chung, Chin-Wook

2014-10-01

As the critical dimension of the nano-device shrinks, an undesired etch profile occurs during plasma etch process. One of the reasons is the local electric field due to the surface charge accumulation. To demonstrate the surface charge accumulation, an anodic aluminum oxide (AAO) membrane which has high aspect ratio is used. The potential difference between top electrode and bottom electrode in an anodic aluminum oxide contact structure is measured during inductively coupled plasma exposure. The voltage difference is changed with external discharge conditions, such as gas pressure, input power, and gas species and the result is analyzed with the measured plasma parameters.

Variable anodic thermal control coating

NASA Technical Reports Server (NTRS)

Gilliland, C. S.; Duckett, J. (Inventor)

1983-01-01

A process for providing a thermal control solar stable surface coating for aluminum surfaces adapted to be exposed to solar radiation wherein selected values within the range of 0.10 to 0.72 thermal emittance (epsilon sub tau) and 0.2 to 0.4 solar absorptance (alpha subs) are reproducibly obtained by anodizing the surface area in a chromic acid solution for a selected period of time. The rate voltage and time, along with the parameters of initial epsilon sub tau and alpha subs, temperature of the chromic acid solution, acid concentration of the solution and the material anodized determines the final values of epsilon/tau sub and alpha sub S. 9 Claims, 5 Drawing Figures.

The influence of surface state and saturation state on the dissolution kinetics of biogenic aragonite in seawater

USGS Publications Warehouse

Acker, James G.; Byrne, R.H.

1989-01-01

Uses several realistic partial molar volume changes (??V) for aragonite dissolution in seawater. Indicates that the molar volume change for aragonite dissolution is within the bounds -37 cm 3/mole ?????V ??? -39.5 cm3/mole. -from Authors

Evidence for interfacial dissolution-precipitation during low-temperature mineral weathering

NASA Astrophysics Data System (ADS)

Ruiz-Agudo, Encarnacion; Putnis, Christine V.; Rodriguez-Navarro, Carlos; Putnis, Andrew

2013-04-01

The dissolution of most common multicomponent minerals and glasses is typically "incongruent" as shown by the nonstoichiometric release of the solid phase components. This frequently results in the formation of so-called surface leached layers. The mechanism of this process has been a recurrent subject of research and debate over the past two decades, due to its relevance to a wide range of natural and technological processes, as well as being crucial in defining rate laws for mineral reactions. Here we report experimental, in situ nanoscale observations that confirm the formation of a cation depleted layer at the mineral-solution interface during dissolution of multicomponent minerals at acidic pH. Our in situ Atomic Force Microscopy studies of the dissolution of wollastonite, CaSiO3, and dolomite, Ca0.5Mg0.5CO3, combined with compositional analysis of reaction products, provide, for the first time, clear direct experimental evidence that cation-depleted (i.e. leached) layers are formed in a tight interface-coupled two step process: stoichiometric dissolution of the pristine mineral surfaces and subsequent precipitation of a secondary phase from a supersaturated boundary layer of fluid in contact with the mineral surface. Such a mechanism presents a new paradigm that differs from the concept of preferential leaching of cations, as postulated by most currently accepted incongruent dissolution models. References Ruiz Agudo, E; Putnis, CV; Rodríguez Navarro, C and Putnis, A. (2012) Mechanism of leached layer formation during chemical weathering of silicate minerals. Geology, 40, 947-950 Urosevic, M; Rodríguez Navarro,C; Putnis, CV; Cardell, C; Putnis, A and Ruiz Agudo, E (2012) In situ nanoscale observations of the dissolution of [10-14] dolomite cleavage surfaces. Geochimica et Cosmochimica Acta, 80, 1-13

Pb 2+–Calcite Interactions under Far-from-Equilibrium Conditions: Formation of Micropyramids and Pseudomorphic Growth of Cerussite

DOE PAGES

Yuan, Ke; De Andrade, Vincent; Feng, Zhange; ...

2018-01-04

The presence of impurity ions is known to significantly influence mineral surface morphology during crystal growth from aqueous solution, but knowledge on impurity ion-mineral interactions during dissolution under far-from equilibrium conditions remains limited. Here we show that calcite (CaCO 3) exhibits a rich array of dissolution features in the presence of Pb. During the initial stage, calcite exhibits non-classical surface features characterized as micro pyramids developed spontaneously in acidic Pb-bearing solutions. Subsequent pseudomorphic growth of cerussite (PbCO 3) was observed, where nucleation occurred entirely within a pore space created by dissolution at the calcite/substrate interface. Uneven growth rates yielded amore » cerussite shell made of lath- or dendritic-shaped crystals. The cerussite phase was separated from the calcite by pores of less than 200 nm under transmission X-ray microscopy, consistent with the interface-coupled dissolution-precipitation mechanism. These results show that impurity metal ions exert significant control over the microscale dissolution features found on mineral surfaces and provide new insights into interpreting and designing micro structures observed in naturally-occurring and synthetic carbonate minerals by dissolution. In addition, heterogeneous micro-environments created in transport limited reactions under pore spaces may lead to unusual growth forms during crystal nucleation and precipitation.« less

Geoengineering impact of open ocean dissolution of olivine on atmospheric CO2, surface ocean pH and marine biology

NASA Astrophysics Data System (ADS)

Köhler, Peter; Abrams, Jesse F.; Völker, Christoph; Hauck, Judith; Wolf-Gladrow, Dieter A.

2013-03-01

Ongoing global warming induced by anthropogenic emissions has opened the debate as to whether geoengineering is a ‘quick fix’ option. Here we analyse the intended and unintended effects of one specific geoengineering approach, which is enhanced weathering via the open ocean dissolution of the silicate-containing mineral olivine. This approach would not only reduce atmospheric CO2 and oppose surface ocean acidification, but would also impact on marine biology. If dissolved in the surface ocean, olivine sequesters 0.28 g carbon per g of olivine dissolved, similar to land-based enhanced weathering. Silicic acid input, a byproduct of the olivine dissolution, alters marine biology because silicate is in certain areas the limiting nutrient for diatoms. As a consequence, our model predicts a shift in phytoplankton species composition towards diatoms, altering the biological carbon pumps. Enhanced olivine dissolution, both on land and in the ocean, therefore needs to be considered as ocean fertilization. From dissolution kinetics we calculate that only olivine particles with a grain size of the order of 1 μm sink slowly enough to enable a nearly complete dissolution. The energy consumption for grinding to this small size might reduce the carbon sequestration efficiency by ˜30%.

Dynamic processes occurring at the Cr IIIaq-manganite (γ-MnOOH) interface: simultaneous adsorption, microprecipitation, oxidation/reduction, and dissolution

NASA Astrophysics Data System (ADS)

Weaver, Robert M.; Hochella, Michael F.; Ilton, Eugene S.

2002-12-01

The complex interaction between Cr IIIaq and manganite (γ-MnOOH) was systematically studied at room temperature over a pH range of 3 to 6, and within a concentration range of 10 -4 to 10 -2 M CrOH 2+aq. Solution compositional changes during batch reactions were characterized by inductively coupled plasma spectroscopy and ultraviolet-visible spectrophotometry. The manganites were characterized before and after reaction with X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), high-resolution field-emission SEM, and energy-dispersive spectroscopy analysis. Fluid-cell atomic force microscopy was used to follow these metal-mineral interactions in situ. The reactions are characterized by (1) sorption of Cr III and the surface-catalyzed microprecipitation of Cr III-hydroxy hydrate on manganite surfaces, (2) the acidic dissolution of the manganite, and (3) the simultaneous reductive dissolution of manganite coupled with the oxidation of Cr IIIaq to highly toxic Cr VIaq. Cr III-hydroxy hydrate was shown to precipitate on the manganite surface while still undersaturated in bulk solution. The rate of manganite dissolution increased with decreasing pH due both to acid-promoted and Mn-reduction-promoted dissolution. Cr oxidation also increased in the lower pH range, this as a result of its direct redox coupling with Mn reduction. Neither Mn II nor Cr VI were ever detected on manganite surfaces, even at the maximum rate of their generation. At the highest pHs of this study, Cr IIIaq was effectively removed from solution to form Cr III-hydroxy hydrate on manganite surfaces and in the bulk solution, and manganite dissolution and Cr VIaq generation were minimized. All interface reactions described above were heterogeneous across the manganite surfaces. This heterogeneity is a direct result of the heterogeneous semiconducting nature of natural manganite crystals and is also an expression of the proximity effect, whereby redox processes on semiconducting surfaces are not limited to next nearest neighbor sites.

Stabilizing contact resistance of isotropically conductive adhesives on various metal surfaces by incorporating sacrificial anode materials

NASA Astrophysics Data System (ADS)

Moon, Kyoung-Sik; Liong, Silvia; Li, Haiying; Wong, C. P.

2004-11-01

The contact resistance stability of isotropically conductive adhesives (ICAs) on non-noble metal surfaces under the 85°C/85% relative humidity (RH) aging test was investigated. Previously, we demonstrated that galvanic corrosion has been shown as the main mechanism of the unstable contact resistance of ICAs on non-noble metal surfaces. A sacrificial anode was introduced into the ICA joint for cathodic protection. Zinc, chromium, and magnesium were employed in the ICA formulations as sacrificial anode materials that have much lower electrode-potential values than the metal pad surface, such as tin or tin-based alloys. The effect of particle sizes and loading levels of sacrificial anode materials were studied. Chromium was not as effective in suppressing corrosion as magnesium or zinc because of its strong tendency to self-passivate. The corrosion potential of ICAs was reduced by half with the addition of zinc and magnesium into the ICA formulation. The addition of zinc and magnesium was very effective in controlling galvanic corrosion that takes place in the ICA joints, resulting in stabilized contact resistance of ICAs on Sn, SnPb, and SnAgCu surfaces during the 85°C/85% RH aging test.

Kinetics of scheelite dissolution in groundwater: defining the release rate of tungsten contamination from a natural source

NASA Astrophysics Data System (ADS)

Montgomery, S. D.; Mckibben, M. A.

2011-12-01

Tungsten, an emerging contaminant, has no EPA standard for its permissible levels in drinking water. At sites in California, Nevada, and Arizona there may be a correlation between elevated levels of tungsten in drinking water and clusters of childhood acute lymphocytic leukemia (ALL). Developing a better understanding of how tungsten is released from rocks into surface and groundwaters is therefore of growing environmental interest. Knowledge of tungstate ore mineral weathering processes, particularly the rates of dissolution of scheelite (CaWO4) in groundwater, could improve models of how tungsten is released and transported in natural waters. Our research is focusing on experimental determination of the rates and products of tungstate mineral dissolution in synthetic groundwater, as a function of temperature, pH and mineral surface area. The initial rate method is being used to develop rate laws. Batch reactor experiments are conducted within constant temperature circulation baths over a pH range of 2-9. Cleaned scheelite powder with grain diameters of 106-150um is placed between two screens in a sample platform and then placed inside a two liter Teflon vessel filled with synthetic groundwater. Ports on the vessel allow sample extraction, temperature and pH measurement, gas inflow, and water circulation. Aliquots of solution are taken periodically for product analysis by ICP -MS. Changes in mineral surface characteristics are monitored using SEM and EDS methods. Results so far reveal that the dissolution of scheelite is incongruent at both neutral and low pH. Solid tungstic acid forms on scheelite mineral surfaces under acidic conditions, implying that this phase controls the dissolution rate in acidic environments. The influence of dissolved CO2 and resultant calcium carbonate precipitation on the dissolution of scheelite at higher pH is also being investigated. The rate law being developed for scheelite dissolution will be useful in reactive-transport computer codes designed to model tungsten contamination in a variety of surface and groundwater settings.

Citrate, not phosphate, can dissolve calcium oxalate monohydrate crystals and detach these crystals from renal tubular cells.

PubMed

Chutipongtanate, Somchai; Chaiyarit, Sakdithep; Thongboonkerd, Visith

2012-08-15

Dissolution therapy of calcium oxalate monohydrate (COM) kidney stone disease has not yet been implemented due to a lack of well characterized COM dissolution agents. The present study therefore aimed to identify potential COM crystal dissolution compounds. COM crystals were treated with deionized water (negative control), 5 mM EDTA (positive control), 5 mM sodium citrate, or 5mM sodium phosphate. COM crystal dissolution activities of these compounds were evaluated by phase-contrast and video-assisted microscopic examinations, semi-quantitative analysis of crystal size, number and total mass, and spectrophotometric oxalate-dissolution assay. In addition, effects of these compounds on detachment of COM crystals, which adhered tightly onto renal tubular cell surface, were also investigated. The results showed that citrate, not phosphate, had a significant dissolution effect on COM crystals as demonstrated by significant reduction of crystal size (approximately 37% decrease), crystal number (approximately 53% decrease) and total crystal mass (approximately 72% decrease) compared to blank and negative controls. Spectrophotometric oxalate-dissolution assay successfully confirmed the COM crystal dissolution property of citrate. Moreover, citrate could detach up to 85% of the adherent COM crystals from renal tubular cell surface. These data indicate that citrate is better than phosphate for dissolution and detachment of COM crystals. Copyright © 2012 Elsevier B.V. All rights reserved.

Size effects in MgO cube dissolution.

PubMed

Baumann, Stefan O; Schneider, Johannes; Sternig, Andreas; Thomele, Daniel; Stankic, Slavica; Berger, Thomas; Grönbeck, Henrik; Diwald, Oliver

2015-03-10

Stability parameters and dissolution behavior of engineered nanomaterials in aqueous systems are critical to assess their functionality and fate under environmental conditions. Using scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, we investigated the stability of cubic MgO particles in water. MgO dissolution proceeding via water dissociation at the oxide surface, disintegration of Mg(2+)-O(2-) surface elements, and their subsequent solvation ultimately leads to precipitation of Mg(OH)2 nanosheets. At a pH ≥ 10, MgO nanocubes with a size distribution below 10 nm quantitatively dissolve within few minutes and convert into Mg(OH)2 nanosheets. This effect is different from MgO cubes originating from magnesium combustion in air. With a size distribution in the range 10 nm ≤ d ≤ 1000 nm they dissolve with a significantly smaller dissolution rate in water. On these particles water induced etching generates (110) faces which, above a certain face area, dissolve at a rate equal to that of (100) planes.1 The delayed solubility of microcrystalline MgO is attributed to surface hydroxide induced self-inhibition effects occurring at the (100) and (110) microplanes. The present work underlines the importance of morphology evolution and surface faceting of engineered nanomaterials particles during their dissolution.

Controlling interferometric properties of nanoporous anodic aluminium oxide

PubMed Central

2012-01-01

A study of reflective interference spectroscopy [RIfS] properties of nanoporous anodic aluminium oxide [AAO] with the aim to develop a reliable substrate for label-free optical biosensing is presented. The influence of structural parameters of AAO including pore diameters, inter-pore distance, pore length, and surface modification by deposition of Au, Ag, Cr, Pt, Ni, and TiO2 on the RIfS signal (Fabry-Perot fringe) was explored. AAO with controlled pore dimensions was prepared by electrochemical anodization of aluminium using 0.3 M oxalic acid at different voltages (30 to 70 V) and anodization times (10 to 60 min). Results show the strong influence of pore structures and surface modifications on the interference signal and indicate the importance of optimisation of AAO pore structures for RIfS sensing. The pore length/pore diameter aspect ratio of AAO was identified as a suitable parameter to tune interferometric properties of AAO. Finally, the application of AAO with optimised pore structures for sensing of a surface binding reaction of alkanethiols (mercaptoundecanoic acid) on gold surface is demonstrated. PMID:22280884

Chemically Crushed Wood Cellulose Fiber towards High-Performance Sodium-Ion Batteries

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

Shen, Fei; Zhu, Hongli; Luo, Wei

Carbon materials have attracted great interest as an anode for sodium-ion batteries (SIBs) due to their high performance and low cost. Here, we studied natural wood fiber derived hard carbon anodes for SIBs considering the abundance and low cost of wood. We discovered that a thermal carbonization of wood fiber led to a porous carbon with a high specific surface area of 586 m2 g–1, while a pretreatment with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) could effectively decrease it to 126 m2 g–1. When evaluating them as anodes for SIBs, we observed that the low surface area carbon resulted in a high initial Coulombicmore » efficiency of 72% compared to 25% of the high surface area carbon. More importantly, the low surface area carbon exhibits an excellent cycling stability that a desodiation capacity of 196 mAh g–1 can be delivered over 200 cycles at a current density of 100 mA g–1, indicating a promising anode for low-cost SIBs.« less

Properties of anodic oxides grown on a hafnium–tantalum–titanium thin film library

PubMed Central

Mardare, Andrei Ionut; Ludwig, Alfred; Savan, Alan; Hassel, Achim Walter

2014-01-01

A ternary thin film combinatorial materials library of the valve metal system Hf–Ta–Ti obtained by co-sputtering was studied. The microstructural and crystallographic analysis of the obtained compositions revealed a crystalline and textured surface, with the exception of compositions with Ta concentration above 48 at.% which are amorphous and show a flat surface. Electrochemical anodization of the composition spread thin films was used for analysing the growth of the mixed surface oxides. Oxide formation factors, obtained from the potentiodynamic anodization curves, as well as the dielectric constants and electrical resistances, obtained from electrochemical impedance spectroscopy, were mapped along two dimensions of the library using a scanning droplet cell microscope. The semiconducting properties of the anodic oxides were mapped using Mott–Schottky analysis. The degree of oxide mixing was analysed qualitatively using x-ray photoelectron spectroscopy depth profiling. A quantitative analysis of the surface oxides was performed and correlated to the as-deposited metal thin film compositions. In the concurrent transport of the three metal cations during oxide growth a clear speed order of Ti > Hf > Ta was proven. PMID:27877648

[Key physical parameters of hawthorn leaf granules by stepwise regression analysis method].

PubMed

Jiang, Qie-Ying; Zeng, Rong-Gui; Li, Zhe; Luo, Juan; Zhao, Guo-Wei; Lv, Dan; Liao, Zheng-Gen

2017-05-01

The purpose of this study was to investigate the effect of key physical properties of hawthorn leaf granule on its dissolution behavior. Hawthorn leaves extract was utilized as a model drug. The extract was mixed with microcrystalline cellulose or starch with the same ratio by using different methods. Appropriate amount of lubricant and disintegrating agent was added into part of the mixed powder, and then the granules were prepared by using extrusion granulation and high shear granulation. The granules dissolution behavior was evaluated by using equilibrium dissolution quantity and dissolution rate constant of the hypericin as the indicators. Then the effect of physical properties on dissolution behavior was analyzed through the stepwise regression analysis method. The equilibrium dissolution quantity of hypericin and adsorption heat constant in hawthorn leaves were positively correlated with the monolayer adsorption capacity and negatively correlated with the moisture absorption rate constant. The dissolution rate constants were decreased with the increase of Hausner rate, monolayer adsorption capacity and adsorption heat constant, and were increased with the increase of Carr index and specific surface area. Adsorption heat constant, monolayer adsorption capacity, moisture absorption rate constant, Carr index and specific surface area were the key physical properties of hawthorn leaf granule to affect its dissolution behavior. Copyright© by the Chinese Pharmaceutical Association.

The Effect of Multiple Surface Treatments on Biological Properties of Ti-6Al-4V Alloy

NASA Astrophysics Data System (ADS)

Parsikia, Farhang; Amini, Pupak; Asgari, Sirous

2014-09-01

In this research, the effect of various surface treatments including laser processing, grit blasting and anodizing on chemical structure, surface topography, and bioactivity of Ti-6Al-4V was investigated. Six groups of samples were prepared by a combination of two alternative laser processes, grit blasting and anodizing. Selected samples were first evaluated using microanalysis techniques and contact roughness testing and were then exposed to in vitro environment. Scanning electron microscopy was used to characterize the corresponding final surface morphologies. Weight measurement and atomic absorption tests were employed for determination of bioactivity limits of different surface conditions. Based on the data obtained in this study, low-energy laser processing generally yields a better biological response. The maximum bioactivity was attained in those samples exposed to a three step treatment including low-energy laser treatment followed by grit blasting and anodizing.

Graphene/Fe3 O4 Nanocomposites as Efficient Anodes to Boost the Lifetime and Current Output of Microbial Fuel Cells.

PubMed

Song, Rong-Bin; Zhao, Cui-E; Gai, Pan-Pan; Guo, Dan; Jiang, Li-Ping; Zhang, Qichun; Zhang, Jian-Rong; Zhu, Jun-Jie

2017-02-01

The enhancement of microbial activity and electrocatalysis through the design of new anode materials is essential to develop microbial fuel cells (MFCs) with longer lifetimes and higher output. In this research, a novel anode material, graphene/Fe 3 O 4 (G/Fe 3 O 4 ) composite, has been designed for Shewanella-inoculated MFCs. Because the Shewanella species could bind to Fe 3 O 4 with high affinity and their growth could be supported by Fe 3 O 4 , the bacterial cells attached quickly onto the anode surface and their long-term activity improved. As a result, MFCs with reduced startup time and improved stability were obtained. Additionally, the introduction of graphene not only provided a large surface area for bacterial attachment, but also offered high electrical conductivity to facilitate extracellular electron transfer (EET). The results showed that the current and power densities of a G/Fe 3 O 4 anode were much higher than those of each individual component as an anode. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

[Efficient Pharmaceutical Formulation Designs and Their Development Using Mathematical and Statistical Analysis].

PubMed

Iwao, Yasunori

2015-01-01

With the aim of directly predicting the functionality and mechanism of pharmaceutical excipients, we investigated an analysis method based on available surface area (S(t)), which is the surface area of a drug in direct contact with the external solvent during dissolution. First, to study the effect of lubricant concentration on the dissolution rate of acetaminophen (APAP), the dissolution behaviors as well as the change over time in S(t) of APAP tablets were examined. In the dissolution tests, a retarded dissolution of APAP was not observed with new lubricant triglycerin full behenate (TR-FB), whereas magnesium stearate (Mg-St) retarded the dissolution. The S(t) profiles for APAP with Mg-St at>0.5% showed downward curvature indicating a gradual decrease in surface area over time. Conversely, with TR-FB, even when its concentration was increased, the S(t) profile for APAP had a maximum value. The differences between Mg-St and TR-FB could be explained by the differences in extensibility deriving from their morphology. Next, we evaluated the effect of disintegtant concentration using five disintegrants. When disintegrant was added to ethenzamide tablet formulation, an increase in the dissolution rate and S(t) dependent on disintegrant concentration was observed, according to the type of disintegrant. It was found that the water absorption ability of disintegrants had strong correlations with the parameters of S(t). Taken together, this study demonstrates that analysis of S(t) can directly provide useful information, especially about the functionality of pharmaceutical excipients.

Surface studies of Li-ion and Mg battery electrodes

NASA Astrophysics Data System (ADS)

Esbenshade, Jennifer

This dissertation focuses on studies of the surfaces of both Li-ion and Mg-ion battery electrodes. A fundamental understanding of processes occurring at the electrode surface is vital to the development of advanced battery systems. Additionally, modifications to the electrode surfaces are made and further characterized for improved performance. LiMn2O4 Cathodes for Li-ion Batteries: Effect of Mn in electrolyte on anode and Au coating to minimize dissolution: LiMn2O4 (LMO) is known to dissolve Mn ions with cycling. This section focuses on both the effect of the dissolution of Mn2+ into the electrolyte as well as Au coating on the LMO to improve electrochemical performance. Electrochemical quartz crystal microbalance (EQCM) was used to monitor changes in mass on the anode, SEM and AES were used to observe changes in surface morphology and chemical composition, and potentiostatic voltammetry was used to monitor charge and discharge capacity. The effect of Cu2+ addition in place of Mn2+ was also studied, as Cu is known to form an underpotential deposition (UPD) monolayer on Au electrodes. Following this, LMO particles were coated with a Au shell by a simple and scalable electroless deposition for use as Li-ion battery cathodes. The Au shell was intended to limit the capacity fade commonly seen with LMO cathodes by reducing the dissolution of Mn. Characterization by SEM, TEM, EELS, and AFM showed that the Au shell was approximately 3 nm thick. The Au shell prevented much of the Mn from dissolving in the electrolyte with 82% and 88% less dissolved Mn in the electrolyte at room temperature and 65 ºC, respectively, as compared to the uncoated LMO. Electrochemical performance studies with half cells showed that the Au shell maintained a higher discharge capacity over 400 cycles by nearly 30% with 110 mA hr g-1 for the 400th cycle as compared to a commercial LMO at 85 mA hr g-1. Similarly, the capacity fade was reduced in full cells: the coated LMO had 47% greater capacity after 400 cycles over the control. Dimensionally Controlled Lithiation of Thin Film and Multilayer Conversion Li-ion Battery Anodes: Oxide conversion reactions are an alternative approach for high capacity Li-ion batteries, but are known to suffer from structural irreversibility associated with the phase separation and reconstitution of reduced metal species and Li2O. The morphology of the reduced metal species is thought to play a critical role in the electrochemical properties of a conversion material. In this section, a model electrode is used with alternating layers of Cr and CrOx to better understand and control these phase changes in real-time and at molecular length scales. Despite lacking crystallinity at the atomic scale, this superstructure is observed (with XR) to lithiate and delithiate in a purely one-dimensional manner, preserving the layered structure. The XR data show that the metal layers act as nucleation sites for the reduction of chromium in the conversion reaction. Irreversibility during delithiation is due to the formation of a ternary phase, LiCrO2, which can be further delithiated at higher potentials. The results reveal that the combination of confining lithiation to nanoscale sheets of Li2O and the availability of reaction sites in the metal layers in the layered structure is a strategy for improving the reversibility and mass transport properties that can be used in a wide range of conversion materials. Following the Cr/CrOx study, the next step was to study intermetallics which can electrochemically alloy to Li4.4M (M = Si, Ge, Sn, etc.), providing order-of-magnitude increases in energy density. The energy density of Si may be combined with the structural reversibility of an intercalation material using a Si/metal silicide multilayer (ML). In operando XR confirms the ML's structural reversibility during Li insertion and extraction, despite an overall 3.3-fold vertical expansion. The ML electrodes also show enhanced long-term cyclability and rate capabilities relative to a comparable Si thin film electrode. This intercalation behavior found by dimensionally constraining Si lithiation promises applicability to a range of conversion reactions. Improving Electrodeposition of Mg through an Open Circuit Potential Hold: In this section, in situ XRD, XPS, SEM and electrochemical methods were used to interrogate the mechanism of Mg electrodeposition from PhMgCl/AlCl3 (APC) and EtMgCl electrolytes. An open circuit potential (OCP) pause following Mg deposition led to retained enhancement of Mg deposition and stripping kinetics along with lowered overpotentials for both. In situ XRD demonstrated that the OCP pause led to a more polycrystalline deposits relative to that without the pause, while SEM presented micrographs that showed smaller deposits with an OCP hold. The improvement is attributed to an 'enhancement layer' that formed on the electrode during the OCP hold. Analysis of XPS data suggests that this 'enhancement layer' consists of Mg and Cl retained on the electrode surface, possibly following electrode depassivation.

Electroless Cu Plating on Anodized Al Substrate for High Power LED.

PubMed

Rha, Sa-Kyun; Lee, Youn-Seoung

2015-03-01

Area-selective copper deposition on screen printed Ag pattern/anodized Al/Al substrate was attempted using a neutral electroless plating processes for printed circuit boards (PCBs), according to a range of variation of pH 6.5-pH 8 at 70 °C. The utilized basic electroless solution consisted of copper(II) sulfate pentahydrate, sodium phosphinate monohydrate, sodium citrate tribasic dihydrate, ammonium chloride, and nickel(II) sulfate hexahydrate. The pH of the copper plating solutions was adjusted from pH 6.5 to pH 8 using NH4OH. Using electroless plating in pH 6.5 and pH 7 baths, surface damage to the anodized Al layer hardly occurred; the structure of the plated Cu-rich films was a typical fcc-Cu, but a small Ni component was co-deposited. In electroless plating at pH 8, the surface of the anodized Al layer was damaged and the Cu film was composed of a lot of Ni and P which were co-deposited with Cu. Finally, in a pH 7 bath, we can make a selectively electroless plated Cu film on a PCB without any lithography and without surface damage to the anodized Al layer.

Effect of Ti Substrate Ion Implantation on the Physical Properties of Anodic TiO2 Nanotubes

NASA Astrophysics Data System (ADS)

Jedi-Soltanabadi, Zahra; Ghoranneviss, Mahmood; Ghorannevis, Zohreh; Akbari, Hossein

2018-03-01

The influence of nitrogen-ion implantation on the titanium (Ti) surface is studied. The nontreated Ti and the Ti treated with ion implantation were anodized in an ethylene-glycol-based electrolyte solution containing 0.3 wt% ammonium fluoride (NH4F) and 3 vol% deionized (DI) water at a potential of 60 V for 1 h at room temperature. The current density during the growth of the TiO2 nanotubes was monitored in-situ. The surface roughnesses of the Ti substrates before and after the ion implantation were investigated with atomic force microscopy (AFM). The surface roughness was lower for the treated Ti substrate. The morphology of the anodic TiO2 nanotubes was studied by using field-emission scanning electron microscopy (FESEM). Clearly, the titanium nanotubes grown on the treated substrate were longer. In addition, some ribs were observed on their walls. The optical band gap of the anodic TiO2 nanotubes was characterized by using a diffuse reflection spectral (DRS) analysis. The anodic TiO2 nanotubes grown on the treated Ti substrate revealed a band gap energy of approximately 3.02 eV.

In situ formation of graphene layers on graphite surfaces for efficient anodes of microbial fuel cells.

PubMed

Tang, Jiahuan; Chen, Shanshan; Yuan, Yong; Cai, Xixi; Zhou, Shungui

2015-09-15

Graphene can be used to improve the performance of the anode in a microbial fuel cell (MFC) due to its good biocompatibility, high electrical conductivity and large surface area. However, the chemical production and modification of the graphene on the anode are environmentally hazardous because of the use of various harmful chemicals. This study reports a novel method based on the electrochemical exfoliation of a graphite plate (GP) for the in situ formation of graphene layers on the surface of a graphite electrode. When the resultant graphene-layer-based graphite plate electrode (GL/GP) was used as an anode in an MFC, a maximum power density of 0.67 ± 0.034 W/m(2) was achieved. This value corresponds to 1.72-, 1.56- and 1.26-times the maximum power densities of the original GP, exfoliated-graphene-modified GP (EG/GP) and chemically-reduced-graphene-modified GP (rGO/GP) anodes, respectively. Electrochemical measurements revealed that the high performance of the GL/GP anode was attributable to its macroporous structure, improved electron transfer and high electrochemical capacitance. The results demonstrated that the proposed method is a facile and environmentally friendly synthesis technique for the fabrication of high-performance graphene-based electrodes for use in microbial energy harvesting. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of NaNO3 concentration on anodic electrochemical behavior on the Sb surface in NaOH solution

NASA Astrophysics Data System (ADS)

He, Yun-long; Xu, Rui-dong; He, Shi-wei; Chen, Han-sen; Li, Kuo; Zhu, Yun; Shen, Qing-feng

2018-03-01

The effect of NaNO3 concentration on the anodic electrochemical behavior of antimony in 4 M NaOH solution was investigated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) analyses. The mechanism of NO 3 - concentration effect on the anodic electrochemical behavior of antimony was proposed, and its availability was confirmed by experimental results. The effect of NaNO3 on the anodic behavior of antimony in NaOH solution can be interpreted as a stepwise formation of different antimony compounds with different NaNO3 concentrations. Metallic antimony is apt to be oxidized into Sb2O3 within the NaNO3 concentration range of 0-0.48 M. NaSbO3 can be found on the antimony surface when the NaNO3 concentration increases gradually. Insoluable NaSbO3 inhibits the anodic oxidation of antimony due to its shielding effect on the mass transport of the reactants and products. Surface morphology and composition were analyzed by X-ray photoelectron spectroscopy (XPS), scanning electronic microscopy (SEM), and electron dispersion spectroscopy (EDS) analyses. Results indicate that the anodic oxidation layer is composed of Sb2O3, NaSbO3, and Sb. The atomic proportion of antimony in the form of NaSbO3 increases with increasing NaNO3 concentration due to the powerful oxidizing property of NaNO3.

Enhanced dissolution of cinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

USGS Publications Warehouse

Ravichandran, Mahalingam; Aiken, George R.; Reddy, Michael M.; Ryan, Joseph N.

1998-01-01

Organic matter isolated from the Florida Everglades caused a dramatic increase in mercury release (up to 35 μM total dissolved mercury) from cinnabar (HgS), a solid with limited solubility. Hydrophobic (a mixture of both humic and fulvic) acids dissolved more mercury than hydrophilic acids and other nonacid fractions of dissolved organic matter (DOM). Cinnabar dissolution by isolated organic matter and natural water samples was inhibited by cations such as Ca2+. Dissolution was independent of oxygen content in experimental solutions. Dissolution experiments conducted in DI water (pH = 6.0) had no detectable (<2.5 nM) dissolved mercury. The presence of various inorganic (chloride, sulfate, or sulfide) and organic ligands (salicylic acid, acetic acid, EDTA, or cysteine) did not enhance the dissolution of mercury from the mineral. Aromatic carbon content in the isolates (determined by 13C NMR) correlated positively with enhanced cinnabar dissolution. ζ-potential measurements indicated sorption of negatively charged organic matter to the negatively charged cinnabar (pHpzc = 4.0) at pH 6.0. Possible mechanisms of dissolution include surface complexation of mercury and oxidation of surface sulfur species by the organic matter.

Surface potential driven dissolution phenomena of [0 0 0 1]-oriented ZnO nanorods grown from ZnO and Pt seed layers

NASA Astrophysics Data System (ADS)

Seo, Youngmi; Kim, Jung Hyeun

2011-06-01

Highly oriented ZnO nanorods are synthesized hydrothermally on ZnO and Pt seed layers, and they are dissolved in KOH solution. The rods grown on ZnO seed layer show uniform dissolution, but those grown on Pt seed layer are rod-selectively dissolved. The ZnO nanorods from both seed layers show the same crystalline structure through XRD and Raman spectrometer data. However, the surface potential analysis reveals big difference for ZnO and Pt seed cases. The surface potential distribution is very uniform for the ZnO seed case, but it is much fluctuated on the Pt seed case. It suggests that the rod-selective dissolution phenomena on Pt seed case are likely due to the surface energy difference.

Formation of Nanostructures on the Nickel Metal Surface in Ionic Liquid under Anodizing

NASA Astrophysics Data System (ADS)

Lebedeva, O. K.; Root, N. V.; Kultin, D. Yu.; Kalmykov, K. B.; Kustov, L. M.

2018-05-01

The formation of nanostructures in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide on the surface of a nickel electrode during anodizing was studied. Hexagonal ordered surface nanostructures were found to form in a narrow range of current densities. The form of the potential transients of the nickel electrode corresponded to the morphology of the nickel surface obtained which was studied by electron microscopy. No other types of nanostructures were found under the electrosynthesis conditions under study.

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

Surface properties, solubility and dissolution kinetics of bamboo phytoliths

NASA Astrophysics Data System (ADS)

Fraysse, Fabrice; Pokrovsky, Oleg S.; Schott, Jacques; Meunier, Jean-Dominique

2006-04-01

Although phytoliths, constituted mainly by micrometric opal, exhibit an important control on silicon cycle in superficial continental environments, their thermodynamic properties and reactivity in aqueous solution are still poorly known. In this work, we determined the solubility and dissolution rates of bamboo phytoliths collected in the Réunion Island and characterized their surface properties via electrophoretic measurements and potentiometric titrations in a wide range of pH. The solubility product of "soil" phytoliths ( pKsp0=2.74 at 25 °C) is equal to that of vitreous silica and is 17 times higher than that of quartz. Similarly, the enthalpy of phytoliths dissolution reaction (ΔHr25-80°C=10.85kJ/mol) is close to that of amorphous silica but is significantly lower than the enthalpy of quartz dissolution. Electrophoretic measurements yield isoelectric point pH IEP = 1.2 ± 0.1 and 2.5 ± 0.2 for "soil" (native) and "heated" (450 °C heating to remove organic matter) phytoliths, respectively. Surface acid-base titrations allowed generation of a 2-p K surface complexation model. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 2 ⩽ pH ⩽ 12, were found to be intermediate between those of quartz and vitreous silica. The dissolution rate dependence on pH was modeled within the concept of surface coordination theory using the equation: R=k1·{>SiOH2+}n+k2·{>SiOH0}+k3·{>SiO-}m, where {> i} stands for the concentration of the surface species present at the SiO 2-H 2O interface, ki are the rate constants of the three parallel reactions and n and m represent the order of the proton- and hydroxy-promoted reactions, respectively. It follows from the results of this study that phytoliths dissolution rates exhibit a minimum at pH ˜ 3. This can explain their good preservation in the acidic soil horizons of Réunion Island. In terms of silicon biogeochemical cycle, phytoliths represent a large buffering reservoir, which can play an important role in the regulation of silica fluxes in terrestrial aquatic environments.

Effect of surface chemistries and characteristics of Ti6Al4V on the Ca and P adsorption and ion dissolution in Hank's ethylene diamine tetra-acetic acid solution.

PubMed

Chang, E; Lee, T M

2002-07-01

This study examined the influence of chemistries and surface characteristics of Ti6Al4V on the adsorption of Ca and P species and ion dissolution behavior of the material exposed in Hank's solution with 8.0 mM ethylene diamine tetra-acetic acid at 37 degrees C. The variation of chemistries of the alloy and nano-surface characteristics (chemistries of nano-surface oxides, amphoteric OH group adsorbed on oxides, and oxide thickness) was effected by surface modification and three passivation methods (34% nitric acid passivation. 400 degrees C heated in air, and aged in 100 degrees C water). X-ray photoelectron spectroscopy and Auger electron spectroscopy were used for surface analyses. The chemistries of nano-surface oxides in a range studied should not change the capability of Ca and P adsorption. Nor is the capability affected significantly by amphoteric OH group and oxide thickness. However, passivations influence the surface oxide thickness and the early stage ion dissolution rate of the alloy. The rate-limiting step of the rate can be best explained by metal-ion transport through the oxide film, rather than hydrolysis of the film. Variation of the chemistries of titanium alloy alters the electromotive force potential of the metal, thereby affecting the corrosion and ion dissolution rate.

The Dissolution of an Interfween Miscible Liquids

NASA Technical Reports Server (NTRS)

Vlad, D.H.; Maher, J.V.

1999-01-01

The disappearance of the surface tension of the interface of a binary mixture, measured using the dynamic surface light scattering technique, is slower for a binary mixture of higher density contrast. A comparison with a naive diffusion model, expected to provide a lower limit for the speed of dissolution in the absence of gravity shows that the interfacial surface tension disappears much slower than even by diffusion with the effect becoming much more pronounced when density contrast between the liquid phases is increased. Thus, the factor most likely to be responsible for this anomalously slow dissolution is gravity. A mechanism could be based on the competition between diffusive relaxation and sedimentation at the dissolving interface.

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.

Nanoporous Anodic Alumina Platforms: Engineered Surface Chemistry and Structure for Optical Sensing Applications

PubMed Central

Kumeria, Tushar; Santos, Abel; Losic, Dusan

2014-01-01

Electrochemical anodization of pure aluminum enables the growth of highly ordered nanoporous anodic alumina (NAA) structures. This has made NAA one of the most popular nanomaterials with applications including molecular separation, catalysis, photonics, optoelectronics, sensing, drug delivery, and template synthesis. Over the past decades, the ability to engineer the structure and surface chemistry of NAA and its optical properties has led to the establishment of distinctive photonic structures that can be explored for developing low-cost, portable, rapid-response and highly sensitive sensing devices in combination with surface plasmon resonance (SPR) and reflective interference spectroscopy (RIfS) techniques. This review article highlights the recent advances on fabrication, surface modification and structural engineering of NAA and its application and performance as a platform for SPR- and RIfS-based sensing and biosensing devices. PMID:25004150

Effect of Applied Current Density on Cavitation-Erosion Characteristics for Anodized Al Alloy.

PubMed

Lee, Seung-Jun; Kim, Seong-Jong

2018-02-01

Surface finishing is as important as selection of material to achieve durability. Surface finishing is a process to provide surface with the desired performance and features by applying external forces such as thermal energy or stress. This study investigated the optimum supply current density for preventing from cavitation damages by applying to an anodizing technique that artificially forms on the surface an oxide coating that has excellent mechanical characteristics, such as hardness, wear resistance. Result of hardness test, the greater hardness was associated with greater brittleness, resulting in deleterious characteristics. Consequently, under conditions such as the electrolyte concentration of 10 vol.%, the processing time of 40 min, the electrolyte temperature of 10 °C, and the current density of 20 mA/cm2 were considered to be the optimum anodizing conditions for improvement of durability in seawater.

Interface effects in the dissolution of silicon into thin gold films

NASA Technical Reports Server (NTRS)

Sankur, H.; Mccaldin, J. O.

1975-01-01

The dissolution of crystalline Si and amorphous Si substrates into thin films of evaporated Au was studied with an electron microprobe and scanning electron microscopy. The dissolution pattern was found to be nonuniform along the plane of the surface and dependent on the crystalline orientation of the Si substrate. The dissolution is greatly facilitated when a very thin layer of Pd is evaporated between the Si substrate and the Au film.

Electromagnetic radiation detector

DOEpatents

Benson, Jay L.; Hansen, Gordon J.

1976-01-01

An electromagnetic radiation detector including a collimating window, a cathode member having a photoelectric emissive material surface angularly disposed to said window whereby radiation is impinged thereon at acute angles, an anode, separated from the cathode member by an evacuated space, for collecting photoelectrons emitted from the emissive cathode surface, and a negatively biased, high transmissive grid disposed between the cathode member and anode.

Hybrid anode for semiconductor radiation detectors

DOEpatents

Yang, Ge; Bolotnikov, Aleksey E; Camarda, Guiseppe; Cui, Yonggang; Hossain, Anwar; Kim, Ki Hyun; James, Ralph B

2013-11-19

The present invention relates to a novel hybrid anode configuration for a radiation detector that effectively reduces the edge effect of surface defects on the internal electric field in compound semiconductor detectors by focusing the internal electric field of the detector and redirecting drifting carriers away from the side surfaces of the semiconductor toward the collection electrode(s).

Laboratory performance of zinc anodes for impressed current cathodic protection of reinforced concrete

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

Brousseau, R.; Arnott, M.; Baldock, B.

1995-08-01

Cathodic protection is used increasingly to mitigate steel reinforcement corrosion in concrete. the performance of zinc materials as impressed current anodes was evaluated. The anode materials investigated included rolled zinc sheets, metallized zinc, and 85% Zn-15% Al. The circuit resistance and the adhesion of the anodes was monitored with polarization time. Overall performance of arc-sprayed zinc was good. However, its adhesion to the concrete surface slowly decreased as the current density, or the polarization period, increased. Penny blank sheets and metallized 85% Zn-15% Al were found unsuitable as impressed current anodes.

Dissolution at porous interfaces VI: Multiple pore systems.

PubMed

Grijseels, H; Crommelin, D J; De Blaey, C J

1984-12-01

With the aid of rapidly dissolving sodium chloride particles, cubic pores were made in the surface of a theophylline tablet. The influence of the pores on the dissolution rate of the surface was investigated in a rotating disk apparatus. Like the drilled pores used in earlier studies, downstream on the surface they caused a turbulent flow regimen with the development of a trough due to enhanced erosion. The phenomenon of a critical pore diameter, discovered with single, drilled pores, seems to be applicable to the cubic pores investigated in this study, although a higher degree of surface coverage with pores caused complications, probably due to particles bordering one another and forming larger pores. The behavior of the porous surfaces at different rotation speeds was studied. Due to the presence of pores the laminar character of the boundary layer flow changes to turbulent, which induces locally an increased dissolution flux in the wake of a pore.

TREATMENT OF URANIUM SURFACES

DOEpatents

Slunder, C.J.

1959-02-01

An improved process is presented for prcparation of uranium surfaces prior to electroplating. The surfacc of the uranium to be electroplated is anodized in a bath comprising a solution of approximately 20 to 602 by weight of phosphoric acid which contains about 20 cc per liter of concentrated hydrochloric acid. Anodization is carried out for approximately 20 minutes at a current density of about 0.5 amperes per square inch at a temperature of about 35 to 45 C. The oxidic film produced by anodization is removed by dipping in strong nitric acid, followed by rinsing with water just prior to electroplating.

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

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.

Dissolution behavior of MgO based inert matrix fuel for the transmutation of minor actinides

NASA Astrophysics Data System (ADS)

Mühr-Ebert, E. L.; Lichte, E.; Bukaemskiy, A.; Finkeldei, S.; Klinkenberg, M.; Brandt, F.; Bosbach, D.; Modolo, G.

2018-07-01

This study explores the dissolution properties of magnesia-based inert matrix nuclear fuel (IMF) containing transuranium elements (TRU). Pure MgO pellets as well as MgO pellets containing CeO2, as surrogate for TRU oxides, and are considered as model systems for genuine magnesia based inert matrix fuel were fabricated. The aim of this study is to identify conditions at which the matrix material can be selectively dissolved during the head-end reprocessing step, allowing a separation of MgO from the actinides, whereas the actinides remain undissolved. The dissolution behavior was studied in macroscopic batch experiments as a function of nitric acid concentration, dissolution medium volume, temperature, stirring velocity, and pellet density (85, 90, 96, and 99%TD). To mimic pellets with various burn-ups the density of the here fabricated pellets was varied. MgO is soluble even under mild conditions (RT, 2.5 mol/L HNO3). The dissolution rates of MgO at different acid concentrations are rather similar, whereas the dissolution rate is strongly dependent on the temperature. Via a microscopic approach, a model was developed to describe the evolution of the pellet surface area during dissolution and determine a surface normalized dissolution rate. Moreover, dissolution rates of the inert matrix fuel containing CeO2 were determined as a function of the acid concentration and temperature. During the dissolution of MgO/CeO2 pellets the MgO dissolves completely, while CeO2 (>99%) remains undissolved. This study intends to provide a profound understanding of the chemical performance of magnesia based IMF containing fissile material. The feasibility of the dissolution of magnesia based IMF with nitric acid is discussed.

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

NASA Astrophysics Data System (ADS)

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong; Chorover, Jon; O'Day, Peggy A.

2017-06-01

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium (U) concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this work, the dissolution rates of K- and Na-compreignacite (K2(UO2)6O4(OH)6·8H2O and Na2(UO2)6O4(OH)6·8H2O, respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved carbonate concentration (ca. 0.2 and 2.8 mmol L-1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area, and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total U mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved U was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57 · 10-10 vs. 1.28 · 10-13 mol m-2 s-1 [log R = -9.81 and -12.89] and 5.79 · 10-10 vs. 3.71 · 10-13 mol m-2 s-1 [log R = -9.24 and -12.43] for K- and Na-compreignacite, respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for U mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. This study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as U in porous geomedia.

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

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

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2(UO 2) 6O 4(OH) 6·8H 2O and Na 2(UO 2) 6O 4(OH) 6·8H 2O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmolmore » L -1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were about 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57·10 -10 vs. 1.28·10 -13 mol m -2 s -1 [log R = -9.81 and -12.89] and 5.79·10 -10 vs. 3.71·10 -13 mol m -2 s -1 [log R = -9.24 and -12.43] for K- and Na-compreignacite respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for uranium mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. Finally, this study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as uranium in porous geomedia.« less

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

DOE PAGES

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong; ...

2017-06-01

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2(UO 2) 6O 4(OH) 6·8H 2O and Na 2(UO 2) 6O 4(OH) 6·8H 2O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmolmore » L -1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were about 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57·10 -10 vs. 1.28·10 -13 mol m -2 s -1 [log R = -9.81 and -12.89] and 5.79·10 -10 vs. 3.71·10 -13 mol m -2 s -1 [log R = -9.24 and -12.43] for K- and Na-compreignacite respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for uranium mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. Finally, this study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as uranium in porous geomedia.« less

Influence of essential onion oil on tin and chromium dissolution from tinplate.

PubMed

Nincević Grassino, A; Grabarić, Z; Pezzani, A; Fasanaro, G; Lo Voi, A

2009-07-01

During food and beverage packaging in tinplate cans the dissolution of tin and chromium into food content may occur. To protect metallic surface different corrosion inhibitors are recommended, nowadays particularly a new group of natural products is of interest. In this work the influence of essential onion oil (EOO) on metals dissolution (tin and chromium) from tinplate sheets before food canning was investigated. The analyses were performed by galvanostatic method and atomic absorption spectroscopy. The values of tin obtained for the internal surface of tinplate covered with EOO (7.31-9.76 gm(-2)) are lower than the values when dioctyl sebacate oil (DOS), as a protective tinplate surface layer for food caning, was used (9.24-11.03 gm(-2)). Obviously, the presence of EOO diminished more efficiently then DOS oil the dissolution of tin in electrolyte during galvanostatic analyses. The efficiency of EOO as corrosion inhibitor was even more pronounced in the case of chromium where the dissolution from 1.8-2.5 mgm(-2) (DOS oil) was lowered to 1.0-1.3 mgm(-2) (EOO). Correlation of results obtained with two different physico-chemical methods was satisfying.

Systematic screening of carbon-based anode materials for microbial fuel cells with Shewanella oneidensis MR-1.

PubMed

Kipf, Elena; Koch, Julia; Geiger, Bettina; Erben, Johannes; Richter, Katrin; Gescher, Johannes; Zengerle, Roland; Kerzenmacher, Sven

2013-10-01

We present a systematic screening of carbon-based anode materials for microbial fuel cells with Shewanella oneidensis MR-1. Under anoxic conditions nanoporous activated carbon cloth is a superior anode material in terms of current density normalized to the projected anode area and anode volume (24.0±0.3 μA cm(-2) and 482±7 μA cm(-3) at -0.2 vs. SCE, respectively). The good performance can be attributed to the high specific surface area of the material, which is available for mediated electron transfer through self-secreted flavins. Under aerated conditions no influence of the specific surface area is observed, which we attribute to a shift from primary indirect electron transfer by mediators to direct electron transfer via adherent cells. Furthermore, we show that an aerated initial growth phase enhances the current density under subsequent anoxic conditions fivefold when compared to a similar experiment that was conducted under permanently anoxic conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

Determination of the Dissolution Slowness Surface by Study of Etched Shapes: II. Comparison of 2D Experimental and Theoretical Etching Shapes

NASA Astrophysics Data System (ADS)

Leblois, T.; Tellier, C. R.; Messaoudi, T.

1997-03-01

The anisotropic etching behavior of quartz crystal in concentrated ammonium bifluoride solution is studied and analyzed in the framework of a tensorial model. This model allows to simulate bi- or three-dimensional etching shapes from the equation for the representative surface of the dissolution slowness. In this paper, we present experimental results such as surface profile and initially circular cross-sectional profiles of differently singly- or doubly-rotated cuts. The polar diagrams of the dissolution slowness vector in several planes are deduced from experimental data. The comparison between predicted surface and cross-sectional profiles and experimental results is detailed and shows a good agreement. In particular, several examples give evidence that the final etched shapes are correlated to the extrema of the dissolution slowness. However, in several cases, experimental shapes cannot be simply correlated to the presence of extrema. Simulation gives effectively evidence for an important role played by more progressive changes in the curvature of the slowness surface. Consequently, analysis of data merits to be treated carefully. Nous nous proposons d'étudier et d'analyser à l'aide du modèle tensoriel de la dissolution l'attaque chimique anisotrope du cristal de quartz dans une solution concentrée de bifluorure d'ammonium. Ce modèle permet de simuler des formes usinées à deux ou trois dimensions à partir de l'équation de la surface représentative de la lenteur de dissolution du cristal de quartz. Dans cet article, nous présentons des résultats expérimentaux concernant des profils de surface et des sections initialement cylindriques de coupes à simple et double rotation. Les diagrammes polaires du vecteur lenteur de dissolution dans différents plans sont déduits de données expérimentales. La comparaison entre les profils de surface et de section théoriques et les résultats expérimentaux est détaillée et montre un bon accord. En particulier plusieurs exemples montrent que la forme finale est corrélée à la présence d'extrema de la lenteur de dissolution. Cependant, la corrélation entre résultats expérimentaux et théoriques n'est pas toujours simple et mérite une analyse soignée. Pour conclure, le modèle 3D est appliqué pour prévoir la forme usinée d'un trou initialement circulaire dans une coupe tournée autour de l'axe Y. Le résultat théorique est comparé avec la forme usinée expérimentale et montre un parfait accord.

A method for preparation and cleaning of uniformly sized arsenopyrite particles

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

Parthasarathy, Hariprasad; Baltrus, John P; Dzombak, David A

The oxidative dissolution of sulfide minerals, such as arsenopyrite (FeAsS), is of critical importance in many geochemical systems. A comprehensive understanding of their dissolution rates entails careful preparation of the mineral surface. Measurements of dissolution rates of arsenic from arsenopyrite are dependent on the size and degree of oxidation of its particles, among other factors. In this work, a method was developed for preparation and cleaning of arsenopyrite particles with size range of 150–250 μm. Four different cleaning methods were evaluated for effectiveness based on the removal of oxidized species of iron (Fe), arsenic (As) and sulfur (S) from themore » surface. The percentage oxidation of the surface was determined using X-ray photoelectron spectroscopy (XPS), and surface stoichiometry was measured using scanning electron microscopy – energy dispersive X-ray spectroscopy (SEM-EDS). Results indicate that sonicating the arsenopyrite particles and then cleaning them with 12N HCl followed by 50% ethanol, and drying in nitrogen was the most effective method. This method was successful in greatly reducing the oxide species of Fe while completely removing oxides of As and S from the arsenopyrite surface. Although sonication and acid cleaning have been widely used for mineral preparation, the method described in this study can significantly reduce grain size heterogeneity as well as surface oxidation, which enables greater control in surface and dissolution experiments.« less

A method for preparation and cleaning of uniformly sized arsenopyrite particles

DOE PAGES

Parthasarathy, Hariprasad; Baltrus, John P; Dzombak, David A; ...

2014-10-11

The oxidative dissolution of sulfide minerals, such as arsenopyrite (FeAsS), is of critical importance in many geochemical systems. A comprehensive understanding of their dissolution rates entails careful preparation of the mineral surface. Measurements of dissolution rates of arsenic from arsenopyrite are dependent on the size and degree of oxidation of its particles, among other factors. In this work, a method was developed for preparation and cleaning of arsenopyrite particles with size range of 150–250 μm. Four different cleaning methods were evaluated for effectiveness based on the removal of oxidized species of iron (Fe), arsenic (As) and sulfur (S) from themore » surface. The percentage oxidation of the surface was determined using X-ray photoelectron spectroscopy (XPS), and surface stoichiometry was measured using scanning electron microscopy – energy dispersive X-ray spectroscopy (SEM-EDS). Results indicate that sonicating the arsenopyrite particles and then cleaning them with 12N HCl followed by 50% ethanol, and drying in nitrogen was the most effective method. This method was successful in greatly reducing the oxide species of Fe while completely removing oxides of As and S from the arsenopyrite surface. Although sonication and acid cleaning have been widely used for mineral preparation, the method described in this study can significantly reduce grain size heterogeneity as well as surface oxidation, which enables greater control in surface and dissolution experiments.« less

Inter-cusp Ion and Electron Transport in a Nstar-derivative Ion Thruster

NASA Technical Reports Server (NTRS)

Foster, John E.

2001-01-01

Diffusion of electrons and ions to anode surfaces between the magnetic cusps of a NASA Solar Electric Propulsion Technology Application Readiness ion thruster has been characterized. Ion flux measurements were made at the anode and at the screen grid electrode. The measurements indicated that the average ion current density at the anode and at the screen grid were approximately equal. Additionally, it was found that the electron flux to the anode between cusps is best described by the classical cross-field diffusion coefficient.

Ion and Electron Transport in an Nstar-derivative Ion Thruster. Revised

NASA Technical Reports Server (NTRS)

Foster, John E.

2001-01-01

Diffusion of electrons and ions to anode surfaces between the magnetic cusps of a NASA Solar Electric Propulsion Technology Application Readiness ion thruster has been characterized. Ion flux measurements were made at the anode and at the screen grid electrode. The measurements indicated that the average ion current density at the anode and at the screen grid were approximately equal. Additionally, it was found that the electron flux to the anode between cusps is best described by the classical cross-field diffusion coefficient.

Pulse-reverse electrodeposition for mesoporous metal films: combination of hydrogen evolution assisted deposition and electrochemical dealloying.

PubMed

Cherevko, Serhiy; Kulyk, Nadiia; Chung, Chan-Hwa

2012-01-21

Hydrogen evolution assisted electrodeposition is a new bottom-up technique allowing the fast and simple synthesis of nanometals. Electrochemical dealloying is a top-down approach with the same purpose. In this work, we show that a combination of these two methods in sequence by pulse-reverse electrodeposition can be used to prepare high-surface-area nanostructured metals. Highly porous adherent platinum is obtained by the deposition of CuPt alloy during the cathodic cycles and the selective dissolution of copper during the anodic cycles. The convection created by the movement of the hydrogen bubbles increases the deposition rate and removes the dissolved copper ions from the diffusion layer, which ensures the deposition of a film with the same stoichiometry throughout the whole process. Due to the relatively high ratio of copper atoms on the surface in the as-deposited layer, it is proposed that the dealloying kinetics is significantly higher than that usually observed during the dealloying process in a model system. The proposed approach has several advantages over other methods, such as a very high growth rate and needlessness of any post-treatment processes. A detailed analysis of the effect of pulse-reverse waveform parameters on the properties of the films is presented. Mesoporous platinum with pores and ligaments having characteristic sizes of less than 10 nm, an equivalent surface area of up to ca. 220 m(2) cm(-3), and a roughness factor of more than 1000 is fabricated.

Kinetics and mechanism of hydroxyapatite crystal dissolution in weak acid buffers using the rotating disk method.

PubMed

Wu, M S; Higuchi, W I; Fox, J L; Friedman, M

1976-01-01

The model given in this report and the rotating disk method provide a useful combination in the study of dental enamel and hydroxyapatite dissolution kinetics. The present approach is a significant improvement over earlier studies, and both the ionic activity product that governs the dissolution reaction and the apparent surface dissolution reaction rate constant may be simultaneously obtained. Thus, these investigations have established the baseline for the dissolution rate studies under sink conditions. Concurrent studies, under conditions where the acidic buffer mediums are partially saturated with respect to hydroxyapatite have shown another dissolution site for hydroxyapatite that operates at a higher ionic activity product but has a much smaller apparent surface reaction rate constant. This has raised the question of whether the presence of this second site may interfere with the proper theoretical analysis of the experimental results obtained under sink conditions. A preliminary analysis of the two-site model has shown that the dissolution kinetics of hydroxyapatite under sink conditions is almost completely governed by the sink condition site (KHAP = 10(-124.5), k' = 174) established in this report. The difference between the predicted dissolution rate for the one-site model and the two-site model are generally of the order of 4 to 5% where the experiments are conducted under sink conditions and over the range of variables covered in the present study.

Atomic-scale imaging of the dissolution of NaCl islands by water at low temperature

NASA Astrophysics Data System (ADS)

Peng, Jinbo; Guo, Jing; Ma, Runze; Meng, Xiangzhi; Jiang, Ying

2017-03-01

The dissolution of sodium chloride (NaCl) in water is a frequently encountered process in our daily lives. While the NaCl dissolution process in liquid water has been extensively studied, whether and how the dissolution occurs below the freezing point is still not clear. Using a low-temperature scanning tunneling microscope (STM), here we were able to directly visualize the dissolution of Au-supported NaCl (0 0 1) bilayer islands by water at atomic level. We found that the single water molecule on the STM tip can assist the extraction of single Na+ from the NaCl surface even at 5 K, while leaving the Cl- intact. When covered with a full water monolayer, the NaCl islands started to dissolve from the step edges and also showed evidence of dissolution inside the terraces as the temperature was raised up to 145 K. At 155 K, the water molecules completely desorbed from the surface, which was accompanied with the decomposition and restructuring of the bilayer NaCl islands. Those results suggest that the dissolution of NaCl may occur well below the freezing point at the ice/NaCl interfaces and is mainly driven by the interaction between the water molecules and the Na+, which is in clear contrast with the NaCl dissolution in liquid water.

In vitro investigation of anodization and CaP deposited titanium surface using MG63 osteoblast-like cells

NASA Astrophysics Data System (ADS)

Lee, J. M.; Lee, J. I.; Lim, Y. J.

2010-03-01

The aim of the present study was to investigate surface characteristics in four different titanium surfaces (AN: anodized at 270 V; AN-CaP: anodic oxidation and CaP deposited; SLA: sandblasted and acid etched; MA: machined) and to evaluate biological behaviors such as cell adhesion, cell proliferation, cytoskeletal organization, and osteogenic protein expression of MG63 osteoblast-like cells at the early stage. Surface analysis was performed using scanning electron microscopy, thin-film X-ray diffractometry, and a confocal laser scanning microscope. In order to evaluate cellular responses, MG63 osteoblast-like cells were used. The cell viability was evaluated by MTT assay. Immunofluorescent analyses of actin, type I collagen, osteonectin and osteocalcin were performed. The anodized and CaP deposited specimen showed homogeneously distributed CaP particles around micropores and exhibited anatase type oxides, titanium, and HA crystalline structures. This experiment suggests that CaP particles on the anodic oxidation surface affect cellular attachment and spreading. When designing an in vitro biological study for CaP coated titanium, it must be taken into account that preincubation in medium prior to cell seeding and the cell culture medium may affect the CaP coatings. All these observations illustrate the importance of the experimental conditions and the physicochemical parameters of the CaP coating. It is considered that further evaluations such as long-term in vitro cellular assays and in vivo experiments should be necessary to figure out the effect of CaP deposition to biological responses.

Microbial Communities and Electrochemical Performance of Titanium-Based Anodic Electrodes in a Microbial Fuel Cell▿

PubMed Central

Michaelidou, Urania; ter Heijne, Annemiek; Euverink, Gerrit Jan W.; Hamelers, Hubertus V. M.; Stams, Alfons J. M.; Geelhoed, Jeanine S.

2011-01-01

Four types of titanium (Ti)-based electrodes were tested in the same microbial fuel cell (MFC) anodic compartment. Their electrochemical performances and the dominant microbial communities of the electrode biofilms were compared. The electrodes were identical in shape, macroscopic surface area, and core material but differed in either surface coating (Pt- or Ta-coated metal composites) or surface texture (smooth or rough). The MFC was inoculated with electrochemically active, neutrophilic microorganisms that had been enriched in the anodic compartments of acetate-fed MFCs over a period of 4 years. The original inoculum consisted of bioreactor sludge samples amended with Geobacter sulfurreducens strain PCA. Overall, the Pt- and Ta-coated Ti bioanodes (electrode-biofilm association) showed higher current production than the uncoated Ti bioanodes. Analyses of extracted DNA of the anodic liquid and the Pt- and Ta-coated Ti electrode biofilms indicated differences in the dominant bacterial communities. Biofilm formation on the uncoated electrodes was poor and insufficient for further analyses. Bioanode samples from the Pt- and Ta-coated Ti electrodes incubated with Fe(III) and acetate showed several Fe(III)-reducing bacteria, of which selected species were dominant, on the surface of the electrodes. In contrast, nitrate-enriched samples showed less diversity, and the enriched strains were not dominant on the electrode surface. Isolated Fe(III)-reducing strains were phylogenetically related, but not all identical, to Geobacter sulfurreducens strain PCA. Other bacterial species were also detected in the system, such as a Propionicimonas-related species that was dominant in the anodic liquid and Pseudomonas-, Clostridium-, Desulfovibrio-, Azospira-, and Aeromonas-related species. PMID:21131513

High temperature dissolution of chromium substituted nickel ferrite in nitrilotriacetic acid medium

NASA Astrophysics Data System (ADS)

Sathyaseelan, V. S.; Chandramohan, P.; Velmurugan, S.

2016-12-01

High temperature (HT) dissolution of chromium substituted nickel ferrite was carried out with relevance to the decontamination of nuclear reactors by way of chemical dissolution of contaminated corrosion product oxides present on stainless steel coolant circuit surfaces. Chromium substituted nickel ferrites of composition, NiFe(2-x)CrxO4 (x ≤ 1), was synthetically prepared and characterized. HT dissolution of these oxides was carried out in nitrilotriacetic acid medium at 160 °C. Dissolution was remarkably increased at 160 °C when compared to at 85 °C in a reducing decontamination formulation. Complete dissolution could be achieved for the oxides with chromium content 0 and 0.2. Increasing the chromium content brought about a marked reduction in the dissolution rate. About 40 fold decrease in rate of dissolution was observed when chromium was increased from 0 to 1. The rate of dissolution was not very significantly reduced in the presence of N2H4. Dissolution of oxide was found to be stoichiometric.

Stability of surface nanobubbles

NASA Astrophysics Data System (ADS)

Maheshwari, Shantanu; van der Hoef, Martin; Zhang, Xuehua; Lohse, Detlef

2015-11-01

We have studied the stability and dissolution of surface nanobubbles on the chemical heterogenous surface by performing Molecular Dynamics (MD) simulations of binary mixture consists of Lennard-Jones (LJ) particles. Recently our group has derived the exact expression for equilibrium contact angle of surface nanobubbles as a function of oversaturation of the gas concentration in bulk liquid and the lateral length of bubble. It has been showed that the contact line pinning and the oversaturation of gas concentration in bulk liquid is crucial in the stability of surface nanobubbles. Our simulations showed that how pinning of the three-phase contact line on the chemical heterogenous surface lead to the stability of the nanobubble. We have calculated the equilibrium contact angle by varying the gas concentration in bulk liquid and the lateral length of the bubble. Our results showed that the equilibrium contact angle follows the expression derived analytically by our group. We have also studied the bubble dissolution dynamics and showed the ''stick-jump'' mechanism which was also observed experimentally in case of dissolution of nanodrops.

Nanoscale Decoration of Electrode Surfaces with an STM

DTIC Science & Technology

1999-05-30

covered gold electrode surfaces at predetermined positions. First, metal is deposited electrochemically onto the STM tip, then the clusters are formed by a...onto the tip, the jump-to-contact occurs in the opposite direction leaving holes in the gold surface. The stability of the metal clusters against anodic...deposition, clusters, a surprisingly high stability of the small Ag Hg/HgSO4 for Ag deposition and a Pt wire for Ni clusters on gold against anodic

Understanding improved osteoblast behavior on select nanoporous anodic alumina

PubMed Central

Ni, Siyu; Li, Changyan; Ni, Shirong; Chen, Ting; Webster, Thomas J

2014-01-01

The aim of this study was to prepare different sized porous anodic alumina (PAA) and examine preosteoblast (MC3T3-E1) attachment and proliferation on such nanoporous surfaces. In this study, PAA with tunable pore sizes (25 nm, 50 nm, and 75 nm) were fabricated by a two-step anodizing procedure in oxalic acid. The surface morphology and elemental composition of PAA were characterized by field emission scanning electron microscopy and X-ray photoelectron spectroscopy analysis. The nanopore arrays on all of the PAA samples were highly regular. X-ray photoelectron spectroscopy analysis suggested that the chemistry of PAA and flat aluminum surfaces were similar. However, contact angles were significantly greater on all of the PAA compared to flat aluminum substrates, which consequently altered protein adsorption profiles. The attachment and proliferation of preosteoblasts were determined for up to 7 days in culture using field emission scanning electron microscopy and a Cell Counting Kit-8. Results showed that nanoporous surfaces did not enhance initial preosteoblast attachment, whereas preosteoblast proliferation dramatically increased when the PAA pore size was either 50 nm or 75 nm compared to all other samples (P<0.05). Thus, this study showed that one can alter surface energy of aluminum by modifying surface nano-roughness alone (and not changing chemistry) through an anodization process to improve osteoblast density, and, thus, should be further studied as a bioactive interface for orthopedic applications. PMID:25045263

Electrochemical decolorization of dye wastewater by surface-activated boron-doped nanocrystalline diamond electrode.

PubMed

Chen, Chienhung; Nurhayati, Ervin; Juang, Yaju; Huang, Chihpin

2016-07-01

Complex organics contained in dye wastewater are difficult to degrade and often require electrochemical advanced oxidation processes (EAOPs) to treat it. Surface activation of the electrode used in such treatment is an important factor determining the success of the process. The performance of boron-doped nanocrystalline diamond (BD-NCD) film electrode for decolorization of Acid Yellow (AY-36) azo dye with respect to the surface activation by electrochemical polarization was studied. Anodic polarization found to be more suitable as electrode pretreatment compared to cathodic one. After anodic polarization, the originally H-terminated surface of BD-NCD was changed into O-terminated, making it more hydrophilic. Due to the oxidation of surface functional groups and some portion of sp(2) carbon in the BD-NCD film during anodic polarization, the electrode was successfully being activated showing lower background current, wider potential window and considerably less surface activity compared to the non-polarized one. Consequently, electrooxidation (EO) capability of the anodically-polarized BD-NCD to degrade AY-36 dye was significantly enhanced, capable of nearly total decolorization and chemical oxygen demand (COD) removal even after several times of re-using. The BD-NCD film electrode favored acidic condition for the dye degradation; and the presence of chloride ion in the solution was found to be more advantageous than sulfate active species. Copyright © 2016. Published by Elsevier B.V.

Dissolution kinetics of soluble nondisintegrating disks.

PubMed

de Blaey, C J; van der Graaff, H

1977-12-01

An equation describing the isotropical dissolution of soluble nondisintegrating disks was developed. It was equivalent to the cube root law only if the height and diameter of the disk were equal. The dissolution kinetics of sodium chloride disks were examined, using a beaker equipped with a centrifugal stirrer as the dissolution chamber. The fit of the experimental data to the cube root law had a coefficient of variation of about 4-5%. It was demonstrated statistically that a fit to a square root of mass versus time relation was significantly better. With increasing porosity, the dissolution process proceeded faster than predicted on the basis of the diffusion-convection model. An explanation is proposed by assuming an increased effective dissolution surface.

Dissolution of quartz in aqueous basic solution, 106-236 C - Surface kinetics of 'perfect' crystallographic faces

NASA Technical Reports Server (NTRS)

Gratz, Andrew J.; Bird, Peter; Quiro, Glenn B.

1990-01-01

A highly accurate method, called the negative crystal method, for determining the rate of dissolution on specific crystallographic faces of crystals was developed, in which the dissolution rates of nominally perfect crystal faces are obtained by measuring the size of individual negative crystals during a sequence of dissolution steps. The method was applied to determine the apparent activation energy and rate constants for the dissolution of quartz in 0.01 M KOH solutions at temperatures from 106 to 236 C. Also investigated were the effects of hydroxyl activity and ionic strength. The apparent activation energies for the dissolution of the prism and of the rhomb were determined.

Anode power in a quasi-steady MPD thruster. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Saber, A. J.

1974-01-01

Local anode heat flux in a quasi-steady MPD thruster is measured by thermocouples attached to the inside surface of a shell anode. Over a range of arc currents J from 5.5 to 44 kiloamperes and argon propellant mass flows m from 1 to 48 g/sec, with the ratio J2/m held constant, the fraction of arc power deposited in the anode is found to decrease with increasing arc power. Specifically, this anode power fraction decreases from 50% at 200 kW arc power, to 10% at 20 MW. In an effort to account for this functional behavior, the current density, plasma potential, and electron temperature in the plasma adjacent to the anode are measured with probes, and the results are used in a theoretical anode heat flux model. The model asserts that energy exchange between electrons and heavy particles in the plasma near the anode occur over distances greater than the anode sheath thickness.

Structural and characteristic variation of anodic oxide on pure Ti with anodization duration

NASA Astrophysics Data System (ADS)

Mizukoshi, Yoshiteru; Ohtsu, Naofhumi; Masahashi, Naoya

2013-10-01

Change in the structural and characteristic of the anodic oxide on pure Ti with the duration of anodization time was investigated. With the progress of the anodization, the phase of the formed TiO2 successively changed from anatase phase to rutile phase. In the transition process, peak intensities of rutile TiO2 1 0 1, 1 1 1 and 2 1 1 planes of X-ray diffraction characteristically increased. The contact angles of water droplets on the anodize TiO2 were monotonously decreased with the progress of the anodization except on the characteristically oriented rutile surface. In the evaluations of acetaldehyde photocatalysis under UV illumination, the anatase TiO2 anodized for short period exhibited high activities. On the other hand, when illuminated with visible light (>422 nm), rutile-structured TiO2 formed by anodization with a long duration exhibited superior photocatalytic activities probably due to high rutile fraction and sulfur incorporation from the electrolyte.

Novel structure formation at the bottom surface of porous anodic alumina fabricated by single step anodization process.

PubMed

Ali, Ghafar; Ahmad, Maqsood; Akhter, Javed Iqbal; Maqbool, Muhammad; Cho, Sung Oh

2010-08-01

A simple approach for the growth of long-range highly ordered nanoporous anodic alumina film in H(2)SO(4) electrolyte through a single step anodization without any additional pre-anodizing procedure is reported. Free-standing porous anodic alumina film of 180 microm thickness with through hole morphology was obtained. A simple and single step process was used for the detachment of alumina from aluminum substrate. The effect of anodizing conditions, such as anodizing voltage and time on the pore diameter and pore ordering is discussed. The metal/oxide and oxide/electrolyte interfaces were examined by high resolution scanning transmission electron microscope. The arrangement of pores on metal/oxide interface was well ordered with smaller diameters than that of the oxide/electrolyte interface. The inter-pore distance was larger in metal/oxide interface as compared to the oxide/electrolyte interface. The size of the ordered domain was found to depend strongly upon anodizing voltage and time. (c) 2010 Elsevier Ltd. All rights reserved.

Dynamics of the spatial structure of pulsed discharges in dense gases in point cathode−plane anode gaps and their erosion effect on the plane electrode surface

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

Baksht, E. Kh.; Blinova, O. M.; Erofeev, M. V., E-mail: mve@loi.hcei.tsc.ru

2016-09-15

The dynamics of the spatial structure of the plasma of pulsed discharges in air and nitrogen in a nonuniform electric field and their erosion effect on the plane anode surface were studied experimentally. It is established that, at a nanosecond front of the voltage pulse, a diffuse discharge forms in the point cathode–plane anode gap due to the ionization wave propagating from the cathode. As the gap length decreases, the diffuse discharge transforms into a spark. A bright spot on the anode appears during the diffuse discharge, while the spark channel forms in the later discharge stage. The microstructure ofmore » autographs of anode spots and spark channels in discharges with durations of several nanoseconds is revealed. The autographs consist of up to 100 and more microcraters 5–100 μm in diameter. It is shown that, due to the short duration of the voltage pulse, a diffuse discharge can be implemented, several pulses of which do not produce appreciable erosion on the plane anode or the soot coating deposited on it.« less

Characterization of Cracking Mechanisms of Carbon Anodes Used in Aluminum Industry by Optical Microscopy and Tomography

NASA Astrophysics Data System (ADS)

Amrani, Salah; Kocaefe, Duygu; Kocaefe, Yasar; Bhattacharyay, Dipankar; Bouazara, Mohamed; Morais, Brigitte

2016-10-01

The objective of this work is to understand the different mechanisms of crack formation in dense anodes used in the aluminum industry. The first approach used is based on the qualitative characterization of the surface cracks and the depth of these cracks. The second approach, which constitutes a quantitative characterization, is carried out by determining the distribution of the crack width along its length as well as the percentage of the surface containing cracks. A qualitative analysis of crack formation was also carried out using 3D tomography. It was observed that mixing and forming conditions have a significant effect on crack formation in green anodes. The devolatilization of pitch during baking causes the formation and propagation of cracks in baked anodes in which large particles control the direction of crack propagation.

Observations of magnetite dissolution in poorly drained soils

USGS Publications Warehouse

Grimley, D.A.; Arruda, N.K.

2007-01-01

Dissolution of strongly magnetic minerals is a common and relatively rapid phenomenon in poorly drained soils of the central United States, resulting in low magnetic susceptibility (MS). Low Eh reducing conditions are primarily responsible for magnetic mineral dissolution; a process likely mediated by iron-reducing bacteria in the presence of soil organic matter. Based on transects across drainage sequences from nine sites, natural magnetic minerals (>5 ??m) extracted from surface soil consist of 54% ?? 18% magnetite, 21% ?? 11% titanomagnetite, and 17% ?? 14% ilmenite. Magnetite and titanomagnetite dissolution, assessed by scanning electron microscopy on a 0-to-3 scale, inversely correlates with surface soil MS (r = 0.53), a proxy for soil drainage at studied transects. Altered magnetite typically displays etch pits 5 ??m) include 26% ?? 18% anthropogenic fly ash that also exhibits greater dissolution in low MS soils (r = 0.38), indicating detectable alteration can occur within 150 years in low Eh soils. Laboratory induced reduction of magnetite, titanomagnetite, and magnetic fly ash, with a citrate-bicarbonate- dithionite solution, resulted in dissolution textures similar to those of in situ soil particles. Although experiments indicate that reductive dissolution of magnetite can occur abiotically under extreme conditions, bacteria likely play an important role in the natural environment. ?? 2007 Lippincott Williams & Wilkins, Inc.

Preparation of RuO2-TiO2/Nano-graphite composite anode for electrochemical degradation of ceftriaxone sodium.

PubMed

Li, Dong; Guo, Xiaolei; Song, Haoran; Sun, Tianyi; Wan, Jiafeng

2018-06-05

Graphite-like material is widely used for preparing various electrodes for wastewater treatment. To enhance the electrochemical degradation efficiency of Nano-graphite (Nano-G) anode, RuO 2 -TiO 2 /Nano-G composite anode was prepared through the sol-gel method and hot-press technology. RuO 2 -TiO 2 /Nano-G composite was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and N 2 adsorption-desorption. Results showed that RuO 2 , TiO 2 and Nano-G were composited successfully, and RuO 2 and TiO 2 nanoparticles were distributed uniformly on the surface of Nano-G sheet. Specific surface area of RuO 2 -TiO 2 /Nano-G composite was higher than that of TiO 2 /Nano-G composite and Nano-G. Electrochemical performances of RuO 2 -TiO 2 /Nano-G anode were investigated by cyclic voltammetry, electrochemical impedance spectroscopy. RuO 2 -TiO 2 /Nano-G anode was applied to electrochemical degradation of ceftriaxone. The generation of hydroxyl radical (OH) was measured. Results demonstrated that RuO 2 -TiO 2 /Nano-G anode displayed enhanced electrochemical degradation efficiency towards ceftriaxone and yield of OH, which is derived from the synergetic effect between RuO 2 , TiO 2 and Nano-G, which enhance the specific surface area, improve the electrochemical oxidation activity and lower the charge transfer resistance. Besides, the possible degradation intermediates and pathways of ceftriaxone sodium were identified. This study may provide a viable and promising prospect for RuO 2 -TiO 2 /Nano-G anode towards effective electrochemical degradation of antibiotics from wastewater. Copyright © 2018 Elsevier B.V. All rights reserved.

Preparing nano-hole arrays by using porous anodic aluminum oxide nano-structural masks for the enhanced emission from InGaN/GaN blue light-emitting diodes

NASA Astrophysics Data System (ADS)

Nguyen, Hoang-Duy; Nguyen, Hieu Pham Trung; Lee, Jae-jin; Mho, Sun-Il

2012-12-01

We report on the achievement of the enhanced cathodoluminescence (CL) from InGaN/GaN light-emitting diodes (LEDs) by using roughening surface. Nanoporous anodic aluminum oxide (AAO) mask was utilized to form nano-hole arrays on the surface of InGaN/GaN LEDs. AAO membranes with ordered hexagonal structures were fabricated from aluminum foils by a two-step anodization method. The average pore densities of ˜1.0 × 1010 cm-2 and 3.0 × 1010 cm-2 were fabricated with the constant anodization voltages of 25 and 40 V, respectively. Anodic porous alumina film with a thickness of ˜600 nm has been used as a mask for the induced couple plasma etching process to fabricate nano-hole arrays on the LED surface. Diameter and depth of nano-holes can be controlled by varying the etching duration and/or the diameter of AAO membranes. Due to the reduction of total internal reflection obtained in the patterned samples, we have observed that the cathodoluminescence intensity of LEDs with nanoporous structures is increased up to eight times compared to that of samples without using nanoporous structure.

Cell Adhesion and in Vivo Osseointegration of Sandblasted/Acid Etched/Anodized Dental Implants

PubMed Central

Kim, Mu-Hyon; Park, Kyeongsoon; Choi, Kyung-Hee; Kim, Soo-Hong; Kim, Se Eun; Jeong, Chang-Mo; Huh, Jung-Bo

2015-01-01

The authors describe a new type of titanium (Ti) implant as a Modi-anodized (ANO) Ti implant, the surface of which was treated by sandblasting, acid etching (SLA), and anodized techniques. The aim of the present study was to evaluate the adhesion of MG-63 cells to Modi-ANO surface treated Ti in vitro and to investigate its osseointegration characteristics in vivo. Four different types of Ti implants were examined, that is, machined Ti (control), SLA, anodized, and Modi-ANO Ti. In the cell adhesion study, Modi-ANO Ti showed higher initial MG-63 cell adhesion and induced greater filopodia growth than other groups. In vivo study in a beagle model revealed the bone-to-implant contact (BIC) of Modi-ANO Ti (74.20% ± 10.89%) was much greater than those of machined (33.58% ± 8.63%), SLA (58.47% ± 12.89), or ANO Ti (59.62% ± 18.30%). In conclusion, this study demonstrates that Modi-ANO Ti implants produced by sandblasting, acid etching, and anodizing improve cell adhesion and bone ongrowth as compared with machined, SLA, or ANO Ti implants. These findings suggest that the application of Modi-ANO surface treatment could improve the osseointegration of dental implant. PMID:25955650

Localised anodic oxidation of aluminium material using a continuous electrolyte jet

NASA Astrophysics Data System (ADS)

Kuhn, D.; Martin, A.; Eckart, C.; Sieber, M.; Morgenstern, R.; Hackert-Oschätzchen, M.; Lampke, T.; Schubert, A.

2017-03-01

Anodic oxidation of aluminium and its alloys is often used as protection against material wearout and corrosion. Therefore, anodic oxidation of aluminium is applied to produce functional oxide layers. The structure and properties of the oxide layers can be influenced by various factors. These factors include for example the properties of the substrate material, like alloy elements and heat treatment or process parameters, like operating temperature, electric parameters or the type of the used electrolyte. In order to avoid damage to the work-piece surface caused by covering materials in masking applications, to minimize the use of resources and to modify the surface in a targeted manner, the anodic oxidation has to be localised to partial areas. Within this study a proper alternative without preparing the substrate by a mask is investigated for generating locally limited anodic oxidation by using a continuous electrolyte jet. Therefore aluminium material EN AW 7075 is machined by applying a continuous electrolyte jet of oxalic acid. Experiments were carried out by varying process parameters like voltage or processing time. The realised oxide spots on the aluminium surface were investigated by optical microscopy, SEM and EDX line scanning. Furthermore, the dependencies of the oxide layer properties from the process parameters are shown.

Corrosion Protection of Al/Au/ZnO Anode for Hybrid Cell Application

PubMed Central

Slaughter, Gymama; Stevens, Brian

2015-01-01

Effective protection of power sources from corrosion is critical in the development of abiotic fuel cells, biofuel cells, hybrid cells and biobateries for implantable bioelectronics. Corrosion of these bioelectronic devices result in device inability to generate bioelectricity. In this paper Al/Au/ZnO was considered as a possible anodic substrate for the development of a hybrid cell. The protective abilities of corrosive resistant aluminum hydroxide and zinc phosphite composite films formed on the surface of Al/Au/ZnO anode in various electrolyte environments were examined by electrochemical methods. The presence of phosphate buffer and physiological saline (NaCl) buffer allows for the formation of aluminum hyrdroxide and zinc phosphite composite films on the surface of the Al/Au/ZnO anode that prevent further corrosion of the anode. The highly protective films formed on the Al/Au/ZnO anode during energy harvesting in a physiological saline environment resulted in 98.5% corrosion protective efficiency, thereby demonstrating that the formation of aluminum hydroxide and zinc phosphite composite films are effective in the prevention of anode corrosion during energy harvesting. A cell assembly consisting of the Al/Au/ZnO anode and platinum cathode resulted in an open circuit voltage of 1.03 V. A maximum power density of 955.3 μW/ cm2 in physiological saline buffer at a cell voltage and current density of 345 mV and 2.89 mA/ cm2, respectively. PMID:26580661

Corrosion Protection of Al/Au/ZnO Anode for Hybrid Cell Application.

PubMed

Slaughter, Gymama; Stevens, Brian

2015-11-16

Effective protection of power sources from corrosion is critical in the development of abiotic fuel cells, biofuel cells, hybrid cells and biobateries for implantable bioelectronics. Corrosion of these bioelectronic devices result in device inability to generate bioelectricity. In this paper Al/Au/ZnO was considered as a possible anodic substrate for the development of a hybrid cell. The protective abilities of corrosive resistant aluminum hydroxide and zinc phosphite composite films formed on the surface of Al/Au/ZnO anode in various electrolyte environments were examined by electrochemical methods. The presence of phosphate buffer and physiological saline (NaCl) buffer allows for the formation of aluminum hyrdroxide and zinc phosphite composite films on the surface of the Al/Au/ZnO anode that prevent further corrosion of the anode. The highly protective films formed on the Al/Au/ZnO anode during energy harvesting in a physiological saline environment resulted in 98.5% corrosion protective efficiency, thereby demonstrating that the formation of aluminum hydroxide and zinc phosphite composite films are effective in the prevention of anode corrosion during energy harvesting. A cell assembly consisting of the Al/Au/ZnO anode and platinum cathode resulted in an open circuit voltage of 1.03 V. A maximum power density of 955.3 mW/ cm² in physiological saline buffer at a cell voltage and current density of 345 mV and 2.89 mA/ cm², respectively.

Copper Antimonide Nanowire Array Lithium Ion Anodes Stabilized by Electrolyte Additives.

PubMed

Jackson, Everett D; Prieto, Amy L

2016-11-09

Nanowires of electrochemically active electrode materials for lithium ion batteries represent a unique system that allows for intensive investigations of surface phenomena. In particular, highly ordered nanowire arrays produced by electrodeposition into anodic aluminum oxide templates can lead to new insights into a material's electrochemical performance by providing a high-surface-area electrode with negligible volume expansion induced pulverization. Here we show that for the Li-Cu x Sb ternary system, stabilizing the surface chemistry is the most critical factor for promoting long electrode life. The resulting solid electrolyte interphase is analyzed using a mix of electron microscopy, X-ray photoelectron spectroscopy, and lithium ion battery half-cell testing to provide a better understanding of the importance of electrolyte composition on this multicomponent alloy anode material.

Photoluminescence emission of nanoporous anodic aluminum oxide films prepared in phosphoric acid

PubMed Central

2012-01-01

The photoluminescence emission of nanoporous anodic aluminum oxide films formed in phosphoric acid is studied in order to explore their defect-based subband electronic structure. Different excitation wavelengths are used to identify most of the details of the subband states. The films are produced under different anodizing conditions to optimize their emission in the visible range. Scanning electron microscopy investigations confirm pore formation in the produced layers. Gaussian analysis of the emission data indicates that subband states change with anodizing parameters, and various point defects can be formed both in the bulk and on the surface of these nanoporous layers during anodizing. PMID:23272786