Process for fabricating ZnO-based varistors

DOEpatents

Lauf, R.J.

The invention is a process for producing ZnO-based varistors incorporating a metal oxide dopant. In one form, the invention comprises providing a varistor powder mix of colloidal particles of ZnO and metal-oxide dopants including Bi/sub 2/O/sub 3/. The mix is hot-pressed to form a compact at temperatures below 850/sup 0/C and under conditions effecting reduction of the ZnO to sub-stoichiometric oxide. This promotes densification while restricting liquid formation and grain growth. The compact then is heated under conditions restoring the zinc oxide to stoichiometric composition, thus improving the varistor properties of the compact. The process produces fine-grain varistors characterized by a high actual breakdown voltage and a high average breakdown voltage per individual grain boundary.

Process for fabricating ZnO-based varistors

DOEpatents

Lauf, Robert J.

1985-01-01

The invention is a process for producing ZnO-based varistors incorporating a metal oxide dopant. In one form, the invention comprises providing a varistor powder mix of colloidal particles of ZnO and metal-oxide dopants including Bi.sub.2 O.sub.3. The mix is hot-pressed to form a compact at temperatures below 850.degree. C. and under conditions effecting reduction of the ZnO to sub-stoichiometric oxide. This promotes densification while restricting liquid formation and grain growth. The compact then is heated under conditions restoring the zinc oxide to stoichiometric composition, thus improving the varistor properties of the compact. The process produces fine-grain varistors characterized by a high actual breakdown voltage and a high average breakdown voltage per individual grain boundary.

High-Temperature Oxidation Behavior of Two Nickel-Based Superalloys Produced by Metal Injection Molding for Aero Engine Applications

NASA Astrophysics Data System (ADS)

Albert, Benedikt; Völkl, Rainer; Glatzel, Uwe

2014-09-01

For different high-temperature applications like aero engines or turbochargers, metal injection molding (MIM) of superalloys is an interesting processing alternative. For operation at high temperatures, oxidation behavior of superalloys produced by MIM needs to match the standard of cast or forged material. The oxidation behavior of nickel-based superalloys Inconel 713 and MAR-M247 in the temperature interval from 1073 K to 1373 K (800 °C to 1100 °C) is investigated and compared to cast material. Weight gain is measured discontinuously at different oxidation temperatures and times. Analysis of oxidized samples is done via SEM and EDX-measurements. MIM samples exhibit homogeneous oxide layers with a thickness up to 4 µm. After processing by MIM, Inconel 713 exhibits lower weight gain and thinner oxide layers than MAR-M247.

Solution-Processed Metal Oxides as Efficient Carrier Transport Layers for Organic Photovoltaics.

PubMed

Choy, Wallace C H; Zhang, Di

2016-01-27

Carrier (electron and hole) transport layers (CTLs) are essential components for boosting the performance of various organic optoelectronic devices such as organic solar cells and organic light-emitting diodes. Considering the drawbacks of conventional CTLs (easily oxidized/unstable, demanding/costly fabrication, etc.), transition metal oxides with good carrier transport/extraction and superior stability have drawn extensive research interest as CTLs for next-generation devices. In recent years, many research efforts have been made toward the development of solution-based metal oxide CTLs with the focus on low- or even room-temperature processes, which can potentially be compatible with the deposition processes of organic materials and can significantly contribute to the low-cost and scale-up of organic devices. Here, the recent progress of different types of solution-processed metal oxide CTLs are systematically reviewed in the context of organic photovoltaics, from synthesis approaches to device performance. Different approaches for further enhancing the performance of solution-based metal oxide CTLs are also discussed, which may push the future development of this exciting field. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The performance and decolourization kinetics of O3/H2O2 oxidation of reactive green 19 dye in wastewater

NASA Astrophysics Data System (ADS)

Sabri, S. N.; Abidin, C. Z. A.; Fahmi; Kow, S. H.; Razali, N. A.

2018-03-01

The degradations characteristic of azo dye Reactive Green 19 (RG19) was investigated using advanced oxidation process (AOPs). It was evaluated based on colour and chemical oxygen demand (COD) removal. The effect of operational parameters such as initial dye concentration, initial dosage of hydrogen peroxide (H2O2), contact time, and pH was also being studied. The samples were treated by ozonation (O3) and peroxone O3/H2O2 process. Advanced oxidation processes (AOPs) involve two stages of oxidation; firstly is the formation of strong oxidant and secondly the reaction of organic contaminants in water. In addition, the term advanced oxidation is referring to the processes in which oxidation of organic contaminants occurs primarily through reactions with hydroxyl radicals. There are several analyses that use to determine the efficiency of the treatment process, which are UV-Vis absorption spectra, COD, Fourier Transform Infrared (FT-IR), and pH. The results demonstrated that the ozone oxidation was efficient in decolourization and good in mineralization, based on the reduction of colour and COD. Additionally, results indicate that H2O2 is able to perform better than ozonation in order to decolourize the dye wastewater with 0.5 mL H2O2/L dye dosage of H2O2 at different initial concentration, initial pH, with contact time.

Titanium surface modification by microarc oxidation in electrolyte based on wollastonite and hydroxyapatite

NASA Astrophysics Data System (ADS)

Sharkeev, Yu. P.; Sedelnikova, M. B.; Komarova, E. G.; Khlusov, I. A.

2015-11-01

An investigation of titanium surface modification by microarc oxidation in the electrolyte based on wollastonite and hydroxyapatite was presented. The dependences of the coating properties on the microarc oxidation parameters were found. A variation of the process parameters allowed producing wollastonite-calcium phosphate coatings with aplate-like structure, thickness 25-30 µm, roughness 2.5-5.0 µm, and adhesion strength 57 MPa. The optimum microarc oxidation parameters such as the electrical voltage of 150 V, process duration of 5-10 min, and pulse duration of 100-300 µs were revealed. The wollastonite addition to the electrolyte based on the aqueous solution of phosphoric acid and hydroxyapatite allowed us to form wollastonite-calcium phosphate coatings on the titanium surface by the microarc oxidation method with enhanced strength properties and an increased ability to osseointegration.

Sequential application of Fenton and ozone-based oxidation process for the abatement of Ni-EDTA containing nickel plating effluents.

PubMed

Zhao, Zilong; Liu, Zekun; Wang, Hongjie; Dong, Wenyi; Wang, Wei

2018-07-01

Treatment of Ni-EDTA in industrial nickel plating effluents was investigated by integrated application of Fenton and ozone-based oxidation processes. Determination of integrated sequence found that Fenton oxidation presented higher apparent kinetic rate constant of Ni-EDTA oxidation and capacity for contamination load than ozone-based oxidation process, the latter, however, was favorable to guarantee the further mineralization of organic substances, especially at a low concentration. Serial-connection mode of two oxidation processes was appraised, Fenton effluent after treated by hydroxide precipitation and filtration negatively affected the overall performance of the sequential system, as evidenced by the removal efficiencies of Ni 2+ and TOC dropping from 99.8% to 98.7%, and from 74.8% to 66.6%, respectively. As a comparison, O 3 /Fe 2+ oxidation process was proved to be more effective than other processes (e.g. O 3 -Fe 2+ , O 3 /H 2 O 2 /Fe 2+ , O 3 /H 2 O 2 -Fe 2+ ), and the final effluent Ni 2+ concentration could satisfied the discharge standard (<0.1 mg L -1 , China) under the optimal conditions (H 2 O 2 dosage of 1.0 mL L -1 , Fe 2+ : H 2 O 2 mole ratio of 1.46, and reaction time of 10 min for Fenton reaction, initial influent pH of 3.0, O 3 dosage of 252 mg L -1 , Fe 2+ of 150 mg L -1 , and reaction time of 30 min for O 3 /Fe 2+ oxidation). Furthermore, pilot-scale test was carried out to study the practical treatability towards the real nickel plating effluent, revealing the effective removal of some other co-existence contaminations. And Fenton reaction has contributed most, with the percentage ranging from 72.41% to 93.76%. The economic cost advantage made it a promising alternative to the continuous Fenton oxidation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Architecting Graphene Oxide Rolled-Up Micromotors: A Simple Paper-Based Manufacturing Technology.

PubMed

Baptista-Pires, Luis; Orozco, Jahir; Guardia, Pablo; Merkoçi, Arben

2018-01-01

A graphene oxide rolled-up tube production process is reported using wax-printed membranes for the fabrication of on-demand engineered micromotors at different levels of oxidation, thickness, and lateral dimensions. The resultant graphene oxide rolled-up tubes can show magnetic and catalytic movement within the addition of magnetic nanoparticles or sputtered platinum in the surface of graphene-oxide-modified wax-printed membranes prior to the scrolling process. As a proof of concept, the as-prepared catalytic graphene oxide rolled-up micromotors are successfully exploited for oil removal from water. This micromotor production technology relies on an easy, operator-friendly, fast, and cost-efficient wax-printed paper-based method and may offer a myriad of hybrid devices and applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process for preparing zinc oxide-based sorbents

DOEpatents

Gangwal, Santosh Kumar [Cary, NC; Turk, Brian Scott [Durham, NC; Gupta, Raghubir Prasad [Durham, NC

2011-06-07

The disclosure relates to zinc oxide-based sorbents, and processes for preparing and using them. The sorbents are preferably used to remove one or more reduced sulfur species from gas streams. The sorbents comprise an active zinc component, optionally in combination with one or more promoter components and/or one or more substantially inert components. The active zinc component is a two phase material, consisting essentially of a zinc oxide (ZnO) phase and a zinc aluminate (ZnAl.sub.2O.sub.4) phase. Each of the two phases is characterized by a relatively small crystallite size of typically less than about 500 Angstroms. Preferably the sorbents are prepared by converting a precursor mixture, comprising a precipitated zinc oxide precursor and a precipitated aluminum oxide precursor, to the two-phase, active zinc oxide containing component.

Water depollution using metal-organic frameworks-catalyzed advanced oxidation processes: A review.

PubMed

Sharma, Virender K; Feng, Mingbao

2017-09-28

This paper presents a review on the environmental applications of metal-organic frameworks (MOFs), which are inorganic-organic hybrid highly porous crystalline materials, prepared from metal ion/clusters and multidentate organic ligands. The emphases are made on the enhancement of the performance of advanced oxidation processes (AOPs) (photocatalysis, Fenton reaction methods, and sulfate radical (SO 4 - )-mediated oxidations) using MOFs materials. MOFs act as adsorption and light absorbers, leading to superior performance of photocatalytic processes. More recent examples of photocatalytic degradation of dyes are presented. Additionally, it is commonly shown that Fe-based MOFs exhibited excellent catalytic performance on the Fenton-based and SO 4 •- -mediated oxidations of organic pollutants (e.g., dyes, phenol and pharmaceuticals). The significantly enhanced generation of reactive species such as OH and/or SO 4 - by both homogeneous and heterogeneous catalysis was proposed as the possible mechanism for water depollution. Based on the existing literature, the challenge and future perspectives in MOF-based AOPs are addressed. Copyright © 2017 Elsevier B.V. All rights reserved.

Highly Attrition Resistant Zinc Oxide-Based Sorbents for H2S Removal by Spray Drying Technique

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

Ryu, C.K.; Lee, J.B.; Ahn, D.H.

2002-09-19

Primary issues for the fluidized-bed/transport reactor process are high attrition resistant sorbent, its high sorption capacity and regenerability, durability, and cost. The overall objective of this project is the development of a superior attrition resistant zinc oxide-based sorbent for hot gas cleanup in integrated coal gasification combined cycle (IGCC). Sorbents applicable to a fluidized-bed hot gas desulfurization process must have a high attrition resistance to withstand the fast solid circulation between a desulfurizer and a regenerator, fast kinetic reactions, and high sulfur sorption capacity. The oxidative regeneration of zinc-based sorbent usually initiated at greater than 600 C with highly exothermicmore » nature causing deactivation of sorbent as well as complication of sulfidation process by side reaction. Focusing on solving the sorbent attrition and regenerability of zinc oxide-based sorbent, we have adapted multi-binder matrices and direct incorporation of regeneration promoter. The sorbent forming was done with a spray drying technique that is easily scalable to commercial quantity.« less

Valorization of GaN based metal-organic chemical vapor deposition dust a semiconductor power device industry waste through mechanochemical oxidation and leaching: A sustainable green process.

PubMed

Swain, Basudev; Mishra, Chinmayee; Lee, Chan Gi; Park, Kyung-Soo; Lee, Kun-Jae

2015-07-01

Dust generated during metal organic vapor deposition (MOCVD) process of GaN based semiconductor power device industry contains significant amounts of gallium and indium. These semiconductor power device industry wastes contain gallium as GaN and Ga0.97N0.9O0.09 is a concern for the environment which can add value through recycling. In the present study, this waste is recycled through mechanochemical oxidation and leaching. For quantitative recovery of gallium, two different mechanochemical oxidation leaching process flow sheets are proposed. In one process, first the Ga0.97N0.9O0.09 of the MOCVD dust is leached at the optimum condition. Subsequently, the leach residue is mechanochemically treated, followed by oxidative annealing and finally re-leached. In the second process, the MOCVD waste dust is mechanochemically treated, followed by oxidative annealing and finally leached. Both of these treatment processes are competitive with each other, appropriate for gallium leaching and treatment of the waste MOCVD dust. Without mechanochemical oxidation, 40.11 and 1.86 w/w% of gallium and Indium are leached using 4M HCl, 100°C and pulp density of 100 kg/m(3,) respectively. After mechanochemical oxidation, both these processes achieved 90 w/w% of gallium and 1.86 w/w% of indium leaching at their optimum condition. Copyright © 2015 Elsevier Inc. All rights reserved.

Dual-step synthesis of 3-dimensional niobium oxide - Zinc oxide

NASA Astrophysics Data System (ADS)

Rani, Rozina Abdul; Zoolfakar, Ahmad Sabirin; Rusop, M.

2018-05-01

A facile fabrication process for constructing 3-dimensional (3D) structure of Niobium oxide - Zinc oxide (Nb2O5-ZnO) consisting of branched ZnO microrods on top of nanoporous Nb2O5 films was developed based on dual-step synthesis approach. The preliminary procedure was anodization of sputtered niobium metal on Fluorine doped Tin Oxide (FTO) to produce nanoporous Nb2O5, and continued with the growth of branched microrods of ZnO by hydrothermal process. This approach offers insight knowledge on the development of novel 3D metal oxide films via dual-step synthesis process, which might potentially use for multi-functional applications ranging from sensing to photoconversion.

Effect of hydrothermal condition on the formation of multi-component oxides of Ni-based metallic glass under high temperature water near the critical point

DOE PAGES

Kim, J. S.; Kim, S. Y.; Kim, D. H.; ...

2015-07-01

The specific feature of multi-component oxides synthesized by hydrothermal process under high temperature (633 K) and highly pressurized water (18.9 MPa) near critical point. Effects of hydrothermal processing duration times 24 hours and 72 hours, respectively, on the oxide formation of the Ni 59Zr 20Ti 16Si 2Sn 3 metallic glass synthesized by powder metallurgy process were characterized by X-ray diffractometer, differential scanning calorimeter along with the particle size, morphology and crystalline phase of the oxides. The crystallization of the needle-shape NiTiO 3, ZrTiO 4 and ZrSnO 4 ternary oxide phases observed on the surface of metallic glass at below glassmore » transition temperature and the morphology of oxide phases changed to plate-shape around 2 μm in diameter by the increase processing time. This hydrothermal processing in subcritical water provides accelerated dense metal oxide crystals due to the reaction medium being at higher pressure than conventional oxidation processing.« less

Iridium Oxide pH Sensor Based on Stainless Steel Wire for pH Mapping on Metal Surface

NASA Astrophysics Data System (ADS)

Shahrestani, S.; Ismail, M. C.; Kakooei, S.; Beheshti, M.; Zabihiazadboni, M.; Zavareh, M. A.

2018-03-01

A simple technique to fabricate the iridium oxide pH sensor is useful in several applications such as medical, food processing and engineering material where it is able to detect the changes of pH. Generally, the fabrication technique can be classified into three types: electro-deposition iridium oxide film (EIrOF), activated iridium oxide film (AIROF) and sputtering iridium oxide film (SIROF). This study focuses on fabricating electrode, calibration and test. Electro-deposition iridium oxide film is a simple and effective method of fabricating this kind of sensor via cyclic voltammetry process. The iridium oxide thick film was successfully electrodeposited on the surface of stainless steel wire with 500 cycles of sweep potential. A further analysis under FESEM shows detailed image of iridium oxide film which has cauliflower-liked microstructure. EDX analysis shows the highest element present are iridium and oxygen which concluded that the process is successful. The iridium oxide based pH sensor has shown a good performance in comparison to conventional glass pH sensor when it is being calibrated in buffer solutions with 2, 4, 7 and 9 pH values. The iridium oxide pH sensor is specifically designed to measure the pH on the surface of metal plate.

Iridium material for hydrothermal oxidation environments

DOEpatents

Hong, Glenn T.; Zilberstein, Vladimir A.

1996-01-01

A process for hydrothermal oxidation of combustible materials in which, during at least a part of the oxidation, corrosive material is present and makes contact with at least a portion of the apparatus over a contact area on the apparatus. At least a portion of the contact surface area comprises iridium, iridium oxide, an iridium alloy, or a base metal overlaid with an iridium coating. Iridium has been found to be highly resistant to environments encountered in the process of hydrothermal oxidation. Such environments typically contain greater than 50 mole percent water, together with oxygen, carbon dioxide, and a wide range of acids, bases and salts. Pressures are typically about 27.5 to about 1000 bar while temperatures range as high as 800.degree. C.

Simultaneous control of Hg0, SO2, and NOx by novel oxidized calcium-based sorbents.

PubMed

Ghorishi, S Behrooz; Singer, Carl F; Jozewicz, Wojciech S; Sedman, Charles B; Srivastava, Ravi K

2002-03-01

Efforts to develop multipollutant control strategies have demonstrated that adding certain oxidants to different classes of Ca-based sorbents leads to a significant improvement in elemental Hg vapor (Hg0), SO2, and NOx removal from simulated flue gases. In the study presented here, two classes of Ca-based sorbents (hydrated limes and silicate compounds) were investigated. A number of oxidizing additives at different concentrations were used in the Ca-based sorbent production process. The Hg0, SO2, and NOx capture capacities of these oxidant-enriched sorbents were evaluated and compared to those of a commercially available activated carbon in bench-scale, fixed-bed, and fluid-bed systems. Calcium-based sorbents prepared with two oxidants, designated C and M, exhibited Hg0 sorption capacities (approximately 100 microg/g) comparable to that of the activated carbon; they showed far superior SO2 and NOx sorption capacities. Preliminary cost estimates for the process utilizing these novel sorbents indicate potential for substantial lowering of control costs, as compared with other processes currently used or considered for control of Hg0, SO2, and NOx emissions from coal-fired boilers. The implications of these findings toward development of multipollutant control technologies and planned pilot and field evaluations of more promising multipollutant sorbents are summarily discussed.

Zinc oxide-based sorbents and processes for preparing and using same

DOEpatents

Gangwal, Santosh Kumar; Turk, Brian Scott; Gupta, Raghubir Prasad

2005-10-04

Zinc oxide-based sorbents, and processes for preparing and using them are provided, wherein the sorbents are preferably used to remove one or more reduced sulfur species from gas streams. The sorbents contain an active zinc component, optionally in combination with one or more promoter components and/or one or more substantially inert components. The active zinc component is a two phase material, consisting essentially of a zinc oxide (ZnO) phase and a zinc aluminate (ZnAl.sub.2 O.sub.4) phase. Each of the two phases is characterized by a relatively small crystallite size of typically less than about 500 Angstroms. Preferably the sorbents are prepared by converting a precursor mixture, containing a precipitated zinc oxide precursor and a precipitated aluminum oxide precursor, to the two-phase, active zinc oxide containing component.

Zinc-oxide-based sorbents and processes for preparing and using same

DOEpatents

Gangwal, Santosh Kumar; Turk, Brian Scott; Gupta, Raghubir Prasael

2010-03-23

Zinc oxide-based sorbents, and processes for preparing and using them are provided. The sorbents are preferably used to remove one or more reduced sulfur species from gas streams. The sorbents comprise an active zinc component, optionally in combination with one or more promoter components and/or one or more substantially inert components. The active zinc component is a two phase material, consisting essentially of a zinc oxide (ZnO) phase and a zinc aluminate (ZnAl.sub.2O.sub.4) phase. Each of the two phases is characterized by a relatively small crystallite size of typically less than about 500 Angstroms. Preferably the sorbents are prepared by converting a precursor mixture, comprising a precipitated zinc oxide precursor and a precipitated aluminum oxide precursor, to the two-phase, active zinc oxide containing component.

Reactive nitrogen oxides in the southeast United States national parks: source identification, origin, and process budget

NASA Astrophysics Data System (ADS)

Tong, Daniel Quansong; Kang, Daiwen; Aneja, Viney P.; Ray, John D.

2005-01-01

We present in this study both measurement-based and modeling analyses for elucidation of source attribution, influence areas, and process budget of reactive nitrogen oxides at two rural southeast United States sites (Great Smoky Mountains national park (GRSM) and Mammoth Cave national park (MACA)). Availability of nitrogen oxides is considered as the limiting factor to ozone production in these areas and the relative source contribution of reactive nitrogen oxides from point or mobile sources is important in understanding why these areas have high ozone. Using two independent observation-based techniques, multiple linear regression analysis and emission inventory analysis, we demonstrate that point sources contribute a minimum of 23% of total NOy at GRSM and 27% at MACA. The influence areas for these two sites, or origins of nitrogen oxides, are investigated using trajectory-cluster analysis. The result shows that air masses from the West and Southwest sweep over GRSM most frequently, while pollutants transported from the eastern half (i.e., East, Northeast, and Southeast) have limited influence (<10% out of all air masses) on air quality at GRSM. The processes responsible for formation and removal of reactive nitrogen oxides are investigated using a comprehensive 3-D air quality model (Multiscale Air Quality SImulation Platform (MAQSIP)). The NOy contribution associated with chemical transformations to NOz and O3, based on process budget analysis, is as follows: 32% and 84% for NOz, and 26% and 80% for O3 at GRSM and MACA, respectively. The similarity between NOz and O3 process budgets suggests a close association between nitrogen oxides and effective O3 production at these rural locations.

Engineering the defect state and reducibility of ceria based nanoparticles for improved anti-oxidation performance

NASA Astrophysics Data System (ADS)

Wang, Yan-Jie; Dong, Hao; Lyu, Guang-Ming; Zhang, Huai-Yuan; Ke, Jun; Kang, Li-Qun; Teng, Jia-Li; Sun, Ling-Dong; Si, Rui; Zhang, Jing; Liu, Yan-Jun; Zhang, Ya-Wen; Huang, Yun-Hui; Yan, Chun-Hua

2015-08-01

Due to their excellent anti-oxidation performance, CeO2 nanoparticles receive wide attention in pharmacological application. Deep understanding of the anti-oxidation mechanism of CeO2 nanoparticles is extremely important to develop potent CeO2 nanomaterials for anti-oxidation application. Here, we report a detailed study on the anti-oxidation process of CeO2 nanoparticles. The valence state and coordination structure of Ce are characterized before and after the addition of H2O2 to understand the anti-oxidation mechanism of CeO2 nanoparticles. Adsorbed peroxide species are detected during the anti-oxidation process, which are responsible for the red-shifted UV-vis absorption spectra of CeO2 nanoparticles. Furthermore, the coordination number of Ce in the first coordination shell slightly increased after the addition of H2O2. On the basis of these experimental results, the reactivity of coordination sites for peroxide species is considered to play a key role in the anti-oxidation performance of CeO2 nanoparticles. Furthermore, we present a robust method to engineer the anti-oxidation performance of CeO2 nanoparticles through the modification of the defect state and reducibility by doping with Gd3+. Improved anti-oxidation performance is also observed in cell culture, where the biocompatible CeO2-based nanoparticles can protect INS-1 cells from oxidative stress induced by H2O2, suggesting the potential application of CeO2 nanoparticles in the treatment of diabetes.Due to their excellent anti-oxidation performance, CeO2 nanoparticles receive wide attention in pharmacological application. Deep understanding of the anti-oxidation mechanism of CeO2 nanoparticles is extremely important to develop potent CeO2 nanomaterials for anti-oxidation application. Here, we report a detailed study on the anti-oxidation process of CeO2 nanoparticles. The valence state and coordination structure of Ce are characterized before and after the addition of H2O2 to understand the anti-oxidation mechanism of CeO2 nanoparticles. Adsorbed peroxide species are detected during the anti-oxidation process, which are responsible for the red-shifted UV-vis absorption spectra of CeO2 nanoparticles. Furthermore, the coordination number of Ce in the first coordination shell slightly increased after the addition of H2O2. On the basis of these experimental results, the reactivity of coordination sites for peroxide species is considered to play a key role in the anti-oxidation performance of CeO2 nanoparticles. Furthermore, we present a robust method to engineer the anti-oxidation performance of CeO2 nanoparticles through the modification of the defect state and reducibility by doping with Gd3+. Improved anti-oxidation performance is also observed in cell culture, where the biocompatible CeO2-based nanoparticles can protect INS-1 cells from oxidative stress induced by H2O2, suggesting the potential application of CeO2 nanoparticles in the treatment of diabetes. Electronic supplementary information (ESI) available: Size distribution of prepared CeO2-based NPs, HRTEM of prepared CeO2-based NPs, XPS analysis of prepared CeO2-based NPs, EELS analysis of prepared CeO2-based NPs, TG curves and FT-IR spectra of CeO2-based NPs, XANES spectra of CeO2 NPs during the reaction with H2O2, Raman spectrum of CeO2 NPs during the reaction with H2O2 for the second and third cycle, ESR analysis during the reaction, the red shift of UV-vis spectra of CeO2-based NPs after the addition of H2O2, H2-TPR test of CeO2 and CeO2:20%Gd NPs, In vitro cytotoxicity of CeO2-based NPs in INS-1 cells. See DOI: 10.1039/c5nr02588e

Process for depositing an oxide epitaxially onto a silicon substrate and structures prepared with the process

DOEpatents

McKee, Rodney A.; Walker, Frederick J.

1993-01-01

A process and structure involving a silicon substrate utilizes an ultra high vacuum and molecular beam epitaxy (MBE) methods to grow an epitaxial oxide film upon a surface of the substrate. As the film is grown, the lattice of the compound formed at the silicon interface becomes stabilized, and a base layer comprised of an oxide having a sodium chloride-type lattice structure grows epitaxially upon the compound so as to cover the substrate surface. A perovskite may then be grown epitaxially upon the base layer to render a product which incorporates silicon, with its electronic capabilities, with a perovskite having technologically-significant properties of its own.

Demonstrating Advanced Oxidation Coupled with Biodegradation for Removal of Carbamazepine (WERF Report INFR6SG09)

EPA Science Inventory

Carbamazepine is an anthropogenic pharmaceutical found in wastewater effluents that is quite resistant to removal by conventional wastewater treatment processes. Hydroxyl radical-based advanced oxidation processes can transform carbamazepine into degradation products but cannot m...

Sol-gel (template) synthesis of macroporous Mo-based catalysts for hydrothermal oxidation of radionuclide-organic complexes

NASA Astrophysics Data System (ADS)

Papynov, E. K.; Palamarchuk, M. S.; Mayorov, V. Yu; Modin, E. B.; Portnyagin, A. S.; Sokol'nitskaya, T. A.; Belov, A. A.; Tananaev, I. G.; Avramenko, V. A.

2017-07-01

Molybdenum compounds are industrially demanding as heterogeneous catalysts for oxidation of various organic substances. Highly porous structure of molybdenum-containing catalysts avoids surface's colmatation and prevents blocking catalytic sites that makes these materials play a key role in processes of hydrothermal oxidation of radionuclide organic complexes. The study presents an original way of sol-gel synthesis of new macroporous molybdenum compounds using ;core-shell; colloid template (polymer latex) as poreforming agent. We have described three individual routs of template removal via thermal decomposition to obtain porous materials based on molybdenum compounds. Thermal treatment conditions (temperature, gaseous atmosphere) have been studied with respect to their influence on composition, structure and catalytic properties of synthesized molybdenum systems. The optimal way to synthesis of crystal molybdenum (VI) oxide with ordered porous structure (mean pore size 100-160 nm) has been suggested. Catalytic properties of macroporous molybdenum materials have been investigated in the process of liquid phase and hydrothermal oxidation of such organic substances thiazine and stable Co-EDTA complex. It was shown that macroporous molybdenum oxides could be applied as prospective catalysts for hydrothermal oxidation of organic radionuclide complexes during the processing of radioactive waste.

SULFATE RADICAL-BASED ADVANCED OXIDATION PROCESSES- ACS MEETING

EPA Science Inventory

This paper will present an overview of sulfate radical-based advanced oxidation technologies for the destruction of environmentally toxic chemicals in wastewater, industrial water, groundwater and sources of water supply. The paper will include fundamental aspects of the generati...

Recrystallization characteristics of oxide dispersion strengthened nickel-base alloys

NASA Technical Reports Server (NTRS)

Hotzler, R. K.; Glasgow, T. K.

1980-01-01

Electron microscopy was employed to study the process of recrystallization in two oxide dispersion strengthened (ODS) mechanically alloyed nickel-base alloys, MA 754 and MA 6000E. MA 754 contained both fine, uniformly dispersed particles and coarser oxides aligned along the working direction. Hot rolled MA 754 had a grain size of 0.5 microns and high dislocation densities. After partial primary recrystallization, the fine grains transformed to large elongated grains via secondary (or abnormal) grain growth. Extruded and rolled MA 6000E contained equiaxed grains of 0.2 micron diameter. Primary recrystallization occurring during working eliminated virtually all dislocations. Conversion from fine to coarse grains was triggered by gamma prime dissolution; this was also a process of secondary or abnormal grain growth. Comparisons were made to conventional and oxide dispersion strengthened nickel-base alloys.

Low-Temperature Oxidation-Free Selective Laser Sintering of Cu Nanoparticle Paste on a Polymer Substrate for the Flexible Touch Panel Applications.

PubMed

Kwon, Jinhyeong; Cho, Hyunmin; Eom, Hyeonjin; Lee, Habeom; Suh, Young Duk; Moon, Hyunjin; Shin, Jaeho; Hong, Sukjoon; Ko, Seung Hwan

2016-05-11

Copper nanomaterials suffer from severe oxidation problem despite the huge cost effectiveness. The effect of two different processes for conventional tube furnace heating and selective laser sintering on copper nanoparticle paste is compared in the aspects of chemical, electrical and surface morphology. The thermal behavior of the copper thin films by furnace and laser is compared by SEM, XRD, FT-IR, and XPS analysis. The selective laser sintering process ensures low annealing temperature, fast processing speed with remarkable oxidation suppression even in air environment while conventional tube furnace heating experiences moderate oxidation even in Ar environment. Moreover, the laser-sintered copper nanoparticle thin film shows good electrical property and reduced oxidation than conventional thermal heating process. Consequently, the proposed selective laser sintering process can be compatible with plastic substrate for copper based flexible electronics applications.

Electrocontact material based on silver dispersion-strengthened by nickel, titanium, and zinc oxides

NASA Astrophysics Data System (ADS)

Zeer, G. M.; Zelenkova, E. G.; Belousov, O. V.; Beletskii, V. V.; Nikolaev, S. V.; Ledyaeva, O. N.

2017-09-01

Samples of a composite electrocontact material based on silver strengthened by the dispersed phases of zinc and titanium oxides have been investigated by the electron microscopy and energy dispersive X-ray spectroscopy. A uniform distribution of the oxide phases containing 2 wt % zinc oxide in the initial charge has been revealed. The increase in the amount of zinc oxide leads to an increase of the size of the oxide phases. It has been shown that at the zinc oxide content of 2 wt %, the minimum wear is observed in the process of electroerosion tests; at 3 wt %, an overheating and welding of the contacts are observed.

Comparison of Iron and Tungsten Based Oxygen Carriers for Hydrogen Production Using Chemical Looping Reforming

NASA Astrophysics Data System (ADS)

Khan, M. N.; Shamim, T.

2017-08-01

Hydrogen production by using a three reactor chemical looping reforming (TRCLR) technology is an innovative and attractive process. Fossil fuels such as methane are the feedstocks used. This process is similar to a conventional steam-methane reforming but occurs in three steps utilizing an oxygen carrier. As the oxygen carrier plays an important role, its selection should be done carefully. In this study, two oxygen carrier materials of base metal iron (Fe) and tungsten (W) are analysed using a thermodynamic model of a three reactor chemical looping reforming plant in Aspen plus. The results indicate that iron oxide has moderate oxygen carrying capacity and is cheaper since it is abundantly available. In terms of hydrogen production efficiency, tungsten oxide gives 4% better efficiency than iron oxide. While in terms of electrical power efficiency, iron oxide gives 4.6% better results than tungsten oxide. Overall, a TRCLR system with iron oxide is 2.6% more efficient and is cost effective than the TRCLR system with tungsten oxide.

Mechanical Properties of Oxide Films on Electrolytic In-process Dressing (ELID) Copper-based Grinding Wheel

NASA Astrophysics Data System (ADS)

Kuai, J. C.; Wang, J. W.; Jiang, C. R.; Zhang, H. L.; Yang, Z. B.

2018-05-01

The mechanical properties of oxide films on copper based grinding wheel were studied by nanoindentation technique. The analysis of load displacement shows that the creep phenomenon occurs during the loading stage. Results show that the oxide film and the matrix have different characteristics, and the rigidity of the copper based grinding wheel is 0.6-1.3mN/nm, which is weaker than that of the matrix; the hardness of the oxide film is 2000-2300MPa, which is higher than the matrix; and the elastic modulus of the oxide film is 100-120GPa, also higher than the matrix.

The Interface Structure of High-Temperature Oxidation-Resistant Aluminum-Based Coatings on Titanium Billet Surface

NASA Astrophysics Data System (ADS)

Xu, Zhefeng; Rong, Ju; Yu, Xiaohua; Kun, Meng; Zhan, Zhaolin; Wang, Xiao; Zhang, Yannan

2017-10-01

A new type of high-temperature oxidation-resistant aluminum-based coating, on a titanium billet surface, was fabricated by the cold spray method, at a high temperature of 1050°C, for 8 h, under atmospheric pressure. The microstructure of the exposed surface was analyzed via optical microscopy, the microstructure of the coating and elemental diffusion was analyzed via field emission scanning electron microscopy, and the interfacial phases were identified via x-ray diffraction. The Ti-Al binary phase diagram and Gibbs free energy of the stable phase were calculated by Thermo-calc. The results revealed that good oxidation resistant 50-μm-thick coatings were successfully obtained after 8 h at 1050°C. Two layers were obtained after the coating process: an Al2O3 oxidation layer and a TiAl3 transition layer on the Ti-based substrate. The large and brittle Al2O3 grains on the surface, which can be easily spalled off from the surface after thermal processing, protected the substrate against oxidation during processing. In addition, the thermodynamic calculation results were in good agreement with the experimental data.

Outcompeting nitrite-oxidizing bacteria in single-stage nitrogen removal in sewage treatment plants: a model-based study.

PubMed

Pérez, Julio; Lotti, Tommaso; Kleerebezem, Robbert; Picioreanu, Cristian; van Loosdrecht, Mark C M

2014-12-01

This model-based study investigated the mechanisms and operational window for efficient repression of nitrite oxidizing bacteria (NOB) in an autotrophic nitrogen removal process. The operation of a continuous single-stage granular sludge process was simulated for nitrogen removal from pretreated sewage at 10 °C. The effects of the residual ammonium concentration were explicitly analyzed with the model. Competition for oxygen between ammonia-oxidizing bacteria (AOB) and NOB was found to be essential for NOB repression even when the suppression of nitrite oxidation is assisted by nitrite reduction by anammox (AMX). The nitrite half-saturation coefficient of NOB and AMX proved non-sensitive for the model output. The maximum specific growth rate of AMX bacteria proved a sensitive process parameter, because higher rates would provide a competitive advantage for AMX. Copyright © 2014 Elsevier Ltd. All rights reserved.

Stabilized tin-oxide-based oxidation/reduction catalysts

NASA Technical Reports Server (NTRS)

Watkins, Anthony Neal (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Jordan, Jeffrey D. (Inventor); Schryer, Jacqueline L. (Inventor)

2008-01-01

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Graphene-based materials supported advanced oxidation processes for water and wastewater treatment: a review.

PubMed

Nidheesh, Puthiya Veetil

2017-12-01

Advanced oxidation processes (AOPs) received much attention in the field of water and wastewater treatment due to its ability to mineralize persistent organic pollutants from water medium. The addition of graphene-based materials increased the efficiency of all AOPs significantly. The present review analyzes the performance of graphene-based materials that supported AOPs in detail. Recent developments in this field are highlighted. A special focus has been awarded for the performance enhancement mechanism of AOPs in the presence of graphene-based materials.

Catalytic processes for space station waste conversion

NASA Technical Reports Server (NTRS)

Schoonover, M. W.; Madsen, R. A.

1986-01-01

Catalytic techniques for processing waste products onboard space vehicles were evaluated. The goal of the study was the conversion of waste to carbon, wash water, oxygen and nitrogen. However, the ultimate goal is conversion to plant nutrients and other materials useful in closure of an ecological life support system for extended planetary missions. The resulting process studied involves hydrolysis at 250 C and 600 psia to break down and compact cellulose material, distillation at 100 C to remove water, coking at 450 C and atmospheric pressure, and catalytic oxidation at 450 to 600 C and atmospheric pressure. Tests were conducted with a model waste to characterize the hydrolysis and coking processes. An oxidizer reactor was sized based on automotive catalytic conversion experience. Products obtained from the hydrolysis and coking steps included a solid residue, gases, water condensate streams, and a volatile coker oil. Based on the data obtained, sufficient component sizing was performed to make a preliminary comparison of the catalytic technique with oxidation for processing waste for a six-man spacecraft. Wet oxidation seems to be the preferred technique from the standpoint of both component simplicity and power consumption.

Oxidation of free-standing and supported borophene

NASA Astrophysics Data System (ADS)

Alvarez-Quiceno, J. C.; Miwa, R. H.; Dalpian, G. M.; Fazzio, A.

2017-06-01

Crystalline 2D boron sheets, known as borophene, are the most recently-discovered type of 2D materials, and very little is known about them. Different configurations of borophene have been reported stable when grown on Ag(1 1 1) surface under well controlled conditions. One of this configurations is partially oxidized while the other one remains quite inert to oxidation when exposed to ambient conditions. In this work, the oxidation process of the free-standing and Ag(1 1 1)-supported borophene is modeled using first-principles calculations based on density functional theory (DFT). On the free-standing case, the oxygen molecule may go through a triplet to singlet transition, followed by a barrierless oxidation process. This transition is not observed upon the presence of the Ag(1 1 1) surface, what accelerates the oxidation process. We also propose that the different structures of borophene reported in the literature can be understood by this oxidation process. Oxidation of the buckled structure could induce the planar structure with an ordered distribution of vacancies.

Equilibrating metal-oxide cluster ensembles for oxidation reactions using oxygen in water

Treesearch

Ira A. Weinstock; Elena M. G. Barbuzzi; Michael W. Wemple; Jennifer J. Cowan; Richard S. Reiner; Dan M. Sonnen; Robert A. Heintz; James S. Bond; Craig L. Hill

2001-01-01

Although many enzymes can readily and selectively use oxygen in water--the most familiar and attractive of all oxidants and solvents, respectively–-the design of synthetic catalysts for selective water-based oxidation processes utilizing molecular oxygen remains a daunting task. Particularly problematic is the fact that oxidation of substrates by O2 involves radical...

Carbon-based composite electrocatalysts for low temperature fuel cells

DOEpatents

Popov, Branko N [Columbia, SC; Lee, Jog-Won [Columbia, SC; Subramanian, Nalini P [Kennesaw, GA; Kumaraguru, Swaminatha P [Honeoye Falls, NY; Colon-Mercado, Hector R [Columbia, SC; Nallathambi, Vijayadurga [T-Nagar, IN; Li, Xuguang [Columbia, SC; Wu, Gang [West Columbia, SC

2009-12-08

A process for synthesis of a catalyst is provided. The process includes providing a carbon precursor material, oxidizing the carbon precursor material whereby an oxygen functional group is introduced into the carbon precursor material, and adding a nitrogen functional group into the oxidized carbon precursor material.

Hafnium transistor process design for neural interfacing.

PubMed

Parent, David W; Basham, Eric J

2009-01-01

A design methodology is presented that uses 1-D process simulations of Metal Insulator Semiconductor (MIS) structures to design the threshold voltage of hafnium oxide based transistors used for neural recording. The methodology is comprised of 1-D analytical equations for threshold voltage specification, and doping profiles, and 1-D MIS Technical Computer Aided Design (TCAD) to design a process to implement a specific threshold voltage, which minimized simulation time. The process was then verified with a 2-D process/electrical TCAD simulation. Hafnium oxide films (HfO) were grown and characterized for dielectric constant and fixed oxide charge for various annealing temperatures, two important design variables in threshold voltage design.

Investigation of Iron Oxide Morphology in a Cyclic Redox Water Splitting Process for Hydrogen Generation

PubMed Central

Bobek, Michael M.; Stehle, Richard C.; Hahn, David W.

2012-01-01

A solar fuels generation research program is focused on hydrogen production by means of reactive metal water splitting in a cyclic iron-based redox process. Iron-based oxides are explored as an intermediary reactive material to dissociate water molecules at significantly reduced thermal energies. With a goal of studying the resulting oxide chemistry and morphology, chemical assistance via CO is used to complete the redox cycle. In order to exploit the unique characteristics of highly reactive materials at the solar reactor scale, a monolithic laboratory scale reactor has been designed to explore the redox cycle at temperatures ranging from 675 to 875 K. Using high resolution scanning electron microscope (SEM) and electron dispersive X-ray spectroscopy (EDS), the oxide morphology and the oxide state are quantified, including spatial distributions. These images show the change of the oxide layers directly after oxidation and after reduction. The findings show a significant non-stoichiometric O/Fe gradient in the atomic ratio following oxidation, which is consistent with a previous kinetics model, and a relatively constant, non-stoichiometric O/Fe atomic ratio following reduction.

A physiologically based kinetic model for bacterial sulfide oxidation.

PubMed

Klok, Johannes B M; de Graaff, Marco; van den Bosch, Pim L F; Boelee, Nadine C; Keesman, Karel J; Janssen, Albert J H

2013-02-01

In the biotechnological process for hydrogen sulfide removal from gas streams, a variety of oxidation products can be formed. Under natron-alkaline conditions, sulfide is oxidized by haloalkaliphilic sulfide oxidizing bacteria via flavocytochrome c oxidoreductase. From previous studies, it was concluded that the oxidation-reduction state of cytochrome c is a direct measure for the bacterial end-product formation. Given this physiological feature, incorporation of the oxidation state of cytochrome c in a mathematical model for the bacterial oxidation kinetics will yield a physiologically based model structure. This paper presents a physiologically based model, describing the dynamic formation of the various end-products in the biodesulfurization process. It consists of three elements: 1) Michaelis-Menten kinetics combined with 2) a cytochrome c driven mechanism describing 3) the rate determining enzymes of the respiratory system of haloalkaliphilic sulfide oxidizing bacteria. The proposed model is successfully validated against independent data obtained from biological respiration tests and bench scale gas-lift reactor experiments. The results demonstrate that the model is a powerful tool to describe product formation for haloalkaliphilic biomass under dynamic conditions. The model predicts a maximum S⁰ formation of about 98 mol%. A future challenge is the optimization of this bioprocess by improving the dissolved oxygen control strategy and reactor design. Copyright © 2012 Elsevier Ltd. All rights reserved.

Synthesis of Cyano-Containing Phenanthridine Derivatives via Catalyst-, Base-, and Oxidant-Free Direct Cyanoalkylarylation of Isocyanides.

PubMed

Song, Weihong; Yan, Peipei; Shen, Dan; Chen, Zhangtao; Zeng, Xiaofei; Zhong, Guofu

2017-04-21

An efficient catalyst-, base-, and oxidant-free direct cyanoalkylarylation of isocyanides with AIBN has been developed under mild conditions. This strategy provides an elusive and rapid access to a wide range of cyano-containing phenanthridine derivatives in good yields via a one-pot alkylation/cyclization radical-cascade process. The mild reaction conditions together with no need of any catalyst, base, or oxidant make this protocol environmentally benign and practical.

Hydrogen generator, via catalytic partial oxidation of methane for fuel cells

NASA Astrophysics Data System (ADS)

Recupero, Vincenzo; Pino, Lidia; Di Leonardo, Raffaele; Lagana', Massimo; Maggio, Gaetano

It is well known that the most acknowledged process for generation of hydrogen for fuel cells is based upon the steam reforming of methane or natural gas. A valid alternative could be a process based on partial oxidation of methane, since the process is mildly exothermic and therefore not energy intensive. Consequently, great interest is expected from conversion of methane into syngas, if an autothermal, low energy intensive, compact and reliable process could be developed. This paper covers the activities, performed by the CNR Institute of Transformation and Storage of Energy (CNR-TAE), on theoretical and experimental studies for a compact hydrogen generator, via catalytic selective partial oxidation of methane, integrated with second generation fuel cells (EC-JOU2 contract). In particular, the project focuses the attention on methane partial oxidation via heterogeneous selective catalysts, in order to: demonstrate the basic catalytic selective partial oxidation of methane (CSPOM) technology in a subscale prototype, equivalent to a nominal output of 5 kWe; develop the CSPOM technology for its application in electric energy production by means of fuel cells; assess, by a balance of plant analysis, and a techno-economic evaluation, the potential benefits of the CSPOM for different categories of fuel cells.

Application of advanced oxidation processes for cleaning of industrial water generated in wet dedusting of shaft furnace gases.

PubMed

Czaplicka, Marianna; Kurowski, Ryszard; Jaworek, Katarzyna; Bratek, Łukasz

2013-01-01

The paper presents results of studies into advanced oxidation processes in 03 and 03/UV systems. An advanced oxidation process (AOP) was conducted to reduce the load of impurities in circulating waters from wet de-dusting of shaft furnace gases. Besides inorganic impurities, i.e. mainly arsenic compounds (16 g As L(-1) on average), lead, zinc, chlorides and sulphates, the waters also contain some organic material. The organic material is composed of a complex mixture that contains, amongst others, aliphatic compounds, phenol and its derivatives, pyridine bases, including pyridine, and its derivatives. The test results show degradation of organic and inorganic compounds during ozonation and photo-oxidation processes. Analysis of the solutions from the processes demonstrated that the complex organic material in the industrial water was oxidized in ozonation and in photo-oxidation, which resulted in formation of aldehydes and carboxylic acids. Kinetic degradation of selected pollutants is presented. Obtained results indicated that the O3/UV process is more effective in degradation of organic matter than ozonation. Depending on the process type, precipitation of the solid phase was observed. The efficiency of solid-phase formation was higher in photo-oxidation with ozone. It was found that the precipitated solid phase is composed mainly of arsenic, iron and oxygen.

STEP wastewater treatment: a solar thermal electrochemical process for pollutant oxidation.

PubMed

Wang, Baohui; Wu, Hongjun; Zhang, Guoxue; Licht, Stuart

2012-10-01

A solar thermal electrochemical production (STEP) pathway was established to utilize solar energy to drive useful chemical processes. In this paper, we use experimental chemistry for efficient STEP wastewater treatment, and suggest a theory based on the decreasing stability of organic pollutants (hydrocarbon oxidation potentials) with increasing temperature. Exemplified by the solar thermal electrochemical oxidation of phenol, the fundamental model and experimental system components of this process outline a general method for the oxidation of environmentally stable organic pollutants into carbon dioxide, which is easily removed. Using thermodynamic calculations we show a sharply decreasing phenol oxidation potential with increasing temperature. The experimental results demonstrate that this increased temperature can be supplied by solar thermal heating. In combination this drives electrochemical phenol removal with enhanced oxidation efficiency through (i) a thermodynamically driven decrease in the energy needed to fuel the process and (ii) improved kinetics to sustain high rates of phenol oxidation at low electrochemical overpotential. The STEP wastewater treatment process is synergistic in that it is performed with higher efficiency than either electrochemical or photovoltaic conversion process acting alone. STEP is a green, efficient, safe, and sustainable process for organic wastewater treatment driven solely by solar energy. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Valorization of GaN based metal-organic chemical vapor deposition dust a semiconductor power device industry waste through mechanochemical oxidation and leaching: A sustainable green process

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

Swain, Basudev, E-mail: Swain@iae.re.kr; Mishra, Chinmayee; Lee, Chan Gi

2015-07-15

Dust generated during metal organic vapor deposition (MOCVD) process of GaN based semiconductor power device industry contains significant amounts of gallium and indium. These semiconductor power device industry wastes contain gallium as GaN and Ga{sub 0.97}N{sub 0.9}O{sub 0.09} is a concern for the environment which can add value through recycling. In the present study, this waste is recycled through mechanochemical oxidation and leaching. For quantitative recovery of gallium, two different mechanochemical oxidation leaching process flow sheets are proposed. In one process, first the Ga{sub 0.97}N{sub 0.9}O{sub 0.09} of the MOCVD dust is leached at the optimum condition. Subsequently, the leachmore » residue is mechanochemically treated, followed by oxidative annealing and finally re-leached. In the second process, the MOCVD waste dust is mechanochemically treated, followed by oxidative annealing and finally leached. Both of these treatment processes are competitive with each other, appropriate for gallium leaching and treatment of the waste MOCVD dust. Without mechanochemical oxidation, 40.11 and 1.86 w/w% of gallium and Indium are leached using 4 M HCl, 100 °C and pulp density of 100 kg/m{sup 3,} respectively. After mechanochemical oxidation, both these processes achieved 90 w/w% of gallium and 1.86 w/w% of indium leaching at their optimum condition. - Highlights: • Waste MOCVD dust is treated through mechanochemical leaching. • GaN is hardly leached, and converted to NaGaO{sub 2} through ball milling and annealing. • Process for gallium recovery from waste MOCVD dust has been developed. • Thermal analysis and phase properties of GaN to Ga{sub 2}O{sub 3} and GaN to NaGaO{sub 2} is revealed. • Solid-state chemistry involved in this process is reported.« less

Estimating global nitrous oxide emissions by lichens and bryophytes with a process-based productivity model

NASA Astrophysics Data System (ADS)

Porada, Philipp; Pöschl, Ulrich; Kleidon, Axel; Beer, Christian; Weber, Bettina

2017-03-01

Nitrous oxide is a strong greenhouse gas and atmospheric ozone-depleting agent which is largely emitted by soils. Recently, lichens and bryophytes have also been shown to release significant amounts of nitrous oxide. This finding relies on ecosystem-scale estimates of net primary productivity of lichens and bryophytes, which are converted to nitrous oxide emissions by empirical relationships between productivity and respiration, as well as between respiration and nitrous oxide release. Here we obtain an alternative estimate of nitrous oxide emissions which is based on a global process-based non-vascular vegetation model of lichens and bryophytes. The model quantifies photosynthesis and respiration of lichens and bryophytes directly as a function of environmental conditions, such as light and temperature. Nitrous oxide emissions are then derived from simulated respiration assuming a fixed relationship between the two fluxes. This approach yields a global estimate of 0.27 (0.19-0.35) (Tg N2O) year-1 released by lichens and bryophytes. This is lower than previous estimates but corresponds to about 50 % of the atmospheric deposition of nitrous oxide into the oceans or 25 % of the atmospheric deposition on land. Uncertainty in our simulated estimate results from large variation in emission rates due to both physiological differences between species and spatial heterogeneity of climatic conditions. To constrain our predictions, combined online gas exchange measurements of respiration and nitrous oxide emissions may be helpful.

Pt(ii) coordination complexes as visible light photocatalysts for the oxidation of sulfides using batch and flow processes.

PubMed

Casado-Sánchez, Antonio; Gómez-Ballesteros, Rocío; Tato, Francisco; Soriano, Francisco J; Pascual-Coca, Gustavo; Cabrera, Silvia; Alemán, José

2016-07-12

A new catalytic system for the photooxidation of sulfides based on Pt(ii) complexes is presented. The catalyst is capable of oxidizing a large number of sulfides containing aryl, alkyl, allyl, benzyl, as well as more complex structures such as heterocycles and methionine amino acid, with complete chemoselectivity. In addition, the first sulfur oxidation in a continuous flow process has been developed.

Methodology for the effective stabilization of tin-oxide-based oxidation/reduction catalysts

NASA Technical Reports Server (NTRS)

Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony N. (Inventor); Summers, Jerry C. (Inventor); Davis, Patricia P. (Inventor); Oglesby, Donald M. (Inventor); Schryer, Jacqueline L. (Inventor); Gulati, Suresh T. (Inventor)

2011-01-01

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Identifying and Quantifying the Intermediate Processes during Nitrate-Dependent Iron(II) Oxidation.

PubMed

Jamieson, James; Prommer, Henning; Kaksonen, Anna H; Sun, Jing; Siade, Adam J; Yusov, Anna; Bostick, Benjamin

2018-05-15

Microbially driven nitrate-dependent iron (Fe) oxidation (NDFO) in subsurface environments has been intensively studied. However, the extent to which Fe(II) oxidation is biologically catalyzed remains unclear because no neutrophilic iron-oxidizing and nitrate reducing autotroph has been isolated to confirm the existence of an enzymatic pathway. While mixotrophic NDFO bacteria have been isolated, understanding the process is complicated by simultaneous abiotic oxidation due to nitrite produced during denitrification. In this study, the relative contributions of biotic and abiotic processes during NDFO were quantified through the compilation and model-based interpretation of previously published experimental data. The kinetics of chemical denitrification by Fe(II) (chemodenitrification) were assessed, and compelling evidence was found for the importance of organic ligands, specifically exopolymeric substances secreted by bacteria, in enhancing abiotic oxidation of Fe(II). However, nitrite alone could not explain the observed magnitude of Fe(II) oxidation, with 60-75% of overall Fe(II) oxidation attributed to an enzymatic pathway for investigated strains: Acidovorax ( A.) strain BoFeN1, 2AN, A. ebreus strain TPSY, Paracoccus denitrificans Pd 1222, and Pseudogulbenkiania sp. strain 2002. By rigorously quantifying the intermediate processes, this study eliminated the potential for abiotic Fe(II) oxidation to be exclusively responsible for NDFO and verified the key contribution from an additional, biological Fe(II) oxidation process catalyzed by NDFO bacteria.

Container for reprocessing and permanent storage of spent nuclear fuel assemblies

DOEpatents

Forsberg, Charles W.

1992-01-01

A single canister process container for reprocessing and permanent storage of spent nuclear fuel assemblies comprising zirconium-based cladding and fuel, which process container comprises a collapsible container, having side walls that are made of a high temperature alloy and an array of collapsible support means wherein the container is capable of withstanding temperature necessary to oxidize the zirconium-based cladding and having sufficient ductility to maintain integrity when collapsed under pressure. The support means is also capable of maintaining their integrity at temperature necessary to oxide the zirconium-based cladding. The process container also has means to introduce and remove fluids to and from the container.

AOX removal from industrial wastewaters using advanced oxidation processes: assessment of a combined chemical-biological oxidation.

PubMed

Luyten, J; Sniegowski, K; Van Eyck, K; Maertens, D; Timmermans, S; Liers, Sven; Braeken, L

2013-01-01

In this paper, the abatement of adsorbable halogenated organic compounds (AOX) from an industrial wastewater containing relatively high chloride concentrations by a combined chemical and biological oxidation is assessed. For chemical oxidation, the O(3)/UV, H(2)O(2)/UV and photo-Fenton processes are evaluated on pilot scale. Biological oxidation is simulated in a 4 h respirometry experiment with periodic aeration. The results show that a selective degradation of AOX with respect to the matrix compounds (expressed as chemical oxygen demand) could be achieved. For O(3)/UV, lowering the ratio of O(3) dosage to UV intensity leads to a better selectivity for AOX. During O(3)-based experiments, the AOX removal is generally less than during the H(2)O(2)-based experiments. However, after biological oxidation, the AOX levels are comparable. For H(2)O(2)/UV, optimal operating parameters for UV and H(2)O(2) dosage are next determined in a second run with another wastewater sample.

Single Crystal Fibers of Yttria-Stabilized Cubic Zirconia with Ternary Oxide Additions

NASA Technical Reports Server (NTRS)

Ritzert, F. J.; Yun, H. M.; Miner, R. V.

1997-01-01

Single crystal fibers of yttria (Y2O3)-stabilized cubic zirconia, (ZrO2) with ternary oxide additions were grown using the laser float zone fiber processing technique. Ternary additions to the ZrO2-Y2O3 binary system were studied aimed at increasing strength while maintaining the high coefficient of thermal expansion of the binary system. Statistical methods aided in identifying the most promising ternary oxide candidate (Ta2O5, Sc2O3, and HfO2) and optimum composition. The yttria, range investigated was 14 to 24 mol % and the ternary oxide component ranged from 1 to 5 mol %. Hafnium oxide was the most promising ternary oxide component based on 816 C tensile strength results and ease of fabrication. The optimum composition for development was 81 ZrO2-14 Y203-5 HfO2 based upon the same elevated temperature strength tests. Preliminary results indicate process improvements could improve the fiber performance. We also investigated the effect of crystal orientation on strength.

Relationship between reaction rate constants of organic pollutants and their molecular descriptors during Fenton oxidation and in situ formed ferric-oxyhydroxides.

PubMed

Jia, Lijuan; Shen, Zhemin; Su, Pingru

2016-05-01

Fenton oxidation is a promising water treatment method to degrade organic pollutants. In this study, 30 different organic compounds were selected and their reaction rate constants (k) were determined for the Fenton oxidation process. Gaussian09 and Material Studio software sets were used to carry out calculations and obtain values of 10 different molecular descriptors for each studied compound. Ferric-oxyhydroxide coagulation experiments were conducted to determine the coagulation percentage. Based upon the adsorption capacity, all of the investigated organic compounds were divided into two groups (Group A and Group B). The percentage adsorption of organic compounds in Group A was less than 15% (wt./wt.) and that in the Group B was higher than 15% (wt./wt.). For Group A, removal of the compounds by oxidation was the dominant process while for Group B, removal by both oxidation and coagulation (as a synergistic process) took place. Results showed that the relationship between the rate constants (k values) and the molecular descriptors of Group A was more pronounced than for Group B compounds. For the oxidation-dominated process, EHOMO and Fukui indices (f(0)x, f(-)x, f(+)x) were the most significant factors. The influence of bond order was more significant for the synergistic process of oxidation and coagulation than for the oxidation-dominated process. The influences of all other molecular descriptors on the synergistic process were weaker than on the oxidation-dominated process. Copyright © 2015. Published by Elsevier B.V.

Ammonia-oxidizing bacteria dominate ammonia oxidation in a full-scale wastewater treatment plant revealed by DNA-based stable isotope probing.

PubMed

Pan, Kai-Ling; Gao, Jing-Feng; Li, Hong-Yu; Fan, Xiao-Yan; Li, Ding-Chang; Jiang, Hao

2018-05-01

A full-scale wastewater treatment plant (WWTP) with three separate treatment processes was selected to investigate the effects of seasonality and treatment process on the community structures of ammonia-oxidizing archaea (AOA) and bacteria (AOB). And then DNA-based stable isotope probing (DNA-SIP) was applied to explore the active ammonia oxidizers. The results of high-throughput sequencing indicated that treatment processes varied AOB communities rather than AOA communities. AOA slightly outnumbered AOB in most of the samples, whose abundance was significantly correlated with temperature. DNA-SIP results showed that the majority of AOB amoA gene was labeled by 13 C-substrate, while just a small amount of AOA amoA gene was labeled. As revealed by high-throughput sequencing of heavy DNA, Nitrosomonadaceae-like AOB, Nitrosomonas sp. NP1, Nitrosomonas oligotropha and Nitrosomonas marina were the active AOB, and Nitrososphaera viennensis dominated the active AOA. The results indicated that AOB, not AOA, dominated active ammonia oxidation in the test WWTP. Copyright © 2018 Elsevier Ltd. All rights reserved.

Antibiotics with anaerobic ammonium oxidation in urban wastewater treatment

NASA Astrophysics Data System (ADS)

Zhou, Ruipeng; Yang, Yuanming

2017-05-01

Biofilter process is based on biological oxidation process on the introduction of fast water filter design ideas generated by an integrated filtration, adsorption and biological role of aerobic wastewater treatment process various purification processes. By engineering example, we show that the process is an ideal sewage and industrial wastewater treatment process of low concentration. Anaerobic ammonia oxidation process because of its advantage of the high efficiency and low consumption, wastewater biological denitrification field has broad application prospects. The process in practical wastewater treatment at home and abroad has become a hot spot. In this paper, anammox bacteria habitats and species diversity, and anaerobic ammonium oxidation process in the form of diversity, and one and split the process operating conditions are compared, focusing on a review of the anammox process technology various types of wastewater laboratory research and engineering applications, including general water quality and pressure filtrate sludge digestion, landfill leachate, aquaculture wastewater, monosodium glutamate wastewater, wastewater, sewage, fecal sewage, waste water salinity wastewater characteristics, research progress and application of the obstacles. Finally, we summarize the anaerobic ammonium oxidation process potential problems during the processing of the actual waste water, and proposed future research focus on in-depth study of water quality anammox obstacle factor and its regulatory policy, and vigorously develop on this basis, and combined process optimization.

Charge transport in metal oxide nanocrystal-based materials

NASA Astrophysics Data System (ADS)

Runnerstrom, Evan Lars

There is probably no class of materials more varied, more widely used, or more ubiquitous than metal oxides. Depending on their composition, metal oxides can exhibit almost any number of properties. Of particular interest are the ways in which charge is transported in metal oxides: devices such as displays, touch screens, and smart windows rely on the ability of certain metal oxides to conduct electricity while maintaining visible transparency. Smart windows, fuel cells, and other electrochemical devices additionally rely on efficient transport of ionic charge in and around metal oxides. Colloidal synthesis has enabled metal oxide nanocrystals to emerge as a relatively new but highly tunable class of materials. Certain metal oxide nanocrystals, particularly highly doped metal oxides, have been enjoying rapid development in the last decade. As in myriad other materials systems, structure dictates the properties of metal oxide nanocrystals, but a full understanding of how nanocrystal synthesis, the processing of nanocrystal-based materials, and the structure of nanocrystals relate to the resulting properties of nanocrystal-based materials is still nascent. Gaining a fundamental understanding of and control over these structure-property relationships is crucial to developing a holistic understanding of metal oxide nanocrystals. The unique ability to tune metal oxide nanocrystals by changing composition through the introduction of dopants or by changing size and shape affords a way to study the interplay between structure, processing, and properties. This overall goal of this work is to chemically synthesize colloidal metal oxide nanocrystals, process them into useful materials, characterize charge transport in materials based on colloidal metal oxide nanocrystals, and develop ways to manipulate charge transport. In particular, this dissertation characterizes how the charge transport properties of metal oxide nanocrystal-based materials depend on their processing and structure. Charge transport can obviously be taken to mean the conduction of electrons, but it also refers to the motion of ions, such as lithium ions and protons. In many cases, the transport of ions is married to the motion of electrons as well, either through an external electrical circuit, or within the same material in the case of mixed ionic electronic conductors. The collective motion of electrons over short length scales, that is, within single nanocrystals, is also a subject of study as it pertains to plasmonic nanocrystals. Finally, charge transport can also be coupled to or result from the formation of defects in metal oxides. All of these modes of charge transport in metal oxides gain further complexity when considered in nanocrystalline systems, where the introduction of numerous surfaces can change the character of charge transport relative to bulk systems, providing opportunities to exploit new physical phenomena. Part I of this dissertation explores the combination of electronic and ionic transport in electrochromic devices based on nanocrystals. Colloidal chemistry and solution processing are used to fabricate nanocomposites based on electrochromic tin-doped indium oxide (ITO) nanocrystals. The nanocomposites, which are completely synthesized using solution processing, consist of ITO nanocrystals and lithium bis(trifluoromethylsulfonyl)amide (LiTFSI) salt dispersed in a lithium ion-conducting polymer matrix of either poly(ethylene oxide) (PEO) or poly(methyl methacrylate) (PMMA). ITO nanocrystals are prepared by colloidal synthetic methods and the nanocrystal surface chemistry is modified to achieve favorable nanocrystal-polymer interactions. Homogeneous solutions containing polymer, ITO nanocrystals, and lithium salt are thus prepared and deposited by spin casting. Characterization by DC electronic measurements, microscopy, and x-ray scattering techniques show that the ITO nanocrystals form a complete, connected electrode within a polymer electrolyte matrix, and that the morphology and properties of the nanocomposites can be manipulated by changing the chemical composition of the deposition solution. Careful application of AC impedance spectroscopy techniques and DC measurements are used to show that the nanocomposites exhibit mixed ionic and electronic conductivity, where electronic charge is transported through the ITO nanocrystal phase, and ionic charge is transported through the polymer matrix phase. The synthetic methods developed here and understanding of charge transport ultimately lead to the fabrication of a solid state nanocomposite electrochromic device based on nanocrystals of ITO and cerium oxide. Part II of this dissertation considers electron transport within individual metal oxide nanocrystals themselves. It primarily examines relationships between synthetic chemistry, doping mechanisms in metal oxides, and the accompanying physics of free carrier scattering within the interior of highly doped metal oxide nanocrystals, with particular mind paid to ITO nanocrystals. Additionally, synthetic methods as well as metal oxide defect chemistry influences the balance between activation and compensation of dopants, which limits the nanocrystals' free carrier concentration. Furthermore, because of ionized impurity scattering of the oscillating electrons by dopant ions, scattering must be treated in a fundamentally different way in semiconductor metal oxide materials when compared with conventional metals. (Abstract shortened by ProQuest.).

Manganese oxide-based materials as electrochemical supercapacitor electrodes.

PubMed

Wei, Weifeng; Cui, Xinwei; Chen, Weixing; Ivey, Douglas G

2011-03-01

Electrochemical supercapacitors (ECs), characteristic of high power and reasonably high energy densities, have become a versatile solution to various emerging energy applications. This critical review describes some materials science aspects on manganese oxide-based materials for these applications, primarily including the strategic design and fabrication of these electrode materials. Nanostructurization, chemical modification and incorporation with high surface area, conductive nanoarchitectures are the three major strategies in the development of high-performance manganese oxide-based electrodes for EC applications. Numerous works reviewed herein have shown enhanced electrochemical performance in the manganese oxide-based electrode materials. However, many fundamental questions remain unanswered, particularly with respect to characterization and understanding of electron transfer and atomic transport of the electrochemical interface processes within the manganese oxide-based electrodes. In order to fully exploit the potential of manganese oxide-based electrode materials, an unambiguous appreciation of these basic questions and optimization of synthesis parameters and material properties are critical for the further development of EC devices (233 references).

Solution-Processed Gallium–Tin-Based Oxide Semiconductors for Thin-Film Transistors

PubMed Central

Zhang, Xue; Lee, Hyeonju; Kim, Jungwon; Kim, Eui-Jik; Park, Jaehoon

2017-01-01

We investigated the effects of gallium (Ga) and tin (Sn) compositions on the structural and chemical properties of Ga–Sn-mixed (Ga:Sn) oxide films and the electrical properties of Ga:Sn oxide thin-film transistors (TFTs). The thermogravimetric analysis results indicate that solution-processed oxide films can be produced via thermal annealing at 500 °C. The oxygen deficiency ratio in the Ga:Sn oxide film increased from 0.18 (Ga oxide) and 0.30 (Sn oxide) to 0.36, while the X-ray diffraction peaks corresponding to Sn oxide significantly reduced. The Ga:Sn oxide film exhibited smaller grains compared to the nanocrystalline Sn oxide film, while the Ga oxide film exhibited an amorphous morphology. We found that the electrical properties of TFTs significantly improve by mixing Ga and Sn. Here, the optimum weight ratio of the constituents in the mixture of Ga and Sn precursor sols was determined to be 1.0:0.9 (Ga precursor sol:Sn precursor sol) for application in the solution-processed Ga:Sn oxide TFTs. In addition, when the Ga(1.0):Sn(0.9) oxide film was thermally annealed at 900 °C, the field-effect mobility of the TFT was notably enhanced from 0.02 to 1.03 cm2/Vs. Therefore, the mixing concentration ratio and annealing temperature are crucial for the chemical and morphological properties of solution-processed Ga:Sn oxide films and for the TFT performance. PMID:29283408

Solid oxide membrane (SOM) process for ytterbium and silicon production from their oxides

NASA Astrophysics Data System (ADS)

Jiang, Yihong

The Solid oxide membrane (SOM) electrolysis is an innovative green technology that produces technologically important metals directly from their respective oxides. A yttria-stabilized zirconia (YSZ) tube, closed at one end is employed to separate the molten salt containing dissolved metal oxides from the anode inside the YSZ tube. When the applied electric potential between the cathode in the molten salt and the anode exceeds the dissociation potential of the desired metal oxides, oxygen ions in the molten salt migrate through the YSZ membrane and are oxidized at the anode while the dissolved metal cations in the flux are reduced to the desired metal at the cathode. Compared with existing metal production processes, the SOM process has many advantages such as one unit operation, less energy consumption, lower capital costs and zero carbon emission. Successful implementation of the SOM electrolysis process would provide a way to mitigate the negative environmental impact of the metal industry. Successful demonstration of producing ytterbium (Yb) and silicon (Si) directly from their respective oxides utilizing the SOM electrolysis process is presented in this dissertation. During the SOM electrolysis process, Yb2O3 was reduced to Yb metal on an inert cathode. The melting point of the supporting electrolyte (LiF-YbF3-Yb2O3) was determined by differential thermal analysis (DTA). Static stability testing confirmed that the YSZ tube was stable with the flux at operating temperature. Yb metal deposit on the cathode was confirmed by scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS). During the SOM electrolysis process for silicon production, a fluoride based flux based on BaF2, MgF2, and YF3 was engineered to serve as the liquid electrolyte for dissolving silicon dioxide. YSZ tube was used to separate the molten salt from an anode current collector in the liquid silver. Liquid tin was chosen as cathode to dissolve the reduced silicon during SOM electrolysis. After electrolysis, upon cooling, silicon crystals precipitated out from the Si-Sn liquid alloy. The presence of high-purity silicon crystals in the liquid tin cathode was confirmed by SEM/EDS. The fluoride based flux was also optimized to improve YSZ membrane stability for long-term use.

Oxide-based thin film transistors for flexible electronics

NASA Astrophysics Data System (ADS)

He, Yongli; Wang, Xiangyu; Gao, Ya; Hou, Yahui; Wan, Qing

2018-01-01

The continuous progress in thin film materials and devices has greatly promoted the development in the field of flexible electronics. As one of the most common thin film devices, thin film transistors (TFTs) are significant building blocks for flexible platforms. Flexible oxide-based TFTs are well compatible with flexible electronic systems due to low process temperature, high carrier mobility, and good uniformity. The present article is a review of the recent progress and major trends in the field of flexible oxide-based thin film transistors. First, an introduction of flexible electronics and flexible oxide-based thin film transistors is given. Next, we introduce oxide semiconductor materials and various flexible oxide-based TFTs classified by substrate materials including polymer plastics, paper sheets, metal foils, and flexible thin glass. Afterwards, applications of flexible oxide-based TFTs including bendable sensors, memories, circuits, and displays are presented. Finally, we give conclusions and a prospect for possible development trends. Project supported in part by the National Science Foundation for Distinguished Young Scholars of China (No. 61425020), in part by the National Natural Science Foundation of China (No. 11674162).

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

Liu, Ao; Liu, Guoxia, E-mail: gxliu@qdu.edu.cn, E-mail: fukaishan@yahoo.com; Zhu, Huihui

Solution-processed p-type oxide semiconductors have recently attracted increasing interests for the applications in low-cost optoelectronic devices and low-power consumption complementary metal-oxide-semiconductor circuits. In this work, p-type nickel oxide (NiO{sub x}) thin films were prepared using low-temperature solution process and integrated as the channel layer in thin-film transistors (TFTs). The electrical properties of NiO{sub x} TFTs, together with the characteristics of NiO{sub x} thin films, were systematically investigated as a function of annealing temperature. By introducing aqueous high-k aluminum oxide (Al{sub 2}O{sub 3}) gate dielectric, the electrical performance of NiO{sub x} TFT was improved significantly compared with those based on SiO{submore » 2} dielectric. Particularly, the hole mobility was found to be 60 times enhancement, quantitatively from 0.07 to 4.4 cm{sup 2}/V s, which is mainly beneficial from the high areal capacitance of the Al{sub 2}O{sub 3} dielectric and high-quality NiO{sub x}/Al{sub 2}O{sub 3} interface. This simple solution-based method for producing p-type oxide TFTs is promising for next-generation oxide-based electronic applications.« less

High-Quality Solution-Processed Silicon Oxide Gate Dielectric Applied on Indium Oxide Based Thin-Film Transistors.

PubMed

Jaehnike, Felix; Pham, Duy Vu; Anselmann, Ralf; Bock, Claudia; Kunze, Ulrich

2015-07-01

A silicon oxide gate dielectric was synthesized by a facile sol-gel reaction and applied to solution-processed indium oxide based thin-film transistors (TFTs). The SiOx sol-gel was spin-coated on highly doped silicon substrates and converted to a dense dielectric film with a smooth surface at a maximum processing temperature of T = 350 °C. The synthesis was systematically improved, so that the solution-processed silicon oxide finally achieved comparable break downfield strength (7 MV/cm) and leakage current densities (<10 nA/cm(2) at 1 MV/cm) to thermally grown silicon dioxide (SiO2). The good quality of the dielectric layer was successfully proven in bottom-gate, bottom-contact metal oxide TFTs and compared to reference TFTs with thermally grown SiO2. Both transistor types have field-effect mobility values as high as 28 cm(2)/(Vs) with an on/off current ratio of 10(8), subthreshold swings of 0.30 and 0.37 V/dec, respectively, and a threshold voltage close to zero. The good device performance could be attributed to the smooth dielectric/semiconductor interface and low interface trap density. Thus, the sol-gel-derived SiO2 is a promising candidate for a high-quality dielectric layer on many substrates and high-performance large-area applications.

Synthesis of graphene oxide and reduced graphene oxide using volumetric method by a novel approach without NaNO2 or NaNO3

NASA Astrophysics Data System (ADS)

Gunda, Rajitha; Madireddy, Buchi Suresh; Dash, Raj Kishora

2018-02-01

In the present work, graphite was processed to graphene oxide (GO) using modified Hummer's method by volumetric titration approach, without attaining zero temperature and the addition of toxic chemicals (NaNO2/NaNO3). The complete oxidation of graphite to graphene oxide was obtained by controlled addition (volumetric titration) of KMnO4. The addition of higher KMnO4 resulted in partial oxidation and 2-3 mono-layers with less defects/disordered structure of reduced graphene oxide (RGO) sheets were achieved. Samples were analyzed by XRD, FT-IR, Raman analysis, and TEM analysis. X-ray diffraction displayed the oxidized peak of graphene oxide at 11.9° and reduced graphene oxide at 23.8°. The prolonged stability of the synthesized GO with lower mole ratios of oxidizing agent was confirmed from UV-visible spectroscopy. Based on the results, processed graphene oxide is found to be a candidate material for thermally stable capacitor application.

Ion beam synthesis of indium-oxide nanocrystals for improvement of oxide resistive random-access memories

NASA Astrophysics Data System (ADS)

Bonafos, C.; Benassayag, G.; Cours, R.; Pécassou, B.; Guenery, P. V.; Baboux, N.; Militaru, L.; Souifi, A.; Cossec, E.; Hamga, K.; Ecoffey, S.; Drouin, D.

2018-01-01

We report on the direct ion beam synthesis of a delta-layer of indium oxide nanocrystals (In2O3-NCs) in silica matrices by using ultra-low energy ion implantation. The formation of the indium oxide phase can be explained by (i) the affinity of indium with oxygen, (ii) the generation of a high excess of oxygen recoils generated by the implantation process in the region where the nanocrystals are formed and (iii) the proximity of the indium-based nanoparticles with the free surface and oxidation from the air. Taking advantage of the selective diffusivity of implanted indium in SiO2 with respect to Si3N4, In2O3-NCs have been inserted in the SiO2 switching oxide of micrometric planar oxide-based resistive random access memory (OxRAM) devices fabricated using the nanodamascene process. Preliminary electrical measurements show switch voltage from high to low resistance state. The devices with In2O3-NCs have been cycled 5 times with identical operating voltages and RESET current meanwhile no switch has been observed for non implanted devices. This first measurement of switching is very promising for the concept of In2O3-NCs based OxRAM memories.

Decomposition of 3,5-dinitrobenzamide in aqueous solution during UV/H2O2 and UV/TiO2 oxidation processes.

PubMed

Yan, Yingjie; Liao, Qi-Nan; Ji, Feng; Wang, Wei; Yuan, Shoujun; Hu, Zhen-Hu

2017-02-01

3,5-Dinitrobenzamide has been widely used as a feed additive to control coccidiosis in poultry, and part of the added 3,5-dinitrobenzamide is excreted into wastewater and surface water. The removal of 3,5-dinitrobenzamide from wastewater and surface water has not been reported in previous studies. Highly reactive hydroxyl radicals from UV/hydrogen peroxide (H 2 O 2 ) and UV/titanium dioxide (TiO 2 ) advanced oxidation processes (AOPs) can decompose organic contaminants efficiently. In this study, the decomposition of 3,5-dinitrobenzamide in aqueous solution during UV/H 2 O 2 and UV/TiO 2 oxidation processes was investigated. The decomposition of 3,5-dinitrobenzamide fits well with a fluence-based pseudo-first-order kinetics model. The decomposition in both two oxidation processes was affected by solution pH, and was inhibited under alkaline conditions. Inorganic anions such as NO 3 - , Cl - , SO 4 2- , HCO 3 - , and CO 3 2- inhibited the degradation of 3,5-dinitrobenzamide during the UV/H 2 O 2 and UV/TiO 2 oxidation processes. After complete decomposition in both oxidation processes, approximately 50% of 3,5-dinitrobenzamide was decomposed into organic intermediates, and the rest was mineralized to CO 2 , H 2 O, and other inorganic anions. Ions such as NH 4 + , NO 3 - , and NO 2 - were released into aqueous solution during the degradation. The primary decomposition products of 3,5-dinitrobenzamide were identified using time-of-flight mass spectrometry (LCMS-IT-TOF). Based on these products and ions release, a possible decomposition pathway of 3,5-dinitrobenzamide in both UV/H 2 O 2 and UV/TiO 2 processes was proposed.

An environmentally compliant cerium-based conversion coating for aluminum protection

NASA Astrophysics Data System (ADS)

Lin, Xuan

Chromate conversion coatings have been extensively used in the aircraft industry for the corrosion protection of aluminum alloys. Unfortunately, hexavalent chromium, which is a primary component in the chromating process, is a confirmed carcinogen. Because of rising remediation and disposal costs caused by increasingly strict regulations, the replacement of the traditional chromate conversion process is becoming a top priority in the metal finishing industry. This research focused on the electrodeposition of cerium-based coatings on 7075-T6 aluminum alloy in an electrolyte containing a cerium salt, an oxidizing agent and an organic solvent. The cerium-rich deposits were characterized by phase composition, oxidation state, coating thickness, surface morphology, deposition mechanism and polarization behavior. Chemical and electrochemical tests were utilized to compare the corrosion resistance between cerium-based coatings and chromate conversion coatings. To characterize and simulate the deposition process, a variety of approaches were utilized to study the oxidation states of cerium in various soluble and precipitated forms as a function of hydrogen peroxide and electrolyte pH. The pH ranges where the oxidation and reduction reactions dominate were determined. Further studies were performed to optimize the corrosion performance of cerium-based coatings and to understand the effects of electrolyte constituents and deposition parameters. The optimum levels for these variables were identified. A patent disclosure on the cerium-based coating process was made to the University of Missouri-Rolla and has now been officially filed with the U.S. Patent Office.

Transformation of Contaminant Candidate List (CCL3) compounds during ozonation and advanced oxidation processes in drinking water: Assessment of biological effects.

PubMed

Mestankova, Hana; Parker, Austa M; Bramaz, Nadine; Canonica, Silvio; Schirmer, Kristin; von Gunten, Urs; Linden, Karl G

2016-04-15

The removal of emerging contaminants during water treatment is a current issue and various technologies are being explored. These include UV- and ozone-based advanced oxidation processes (AOPs). In this study, AOPs were explored for their degradation capabilities of 25 chemical contaminants on the US Environmental Protection Agency's Contaminant Candidate List 3 (CCL3) in drinking water. Twenty-three of these were found to be amenable to hydroxyl radical-based treatment, with second-order rate constants for their reactions with hydroxyl radicals (OH) in the range of 3-8 × 10(9) M(-1) s(-1). The development of biological activity of the contaminants, focusing on mutagenicity and estrogenicity, was followed in parallel with their degradation using the Ames and YES bioassays to detect potential changes in biological effects during oxidative treatment. The majority of treatment cases resulted in a loss of biological activity upon oxidation of the parent compounds without generation of any form of estrogenicity or mutagenicity. However, an increase in mutagenic activity was detected by oxidative transformation of the following CCL3 parent compounds: nitrobenzene (OH, UV photolysis), quinoline (OH, ozone), methamidophos (OH), N-nitrosopyrolidine (OH), N-nitrosodi-n-propylamine (OH), aniline (UV photolysis), and N-nitrosodiphenylamine (UV photolysis). Only one case of formation of estrogenic activity was observed, namely, for the oxidation of quinoline by OH. Overall, this study provides fundamental and practical information on AOP-based treatment of specific compounds of concern and represents a framework for evaluating the performance of transformation-based treatment processes. Copyright © 2016 Elsevier Ltd. All rights reserved.

A FLUORESCENCE BASED ASSAY FOR DNA DAMAGE INDUCED BY STYRENE OXIDE

EPA Science Inventory

A rapid and simple assay to detect DNA damage to calf thymus DNA caused by styrene oxide (SO) is reported. This assay is based on changes observed in the melting and annealing behavior of the damaged DNA. The melting annealing process was monitored using a fluorescence indicat...

Particulate Formation from a Copper Oxide-Based Oxygen Carrier in Chemical Looping Combustion for CO2 Capture

EPA Science Inventory

Attrition behavior and particle loss of a copper oxide-based oxygen carrier from a methane chemical looping combustion (CLC) process was investigated in a fluidized bed reactor. The aerodynamic diameters of most elutriated particulates, after passing through a horizontal settling...

Process for depositing epitaxial alkaline earth oxide onto a substrate and structures prepared with the process

DOEpatents

McKee, Rodney A.; Walker, Frederick J.

1996-01-01

A process and structure involving a silicon substrate utilize molecular beam epitaxy (MBE) and/or electron beam evaporation methods and an ultra-high vacuum facility to grow a layup of epitaxial alkaline earth oxide films upon the substrate surface. By selecting metal constituents for the oxides and in the appropriate proportions so that the lattice parameter of each oxide grown closely approximates that of the substrate or base layer upon which oxide is grown, lattice strain at the film/film or film/substrate interface of adjacent films is appreciably reduced or relieved. Moreover, by selecting constituents for the oxides so that the lattice parameters of the materials of adjacent oxide films either increase or decrease in size from one parameter to another parameter, a graded layup of films can be grown (with reduced strain levels therebetween) so that the outer film has a lattice parameter which closely approximates that of, and thus accomodates the epitaxial growth of, a pervoskite chosen to be grown upon the outer film.

Spin-on metal oxide materials for N7 and beyond patterning applications

NASA Astrophysics Data System (ADS)

Mannaert, G.; Altamirano-Sanchez, E.; Hopf, T.; Sebaai, F.; Lorant, C.; Petermann, C.; Hong, S.-E.; Mullen, S.; Wolfer, E.; Mckenzie, D.; Yao, H.; Rahman, D.; Cho, J.-Y.; Padmanaban, M.; Piumi, D.

2017-04-01

There is a growing interest in new spin on metal oxide hard mask materials for advanced patterning solutions both in BEOL and FEOL processing. Understanding how these materials respond to plasma conditions may create a competitive advantage. In this study patterning development was done for two challenging FEOL applications where the traditional Si based films were replaced by EMD spin on metal oxides, which acted as highly selective hard masks. The biggest advantage of metal oxide hard masks for advanced patterning lays in the process window improvement at lower or similar cost compared to other existing solutions.

Oxidation processes in magneto-optic and related materials

NASA Technical Reports Server (NTRS)

Lee, Paul A.; Armstrong, Neal R.; Danzinger, James L.; England, Craig D.

1992-01-01

The surface oxidation processes of thin films of magneto-optic materials, such as the rare-earth transition metal alloys have been studied, starting in ultrahigh vacuum environments, using surface analysis techniques, as a way of modeling the oxidation processes which occur at the base of a defect in an overcoated material, at the instant of exposure to ambient environments. Materials examined have included FeTbCo alloys, as well as those same materials with low percentages of added elements, such a Ta, and their reactivities to both O2 and H2O compared with materials such as thin Fe films coated with ultrathin adlayers of Ti. The surface oxidation pathways for these materials is reviewed, and XPS data presented which indicates the type of oxides formed, and a critical region of Ta concentration which provides optimum protection.

Temperature of frozen storage affects the nature and consequences of protein oxidation in beef patties.

PubMed

Utrera, Mariana; Morcuende, David; Estévez, Mario

2014-03-01

The effect of three frozen storage temperatures (-8, -18 and -80 °C) on protein oxidation in beef patties was studied through the analysis of novel oxidation markers. Additionally, the connection between lipid and protein oxidation and the impact of the latter on particular quality traits (water holding capacity, color and texture) of subsequently processed beef patties (cooking/cold-stored) were investigated. Protein oxidation was measured as the loss of tryptophan fluorescence and formation of diverse lysine oxidation products (α-aminoadipic semialdehyde, α-aminoadipic acid and Schiff bases). Lipid oxidation was assessed by levels of thiobarbituric acid reactive substances and hexanal. A significant effect of storage temperature on protein oxidation was detected. Frozen storage increased the susceptibility of meat proteins to undergo further oxidation during processing. Timely interactions were found between lipid and protein oxidation. Plausible mechanisms by which oxidative damage to proteins may have an impact in particular quality traits are thoroughly discussed. © 2013.

Ceramification: A plutonium immobilization process

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

Rask, W.C.; Phillips, A.G.

1996-05-01

This paper describes a low temperature technique for stabilizing and immobilizing actinide compounds using a combination process/storage vessel of stainless steel, in which measured amounts of actinide nitrate solutions and actinide oxides (and/or residues) are systematically treated to yield a solid article. The chemical ceramic process is based on a coating technology that produces rare earth oxide coatings for defense applications involving plutonium. The final product of this application is a solid, coherent actinide oxide with process-generated encapsulation that has long-term environmental stability. Actinide compounds can be stabilized as pure materials for ease of re-use or as intimate mixtures withmore » additives such as rare earth oxides to increase their degree of proliferation resistance. Starting materials for the process can include nitrate solutions, powders, aggregates, sludges, incinerator ashes, and others. Agents such as cerium oxide or zirconium oxide may be added as powders or precursors to enhance the properties of the resulting solid product. Additives may be included to produce a final product suitable for use in nuclear fuel pellet production. The process is simple and reduces the time and expense for stabilizing plutonium compounds. It requires a very low equipment expenditure and can be readily implemented into existing gloveboxes. The process is easily conducted with less associated risk than proposed alternative technologies.« less

Container for reprocessing and permanent storage of spent nuclear fuel assemblies

DOEpatents

Forsberg, C.W.

1992-03-24

A single canister process container is described for reprocessing and permanent storage of spent nuclear fuel assemblies comprising zirconium-based cladding and fuel, which process container comprises a collapsible container, having side walls that are made of a high temperature alloy and an array of collapsible support means wherein the container is capable of withstanding temperature necessary to oxidize the zirconium-based cladding and having sufficient ductility to maintain integrity when collapsed under pressure. The support means is also capable of maintaining its integrity at a temperature necessary to oxidize the zirconium-based cladding. The process container also has means to introduce and remove fluids to and from the container. 10 figs.

Lowering the environmental impact of high-kappa/ metal gate stack surface preparation processes

NASA Astrophysics Data System (ADS)

Zamani, Davoud

ABSTRACT Hafnium based oxides and silicates are promising high-κ dielectrics to replace SiO2 as gate material for state-of-the-art semiconductor devices. However, integrating these new high-κ materials into the existing complementary metal-oxide semiconductor (CMOS) process remains a challenge. One particular area of concern is the use of large amounts of HF during wet etching of hafnium based oxides and silicates. The patterning of thin films of these materials is accomplished by wet etching in HF solutions. The use of HF allows dissolution of hafnium as an anionic fluoride complex. Etch selectivity with respect to SiO2 is achieved by appropriately diluting the solutions and using slightly elevated temperatures. From an ESH point of view, it would be beneficial to develop methods which would lower the use of HF. The first objective of this study is to find new chemistries and developments of new wet etch methods to reduce fluoride consumption during wet etching of hafnium based high-κ materials. Another related issue with major environmental impact is the usage of large amounts of rinsing water for removal of HF in post-etch cleaning step. Both of these require a better understanding of the HF interaction with the high-κ surface during the etching, cleaning, and rinsing processes. During the rinse, the cleaning chemical is removed from the wafers. Ensuring optimal resource usage and cycle time during the rinse requires a sound understanding and quantitative description of the transport effects that dominate the removal rate of the cleaning chemicals from the surfaces. Multiple processes, such as desorption and re-adsorption, diffusion, migration and convection, all factor into the removal rate of the cleaning chemical during the rinse. Any of these processes can be the removal rate limiting process, the bottleneck of the rinse. In fact, the process limiting the removal rate generally changes as the rinse progresses, offering the opportunity to save resources. The second objective of this study is to develop new rinse methods to reduce water and energy usage during rinsing and cleaning of hafnium based high-κ materials in single wafer-cleaning tools. It is necessary to have a metrology method which can study the effect of all process parameters that affect the rinsing by knowing surface concentration of contaminants in patterned hafnium based oxides and silicate wafers. This has been achieved by the introduction of a metrology method at The University of Arizona which monitors the transport of contaminant concentrations inside micro- and nano- structures. This is the only metrology which will be able to provide surface concentration of contaminants inside hafnium based oxides and silicate micro-structures while the rinsing process is taking place. The goal of this research is to study the effect of various process parameters on rinsing of patterned hafnium based oxides and silicate wafers, and modify a metrology method for end point detection.

Low-Temperature Postfunctionalization of Highly Conductive Oxide Thin-Films toward Solution-Based Large-Scale Electronics.

PubMed

Ban, Seok-Gyu; Kim, Kyung-Tae; Choi, Byung Doo; Jo, Jeong-Wan; Kim, Yong-Hoon; Facchetti, Antonio; Kim, Myung-Gil; Park, Sung Kyu

2017-08-09

Although transparent conducting oxides (TCOs) have played a key role in a wide range of solid-state electronics from conventional optoelectronics to emerging electronic systems, the processing temperature and conductivity of solution-processed materials seem to be far exceeding the thermal limitations of soft materials and insufficient for high-perfomance large-area systems, respectively. Here, we report a strategy to form highly conductive and scalable solution-processed oxide materials and their successful translation into large-area electronic applications, which is enabled by photoassisted postfunctionalization at low temperature. The low-temperature fabrication of indium-tin-oxide (ITO) thin films was achieved by using photoignited combustion synthesis combined with photoassisted reduction process under hydrogen atmosphere. It was noteworthy that the photochemically activated hydrogens on ITO surface could be triggered to facilitate highly crystalline oxygen deficient structure allowing significant increase of carrier concentration and mobility through film microstructure modifications. The low-temperature postfunctionalized ITO films demonstrated conductivity of >1607 S/cm and sheet resistance of <104 Ω/□ under the process temperature of less than 300 °C, which are comparable to those of vacuum-deposited and high-temperature annealed ITO films. Based on the photoassisted postfunctionalization route, all-solution-processed transparent metal-oxide thin-film-transistors and large-area integrated circuits with the ITO bus lines were demonstrated, showing field-effect mobilities of >6.5 cm 2 V -1 s -1 with relatively good operational stability and oscillation frequency of more than 1 MHz in 7-stage ring oscillators, respectively.

Gold-catalyzed synthesis of benzil derivatives and α-keto imides via oxidation of alkynes.

PubMed

Xu, Cheng-Fu; Xu, Mei; Jia, Yi-Xia; Li, Chuan-Ying

2011-03-18

An efficient process based on the gold-catalyzed redox reaction has been developed to oxidize 1,2-diarylacetylene or ynamide to 1,2-diaryldiketone or α-keto imide respectively. This process can tolerate a variety of functional groups and affords 1,2-dicarbonyl compounds in excellent yields under mild reaction conditions.

Efficient indium-tin-oxide free inverted organic solar cells based on aluminum-doped zinc oxide cathode and low-temperature aqueous solution processed zinc oxide electron extraction layer

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

Chen, Dazheng; Zhang, Chunfu, E-mail: cfzhang@xidian.edu.cn; Wang, Zhizhe

Indium-tin-oxide (ITO) free inverted organic solar cells (IOSCs) based on aluminum-doped zinc oxide (AZO) cathode, low-temperature aqueous solution processed zinc oxide (ZnO) electron extraction layer, and poly(3-hexylthiophene-2, 5-diyl):[6, 6]-phenyl C{sub 61} butyric acid methyl ester blend were realized in this work. The resulted IOSC with ZnO annealed at 150 °C shows the superior power conversion efficiency (PCE) of 3.01%, if decreasing the ZnO annealing temperature to 100 °C, the obtained IOSC also shows a PCE of 2.76%, and no light soaking issue is observed. It is found that this ZnO film not only acts as an effective buffer layer but also slightlymore » improves the optical transmittance of AZO substrates. Further, despite the relatively inferior air-stability, these un-encapsulated AZO/ZnO IOSCs show comparable PCEs to the referenced ITO/ZnO IOSCs, which demonstrates that the AZO cathode is a potential alternative to ITO in IOSCs. Meanwhile, this simple ZnO process is compatible with large area deposition and plastic substrates, and is promising to be widely used in IOSCs and other relative fields.« less

Laser shock processing effects on isothermal oxidation resistance of GH586 superalloy

NASA Astrophysics Data System (ADS)

Hua, Yinqun; Rong, Zhen; Ye, Yunxia; Chen, Kangmin; Chen, Ruifang; Xue, Qing; Liu, Haixia

2015-03-01

The oxidation is one of the main failure mode of Ni-based alloy at high temperature, laser shock processing not only can improve the mechanical properties but also the oxidation resistance. So the study on laser shock processing effects on oxidation resistance of this alloy is necessary. The aim of this paper is to investigate the effects of laser shock processing on microstructure, micro-hardness and isothermal oxidation resistance of GH586 superalloy. Scanning electron microscopy, energy-dispersive spectrum, transmission electron microscope, and X-ray diffraction technique were used to analyze the microstructure changes and the surface morphologies of the oxide scales. In addition, micro-hardness of LSP-treated samples was measured. The results show that the average grains size on the surfaces of LSP specimen was found to be significantly finer compared to the untreated one (33.3 μm vs. 18.5 μm). Highly tangled and dense dislocation arrangements and a high amount of twins have been observed. After the oxidation, the defects density (dislocations and twins) in the specimen decreased. The oxidation kinetics approximately followed a parabolic oxidation law at 800 °C and 900 °C. The oxidation layer was composed of Cr2O3, NiCr2O4, TiO2, and Al2O3, which generated more quickly on the surface treated by LSP during initial oxidation. The average oxidation rate was lower after LSP due to the dense, tiny and homogeneous oxidation layer. The results show that the specimens treated by LSP have a better high temperature oxidation resistance.

Processing, Structure and High Temperature Oxidation Properties of Polymer-Derived and Hafnium Oxide Based Ceramic Systems

NASA Astrophysics Data System (ADS)

Terauds, Kalvis

Demands for hypersonic aircraft are driving the development of ultra-high temperature structural materials. These aircraft, envisioned to sustain Mach 5+, are expected to experience continuous temperatures of 1200--1800°C on the aircraft surface and temperatures as high as 2800°C in combustion zones. Breakthroughs in the development of fiber based ceramic matrix composites (CMCs) are opening the door to a new class of high-tech UHT structures for aerospace applications. One limitation with current carbon fiber or silicon carbide fiber based CMC technology is the inherent problem of material oxidation, requiring new approaches for protective environmental barrier coatings (EBC) in extreme environments. This thesis focuses on the development and characterization of SiCN-HfO2 based ceramic composite EBC systems to be used as a protective layer for silicon carbide fiber based CMCs. The presented work covers three main architectures for protection (i) multilayer films, (ii) polymer-derived HfSiCNO, and (iii) composite SiCN-HfO 2 infiltration. The scope of this thesis covers processing development, material characterization, and high temperature oxidation behavior of these three SiCN-HfO2 based systems. This work shows that the SiCN-HfO 2 composite materials react upon oxidation to form HfSiO4, offering a stable EBC in streaming air and water vapor at 1600°C.

Active Oxidation of a UHTC-Based CMC

NASA Technical Reports Server (NTRS)

Glass, David E.; Splinter, Scott C.

2012-01-01

The active oxidation of ceramic matrix composites (CMC) is a severe problem that must be avoided for multi-use hypersonic vehicles. Much work has been performed studying the active oxidation of silicon-based CMCs such as C/SiC and SiC-coated carbon/carbon (C/C). Ultra high temperature ceramics (UTHC) have been proposed as a possible material solution for high-temperature applications on hypersonic vehicles. However, little work has been performed studying the active oxidation of UHTCs. The intent of this paper is to present test data indicating an active oxidation process for a UHTC-based CMC similar to the active oxidation observed with Si-based CMCs. A UHTC-based CMC was tested in the HyMETS arc-jet facility (or plasma wind tunnel, PWT) at NASA Langley Research Center, Hampton, VA. The coupon was tested at a nominal surface temperature of 3000 F (1650 C), with a stagnation pressure of 0.026 atm. A sudden and large increase in surface temperature was noticed with negligible increase in the heat flux, indicative of the onset of active oxidation. It is shown that the surface conditions, both temperature and pressure, fall within the region for a passive to active transition (PAT) of the oxidation.

Aerosol Processing of Crumpled Graphene Oxide-based Nanocomposites for Drug Delivery.

PubMed

Wang, Wei-Ning; He, Xiang

2016-01-01

The flexibility of graphene oxide (GO) nanosheets and their unique properties enable them to be excellent two dimensional (2D) building blocks for designing functional materials. Aerosol routes are proved to be a rational approach to fold the 2D flat GO nanosheets into 3D crumpled spheres to mitigate the restacking issue for large-scale applications, such as for drug delivery. The fundamentals of graphene, GO, and the crumpling process of GO nanosheets are summarized. Various crumpled graphene oxide (CGO)-based nanocomposites have been synthesized by aerosol routes. This mini review focuses on the state-of-the-art in the design and fabrication of these nanocomposites for a specific application in drug delivery. Various techniques are demonstrated and discussed to control the release rates, tailor the morphology, and adjust the components inside the nanocomposites. Potential risks and possible trends are also pointed out. Aerosol processing of CGO-based nanocomposites provides a promising approach to design functional nanomaterials for drug delivery and other related applications.

Optimization of the p-xylene oxidation process by a multi-objective differential evolution algorithm with adaptive parameters co-derived with the population-based incremental learning algorithm

NASA Astrophysics Data System (ADS)

Guo, Zhan; Yan, Xuefeng

2018-04-01

Different operating conditions of p-xylene oxidation have different influences on the product, purified terephthalic acid. It is necessary to obtain the optimal combination of reaction conditions to ensure the quality of the products, cut down on consumption and increase revenues. A multi-objective differential evolution (MODE) algorithm co-evolved with the population-based incremental learning (PBIL) algorithm, called PBMODE, is proposed. The PBMODE algorithm was designed as a co-evolutionary system. Each individual has its own parameter individual, which is co-evolved by PBIL. PBIL uses statistical analysis to build a model based on the corresponding symbiotic individuals of the superior original individuals during the main evolutionary process. The results of simulations and statistical analysis indicate that the overall performance of the PBMODE algorithm is better than that of the compared algorithms and it can be used to optimize the operating conditions of the p-xylene oxidation process effectively and efficiently.

An improvement in the calculation of the efficiency of oxidative phosphorylation and rate of energy dissipation in mitochondria

NASA Astrophysics Data System (ADS)

Ghafuri, Mohazabeh; Golfar, Bahareh; Nosrati, Mohsen; Hoseinkhani, Saman

2014-12-01

The process of ATP production is one of the most vital processes in living cells which happens with a high efficiency. Thermodynamic evaluation of this process and the factors involved in oxidative phosphorylation can provide a valuable guide for increasing the energy production efficiency in research and industry. Although energy transduction has been studied qualitatively in several researches, there are only few brief reviews based on mathematical models on this subject. In our previous work, we suggested a mathematical model for ATP production based on non-equilibrium thermodynamic principles. In the present study, based on the new discoveries on the respiratory chain of animal mitochondria, Golfar's model has been used to generate improved results for the efficiency of oxidative phosphorylation and the rate of energy loss. The results calculated from the modified coefficients for the proton pumps of the respiratory chain enzymes are closer to the experimental results and validate the model.

The Development of HfO2-Rare Earth Based Oxide Materials and Barrier Coatings for Thermal Protection Systems

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Harder, Bryan James

2014-01-01

Advanced hafnia-rare earth oxides, rare earth aluminates and silicates have been developed for thermal environmental barrier systems for aerospace propulsion engine and thermal protection applications. The high temperature stability, low thermal conductivity, excellent oxidation resistance and mechanical properties of these oxide material systems make them attractive and potentially viable for thermal protection systems. This paper will focus on the development of the high performance and high temperature capable ZrO2HfO2-rare earth based alloy and compound oxide materials, processed as protective coating systems using state-or-the-art processing techniques. The emphasis has been in particular placed on assessing their temperature capability, stability and suitability for advanced space vehicle entry thermal protection systems. Fundamental thermophysical and thermomechanical properties of the material systems have been investigated at high temperatures. Laser high-heat-flux testing has also been developed to validate the material systems, and demonstrating durability under space entry high heat flux conditions.

Enhance the pyroelectricity of polyvinylidene fluoride by graphene-oxide doping.

PubMed

Hu, Yuh-Chung; Hsu, Wei-Li; Wang, Yi-Ta; Ho, Cheng-Tao; Chang, Pei-Zen

2014-04-16

The high quality properties and benefits of graphene-oxide have generated an active area of research where many investigations have shown potential applications in various technological fields. This paper proposes a methodology for enhancing the pyro-electricity of PVDF by graphene-oxide doping. The PVDF film with graphene-oxide is prepared by the sol-gel method. Firstly, PVDF and graphene-oxide powders are dispersed into dimethylformamide as solvent to form a sol solution. Secondly, the sol solution is deposited on a flexible ITO/PET substrate by spin-coating. Thirdly, the particles in the sol solution are polymerized through baking off the solvent to produce a gel in a state of a continuous network of PVDF and graphene-oxide. The final annealing process pyrolyzes the gel and form a β-phase PVDF film with graphene-oxide doping. A complete study on the process of the graphene oxide doping of PVDF is accomplished. Some key points about the process are addressed based on experiments. The solutions to some key issues are found in this work, such as the porosity of film, the annealing temperature limitation by the use of flexible PET substrate, and the concentrations of PVDF and graphene-oxide.

Degradation of the commercial surfactant nonylphenol ethoxylate by advanced oxidation processes.

PubMed

da Silva, Salatiel Wohlmuth; Klauck, Cláudia Regina; Siqueira, Marco Antônio; Bernardes, Andréa Moura

2015-01-23

Four different oxidation process, namely direct photolysis (DP) and three advanced oxidation processes (heterogeneous photocatalysis - HP, eletrochemical oxidation - EO and photo-assisted electrochemical oxidation - PEO) were applied in the treatment of wastewater containing nonylphenol ethoxylate (NPnEO). The objective of this work was to determine which treatment would be the best option in terms of degradation of NPnEO without the subsequent generation of toxic compounds. In order to investigate the degradation of the surfactant, the processes were compared in terms of UV/Vis spectrum, mineralization (total organic carbon), reaction kinetics, energy efficiency and phytotoxicity. A solution containing NPnEO was prepared as a surrogate of the degreasing wastewater, was used in the processes. The results showed that the photo-assisted processes degrade the surfactant, producing biodegradable intermediates in the reaction. On the other hand, the electrochemical process influences the mineralization of the surfactant. The process of PEO carried out with a 250W lamp and a current density of 10mA/cm(2) showed the best results in terms of degradation, mineralization, reaction kinetics and energy consumption, in addition to not presenting phytotoxicity. Based on this information, this process can be a viable alternative for treating wastewater containing NPnEO, avoiding the contamination of water resources. Copyright © 2014 Elsevier B.V. All rights reserved.

In-situ XPS analysis of oxidized and reduced plasma deposited ruthenium-based thin catalytic films

NASA Astrophysics Data System (ADS)

Balcerzak, Jacek; Redzynia, Wiktor; Tyczkowski, Jacek

2017-12-01

A novel in-situ study of the surface molecular structure of catalytically active ruthenium-based films subjected to the oxidation (in oxygen) and reduction (in hydrogen) was performed in a Cat-Cell reactor combined with a XPS spectrometer. The films were produced by the plasma deposition method (PEMOCVD). It was found that the films contained ruthenium at different oxidation states: metallic (Ru0), RuO2 (Ru+4), and other RuOx (Ru+x), of which content could be changed by the oxidation or reduction, depending on the process temperature. These results allow to predict the behavior of the Ru-based catalysts in different redox environments.

Characterisation and Processing of Some Iron Ores of India

NASA Astrophysics Data System (ADS)

Krishna, S. J. G.; Patil, M. R.; Rudrappa, C.; Kumar, S. P.; Ravi, B. P.

2013-10-01

Lack of process characterization data of the ores based on the granulometry, texture, mineralogy, physical, chemical, properties, merits and limitations of process, market and local conditions may mislead the mineral processing entrepreneur. The proper implementation of process characterization and geotechnical map data will result in optimized sustainable utilization of resource by processing. A few case studies of process characterization of some Indian iron ores are dealt with. The tentative ascending order of process refractoriness of iron ores is massive hematite/magnetite < marine black iron oxide sands < laminated soft friable siliceous ore fines < massive banded magnetite quartzite < laminated soft friable clayey aluminous ore fines < massive banded hematite quartzite/jasper < massive clayey hydrated iron oxide ore < manganese bearing iron ores massive < Ti-V bearing magnetite magmatic ore < ferruginous cherty quartzite. Based on diagnostic process characterization, the ores have been classified and generic process have been adopted for some Indian iron ores.

Elimination study of the chemotherapy drug tamoxifen by different advanced oxidation processes: Transformation products and toxicity assessment.

PubMed

Ferrando-Climent, Laura; Gonzalez-Olmos, Rafael; Anfruns, Alba; Aymerich, Ignasi; Corominas, Lluis; Barceló, Damià; Rodriguez-Mozaz, Sara

2017-02-01

Tamoxifen is a chemotherapy drug considered as recalcitrant contaminant (with low biodegradability in conventional activated sludge wastewater treatment), bioaccumulative, ubiquitous, and potentially hazardous for the environment. This work studies the removal of Tamoxifen from water by advanced oxidation processes, paying special attention to the formation of transformation products (TPs) and to the evolution of toxicity (using the Microtox ® bioassay) during the oxidation processes. Five types of treatments were evaluated combining different technologies based on ozone, hydrogen peroxide and UV radiation: i) O 3 , ii) O 3 /UV, iii) O 3 /H 2 O 2 (peroxone), iv) UV and v) UV/H 2 O 2 . Complete removal of tamoxifen was achieved after 30 min for all the treatments carried out with O 3 while a residual concentration (about 10% of initial one) was observed in the treatments based on UV and UV/H 2 O 2 after 4 h of reaction. Eight TPs were tentatively identified and one (non-ionizable molecule) was suspected to be present by using ultra high performance liquid chromatography coupled to high resolution mass spectrometry. An increase of toxicity was observed during all the oxidation processes. In the case of ozone-based treatments that increase was attributed to the presence of some of the TPs identified, whereas in the case of UV-based treatments there was no clear correlation between toxicity and the identified TPs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Application of sludge-based carbonaceous materials in a hybrid water treatment process based on adsorption and catalytic wet air oxidation.

PubMed

Julcour Lebigue, Carine; Andriantsiferana, Caroline; N'Guessan Krou; Ayral, Catherine; Mohamed, Elham; Wilhelm, Anne-Marie; Delmas, Henri; Le Coq, Laurence; Gerente, Claire; Smith, Karl M; Pullket, Suangusa; Fowler, Geoffrey D; Graham, Nigel J D

2010-12-01

This paper describes a preliminary evaluation of the performance of carbonaceous materials prepared from sewage sludges (SBCMs) in a hybrid water treatment process based on adsorption and catalytic wet air oxidation; phenol was used as the model pollutant. Three different sewage sludges were treated by either carbonisation or steam activation, and the physico-chemical properties of the resultant carbonaceous materials (e.g. hardness, BET surface area, ash and elemental content, surface chemistry) were evaluated and compared with a commercial reference activated carbon (PICA F22). The adsorption capacity for phenol of the SBCMs was greater than suggested by their BET surface area, but less than F22; a steam activated, dewatered raw sludge (SA_DRAW) had the greatest adsorption capacity of the SBCMs in the investigated range of concentrations (<0.05 mol L(-1)). In batch oxidation tests, the SBCMs demonstrated catalytic behaviour arising from their substrate adsorptivity and metal content. Recycling of SA_DRAW in successive oxidations led to significant structural attrition and a hardened SA_DRAW was evaluated, but found to be unsatisfactory during the oxidation step. In a combined adsorption-oxidation sequence, both the PICA carbon and a selected SBCM showed deterioration in phenol adsorption after oxidative regeneration, but a steady state performance was reached after 2 or 3 cycles. Copyright © 2010 Elsevier Ltd. All rights reserved.

Crystallization Behavior of Copper Smelter Slag During Molten Oxidation

NASA Astrophysics Data System (ADS)

Fan, Yong; Shibata, Etsuro; Iizuka, Atsushi; Nakamura, Takashi

2015-10-01

Copper slag is composed of iron silicate obtained by smelting copper concentrate and silica flux. One of the most important criteria for the utilization of this secondary resource is the recovery of iron from the slag matrix to decrease the volume of dumped slag. The molten oxidation process with crushing magnetic separation appears to be a more sustainable approach and is based on directly blowing oxidizing gas onto molten slag after the copper smelting process. In the current study, using an infrared furnace, the crystallization behavior of the slag during molten oxidation was studied to better understand the trade-off between magnetite and hematite precipitations, as assessed by X-ray diffraction (using an internal standard). Furthermore, the crystal morphology was examined using a laser microscope and Raman imaging system to understand the iron oxide transformation, and the distribution of impurities such as Cu, Zn, As, Cr, and Pb were complemented with scanning electron microscopy and energy dispersive spectroscopy. In addition, the reaction mechanism was investigated with a focus on the oxidation processes.

Soot Reaction Properties (Ground-Based Study)

NASA Technical Reports Server (NTRS)

Dai, Z.; El-Leathy, A. M.; Lin, K.-C.; Sunderland, P. B.; Xu, F.; Faeth, G. M.; Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

2000-01-01

Three major soot reaction processes are needed to predict soot properties in flame environments: soot growth, or the formation of soot on soot nuclei and soot particles; soot oxidation, or the reaction of soot with oxidizing species to yield the combustion products of soot oxidation; and soot nucleation, or the formation of soot nuclei from soot precursors having large molecular weights (generally thought to be large and particularly stable PAH molecules in flame environments, called stabilomers). These processes are addressed in the following, considering soot growth, oxidation and nucleation, in turn, by exploiting the soot and flame structure results for premixed and diffusion flames already discussed in Section 2.

Method for fabricating solar cells having integrated collector grids

NASA Technical Reports Server (NTRS)

Evans, J. C., Jr. (Inventor)

1979-01-01

A heterojunction or Schottky barrier photovoltaic device comprising a conductive base metal layer compatible with and coating predominately the exposed surface of the p-type substrate of the device such that a back surface field region is formed at the interface between the device and the base metal layer, a transparent, conductive mixed metal oxide layer in integral contact with the n-type layer of the heterojunction or Schottky barrier device having a metal alloy grid network of the same metal elements of the oxide constituents of the mixed metal oxide layer embedded in the mixed metal oxide layer, an insulating layer which prevents electrical contact between the conductive metal base layer and the transparent, conductive metal oxide layer, and a metal contact means covering the insulating layer and in intimate contact with the metal grid network embedded in the transparent, conductive oxide layer for conducting electrons generated by the photovoltaic process from the device.

Memory and learning behaviors mimicked in nanogranular SiO2-based proton conductor gated oxide-based synaptic transistors

NASA Astrophysics Data System (ADS)

Wan, Chang Jin; Zhu, Li Qiang; Zhou, Ju Mei; Shi, Yi; Wan, Qing

2013-10-01

In neuroscience, signal processing, memory and learning function are established in the brain by modifying ionic fluxes in neurons and synapses. Emulation of memory and learning behaviors of biological systems by nanoscale ionic/electronic devices is highly desirable for building neuromorphic systems or even artificial neural networks. Here, novel artificial synapses based on junctionless oxide-based protonic/electronic hybrid transistors gated by nanogranular phosphorus-doped SiO2-based proton-conducting films are fabricated on glass substrates by a room-temperature process. Short-term memory (STM) and long-term memory (LTM) are mimicked by tuning the pulse gate voltage amplitude. The LTM process in such an artificial synapse is due to the proton-related interfacial electrochemical reaction. Our results are highly desirable for building future neuromorphic systems or even artificial networks via electronic elements.In neuroscience, signal processing, memory and learning function are established in the brain by modifying ionic fluxes in neurons and synapses. Emulation of memory and learning behaviors of biological systems by nanoscale ionic/electronic devices is highly desirable for building neuromorphic systems or even artificial neural networks. Here, novel artificial synapses based on junctionless oxide-based protonic/electronic hybrid transistors gated by nanogranular phosphorus-doped SiO2-based proton-conducting films are fabricated on glass substrates by a room-temperature process. Short-term memory (STM) and long-term memory (LTM) are mimicked by tuning the pulse gate voltage amplitude. The LTM process in such an artificial synapse is due to the proton-related interfacial electrochemical reaction. Our results are highly desirable for building future neuromorphic systems or even artificial networks via electronic elements. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr02987e

Structure sensitivity in oxide catalysis: First-principles kinetic Monte Carlo simulations for CO oxidation at RuO 2(111)

DOE PAGES

Wang, Tongyu; Reuter, Karsten

2015-11-24

We present a density-functional theory based kinetic Monte Carlo study of CO oxidation at the (111) facet of RuO 2. We compare the detailed insight into elementary processes, steady-state surface coverages, and catalytic activity to equivalent published simulation data for the frequently studied RuO 2(110) facet. Qualitative differences are identified in virtually every aspect ranging from binding energetics over lateral interactions to the interplay of elementary processes at the different active sites. Nevertheless, particularly at technologically relevant elevated temperatures, near-ambient pressures and near-stoichiometric feeds both facets exhibit almost identical catalytic activity. As a result, these findings challenge the traditional definitionmore » of structure sensitivity based on macroscopically observable turnover frequencies and prompt scrutiny of the applicability of structure sensitivity classifications developed for metals to oxide catalysis.« less

Method for separating metal chelates from other materials based on solubilities in supercritical fluids

DOEpatents

Wai, Chien M.; Smart, Neil G.; Phelps, Cindy

2001-01-01

A method for separating a desired metal or metalloi from impurities using a supercritical extraction process based on solubility differences between the components, as well as the ability to vary the solvent power of the supercritical fluid, is described. The use of adduct-forming agents, such as phosphorous-containing ligands, to separate metal or metalloid chelates in such processes is further disclosed. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of .beta.-diketones; phosphine oxides, such as trialkylphosphine oxides, triarylphosphine oxides and alkylarylphosphine oxides; phosphinic acids; carboxylic acids; phosphates, such as trialkylphosphates, triarylphosphates and alkylarylphosphates; crown ethers; dithiocarbamates; phosphine sulfides; phosphorothioic acids; thiophosphinic acids; halogenated analogs of these chelating agents; and mixtures of these chelating agents. In especially preferred embodiments, at least one of the chelating agents is fluorinated.

Structure sensitivity in oxide catalysis: First-principles kinetic Monte Carlo simulations for CO oxidation at RuO{sub 2}(111)

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

Wang, Tongyu; Reuter, Karsten, E-mail: karsten.reuter@ch.tum.de; SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory and Stanford University, 443 Via Ortega, Stanford, California 94035-4300

2015-11-28

We present a density-functional theory based kinetic Monte Carlo study of CO oxidation at the (111) facet of RuO{sub 2}. We compare the detailed insight into elementary processes, steady-state surface coverages, and catalytic activity to equivalent published simulation data for the frequently studied RuO{sub 2}(110) facet. Qualitative differences are identified in virtually every aspect ranging from binding energetics over lateral interactions to the interplay of elementary processes at the different active sites. Nevertheless, particularly at technologically relevant elevated temperatures, near-ambient pressures and near-stoichiometric feeds both facets exhibit almost identical catalytic activity. These findings challenge the traditional definition of structure sensitivitymore » based on macroscopically observable turnover frequencies and prompt scrutiny of the applicability of structure sensitivity classifications developed for metals to oxide catalysis.« less

Effects of Some Light Alloying Elements on the Oxidation Behavior of Fe and Ni-Cr Based Alloys During Air Plasma Spraying

NASA Astrophysics Data System (ADS)

Zeng, Zhensu; Kuroda, Seiji; Kawakita, Jin; Komatsu, Masayuki; Era, Hidenori

2010-01-01

The oxidation behavior of iron binary powders with addition of Si (1, 4 wt.%) and B (1, 3 wt.%) and that of a Ni-Cr based alloy powder with Si (4.3 wt.%), B (3.0 wt.%), and C (0.8 wt.%) additions during atmosphere plasma spray (APS) have been investigated. Analysis of the chemical composition and phases of oxides in the captured in-flight particles and deposited coatings was carried out. The results show that the addition of Si and B to iron effectively reduced the oxygen contents in the coatings, especially during the in-flight period at higher particles temperature. Ni-Cr based alloy powder with Si, B, and C additions reduced the oxidation of the base alloys significantly. Preferential oxidation and subsequent vaporization of Si, B, and C from the surface of the sprayed particles are believed to play a major role in controlling oxidation in the APS process.

Simulation of Triple Oxidation Ditch Wastewater Treatment Process

NASA Astrophysics Data System (ADS)

Yang, Yue; Zhang, Jinsong; Liu, Lixiang; Hu, Yongfeng; Xu, Ziming

2010-11-01

This paper presented the modeling mechanism and method of a sewage treatment system. A triple oxidation ditch process of a WWTP was simulated based on activated sludge model ASM2D with GPS-X software. In order to identify the adequate model structure to be implemented into the GPS-X environment, the oxidation ditch was divided into several completely stirred tank reactors depended on the distribution of aeration devices and dissolved oxygen concentration. The removal efficiency of COD, ammonia nitrogen, total nitrogen, total phosphorus and SS were simulated by GPS-X software with influent quality data of this WWTP from June to August 2009, to investigate the differences between the simulated results and the actual results. The results showed that, the simulated values could well reflect the actual condition of the triple oxidation ditch process. Mathematical modeling method was appropriate in effluent quality predicting and process optimizing.

A comparison of disinfection by-products formation during sequential or simultaneous disinfection of surface waters with chlorine dioxide and chlor(am)ine.

PubMed

Shi, Yanwei; Ling, Wencui; Qiang, Zhimin

2013-01-01

The effect of chlorine dioxide (ClO2) oxidation on the formation of disinfection by-products (DBPs) during sequential (ClO2 pre-oxidation for 30 min) and simultaneous disinfection processes with free chlorine (FC) or monochloramine (MCA) was investigated. The formation of DBPs from synthetic humic acid (HA) water and three natural surface waters containing low bromide levels (11-27 microg/L) was comparatively examined in the FC-based (single FC, sequential ClO2-FC, and simultaneous ClO2/FC) and MCA-based (single MCA, ClO2-MCA, and ClO2/MCA) disinfection processes. The results showed that much more DBPs were formed from the synthetic HA water than from the three natural surface waters with comparative levels of dissolved organic carbon. In the FC-based processes, ClO2 oxidation could reduce trihalomethanes (THMs) by 27-35% and haloacetic acids (HAAs) by 14-22% in the three natural surface waters, but increased THMs by 19% and HAAs by 31% in the synthetic HA water after an FC contact time of 48 h. In the MCA-based processes, similar trends were observed although DBPs were produced at a much lower level. There was an insignificant difference in DBPs formation between the sequential and simultaneous processes. The presence of a high level of bromide (320 microg/L) remarkably promoted the DBPs formation in the FC-based processes. Therefore, the simultaneous disinfection process of ClO2/MCA is recommended particularly for waters with a high bromide level.

Use of Raman spectroscopy to assess the efficiency of MgAl mixed oxides in removing cyanide from aqueous solutions

NASA Astrophysics Data System (ADS)

Cosano, Daniel; Esquinas, Carlos; Jiménez-Sanchidrián, César; Ruiz, José Rafael

2016-02-01

Calcining magnesium/aluminium layered double hydroxides (Mg/Al LDHs) at 450 °C provides excellent sorbents for removing cyanide from aqueous solutions. The process is based on the "memory effect" of LDHs; thus, rehydrating a calcined LDH in an aqueous solution restores its initial structure. The process, which conforms to a first-order kinetics, was examined by Raman spectroscopy. The metal ratio of the LDH was found to have a crucial influence on the adsorption capacity of the resulting mixed oxide. In this work, Raman spectroscopy was for the first time use to monitor the adsorption process. Based on the results, this technique is an effective, expeditious choice for the intended purpose and affords in situ monitoring of the adsorption process. The target solids were characterized by using various instrumental techniques including X-ray diffraction spectroscopy, which confirmed the layered structure of the LDHs and the periclase-like structure of the mixed oxides obtained by calcination.

Antibiotics mineralization by electrochemical and UV-based hybrid processes: evaluation of the synergistic effect.

PubMed

Wohlmuth da Silva, Salatiel; Arenhart Heberle, Alan Nelson; Pereira Santos, Alexia; Siqueira Rodrigues, Marco Antônio; Pérez-Herranz, Valentín; Moura Bernardes, Andréa

2018-05-29

Antibiotics are not efficiently removed in conventional wastewater treatments. In fact, different advanced oxidation process (AOPs), including ozone, peroxide, UV radiation, among others, are being investigated in the elimination of microcontaminants. Most of AOPs proved to be efficient on the degradation of antibiotics, but the mineralization is on the one hand not evaluated or on the other hand not high. At this work, the UV-based hybrid process, namely Photo-assisted electrochemical oxidation (PEO), was applied, aiming the mineralization of microcontaminants such as the antibiotics Amoxicillin (AMX), Norfloxacin (NOR) and Azithromycin (AZI). The influence of the individual contributions of electrochemical oxidation (EO) and the UV-base processes on the hybrid process (PEO) was analysed. Results showed that AMX and NOR presented higher mineralization rate under direct photolysis than AZI due to the high absorption of UV radiation. For the EO processes, a low mineralization was found for all antibiotics, what was associated to a mass-transport limitation related to the low concentration of contaminants (200 µg/L). Besides that, an increase in mineralization was found, when heterogeneous photocatalysis and EO are compared, due to the influence of UV radiation, which overcomes the mass-transport limitations. Although the UV-based processes control the reaction pathway that leads to mineralization, the best results to mineralize the antibiotics were achieved by PEO hybrid process. This can be explained by the synergistic effect of the processes that constitute them. A higher mineralization was achieved, which is an important and useful finding to avoid the discharge of microcontaminants in the environment.

Porous graphene-based membranes for water purification from metal ions at low differential pressures.

PubMed

Park, Jaewoo; Bazylewski, Paul; Fanchini, Giovanni

2016-05-14

A new generation of membranes for water purification based on weakly oxidized and nanoporous few-layer graphene is here introduced. These membranes dramatically decrease the high energy requirements of water purification by reverse osmosis. They combine the advantages of porous and non-oxidized single-layer graphene, offering energy-efficient water filtration at relatively low differential pressures, and highly oxidized graphene oxide, exhibiting high performance in terms of impurity adsorption. In the reported fabrication process, leaks between juxtaposed few-layer graphene flakes are sealed by thermally annealed colloidal silica, in a treatment that precedes the opening of (sub)nanometre-size pores in graphene. This process, explored for the first time in this work, results in nanoporous graphene flakes that are water-tight at the edges without occluding the (sub)nanopores. With this method, removal of impurities from water occurs through a combination of size-based pore rejection and pore-edge adsorption. Thinness of graphene flakes allows these membranes to achieve water purification from metal ions in concentrations of few parts-per-million at differential pressures as low as 30 kPa, outperforming existing graphene or graphene oxide purification systems with comparable flow rates.

Porous graphene-based membranes for water purification from metal ions at low differential pressures

NASA Astrophysics Data System (ADS)

Park, Jaewoo; Bazylewski, Paul; Fanchini, Giovanni

2016-05-01

A new generation of membranes for water purification based on weakly oxidized and nanoporous few-layer graphene is here introduced. These membranes dramatically decrease the high energy requirements of water purification by reverse osmosis. They combine the advantages of porous and non-oxidized single-layer graphene, offering energy-efficient water filtration at relatively low differential pressures, and highly oxidized graphene oxide, exhibiting high performance in terms of impurity adsorption. In the reported fabrication process, leaks between juxtaposed few-layer graphene flakes are sealed by thermally annealed colloidal silica, in a treatment that precedes the opening of (sub)nanometre-size pores in graphene. This process, explored for the first time in this work, results in nanoporous graphene flakes that are water-tight at the edges without occluding the (sub)nanopores. With this method, removal of impurities from water occurs through a combination of size-based pore rejection and pore-edge adsorption. Thinness of graphene flakes allows these membranes to achieve water purification from metal ions in concentrations of few parts-per-million at differential pressures as low as 30 kPa, outperforming existing graphene or graphene oxide purification systems with comparable flow rates.

Preliminary study of oxide-dispersion-strengthened B-1900 prepared by mechanical alloys

NASA Technical Reports Server (NTRS)

Glasgow, T. K.; Quatinetz, M.

1975-01-01

An experimental oxide dispersion strengthened (ODS) alloy based on the B-1900 composition was produced by the mechanical alloying process. Without optimization of the processing for the alloy or the alloy for the processing, recrystallization of the extruded product to large elongated grains was achieved. Materials having grain length-width ratios of 3 and 5.5 were tested in tension and stress-rupture. The ODS B-1900 exhibited tensile strength similar to that of cast B-1900. Its stress-rupture life was lower than that of cast B-1900 at 760 C. At 1095 C the ODS B-1900 with the higher grain length-width ratio (5.5) had stress-rupture life superior to that of cast B-1900. It was concluded that, with optimization, oxide dispersion strengthening of B-1900 and other complex cast nickel-base alloys has potential for improving high temperature properties over those of the cast alloy counterparts.

A modelling approach for the heterogeneous oxidation of elastomers

NASA Astrophysics Data System (ADS)

Herzig, A.; Sekerakova, L.; Johlitz, M.; Lion, A.

2017-09-01

The influence of oxygen on elastomers, known as oxidation, is one of the most important ageing processes and becomes more and more important for nowadays applications. The interaction with thermal effects as well as antioxidants makes oxidation of polymers a complex process. Based on the polymer chosen and environmental conditions, the ageing processes may behave completely different. In a lot of cases the influence of oxygen is limited to the surface layer of the samples, commonly referred to as diffusion-limited oxidation. For the lifetime prediction of elastomer components, it is essential to have detailed knowledge about the absorption and diffusion behaviour of oxygen molecules during thermo-oxidative ageing and how they react with the elastomer. Experimental investigations on industrially used elastomeric materials are executed in order to develop and fit models, which shall be capable of predicting the permeation and consumption of oxygen as well as changes in the mechanical properties. The latter are of prime importance for technical applications of rubber components. Oxidation does not occur homogeneously over the entire elastomeric component. Hence, material models which include ageing effects have to be amplified in order to consider heterogeneous ageing, which highly depends on the ageing temperature. The influence of elevated temperatures upon accelerated ageing has to be critically analysed, and influences on the permeation and diffusion coefficient have to be taken into account. This work presents phenomenological models which describe the oxygen uptake and the diffusion into elastomers based on an improved understanding of ongoing chemical processes and diffusion limiting modifications. On the one side, oxygen uptake is modelled by means of Henry's law in which solubility is a function of the temperature as well as the ageing progress. The latter is an irreversible process and described by an inner differential evolution equation. On the other side, further diffusion of oxygen into the material is described by a model based on Fick's law, which is modified by a reaction term. The evolved diffusion-reaction equation depends on the ageing temperature as well as on the progress of ageing and is able to describe diffusion-limited oxidation.

Effect of different alloyed layers on the high temperature oxidation behavior of newly developed Ti 2AlNb-based alloys

NASA Astrophysics Data System (ADS)

Wu, Hongyan; Zhang, Pingze; Zhao, Haofeng; Wang, Ling; Xie, Aigen

2011-01-01

The application of titanium aluminide orthorhombic alloys (O-phase alloys) as potential materials in aircraft and jet engines was limited by their poor oxidation resistance at high temperature. The Ti 2AlNb-based alloys were chromised (Cr), chromium-tungstened (Cr-W) and nickel-chromised (Ni-Cr) by the double glow plasma surface alloying process to improve their high temperature oxidation resistance. The discontinuous oxidative behavior of Cr, Cr-W and Ni-Cr alloyed layers on Ti 2AlNb-based alloy at 1093 K was explored in this study. After exposing at 1093 K, the TiO 2 layer was formed on the bare alloy and accompanied by the occurrence of crack, which promoted oxidation rate. The oxidation behavior of Ti 2AlNb-based alloys was improved by surface alloying due to the formation of protective Al 2O 3 scale or continuous and dense NiCr 2O 4 film. The Ni-Cr alloyed layer presented the best high-temperature oxidation resistance among three alloyed layers.

Laminar Soot Processes (Lsp) Experiment: Findings From Ground-Based Measurements

NASA Technical Reports Server (NTRS)

Kim, C. H.; El-Leathy, A. M.; Faeth, G. M.; Xu, F.

2003-01-01

Processes of soot formation and oxidation must be understood in order to achieve reliable computational combustion calculations for nonpremixed (diffusion) flames involving hydrocarbon fuels. Motivated by this observation, the present investigation extended earlier work on soot formation and oxidation in laminar jet ethylene/air and methane/oxygen premixed and acetylene-nitrogen/air diffusion flames at atmospheric pressure in this laboratory, emphasizing soot surface growth and early soot surface oxidation in laminar diffusion flames fueled with a variety of hydrocarbons at pressures in the range 0.1 - 1.0 atm.

Kinetics and thermodynamics of oxidation mediated reaction in L-cysteine and its methyl and ethyl esters in dimethyl sulfoxide-d6 by NMR spectroscopy

NASA Astrophysics Data System (ADS)

Dougherty, Ryan J.; Singh, Jaideep; Krishnan, V. V.

2017-03-01

L-Cysteine (L-Cys), L-Cysteine methyl ester (L-CysME) or L-Cysteine ethyl ester (L-CysEE), when dissolved in dimethyl sulfoxide, undergoes an oxidation process. This process is slow enough and leads to nuclear magnetic resonance (NMR) spectral changes that could be monitored in real time. The oxidation mediated transition is modeled as a pseudo-first order kinetics and the thermodynamic parameters are estimated using the Eyring's formulation. L-Cysteine and their esters are often used as biological models due to the remarkable thiol group that can be found in different oxidation states. This oxidation mediated transition is due to the combination of thiol oxidation to a disulfide followed by solvent-induced effects may be relevant in designing cysteine-based molecular models.

Integration between chemical oxidation and membrane thermophilic biological process.

PubMed

Bertanza, G; Collivignarelli, M C; Crotti, B M; Pedrazzani, R

2010-01-01

Full scale applications of activated sludge thermophilic aerobic process for treatment of liquid wastes are rare. This experimental work was carried out at a facility, where a thermophilic reactor (1,000 m(3) volume) is operated. In order to improve the global performance of the plant, it was decided to upgrade it, by means of two membrane filtration units (ultrafiltration -UF-, in place of the final sedimentation, and nanofiltration -NF-). Subsequently, the integration with chemical oxidation (O(3) and H(2)O(2)/UV processes) was taken into consideration. Studied solutions dealt with oxidation of both the NF effluents (permeate and concentrate). Based on experimental results and economic evaluation, an algorithm was proposed for defining limits of convenience of this process.

Biobased, environmentally friendly lubricants for processing plants

USDA-ARS?s Scientific Manuscript database

Vegetable oil based lubricants have excellent lubricity, biodegradability, good viscosity temperature characteristics and low evaporation loss, but poor thermos-oxidative stability and cold flow properties. This paper presents a systematic approach to improve the oxidative and cold flow behavior of...

Low-Temperature UV-Assisted Fabrication of Metal Oxide Thin Film Transistor

NASA Astrophysics Data System (ADS)

Zhu, Shuanglin

Solution processed metal oxide semiconductors have attracted intensive attention in the last several decades and have emerged as a promising candidate for the application of thin film transistor (TFT) due to their nature of transparency, flexibility, high mobility, simple processing technique and potential low manufacturing cost. However, metal oxide thin film fabricated by solution process usually requires a high temperature (over 300 °C), which is above the glass transition temperature of some conventional polymer substrates. In order to fabricate the flexible electronic device on polymer substrates, it is necessary to find a facile approach to lower the fabrication temperature and minimize defects in metal oxide thin film. In this thesis, the electrical properties dependency on temperature is discussed and an UV-assisted annealing method incorporating Deep ultraviolet (DUV)-decomposable additives is demonstrated, which can effectively improve electrical properties solution processed metal oxide semiconductors processed at temperature as low as 220 °C. By studying a widely used indium oxide (In2O3) TFT as a model system, it is worth noted that compared with the sample without UV treatment, the linear mobility and saturation mobility of UV-annealing sample are improved by 56% and 40% respectively. Meanwhile, the subthreshold swing is decreased by 32%, indicating UV-treated device could turn on and off more efficiently. In addition to pure In2O3 film, the similar phenomena have also been observed in indium oxide based Indium-Gallium-Zinc Oxide (IGZO) system. These finding presented in this thesis suggest that the UV assisted annealing process open a new route to fabricate high performance metal oxide semiconductors under low temperatures.

Advanced Oxidation Processes: Process Mechanisms, Affecting Parameters and Landfill Leachate Treatment.

PubMed

Su-Huan, Kow; Fahmi, Muhammad Ridwan; Abidin, Che Zulzikrami Azner; Soon-An, Ong

2016-11-01

  Advanced oxidation processes (AOPs) are of special interest in treating landfill leachate as they are the most promising procedures to degrade recalcitrant compounds and improve the biodegradability of wastewater. This paper aims to refresh the information base of AOPs and to discover the research gaps of AOPs in landfill leachate treatment. A brief overview of mechanisms involving in AOPs including ozone-based AOPs, hydrogen peroxide-based AOPs and persulfate-based AOPs are presented, and the parameters affecting AOPs are elaborated. Particularly, the advancement of AOPs in landfill leachate treatment is compared and discussed. Landfill leachate characterization prior to method selection and method optimization prior to treatment are necessary, as the performance and practicability of AOPs are influenced by leachate matrixes and treatment cost. More studies concerning the scavenging effects of leachate matrixes towards AOPs, as well as the persulfate-based AOPs in landfill leachate treatment, are necessary in the future.

Engineering application of anaerobic ammonium oxidation process in wastewater treatment.

PubMed

Mao, Nianjia; Ren, Hongqiang; Geng, Jinju; Ding, Lili; Xu, Ke

2017-08-01

Anaerobic ammonium oxidation (Anammox), a promising biological nitrogen removal process, has been verified as an efficient, sustainable and cost-effective alternative to conventional nitrification and denitrification processes. To date, more than 110 full-scale anammox plants have been installed and are in operation, treating industrial NH 4 + -rich wastewater worldwide, and anammox-based technologies are flourishing. This review the current state of the art for engineering applications of the anammox process, including various anammox-based technologies, reactor selection and attempts to apply it at different wastewater plants. Process control and implementation for stable performance are discussed as well as some remaining issues concerning engineering application are exposed, including the start-up period, process disturbances, greenhouse gas emissions and especially mainstream anammox applications. Finally, further development of the anammox engineering application is proposed in this review.

Ultrapure glass optical waveguide: Development in microgravity by the sol gel process

NASA Technical Reports Server (NTRS)

Mukherjee, S. P.; Debsikdar, J. C.; Beam, T.

1983-01-01

The sol-gel process for the preparation of homogeneous gels in three binary oxide systems was investigated. The glass forming ability of certain compositions in the selected oxide systems (SiO-GeO2, GeO2-PbO, and SiO2-TiO2) were studied based on their potential importance in the design of optical waveguide at longer wavelengths.

Ultra-fast 160:10 Gbit/s time demultiplexing by four wave mixing in 1 m-long B 2O 3-based fiber

NASA Astrophysics Data System (ADS)

Scaffardi, M.; Fresi, F.; Meloni, G.; Bogoni, A.; Potì, L.; Calabretta, N.; Guglielmucci, M.

2006-12-01

One meter-long spool of bismuth oxide-based fiber, with nonlinear coefficient of 1250 W -1 km -1, is used to realize an optical 160-to-10 Gbit/s demultiplexer based on four wave mixing. Bit-Error-Rate measurements demonstrate a demultiplexing penalty lower than 2 dB confirming the suitability of bismuth oxide-based fiber for 160 Gbit/s all-optical processing.

Visualizing the Cu/Cu2(O) Interface Transition in Nanoparticles with Environmental Scanning Transmission Electron Microscopy.

PubMed

LaGrow, Alec P; Ward, Michael R; Lloyd, David C; Gai, Pratibha L; Boyes, Edward D

2017-01-11

Understanding the oxidation and reduction mechanisms of catalytically active transition metal nanoparticles is important to improve their application in a variety of chemical processes. In nanocatalysis the nanoparticles can undergo oxidation or reduction in situ, and thus the redox species are not what are observed before and after reactions. We have used the novel environmental scanning transmission electron microscope (ESTEM) with 0.1 nm resolution in systematic studies of complex dynamic oxidation and reduction mechanisms of copper nanoparticles. The oxidation of copper has previously been reported to be dependent on its crystallography and its interaction with the substrate. By following the dynamic oxidation process in situ in real time with high-angle annular dark-field imaging in the ESTEM, we use conditions ideal to track the oxidation front as it progresses across a copper nanoparticle by following the changes in the atomic number (Z) contrast with time. The oxidation occurs via the nucleation of the oxide phase (Cu 2 O) from one area of the nanoparticle which then progresses unidirectionally across the particle, with the Cu-to-Cu 2 O interface having a relationship of Cu{111}//Cu 2 O{111}. The oxidation kinetics are related to the temperature and oxygen pressure. When the process is reversed in hydrogen, the reduction process is observed to be similar to the oxidation, with the same crystallographic relationship between the two phases. The dynamic observations provide unique insights into redox mechanisms which are important to understanding and controlling the oxidation and reduction of copper-based nanoparticles.

Laser induced single spot oxidation of titanium

NASA Astrophysics Data System (ADS)

Jwad, Tahseen; Deng, Sunan; Butt, Haider; Dimov, S.

2016-11-01

Titanium oxides have a wide range of applications in industry, and they can be formed on pure titanium using different methods. Laser-induced oxidation is one of the most reliable methods due to its controllability and selectivity. Colour marking is one of the main applications of the oxidation process. However, the colourizing process based on laser scanning strategies is limited by the relative large processing area in comparison to the beam size. Single spot oxidation of titanium substrates is proposed in this research in order to increase the resolution of the processed area and also to address the requirements of potential new applications. The method is applied to produce oxide films with different thicknesses and hence colours on titanium substrates. High resolution colour image is imprinted on a sheet of pure titanium by converting its pixels' colours into laser parameter settings. Optical and morphological periodic surface structures are also produced by an array of oxide spots and then analysed. Two colours have been coded into one field and the dependencies of the reflected colours on incident and azimuthal angles of the light are discussed. The findings are of interest to a range of application areas, as they can be used to imprint optical devices such as diffusers and Fresnel lenses on metallic surfaces as well as for colour marking.

Second-Order Biomimicry: In Situ Oxidative Self-Processing Converts Copper(I)/Diamine Precursor into a Highly Active Aerobic Oxidation Catalyst.

PubMed

McCann, Scott D; Lumb, Jean-Philip; Arndtsen, Bruce A; Stahl, Shannon S

2017-04-26

A homogeneous Cu-based catalyst system consisting of [Cu(MeCN) 4 ]PF 6 , N , N '-di- tert -butylethylenediamine (DBED), and p -( N , N -dimethylamino)pyridine (DMAP) mediates efficient aerobic oxidation of alcohols. Mechanistic study of this reaction shows that the catalyst undergoes an in situ oxidative self-processing step, resulting in conversion of DBED into a nitroxyl that serves as an efficient cocatalyst for aerobic alcohol oxidation. Insights into this behavior are gained from kinetic studies, which reveal an induction period at the beginning of the reaction that correlates with the oxidative self-processing step, EPR spectroscopic analysis of the catalytic reaction mixture, which shows the buildup of the organic nitroxyl species during steady state turnover, and independent synthesis of oxygenated DBED derivatives, which are shown to serve as effective cocatalysts and eliminate the induction period in the reaction. The overall mechanism bears considerable resemblance to enzymatic reactivity. Most notable is the "oxygenase"-type self-processing step that mirrors generation of catalytic cofactors in enzymes via post-translational modification of amino acid side chains. This higher-order function within a synthetic catalyst system presents new opportunities for the discovery and development of biomimetic catalysts.

The electrochemical reduction processes of solid compounds in high temperature molten salts.

PubMed

Xiao, Wei; Wang, Dihua

2014-05-21

Solid electrode processes fall in the central focus of electrochemistry due to their broad-based applications in electrochemical energy storage/conversion devices, sensors and electrochemical preparation. The electrolytic production of metals, alloys, semiconductors and oxides via the electrochemical reduction of solid compounds (especially solid oxides) in high temperature molten salts has been well demonstrated to be an effective and environmentally friendly process for refractory metal extraction, functional materials preparation as well as spent fuel reprocessing. The (electro)chemical reduction of solid compounds under cathodic polarizations generally accompanies a variety of changes at the cathode/melt electrochemical interface which result in diverse electrolytic products with different compositions, morphologies and microstructures. This report summarizes various (electro)chemical reactions taking place at the compound cathode/melt interface during the electrochemical reduction of solid compounds in molten salts, which mainly include: (1) the direct electro-deoxidation of solid oxides; (2) the deposition of the active metal together with the electrochemical reduction of solid oxides; (3) the electro-inclusion of cations from molten salts; (4) the dissolution-electrodeposition process, and (5) the electron hopping process and carbon deposition with the utilization of carbon-based anodes. The implications of the forenamed cathodic reactions on the energy efficiency, chemical compositions and microstructures of the electrolytic products are also discussed. We hope that a comprehensive understanding of the cathodic processes during the electrochemical reduction of solid compounds in molten salts could form a basis for developing a clean, energy efficient and affordable production process for advanced/engineering materials.

Fluorine and oxygen plasma influence on nanoparticle formation and aggregation in metal oxide thin film transistors

NASA Astrophysics Data System (ADS)

MÄ dzik, Mateusz; Elamurugu, Elangovan; Viegas, Jaime

2017-03-01

Despite recent advances in metal oxide thin-film transistor technology, there are no foundry processes available yet for large-scale deployment of metal oxide electronics and photonics, in a similar way as found for silicon based electronics and photonics. One of the biggest challenges of the metal oxide platform is the stability of the fabricated devices. Also, there is wide dispersion on the measured specifications of fabricated TFT, from lot-to-lot and from different research groups. This can be partially explained by the importance of the deposition method and its parameters, which determine thin film microstructure and thus its electrical properties. Furthermore, substrate pretreatment is an important factor, as it may act as a template for material growth. Not so often mentioned, plasma processes can also affect the morphology of deposited films on further deposition steps, such as inducing nanoparticle formation, which strongly impact the conduction mechanism in the channel layer of the TFT. In this study, molybdenum doped indium oxide is sputtered onto ALD deposited HfO2 with or without pattering, and etched by RIE chlorine based processing. Nanoparticle formation is observed when photoresist is removed by oxygen plasma ashing. HfO2 etching in CF4/Ar plasma prior to resist stripping in oxygen plasma promotes the aggregation of nanoparticles into nanosized branched structures. Such nanostructuring is absent when oxygen plasma steps are replaced by chemical wet processing with acetone. Finally, in order to understand the electronic transport effect of the nanoparticles on metal oxide thin film transistors, TFT have been fabricated and electrically characterized.

In-situ XRD and EDS method study on the oxidation behaviour of Ni-Cu sulphide ore.

PubMed

Li, Guangshi; Cheng, Hongwei; Xiong, Xiaolu; Lu, Xionggang; Xu, Cong; Lu, Changyuan; Zou, Xingli; Xu, Qian

2017-06-12

The oxidation mechanism of sulfides is the key issue during the sulphide-metallurgy process. In this study, the phase transformation and element migration were clearly demonstrated by in-situ laboratory-based X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS), respectively. The reaction sequence and a four-step oxidation mechanism were proposed and identified. The elemental distribution demonstrated that at a low temperature, the Fe atoms diffused outward and the Ni/Cu atoms migrated toward the inner core, whereas the opposite diffusion processes were observed at a higher temperature. Importantly, the unique visual presentation of the oxidation behaviour provided by the combination of in-situ XRD and EDS might be useful for optimising the process parameters to improve the Ni/Cu extraction efficiency during Ni-Cu sulphide metallurgy.

Direct reduction processes for titanium oxide in molten salt

NASA Astrophysics Data System (ADS)

Suzuki, Ryosuke O.

2007-02-01

Molten salt electrolysis using CaCl2 is employed to produce pure titanium and its alloys directly from TiO2 and a mixture of elemental oxides, respectively, as an alternate to the Kroll process. This is because CaO, which is a reduction by-product, is highly soluble in CaCl2. Good-quality titanium containing only a small amount of residual oxygen has been successfully produced and scaled to industrial levels. Thermochemical and electrochemical bases are reviewed to optimize the process conditions. Several processes using molten salt are being examined for future progress in titanium processing.

Gas Sensors Based on One Dimensional Nanostructured Metal-Oxides: A Review

PubMed Central

Arafat, M. M.; Dinan, B.; Akbar, Sheikh A.; Haseeb, A. S. M. A.

2012-01-01

Recently one dimensional (1-D) nanostructured metal-oxides have attracted much attention because of their potential applications in gas sensors. 1-D nanostructured metal-oxides provide high surface to volume ratio, while maintaining good chemical and thermal stabilities with minimal power consumption and low weight. In recent years, various processing routes have been developed for the synthesis of 1-D nanostructured metal-oxides such as hydrothermal, ultrasonic irradiation, electrospinning, anodization, sol-gel, molten-salt, carbothermal reduction, solid-state chemical reaction, thermal evaporation, vapor-phase transport, aerosol, RF sputtering, molecular beam epitaxy, chemical vapor deposition, gas-phase assisted nanocarving, UV lithography and dry plasma etching. A variety of sensor fabrication processing routes have also been developed. Depending on the materials, morphology and fabrication process the performance of the sensor towards a specific gas shows a varying degree of success. This article reviews and evaluates the performance of 1-D nanostructured metal-oxide gas sensors based on ZnO, SnO2, TiO2, In2O3, WOx, AgVO3, CdO, MoO3, CuO, TeO2 and Fe2O3. Advantages and disadvantages of each sensor are summarized, along with the associated sensing mechanism. Finally, the article concludes with some future directions of research. PMID:22969344

Involvement of oxidatively damaged DNA and repair in cancer development and aging

PubMed Central

Tudek, Barbara; Winczura, Alicja; Janik, Justyna; Siomek, Agnieszka; Foksinski, Marek; Oliński, Ryszard

2010-01-01

DNA damage and DNA repair may mediate several cellular processes, like replication and transcription, mutagenesis and apoptosis and thus may be important factors in the development and pathology of an organism, including cancer. DNA is constantly damaged by reactive oxygen species (ROS) and reactive nitrogen species (RNS) directly and also by products of lipid peroxidation (LPO), which form exocyclic adducts to DNA bases. A wide variety of oxidatively-generated DNA lesions are present in living cells. 8-oxoguanine (8-oxoGua) is one of the best known DNA lesions due to its mutagenic properties. Among LPO-derived DNA base modifications the most intensively studied are ethenoadenine and ethenocytosine, highly miscoding DNA lesions considered as markers of oxidative stress and promutagenic DNA damage. Although at present it is impossible to directly answer the question concerning involvement of oxidatively damaged DNA in cancer etiology, it is likely that oxidatively modified DNA bases may serve as a source of mutations that initiate carcinogenesis and are involved in aging (i.e. they may be causal factors responsible for these processes). To counteract the deleterious effect of oxidatively damaged DNA, all organisms have developed several DNA repair mechanisms. The efficiency of oxidatively damaged DNA repair was frequently found to be decreased in cancer patients. The present work reviews the basis for the biological significance of DNA damage, particularly effects of 8-oxoGua and ethenoadduct occurrence in DNA in the aspect of cancer development, drawing attention to the multiplicity of proteins with repair activities. PMID:20589166

Methyltrimethoxysilane (MTMS)-based silica-iron oxide superhydrophobic nanocomposites.

PubMed

Nadargi, Digambar; Gurav, Jyoti; Marioni, Miguel A; Romer, Sara; Matam, Santhosh; Koebel, Matthias M

2015-12-01

We report a facile synthesis of superhydrophobic silica-iron oxide nanocomposites via a co-precursor sol-gel process. The choice of the silica precursor (Methyltrimethoxysilane, MTMS) in combination with iron nitrate altered the pore structure dramatically. The influence of iron oxide doping on the structural properties of pristine MTMS aerogel is discussed. Copyright © 2015 Elsevier Inc. All rights reserved.

Oxidized C5-methyl cytosine bases in DNA: 5-Hydroxymethylcytosine; 5-formylcytosine; and 5-carboxycytosine.

PubMed

Klungland, Arne; Robertson, Adam B

2017-06-01

Recent reports suggest that the Tet enzyme family catalytically oxidize 5-methylcytosine in mammalian cells. The oxidation of 5-methylcytosine can result in three chemically distinct species - 5-hydroxymethylcytsine, 5-formylcytosine, and 5-carboxycytosine. While the base excision repair machinery processes 5-formylcytosine and 5-carboxycytosine rapidly, 5-hydroxymethylcytosine is stable under physiological conditions. As a stable modification 5-hydroxymethylcytosine has a broad range of functions, from stem cell pluriopotency to tumorigenesis. The subsequent oxidation products, 5-formylcytosine and 5-carboxycytosine, are suggested to be involved in an active DNA demethylation pathway. This review provides an overview of the biochemistry and biology of 5-methylcytosine oxidation products. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

Post-treatment of reclaimed waste water based on an electrochemical advanced oxidation process

NASA Technical Reports Server (NTRS)

Verostko, Charles E.; Murphy, Oliver J.; Hitchens, G. D.; Salinas, Carlos E.; Rogers, Tom D.

1992-01-01

The purification of reclaimed water is essential to water reclamation technology life-support systems in lunar/Mars habitats. An electrochemical UV reactor is being developed which generates oxidants, operates at low temperatures, and requires no chemical expendables. The reactor is the basis for an advanced oxidation process in which electrochemically generated ozone and hydrogen peroxide are used in combination with ultraviolet light irradiation to produce hydroxyl radicals. Results from this process are presented which demonstrate concept feasibility for removal of organic impurities and disinfection of water for potable and hygiene reuse. Power, size requirements, Faradaic efficiency, and process reaction kinetics are discussed. At the completion of this development effort the reactor system will be installed in JSC's regenerative water recovery test facility for evaluation to compare this technique with other candidate processes.

Microstructure and High Temperature Oxidation Property of Fe-Cr-B Based Metal/Ceramic Composite Manufactured by Powder Injection Molding Process

NASA Astrophysics Data System (ADS)

Joo, Yeun-Ah; Kim, Young-Kyun; Yoon, Tae-Sik; Lee, Kee-Ahn

2018-03-01

This study investigated the microstructure and high temperature oxidation property of Fe-Cr-B metal/ceramic composite manufactured using powder injection molding process. Observations of initial microstructure showed a unique structure where α-Fe and (Cr, Fe)2B form a continuous three-dimensional network. High temperature oxidation tests were performed at 900, 1000 and 1100 °C, for 24 h, and the oxidation weight gain according to each temperature condition was 0.13, 0.84 and 6.4 mg/cm2, respectively. The oxidation results according to time at 900 and 1000 °C conditions represented parabolic curves, and at 1100 °C condition formed a rectilinear curve. Observation and phase analysis results of the oxides identified Cr2O3 and SiO2 at 900 and 1000 °C. In addition to Cr2O3 and SiO2, CrBO3 and FeCr2O4 formed due to phase decomposition of boride were identified at 1100 °C. Based on the findings above, this study suggested the high temperature oxidation mechanism of Fe-Cr-B metal/ceramic composite manufactured using powder injection molding, and the possibility of its application as a high temperature component material was also discussed.

Chemical interaction matrix between reagents in a Purex based process

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

Brahman, R.K.; Hennessy, W.P.; Paviet-Hartmann, P.

2008-07-01

The United States Department of Energy (DOE) is the responsible entity for the disposal of the United States excess weapons grade plutonium. DOE selected a PUREX-based process to convert plutonium to low-enriched mixed oxide fuel for use in commercial nuclear power plants. To initiate this process in the United States, a Mixed Oxide (MOX) Fuel Fabrication Facility (MFFF) is under construction and will be operated by Shaw AREVA MOX Services at the Savannah River Site. This facility will be licensed and regulated by the U.S. Nuclear Regulatory Commission (NRC). A PUREX process, similar to the one used at La Hague,more » France, will purify plutonium feedstock through solvent extraction. MFFF employs two major process operations to manufacture MOX fuel assemblies: (1) the Aqueous Polishing (AP) process to remove gallium and other impurities from plutonium feedstock and (2) the MOX fuel fabrication process (MP), which processes the oxides into pellets and manufactures the MOX fuel assemblies. The AP process consists of three major steps, dissolution, purification, and conversion, and is the center of the primary chemical processing. A study of process hazards controls has been initiated that will provide knowledge and protection against the chemical risks associated from mixing of reagents over the life time of the process. This paper presents a comprehensive chemical interaction matrix evaluation for the reagents used in the PUREX-based process. Chemical interaction matrix supplements the process conditions by providing a checklist of any potential inadvertent chemical reactions that may take place. It also identifies the chemical compatibility/incompatibility of the reagents if mixed by failure of operations or equipment within the process itself or mixed inadvertently by a technician in the laboratories. (aut0010ho.« less

Cermet anode with continuously dispersed alloy phase and process for making

DOEpatents

Marschman, Steven C.; Davis, Norman C.

1989-01-01

Cermet electrode compositions and methods for making are disclosed which comprise NiO--NiFe.sub.2 O.sub.4 --Cu--Ni. Addition of an effective amount of a metallic catalyst/reactant to a composition of a nickel/iron/oxide, NiO, copper, and nickel produces a stable electrode having significantly increased electrical conductivity. The metallic catalyst functions to disperse the copper and nickel as an alloy continuously throughout the oxide phase of the cermet to render the electrode compositon more highly electrically conductive than were the third metal not present in the base composition. The third metal is preferably added to the base composition as elemental metal and includes aluminum, magnesium, sodium and gallium. The elemental metal is converted to a metal oxide during the sintering process.

Enhanced thermal diffusivity of copperbased composites using copper-RGO sheets

NASA Astrophysics Data System (ADS)

Kim, Sangwoo; Kwon, Hyouk-Chon; Lee, Dohyung; Lee, Hyo-Soo

2017-11-01

The synthesis of copper-reduced graphene oxide (RGO) sheets was investigated in order to control the agglutination of interfaces and develop a manufacturing process for copper-based composite materials based on spark plasma sintering. To this end, copper-GO (graphene oxide) composites were synthesized using a hydrothermal method, while the copper-reduced graphene oxide composites were made by hydrogen reduction. Graphene oxide-copper oxide was hydrothermally synthesized at 80 °C for 5 h, and then annealed at 800 °C for 5 h in argon and hydrazine rate 9:1 to obtain copper-RGO flakes. The morphology and structure of these copper-RGO sheets were characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. After vibratory mixing of the synthesized copper-RGO composites (0-2 wt%) with copper powder, they were sintered at 600 °C for 5 min under100 MPa of pressure by spark plasma sintering process. The thermal diffusivity of the resulting sintered composite was characterized by the laser flash method at 150 °C.

Base Excision Repair of Oxidative DNA Damage

PubMed Central

David, Sheila S.; O’Shea, Valerie L.; Kundu, Sucharita

2010-01-01

Base excision repair plays an important role in preventing mutations associated with the common product of oxidative damage, 8-oxoguanine. Recent structural studies have shown that 8-oxoguanine glycosylases use an intricate series of steps to efficiently search and locate 8-oxoguanine lesions within the multitude of undamaged bases. The importance of prevention of mutations associated with 8-oxoguanine has also been illustrated by direct connections between defects in the BER glycosylase MUTYH and colorectal cancer. In addition, the properties of other guanine oxidation products and the BER glycosylases that remove them are being uncovered. This work is providing surprising and intriguing new insights into the process of base excision repair. PMID:17581577

Isothermal and cyclic oxidation at 1000 and 1100 deg C of four nickel-base alloys: NASA-TRW VIA, B-1900, 713C, and 738X

NASA Technical Reports Server (NTRS)

Barrett, C. A.; Santoro, G. J.; Lowell, C. E.

1973-01-01

The isothermal and cyclic oxidation resistance of four cast Ni-base gamma + gamma prime alloys, NASA-TRW Via, B-1900, 713C, and 738X, was determined in still air at 1000 and 1100 C. The oxidation process was evaluated by specific sample weight change with time, sample thickness change, X-ray diffraction of the scales, and sample metallography. The behavior is discussed in terms of the Cr, Al, and refractory metal contents of the alloys.

Nanoscale reduction of graphene oxide thin films and its characterization

NASA Astrophysics Data System (ADS)

Lorenzoni, M.; Giugni, A.; Di Fabrizio, E.; Pérez-Murano, Francesc; Mescola, A.; Torre, B.

2015-07-01

In this paper, we report on a method to reduce thin films of graphene oxide (GO) to a spatial resolution better than 100 nm over several tens of micrometers by means of an electrochemical scanning probe based lithography. In situ tip-current measurements show that an edged drop in electrical resistance characterizes the reduced areas, and that the reduction process is, to a good approximation, proportional to the applied bias between the onset voltage and the saturation thresholds. An atomic force microscope (AFM) quantifies the drop of the surface height for the reduced profile due to the loss of oxygen. Complementarily, lateral force microscopy reveals a homogeneous friction coefficient of the reduced regions that is remarkably lower than that of native graphene oxide, confirming a chemical change in the patterned region. Micro Raman spectroscopy, which provides access to insights into the chemical process, allows one to quantify the restoration and de-oxidation of the graphitic network driven by the electrochemical reduction and to determine characteristic length scales. It also confirms the homogeneity of the process over wide areas. The results shown were obtained from accurate analysis of the shift, intensity and width of Raman peaks for the main vibrational bands of GO and reduced graphene oxide (rGO) mapped over large areas. Concerning multilayered GO thin films obtained by drop-casting we have demonstrated an unprecedented lateral resolution in ambient conditions as well as an improved control, characterization and understanding of the reduction process occurring in GO randomly folded multilayers, useful for large-scale processing of graphene-based material.

Culture-Dependent and -Independent Identification of Polyphosphate-Accumulating Dechloromonas spp. Predominating in a Full-Scale Oxidation Ditch Wastewater Treatment Plant.

PubMed

Terashima, Mia; Yama, Ayano; Sato, Megumi; Yumoto, Isao; Kamagata, Yoichi; Kato, Souichiro

2016-12-23

The oxidation ditch process is one of the most economical approaches currently used to simultaneously remove organic carbon, nitrogen, and also phosphorus (P) from wastewater. However, limited information is available on biological P removal in this process. In the present study, microorganisms contributing to P removal in a full-scale oxidation ditch reactor were investigated using culture-dependent and -independent approaches. A microbial community analysis based on 16S rRNA gene sequencing revealed that a phylotype closely related to Dechloromonas spp. in the family Rhodocyclaceae dominated in the oxidation ditch reactor. This dominant Dechloromonas sp. was successfully isolated and subjected to fluorescent staining for polyphosphate, followed by microscopic observations and a spectrofluorometric analysis, which clearly demonstrated that the Dechloromonas isolate exhibited a strong ability to accumulate polyphosphate within its cells. These results indicate the potential key role of Dechloromonas spp. in efficient P removal in the oxidation ditch wastewater treatment process.

Culture-Dependent and -Independent Identification of Polyphosphate-Accumulating Dechloromonas spp. Predominating in a Full-Scale Oxidation Ditch Wastewater Treatment Plant

PubMed Central

Terashima, Mia; Yama, Ayano; Sato, Megumi; Yumoto, Isao; Kamagata, Yoichi; Kato, Souichiro

2016-01-01

The oxidation ditch process is one of the most economical approaches currently used to simultaneously remove organic carbon, nitrogen, and also phosphorus (P) from wastewater. However, limited information is available on biological P removal in this process. In the present study, microorganisms contributing to P removal in a full-scale oxidation ditch reactor were investigated using culture-dependent and -independent approaches. A microbial community analysis based on 16S rRNA gene sequencing revealed that a phylotype closely related to Dechloromonas spp. in the family Rhodocyclaceae dominated in the oxidation ditch reactor. This dominant Dechloromonas sp. was successfully isolated and subjected to fluorescent staining for polyphosphate, followed by microscopic observations and a spectrofluorometric analysis, which clearly demonstrated that the Dechloromonas isolate exhibited a strong ability to accumulate polyphosphate within its cells. These results indicate the potential key role of Dechloromonas spp. in efficient P removal in the oxidation ditch wastewater treatment process. PMID:27867159

Bipolar resistive switching in room temperature grown disordered vanadium oxide thin-film devices

NASA Astrophysics Data System (ADS)

Wong, Franklin J.; Sriram, Tirunelveli S.; Smith, Brian R.; Ramanathan, Shriram

2013-09-01

We demonstrate bipolar switching with high OFF/ON resistance ratios (>104) in Pt/vanadium oxide/Cu structures deposited entirely at room temperature. The SET (RESET) process occurs when negative (positive) bias is applied to the top Cu electrode. The vanadium oxide (VOx) films are amorphous and close to the vanadium pentoxide stoichiometry. We also investigated Cu/VOx/W structures, reversing the position of the Cu electrode, and found the same polarity dependence with respect to the top and bottom electrodes, which suggests that the bipolar nature is linked to the VOx layer itself. Bipolar switching can be observed at 100 °C, indicating that it not due to a temperature-induced metal-insulator transition of a vanadium dioxide second phase. We discuss how ionic drift can lead to the bipolar electrical behavior of our junctions, similar to those observed in devices based on several other defective oxides. Such low-temperature processed oxide switches could be of relevance to back-end or package integration processing schemes.

Process for strengthening silicon based ceramics

DOEpatents

Kim, Hyoun-Ee; Moorhead, A. J.

1993-01-01

A process for strengthening silicon based ceramic monolithic materials and omposite materials that contain silicon based ceramic reinforcing phases that requires that the ceramic be exposed to a wet hydrogen atmosphere at about 1400.degree. C. The process results in a dense, tightly adherent silicon containing oxide layer that heals, blunts , or otherwise negates the detrimental effect of strength limiting flaws on the surface of the ceramic body.

Process for strengthening silicon based ceramics

DOEpatents

Kim, Hyoun-Ee; Moorhead, A. J.

1993-04-06

A process for strengthening silicon based ceramic monolithic materials and omposite materials that contain silicon based ceramic reinforcing phases that requires that the ceramic be exposed to a wet hydrogen atmosphere at about 1400.degree. C. The process results in a dense, tightly adherent silicon containing oxide layer that heals, blunts , or otherwise negates the detrimental effect of strength limiting flaws on the surface of the ceramic body.

Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study (in Korean)

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

Kwon, K.D.; Sposito, G.

2010-02-01

Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

Laser Surface Treatment of Sintered Alumina

NASA Astrophysics Data System (ADS)

Hagemann, R.; Noelke, C.; Kaierle, S.; Wesling, V.

Sintered alumina ceramics are used as refractory materials for industrial aluminum furnaces. In this environment the ceramic surface is in permanent contact with molten aluminum resulting in deposition of oxidic material on its surface. Consequently, a lower volume capacity as well as thermal efficiency of the furnaces follows. To reduce oxidic adherence of the ceramic material, two laser-based surface treatment processes were investigated: a powder- based single-step laser cladding and a laser surface remelting. Main objective is to achieve an improved surface quality of the ceramic material considering the industrial requirements as a high process speed.

Influence of Processing on the Microstructure and Mechanical Properties of a NbAl3-Base Alloy

NASA Technical Reports Server (NTRS)

Hebsur, Mohan G.; Locci, Ivan E.; Raj, S. V.; Nathal, Michael V.

1992-01-01

Induction melting and rapid solidification processing, followed by grinding to 75-micron powder and P/M consolidation, have been used to produce a multiphase, NbAl3-based, oxidation-resistant alloy of Nb-67Al-7Cr-0.5Y-0.25W composition whose strength and ductility are significantly higher than those of the induction-melted alloy at test temperatures of up to 1200 K. Attention is given to the beneficial role of microstructural refinement; the major second phase, AlNbCr, improves both oxidation resistance and mechanical properties.

TiOx-based thin-film transistors prepared by femtosecond laser pre-annealing

NASA Astrophysics Data System (ADS)

Shan, Fei; Kim, Sung-Jin

2018-02-01

We report on thin-film transistors (TFTs) based on titanium oxide (TiOx) prepared using femtosecond laser pre-annealing for electrical application of n-type channel oxide transparent TFTs. Amorphous TFTs using TiOx semiconductors as an active layer have a low-temperature process and show remarkable electrical performance. And the femtosecond laser pre-annealing process has greater flexibility and development space for semiconductor production activity, with a fast preparation method. TFTs with a TiOx semiconductor pre-annealed via femtosecond laser at 3 W have a pinhole-free and smooth surface without crystal grains.

Monitoring Interfacial Lipid Oxidation in Oil-in-Water Emulsions Using Spatially Resolved Optical Techniques.

PubMed

Banerjee, Chiranjib; Westberg, Michael; Breitenbach, Thomas; Bregnhøj, Mikkel; Ogilby, Peter R

2017-06-06

The oxidation of lipids is an important phenomenon with ramifications for disciplines that range from food science to cell biology. The development and characterization of tools and techniques to monitor lipid oxidation are thus relevant. Of particular significance in this regard are tools that facilitate the study of oxidations at interfaces in heterogeneous samples (e.g., oil-in-water emulsions, cell membranes). In this article, we establish a proof-of-principle for methods to initiate and then monitor such oxidations with high spatial resolution. The experiments were performed using oil-in-water emulsions of polyunsaturated fatty acids (PUFAs) prepared from cod liver oil. We produced singlet oxygen at a point near the oil-water interface of a given PUFA droplet in a spatially localized two-photon photosensitized process. We then followed the oxidation reactions initiated by this process with the fluorescence-based imaging technique of structured illumination microscopy (SIM). We conclude that the approach reported herein has attributes well-suited to the study of lipid oxidation in heterogeneous samples.

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater.

PubMed

Gu, Di; Gao, Simeng; Jiang, TingTing; Wang, Baohui

2017-03-15

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO 2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process.

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater

PubMed Central

Gu, Di; Gao, Simeng; Jiang, TingTing; Wang, Baohui

2017-01-01

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process. PMID:28294180

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater

NASA Astrophysics Data System (ADS)

Gu, Di; Gao, Simeng; Jiang, Tingting; Wang, Baohui

2017-03-01

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process.

Biomarker analysis of liver cells exposed to surfactant-wrapped and oxidized multi-walled carbon nanotubes (MWCNTs)

EPA Science Inventory

Carbon nanotubes (CNTs) have great potential in industrial, consumer, and mechanical applications, based partly on their unique structural, optical and electronic properties. CNTs are commonly oxidized or treated with surfactants to facilitate aqueous solution processing, and the...

Activation of Magnesium Lignosulfonate and Kraft Lignin: Influence on the Properties of Phenolic Resin-Based Composites for Potential Applications in Abrasive Materials

PubMed Central

Klapiszewski, Lukasz; Jamrozik, Artur; Strzemiecka, Beata; Matykiewicz, Danuta; Voelkel, Adam; Jesionowski, Teofil

2017-01-01

Magnesium lignosulfonate and kraft lignin were activated by different oxidizing agents for use in phenolic resin composites used for the production of abrasive components. The physicochemical properties of the oxidized materials were analyzed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), dynamic mechanical-thermal analysis (DMTA) and inverse gas chromatography (IGC). The homogeneity of the model abrasive composites containing the studied products was assessed based on observations obtained using a scanning electron microscope (SEM). FTIR and XPS analysis of the oxidized products indicated that the activation process leads mainly to the formation of carbonyl groups. The IGC technique was used to assess changes in the surface energy and the acid–base properties of the studied biopolymers. The changes in the acid–base properties suggest that more groups acting as electron donors appear on the oxidized surface of the materials. DMTA studies showed that the model composites with 5% magnesium lignosulfonate oxidized by H2O2 had the best thermomechanical properties. Based on the results it was possible to propose a hypothetical mechanism of the oxidation of the natural polymers. The use of such oxidized products may improve the thermomechanical properties of abrasive articles. PMID:28594358

Simultaneous Improvement of Oxidative and Hydrolytic Resistance of Polycarbonate Urethanes Based on Polydimethylsiloxane/Poly(hexamethylene carbonate) Mixed Macrodiols.

PubMed

Li, Zhen; Yang, Jian; Ye, Heng; Ding, Mingming; Luo, Feng; Li, Jianshu; Li, Jiehua; Tan, Hong; Fu, Qiang

2018-06-11

The degradation behaviors including oxidation and hydrolysis of silicone modified polycarbonate urethanes were thoroughly investigated. These polyurethanes were based on polyhexamethylene carbonate (PHMC)/polydimethylsiloxane (PDMS) mixed macrodiols with molar ratio of PDMS ranging from 5% to 30%. It was proved that PDMS tended to migrate toward surface and even a small amount of PDMS could form a silicone-like surface. Macrophages-mediated oxidation process indicated that the PDMS surface layer was desirable to protect the fragile soft PHMC from the attack of degradative species. Hydrolysis process was probed in detail after immersing in boiling buffered water using combined analytical tools. Hydrolytically stable PDMS could act as protective shields for the bulk to hinder the chain scission of polycarbonate carbonyls whereas the hydrolysis of urethane linkages was less affected. Although the promoted phase separation at higher PDMS fractions lead to possible physical defects and mechanical compromise after degradation, simultaneously enhanced oxidation and hydrolysis resistance could be achieved for the polyurethanes with proper PDMS incorporation.

A family of oxide ion conductors based on the ferroelectric perovskite Na0.5Bi0.5TiO3.

PubMed

Li, Ming; Pietrowski, Martha J; De Souza, Roger A; Zhang, Huairuo; Reaney, Ian M; Cook, Stuart N; Kilner, John A; Sinclair, Derek C

2014-01-01

Oxide ion conductors find important technical applications in electrochemical devices such as solid-oxide fuel cells (SOFCs), oxygen separation membranes and sensors. Na0.5Bi0.5TiO3 (NBT) is a well-known lead-free piezoelectric material; however, it is often reported to possess high leakage conductivity that is problematic for its piezo- and ferroelectric applications. Here we report this high leakage to be oxide ion conduction due to Bi-deficiency and oxygen vacancies induced during materials processing. Mg-doping on the Ti-site increases the ionic conductivity to ~0.01 S cm(-1) at 600 °C, improves the electrolyte stability in reducing atmospheres and lowers the sintering temperature. This study not only demonstrates how to adjust the nominal NBT composition for dielectric-based applications, but also, more importantly, gives NBT-based materials an unexpected role as a completely new family of oxide ion conductors with potential applications in intermediate-temperature SOFCs and opens up a new direction to design oxide ion conductors in perovskite oxides.

Coupling Between the Thermosphere and the Stratosphere: the Role of Nitric Oxide

NASA Technical Reports Server (NTRS)

Brasseur, G.

1984-01-01

In order to understand the lower ionosphere and its probable control by dynamical processes, the behavior of nitric oxide below 100 km was investigated. A two dimensional model with coupled chemical and dynamical processes was constructed. Calculations based on the model reveal that the chemical conditions at the stratopause are related to the state of the thermosphere. This coupling mechanism can be partly explained by the downward transport of nitric oxide during the winter season, and consequently depends on the dynamical conditions in the mesosphere and in the lower thermosphere (mean circulation and waves). In summer, the photodissociation of nitric oxide plays an important role and the thermospheric NO abundance modulates the radiation field reaching the upper stratosphere. Perturbations in the nitric oxide concentration above the mesopause could therefore have an impact in the vicinity of the stratopause.

Multifunctional Organic-Semiconductor Interfacial Layers for Solution-Processed Oxide-Semiconductor Thin-Film Transistor.

PubMed

Kwon, Guhyun; Kim, Keetae; Choi, Byung Doo; Roh, Jeongkyun; Lee, Changhee; Noh, Yong-Young; Seo, SungYong; Kim, Myung-Gil; Kim, Choongik

2017-06-01

The stabilization and control of the electrical properties in solution-processed amorphous-oxide semiconductors (AOSs) is crucial for the realization of cost-effective, high-performance, large-area electronics. In particular, impurity diffusion, electrical instability, and the lack of a general substitutional doping strategy for the active layer hinder the industrial implementation of copper electrodes and the fine tuning of the electrical parameters of AOS-based thin-film transistors (TFTs). In this study, the authors employ a multifunctional organic-semiconductor (OSC) interlayer as a solution-processed thin-film passivation layer and a charge-transfer dopant. As an electrically active impurity blocking layer, the OSC interlayer enhances the electrical stability of AOS TFTs by suppressing the adsorption of environmental gas species and copper-ion diffusion. Moreover, charge transfer between the organic interlayer and the AOS allows the fine tuning of the electrical properties and the passivation of the electrical defects in the AOS TFTs. The development of a multifunctional solution-processed organic interlayer enables the production of low-cost, high-performance oxide semiconductor-based circuits. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High Dielectric Performance of Solution-Processed Aluminum Oxide-Boron Nitride Composite Films

NASA Astrophysics Data System (ADS)

Yu, Byoung-Soo; Ha, Tae-Jun

2018-04-01

The material compositions of oxide films have been extensively investigated in an effort to improve the electrical characteristics of dielectrics which have been utilized in various electronic devices such as field-effect transistors, and storage capacitors. Significantly, solution-based compositions have attracted considerable attention as a highly effective and practical technique to replace vacuum-based process in large-area. Here, we demonstrate solution-processed composite films consisting of aluminum oxide (Al2O3) and boron nitride (BN), which exhibit remarkable dielectric properties through the optimization process. The leakage current of the optimized Al2O3-BN thin films was decreased by a factor of 100 at 3V, compared to pristine Al2O3 thin film without a loss of the dielectric constant or degradation of the morphological roughness. The characterization by X-ray photoelectron spectroscopy measurements revealed that the incorporation of BN with an optimized concentration into the Al2O3 dielectric film reduced the density of oxygen vacancies which act as defect states, thereby improving the dielectric characteristics.

Research on filling process of fuel and oxidant during detonation based on absorption spectrum technology

NASA Astrophysics Data System (ADS)

Lv, Xiao-Jing; Li, Ning; Weng, Chun-Sheng

2014-12-01

Research on detonation process is of great significance for the control optimization of pulse detonation engine. Based on absorption spectrum technology, the filling process of fresh fuel and oxidant during detonation is researched. As one of the most important products, H2O is selected as the target of detonation diagnosis. Fiber distributed detonation test system is designed to enable the detonation diagnosis under adverse conditions in detonation process. The test system is verified to be reliable. Laser signals at different working frequency (5Hz, 10Hz and 20Hz) are detected. Change of relative laser intensity in one detonation circle is analyzed. The duration of filling process is inferred from the change of laser intensity, which is about 100~110ms. The peak of absorption spectrum is used to present the concentration of H2O during the filling process of fresh fuel and oxidant. Absorption spectrum is calculated, and the change of absorption peak is analyzed. Duration of filling process calculated with absorption peak consisted with the result inferred from the change of relative laser intensity. The pulse detonation engine worked normally and obtained the maximum thrust at 10Hz under experiment conditions. The results are verified through H2O gas concentration monitoring during detonation.

Effects of the Fabrication Process and Thermal Cycling on the Oxidation of Zirconium-Niobium Pressure Tubes

NASA Astrophysics Data System (ADS)

Nam, Cheol

2009-12-01

Pressure tubes made of Zr-2.5%Nb alloy are used to contain fuels and coolant in CANDU nuclear power reactors The pressure tube oxidizes during reactor operation and hydrogen ingress through the oxide grown on the tube limits its lifetime. Little attention was paid to the intermediate tube manufacturing processes in enhancing the oxidation resistance. In addition, the oxide grown on the tube experiences various thermal cycles depending on the reactor shutdown and startup cycles. To address these two aspects and to better understand the oxidation process of the Zr-2.5Nb tube, research was conducted in two parts: (i) effects of tube fabrication on oxidation behavior, and (ii) thermal cycling behaviors of oxides grown on a pressure tube. In the first part, the optimum manufacturing process was pursued to improve the corrosion resistance of Zr-2.5Nb tubes. Experimental micro-tubes were fabricated with various manufacturing routes in the stages of billet preparation, hot extrusion and cold drawing. These were oxidized in air at 400°C and 500°C, and in an autoclave at 360°C lithiated water. Microstructure and texture of the tubes and oxides were characterized with X-ray diffraction, scanning electron microscope and optical microscope. Special emphasis was given to examinations of the metal/oxide interface structures. A correlation between the manufacturing process and oxidation resistance was investigated in terms of tube microstructure and the metal/oxide interface structure. As a result, it was consistently observed that uniform interface structures were formed on the tubes which had a fine distribution of secondary phases. These microstructures were found to be beneficial in enhancing the oxidation resistance as opposed to the tubes that had coarse and continuous beta-Zr phases. Based on these observations, a schematic model of the oxidation process was proposed with respect to the oxidation resistance under oxidizing temperatures of 360°C, 400°C and 500°C. In the second part, the oxides grown on a standard Zr-2.5Nb pressure tube were analyzed by X-ray diffraction peak broadening and line shift. Crystallite size, t-ZrO2 fraction and residual stress of the zirconium oxides were investigated upon several thermal cycles at DeltaT range of 500°C--750°C. The oxide residual stresses measured by the sin2psi method were always compressive around 2 GPa. Different stress-states were noticed with the oxides grown on different sections of pressure tube. The compressive stress was released when the oxide was thermally cycled at the highest DeltaT of 750°C. Discussion was given to the effects of anisotropic nature of thermal expansion coefficients and crystallographic texture on the stress-state of Zr oxides.

Advanced treatment of biologically pretreated coal gasification wastewater by a novel integration of heterogeneous Fenton oxidation and biological process.

PubMed

Xu, Peng; Han, Hongjun; Zhuang, Haifeng; Hou, Baolin; Jia, Shengyong; Xu, Chunyan; Wang, Dexin

2015-04-01

Laboratorial scale experiments were conducted in order to investigate a novel system integrating heterogeneous Fenton oxidation (HFO) with anoxic moving bed biofilm reactor (ANMBBR) and biological aerated filter (BAF) process on advanced treatment of biologically pretreated coal gasification wastewater (CGW). The results indicated that HFO with the prepared catalyst (FeOx/SBAC, sewage sludge based activated carbon (SBAC) which loaded Fe oxides) played a key role in eliminating COD and COLOR as well as in improving the biodegradability of raw wastewater. The surface reaction and hydroxyl radicals (OH) oxidation were the mechanisms for FeOx/SBAC catalytic reaction. Compared with ANMBBR-BAF process, the integrated system was more effective in abating COD, BOD5, total phenols (TPs), total nitrogen (TN) and COLOR and could shorten the retention time. Therefore, the integrated system was a promising technology for engineering applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

Use of ultrasmall superparamagnetic iron oxide particles for imaging carotid atherosclerosis.

PubMed

Usman, Ammara; Sadat, Umar; Patterson, Andrew J; Tang, Tjun Y; Varty, Kevin; Boyle, Jonathan R; Armon, Mathew P; Hayes, Paul D; Graves, Martin J; Gillard, Jonathan H

2015-10-01

Based on the results of histopathological studies, inflammation within atherosclerotic tissue is now widely accepted as a key determinant of the disease process. Conventional imaging methods can highlight the location and degree of luminal stenosis but not the inflammatory activity of the plaque. Iron oxide-based MRI contrast media particularly ultrasmall supermagnetic particles of iron oxide have shown potential in assessing atheromatous plaque inflammation and in determining efficacy of antiatherosclerosis pharmacological treatments. In this paper, we review current data on the use of ultrasmall superparamagnetic iron oxides in atherosclerosis imaging with focus on ferumoxtran-10 and ferumoxytol. The basic chemistry, pharmacokinetics and dynamics, potential applications, limitations and future perspectives of these contrast media nanoparticles are discussed.

Carbohydrate-Assisted Combustion Synthesis To Realize High-Performance Oxide Transistors.

PubMed

Wang, Binghao; Zeng, Li; Huang, Wei; Melkonyan, Ferdinand S; Sheets, William C; Chi, Lifeng; Bedzyk, Michael J; Marks, Tobin J; Facchetti, Antonio

2016-06-08

Owing to high carrier mobilities, good environmental/thermal stability, excellent optical transparency, and compatibility with solution processing, thin-film transistors (TFTs) based on amorphous metal oxide semiconductors (AOSs) are promising alternatives to those based on amorphous silicon (a-Si:H) and low-temperature (<600 °C) poly-silicon (LTPS). However, solution-processed display-relevant indium-gallium-tin-oxide (IGZO) TFTs suffer from low carrier mobilities and/or inferior bias-stress stability versus their sputtered counterparts. Here we report that three types of environmentally benign carbohydrates (sorbitol, sucrose, and glucose) serve as especially efficient fuels for IGZO film combustion synthesis to yield high-performance TFTs. The results indicate that these carbohydrates assist the combustion process by lowering the ignition threshold temperature and, for optimal stoichiometries, enhancing the reaction enthalpy. IGZO TFT mobilities are increased to >8 cm(2) V(-1) s(-1) on SiO2/Si gate dielectrics with significantly improved bias-stress stability. The first correlations between precursor combustion enthalpy and a-MO densification/charge transport are established.

Chemical, electrochemical and photochemical molecular water oxidation catalysts.

PubMed

Bofill, Roger; García-Antón, Jordi; Escriche, Lluís; Sala, Xavier

2015-11-01

Hydrogen release from the splitting of water by simply using sunlight as the only energy source is an old human dream that could finally become a reality. This process involves both the reduction and oxidation of water into hydrogen and oxygen, respectively. While the first process has been fairly overcome, the conversion of water into oxygen has been traditionally the bottleneck process hampering the development of a sustainable hydrogen production based on water splitting. Fortunately, a revolution in this field has occurred during the past decade, since many research groups have been conducting an intense research in this area. Thus, while molecular, well-characterized catalysts able to oxidize water were scarce just five years ago, now a wide range of transition metal based compounds has been reported as active catalysts for this transformation. This review reports the most prominent key advances in the field, covering either examples where the catalysis is triggered chemically, electrochemically or photochemically. Copyright © 2014 Elsevier B.V. All rights reserved.

Low-Energy, Low-Cost Production of Ethylene by Low- Temperature Oxidative Coupling of Methane

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

Radaelli, Guido; Chachra, Gaurav; Jonnavittula, Divya

In this project, we develop a catalytic process technology for distributed small-scale production of ethylene by oxidative coupling of methane at low temperatures using an advanced catalyst. The Low Temperature Oxidative Coupling of Methane (LT-OCM) catalyst system is enabled by a novel chemical catalyst and process pioneered by Siluria, at private expense, over the last six years. Herein, we develop the LT-OCM catalyst system for distributed small-scale production of ethylene by identifying and addressing necessary process schemes, unit operations and process parameters that limit the economic viability and mass penetration of this technology to manufacture ethylene at small-scales. The outputmore » of this program is process concepts for small-scale LT-OCM catalyst based ethylene production, lab-scale verification of the novel unit operations adopted in the proposed concept, and an analysis to validate the feasibility of the proposed concepts.« less

Manganese Oxide Nanoarray-Based Monolithic Catalysts: Tunable Morphology and High Efficiency for CO Oxidation

DOE PAGES

Chen, Sheng-Yu; Song, Wenqiao; Lin, Hui-Jan; ...

2016-03-08

In this work, a generic one-pot hydrothermal synthesis route has been successfully designed and utilized to in situ grow uniform manganese oxide nanorods and nanowires onto the cordierite honeycomb monolithic substrates, forming a series of nanoarray-based monolithic catalysts. During the synthesis process, three types of potassium salt oxidants have been used with different reduction potentials, i.e., K 2Cr 2O 7, KClO 3, and K 2S 2O 8, denoted as HM-DCM, HM-PCR, and HM-PSF, respectively. The different reduction potentials of the manganese source (Mn 2+) and oxidants induced the formation of manganese oxide nanoarrays with different morphology, surface area, and reactivitymore » of carbon monoxide (CO) oxidation. K 2Cr 2O 7 and KClO 3 can induce sharp and long nanowires with slow growth rates due to their low reduction potentials. In comparison, the nanoarrays of HM-PSF presented shorter nanorods but displayed an efficient 90% CO oxidation conversion at 200 °C (T90) without noble-metal loading. Reducibility tests for the three monolithic catalysts by hydrogen temperature-programmed reduction revealed an activation energy order of HM-PSF > HM-DCM > HM-PCR for CO oxidation. The characterizations of oxygen temperature-programmed desorption and X-ray photoelectron spectroscopy indicated the abundant surface-adsorbed oxygen and lattice oxygen contributing to the superior reactivity of HM-PSF. Finally, the straightforward synthetic process showed a scalable, low-cost, and template-free method to fabricate manganese oxide nanoarray monolithic catalysts for exhaust treatment.« less

Reflectometry-Ellipsometry Reveals Thickness, Growth Rate, and Phase Composition in Oxidation of Copper.

PubMed

Diaz Leon, Juan J; Fryauf, David M; Cormia, Robert D; Zhang, Min-Xian Max; Samuels, Kathryn; Williams, R Stanley; Kobayashi, Nobuhiko P

2016-08-31

The oxidation of copper is a complicated process. Copper oxide develops two stable phases at room temperature and standard pressure (RTSP): cuprous oxide (Cu2O) and cupric oxide (CuO). Both phases have different optical and electrical characteristics that make them interesting for applications such as solar cells or resistive switching devices. For a given application, it is necessary to selectively control oxide thickness and cupric/cuprous oxide phase volume fraction. The thickness and composition of a copper oxide film growing on the surface of copper widely depend on the characteristics of as-deposited copper. In this Research Article, two samples, copper films prepared by two different deposition techniques, electron-beam evaporation and sputtering, were studied. As the core part of the study, the formation of the oxidized copper was analyzed routinely over a period of 253 days using spectroscopic polarized reflectometry-spectroscopic ellipsometry (RE). An effective medium approximation (EMA) model was used to fit the RE data. The RE measurements were complemented and validated by using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and X-ray diffraction (XRD). Our results show that the two samples oxidized under identical laboratory ambient conditions (RTSP, 87% average relative humidity) developed unique oxide films following an inverse-logarithmic growth rate with thickness and composition different from each other over time. Discussion is focused on the ability of RE to simultaneously extract thickness (i.e., growth rate) and composition of copper oxide films and on plausible physical mechanisms responsible for unique oxidation habits observed in the two copper samples. It appears that extended surface characteristics (i.e., surface roughness and grain boundaries) and preferential crystalline orientation of as-deposited polycrystalline copper films control the growth kinetics of the copper oxide film. Analysis based on a noncontact and nondestructive measurement, such as RE, to extract key material parameters is beneficial for conveniently understanding the oxidation process that would ultimately enable copper oxide-based devices at manufacturing scales.

Second-Order Biomimicry: In Situ Oxidative Self-Processing Converts Copper(I)/Diamine Precursor into a Highly Active Aerobic Oxidation Catalyst

PubMed Central

2017-01-01

A homogeneous Cu-based catalyst system consisting of [Cu(MeCN)4]PF6, N,N′-di-tert-butylethylenediamine (DBED), and p-(N,N-dimethylamino)pyridine (DMAP) mediates efficient aerobic oxidation of alcohols. Mechanistic study of this reaction shows that the catalyst undergoes an in situ oxidative self-processing step, resulting in conversion of DBED into a nitroxyl that serves as an efficient cocatalyst for aerobic alcohol oxidation. Insights into this behavior are gained from kinetic studies, which reveal an induction period at the beginning of the reaction that correlates with the oxidative self-processing step, EPR spectroscopic analysis of the catalytic reaction mixture, which shows the buildup of the organic nitroxyl species during steady state turnover, and independent synthesis of oxygenated DBED derivatives, which are shown to serve as effective cocatalysts and eliminate the induction period in the reaction. The overall mechanism bears considerable resemblance to enzymatic reactivity. Most notable is the “oxygenase”-type self-processing step that mirrors generation of catalytic cofactors in enzymes via post-translational modification of amino acid side chains. This higher-order function within a synthetic catalyst system presents new opportunities for the discovery and development of biomimetic catalysts. PMID:28470049

A niobium oxide-tantalum oxide selector-memristor self-aligned nanostack

NASA Astrophysics Data System (ADS)

Diaz Leon, Juan J.; Norris, Kate J.; Yang, J. Joshua; Sevic, John F.; Kobayashi, Nobuhiko P.

2017-03-01

The integration of nonlinear current-voltage selectors and bi-stable memristors is a paramount step for reliable operation of crossbar arrays. In this paper, the self-aligned assembly of a single nanometer-scale device that contains both a selector and a memristor is presented. The two components (i.e., selector and memristor) are vertically assembled via a self-aligned fabrication process combined with electroforming. In designing the device, niobium oxide and tantalum oxide are chosen as materials for selector and memristor, respectively. The formation of niobium oxide is visualized by exploiting the self-limiting reaction between niobium and tantalum oxide; crystalline niobium (di)oxide forms at the interface between metallic niobium and tantalum oxide via electrothermal heating, resulting in a niobium oxide selector self-aligned to a tantalum oxide memristor. A steady-state finite element analysis is used to assess the electrothermal heating expected to occur in the device. Current-voltage measurements and structural/chemical analyses conducted for the virgin device, the electroforming process, and the functional selector-memristor device are presented. The demonstration of a self-aligned, monolithically integrated selector-memristor device would pave a practical pathway to various circuits based on memristors attainable at manufacturing scales.

Oxidation resistant slurry coating for carbon-based materials

NASA Technical Reports Server (NTRS)

Smialek, J. L.; Rybicki, G. C. (Inventor)

1985-01-01

An oxidation resistant coating is produced on carbon-base materials, and the same processing step effects an infiltration of the substrate with silicon containing material. The process comprises making a slurry of nickel and silicon powders in a nitrocellulose lacquer, spraying onto the graphite or carbon-carbon substrate, and sintering in vacuum to form a fused coating that wets and covers the surface as well as penetrates into the pores of the substrate. Optimum wetting and infiltration occurs in the range of Ni-60 w/o Si to Ni-90 w/o Si with deposited thicknesses of 25-100 mg/sq. cm. Sintering temperatures of about 1200 C to about 1400 C are used, depending on the melting point of the specific coating composition. The sintered coating results in Ni-Si intermetallic phases and SiC, both of which are highly oxidation resistant.

Biogenic VOC Oxidation is Modulated by Anthropogenic Pollution in the South East US

NASA Astrophysics Data System (ADS)

Misztal, P. K.; Romer, P.; Duffey, K.; Cohen, R. C.; Kaser, L.; Seco, R.; Park, J.; Kim, S.; Guenther, A. B.; Goldstein, A. H.

2013-12-01

Biogenic volatile organic compounds (VOC) are known to play important roles for atmospheric chemistry, formation of secondary organic aerosol (SOA), and thus climate. However, the impacts of anthropogenic emissions on the BVOC oxidation mechanisms and SOA formation processes are not yet well understood. The SOAS summer 2013 campaign goals include looking holistically at physicochemical processes of BVOC emission, oxidation, and subsequent SOA formation and the role of anthropogenic emissions in those processes. Gas-phase composition changes of the broad range of VOCs were measured by PTR-ToF-MS at the Centreville SEARCH site located in a mixed deciduous forest near Brent, Alabama. The instrument sampled from the top of the tower at a high acquisition rate (10 Hz) using an inlet collocated with other measurements (wind, radicals, nitrogen oxides, etc.). Isoprene concentrations were extremely high, peaking at up to approximately 10 ppb during the hottest and sunniest days. Isoprene oxidation chemistry was clearly affected by anthropogenic influences. The rate of isoprene oxidation and the abundance of the first (MVK, MAC, etc.) and second (hydroxyacetone, etc.) order products were significantly different under cleaner conditions than under more polluted conditions. Isoprene oxidation likely is more dominated by the hydroperoxyl pathway under clean conditions while the NO pathway is more important under pollution conditions. Observations of the full range of detected isoprene oxidation products will be discussed and examined under relatively clean and polluted conditions. Both daytime and nighttime oxidation pathways will be examined, and comparison with airborne measurements will be shown to relate our ground based observations to more regional photochemical VOC processing.

Charge Transport in Low-Temperature Processed Thin-Film Transistors Based on Indium Oxide/Zinc Oxide Heterostructures.

PubMed

Krausmann, Jan; Sanctis, Shawn; Engstler, Jörg; Luysberg, Martina; Bruns, Michael; Schneider, Jörg J

2018-06-20

The influence of the composition within multilayered heterostructure oxide semiconductors has a critical impact on the performance of thin-film transistor (TFT) devices. The heterostructures, comprising alternating polycrystalline indium oxide and zinc oxide layers, are fabricated by a facile atomic layer deposition (ALD) process, enabling the tuning of its electrical properties by precisely controlling the thickness of the individual layers. This subsequently results in enhanced TFT performance for the optimized stacked architecture after mild thermal annealing at temperatures as low as 200 °C. Superior transistor characteristics, resulting in an average field-effect mobility (μ sat. ) of 9.3 cm 2 V -1 s -1 ( W/ L = 500), an on/off ratio ( I on / I off ) of 5.3 × 10 9 , and a subthreshold swing of 162 mV dec -1 , combined with excellent long-term and bias stress stability are thus demonstrated. Moreover, the inherent semiconducting mechanism in such multilayered heterostructures can be conveniently tuned by controlling the thickness of the individual layers. Herein, devices comprising a higher In 2 O 3 /ZnO ratio, based on individual layer thicknesses, are predominantly governed by percolation conduction with temperature-independent charge carrier mobility. Careful adjustment of the individual oxide layer thicknesses in devices composed of stacked layers plays a vital role in the reduction of trap states, both interfacial and bulk, which consequently deteriorates the overall device performance. The findings enable an improved understanding of the correlation between TFT performance and the respective thin-film composition in ALD-based heterostructure oxides.

Carbon Inputs From Riparian Vegetation Limit Oxidation of Physically Bound Organic Carbon Via Biochemical and Thermodynamic Processes: OC Oxidation Processes Across Vegetation

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

Graham, Emily B.; Tfaily, Malak M.; Crump, Alex R.

In light of increasing terrestrial carbon (C) transport across aquatic boundaries, the mechanisms governing organic carbon (OC) oxidation along terrestrial-aquatic interfaces are crucial to future climate predictions. Here, we investigate biochemistry, metabolic pathways, and thermodynamics corresponding to OC oxidation in the Columbia River corridor. We leverage natural vegetative differences to encompass variation in terrestrial C inputs. Our results suggest that decreases in terrestrial C deposition associated with diminished riparian vegetation induce oxidation of physically-bound (i.e., mineral and microbial) OC at terrestrial-aquatic interfaces. We also find that contrasting metabolic pathways oxidize OC in the presence and absence of vegetation and—in directmore » conflict with the concept of ‘priming’—that inputs of water-soluble and thermodynamically-favorable terrestrial OC protects bound-OC from oxidation. Based on our results, we propose a mechanistic conceptualization of OC oxidation along terrestrial-aquatic interfaces that can be used to model heterogeneous patterns of OC loss under changing land cover distributions.« less

Processing of fused silicide coatings for carbon-based materials

NASA Technical Reports Server (NTRS)

Smialek, J. L.

1982-01-01

The processing and oxidation resistance of fused Al-Si and Ni-Si slurry coatings on ATJ graphite was studied. Ni-Si coatings in the 70 to 90 percent Si range were successfully processed to melt, wet, and bond to the graphite. The molten coatings also infiltrated the porosity in graphite and reacted with it to form SiC in the coating. Cyclic oxidation at 1200 C showed that these coatings were not totally protective because of local attack of the substrate, due to the extreme thinness of the coatings in combination with coating cracks.

In-Vivo Imaging of Cell Migration Using Contrast Enhanced MRI and SVM Based Post-Processing.

PubMed

Weis, Christian; Hess, Andreas; Budinsky, Lubos; Fabry, Ben

2015-01-01

The migration of cells within a living organism can be observed with magnetic resonance imaging (MRI) in combination with iron oxide nanoparticles as an intracellular contrast agent. This method, however, suffers from low sensitivity and specificty. Here, we developed a quantitative non-invasive in-vivo cell localization method using contrast enhanced multiparametric MRI and support vector machines (SVM) based post-processing. Imaging phantoms consisting of agarose with compartments containing different concentrations of cancer cells labeled with iron oxide nanoparticles were used to train and evaluate the SVM for cell localization. From the magnitude and phase data acquired with a series of T2*-weighted gradient-echo scans at different echo-times, we extracted features that are characteristic for the presence of superparamagnetic nanoparticles, in particular hyper- and hypointensities, relaxation rates, short-range phase perturbations, and perturbation dynamics. High detection quality was achieved by SVM analysis of the multiparametric feature-space. The in-vivo applicability was validated in animal studies. The SVM detected the presence of iron oxide nanoparticles in the imaging phantoms with high specificity and sensitivity with a detection limit of 30 labeled cells per mm3, corresponding to 19 μM of iron oxide. As proof-of-concept, we applied the method to follow the migration of labeled cancer cells injected in rats. The combination of iron oxide labeled cells, multiparametric MRI and a SVM based post processing provides high spatial resolution, specificity, and sensitivity, and is therefore suitable for non-invasive in-vivo cell detection and cell migration studies over prolonged time periods.

Biologically tunable reactivity of energetic nanomaterials using protein cages.

PubMed

Slocik, Joseph M; Crouse, Christopher A; Spowart, Jonathan E; Naik, Rajesh R

2013-06-12

The performance of aluminum nanomaterial based energetic formulations is dependent on the mass transport, diffusion distance, and stability of reactive components. Here we use a biologically inspired approach to direct the assembly of oxidizer loaded protein cages onto the surface of aluminum nanoparticles to improve reaction kinetics by reducing the diffusion distance between the reactants. Ferritin protein cages were loaded with ammonium perchlorate (AP) or iron oxide and assembled with nAl to create an oxidation-reduction based energetic reaction and the first demonstration of a nanoscale biobased thermite material. Both materials showed enhanced exothermic behavior in comparison to nanothermite mixtures of bulk free AP or synthesized iron oxide nanopowders prepared without the use of ferritin. In addition, by utilizing a layer-by-layer (LbL) process to build multiple layers of protein cages containing iron oxide and iron oxide/AP on nAl, stoichiometric conditions and energetic performance can be optimized.

Detailed electrochemical studies of the tetraruthenium polyoxometalate water oxidation catalyst in acidic media: identification of an extended oxidation series using Fourier transformed alternating current voltammetry.

PubMed

Lee, Chong-Yong; Guo, Si-Xuan; Murphy, Aidan F; McCormac, Timothy; Zhang, Jie; Bond, Alan M; Zhu, Guibo; Hill, Craig L; Geletii, Yurii V

2012-11-05

The electrochemistry of the water oxidation catalyst, Rb(8)K(2)[{Ru(4)O(4)(OH)(2)(H(2)O)(4)}(γ-SiW(10)O(36))(2)] (Rb(8)K(2)-1(0)) has been studied in the presence and absence of potassium cations in both hydrochloric and sulfuric acid solutions by transient direct current (dc) cyclic voltammetry, a steady state dc method in the rotating disk configuration and the kinetically sensitive technique of Fourier transformed large-amplitude alternating current (ac) voltammetry. In acidic media, the presence of potassium ions affects the kinetics (apparent rate of electron transfer) and thermodynamics (reversible potentials) of the eight processes (A'/A to H/H') that are readily detected under dc voltammetric conditions. The six most positive processes (A'/A to F/F'), each involve a one electron ruthenium based charge transfer step (A'/A, B'/B are Ru(IV/V) oxidation and C/C' to F/F' are Ru(IV/III) reduction). The apparent rate of electron transfer of the ruthenium centers in sulfuric acid is higher than in hydrochloric acid. The addition of potassium cations increases the apparent rates and gives rise to a small shift of reversible potential. Simulations of the Fourier transformed ac voltammetry method show that the B'/B, E/E', and F/F' processes are quasi-reversible, while the others are close to reversible. A third Ru(IV/V) oxidation process is observed just prior to the positive potential limit via dc methods. Importantly, the ability of the higher harmonic components of the ac method to discriminate against the irreversible background solvent process allows this (process I) as well as an additional fourth reversible ruthenium based process (J) to be readily identified. The steady-state rotating disk electrode (RDE) method confirmed that all four Ru-centers in Rb(8)K(2)-1(0) are in oxidation state IV. The dc and ac data indicate that reversible potentials of the four ruthenium centers are evenly spaced, which may be relevant to understanding of the water oxidation electrocatalysis. A profound effect of the potassium cation is observed for the one-electron transfer process (G/G') assigned to Ru(III/II) reduction and the multiple electron transfer reduction process (H/H') that arise from the tungstate polyoxometalate framework. A significant shift of E°' to a more positive potential value for process H/H' was observed on removal of K(+) (~100 mV in H(2)SO(4) and ~50 mV in HCl).

Influence of oxalic acid on the dissolution kinetics of manganese oxide

NASA Astrophysics Data System (ADS)

Godunov, E. B.; Artamonova, I. V.; Gorichev, I. G.; Lainer, Yu. A.

2012-11-01

The kinetics and electrochemical processes of the dissolution of manganese oxides with various oxidation states in sulfuric acid solutions containing oxalate ion additives is studied under variable conditions (concentration, pH, temperature). The parameters favoring a higher degree of the dissolution of manganese oxides in acidic media are determined. The optimal conditions are found for the dissolution of manganese oxides in acidic media in the presence of oxalate ions. The mechanism proposed for the dissolution of manganese oxides in sulfuric acid solutions containing oxalic acid is based on the results of kinetic and electrochemical studies. The steps of the dissolution mechanism are discussed.

PRECIPITATION CHEMISTRY OF MAGNESIUM SULFITE HYDRATES IN MAGNESIUM OXIDE SCRUBBING

EPA Science Inventory

The report gives results of laboratory studies defining the precipitation chemistry of MgSO3 hydrates. The results apply to the design of Mg-based scrubbing processes for SO2 removal from combustion flue gas. In Mg-based scrubbing processes, MgSO3 precipitates as either trihydrat...

A green lead hydrometallurgical process based on a hydrogen-lead oxide fuel cell.

PubMed

Pan, Junqing; Sun, Yanzhi; Li, Wei; Knight, James; Manthiram, Arumugam

2013-01-01

The automobile industry consumed 9 million metric tons of lead in 2012 for lead-acid batteries. Recycling lead from spent lead-acid batteries is not only related to the sustainable development of the lead industry, but also to the reduction of lead pollution in the environment. The existing lead pyrometallurgical processes have two main issues, toxic lead emission into the environment and high energy consumption; the developing hydrometallurgical processes have the disadvantages of high electricity consumption, use of toxic chemicals and severe corrosion of metallic components. Here we demonstrate a new green hydrometallurgical process to recover lead based on a hydrogen-lead oxide fuel cell. High-purity lead, along with electricity, is produced with only water as the by-product. It has a >99.5% lead yield, which is higher than that of the existing pyrometallurgical processes (95-97%). This greatly reduces lead pollution to the environment.

Study of weathering effects on the distribution of aromatic steroid hydrocarbons in crude oils and oil residues.

PubMed

Wang, Chuanyuan; Chen, Bing; Zhang, Baiyu; Guo, Ping; Zhao, Mingming

2014-01-01

The composition and distribution of triaromatic steroid hydrocarbons in oil residues after biodegradation and photo-oxidation processes were detected, and the diagnostic ratios for oil spill identification were developed and evaluated based on the relative standard deviation (RSD) and the repeatability limit. The preferential loss of C27 methyl triaromatic steranes (MTAS) relative to C28 MTAS and C29 MTAS was shown during the photo-oxidation process. In contrast to the photochemical degradation, the MTAS with the original 20R biological configuration was preferentially degraded during the biodegradation process. The RSD of most of the diagnostic ratios of MTAS ranged from 9 to 84% during the photo-oxidation process. However, the RSDs of such ratios derived from MTAS were all <5% even in high biodegradation, and such parameters may also provide new methods on oil spill identification. The parameters of monoaromatic sterane and monoaromatic sterane are not used well for oil spill identification after photo-oxidation. The triaromatic steroid hydrocarbons retained their molecular compositions after biodegradation and photo-oxidation and most of the diagnostic ratios derived from them could be efficiently used in oil spill identification.

Artifacts associated with the measurement of oxidized DNA bases.

PubMed Central

Cadet, J; Douki, T; Ravanat, J L

1997-01-01

In this paper we review recent aspects of the measurement of oxidized DNA bases, currently a matter of debate. There has long been an interest in the determination of the level of oxidized bases in cellular DNA under both normal and oxidative stress conditions. In this respect, the situation is confusing because variations that may be as large as two orders of magnitude have been reported for the yield of the formation of 8-oxo-7,8-dihydroguanine (8-oxoGua) in similar DNA samples. However, recent findings clearly show that application of several assays like gas chromatography-mass spectrometry (GC-MS) and -32P--postlabeling may lead to a significant overestimation of the level of oxidized bases in cellular DNA. In particular, the silylation step, which is required to make the samples volatile for the GC-MS analysis, has been shown to induce oxidation of normal bases at the level of about one oxidized base per 10(4) normal bases. This has been found to be a general process that applies in particular to 8-oxoGua, 8-oxo-7, 8-dihydroadenine,5-hydroxycytosine, 5-(hydroxymethyl)uracil, and 5-formyluracil. Interestingly, prepurification of the oxidized bases from DNA hydrolysate prior to the derivatization reaction prevents artefactual oxidation. Under these conditions, the level of oxidized bases measured by GC-MS is similar to that obtained by HPLC associated with electrochemical detection (HPLC-EC). It should be added that the level of 8-oxo-7,8-dihydro-2;-deoxyguanosine in control cellular DNA has been found to be about fivefold lower than in earlier HPLC-EC measurements by using appropriate conditions of extraction and enzymatic digestion of DNA. Similar conclusions were reached by measuring formamidopyrimidine-DNA glycosylase sensitive sites as revealed by the single cell gel electrophoresis (comet) assay. Images Figure 1. PMID:9349826

Patterning of a-C DLC films: exploration of an aqueous electro-oxidative mechanism

NASA Astrophysics Data System (ADS)

Mühl, Thomas; Myhra, Sverre

2007-06-01

Conducting ion-beam assisted CVD deposited a-C type DLC films can be patterned electro-oxidatively by masked and maskless probe-induced STM-based lithography. The former constitutes a parallel rapid processing technology, with the tip acting as a distant stationary electrode. The latter is a higher spatial resolution serial technology, with the tip defining a travelling local electro-chemical cell. The mechanism is based on electro-oxidative conversion of solid carbon to gaseous CO or CO2 in the presence of an aqueous phase, either as a bulk fluid or as a thin adsorbed film. The process is constrained kinetically in the early stages by limitations on charge transport through the surface barrier at the fluid-to-solid interface and subsequently by the availability of oxidants and by their transport to reactive sites. The as-received surface is terminated by chemisorbed oxygen, leading to the formation of an insulating surface barrier. The threshold potential for initiation of conversion depends on the width of the barrier. The results may have implications for new technologies exploiting the properties of carbon-based materials, but may also add to the present understanding of the electrochemistry of carbon solids.

Microbiology, ecology, and application of the nitrite-dependent anaerobic methane oxidation process

PubMed Central

Shen, Li-Dong; He, Zhan-Fei; Zhu, Qun; Chen, Dong-Qing; Lou, Li-Ping; Xu, Xiang-Yang; Zheng, Ping; Hu, Bao-Lan

2012-01-01

Nitrite-dependent anaerobic methane oxidation (n-damo), which couples the anaerobic oxidation of methane to denitrification, is a recently discovered process mediated by “Candidatus Methylomirabilis oxyfera.” M. oxyfera is affiliated with the “NC10” phylum, a phylum having no members in pure culture. Based on the isotopic labeling experiments, it is hypothesized that M. oxyfera has an unusual intra-aerobic pathway for the production of oxygen via the dismutation of nitric oxide into dinitrogen gas and oxygen. In addition, the bacterial species has a unique ultrastructure that is distinct from that of other previously described microorganisms. M. oxyfera-like sequences have been recovered from different natural habitats, suggesting that the n-damo process potentially contributes to global carbon and nitrogen cycles. The n-damo process is a process that can reduce the greenhouse effect, as methane is more effective in heat-trapping than carbon dioxide. The n-damo process, which uses methane instead of organic matter to drive denitrification, is also an economical nitrogen removal process because methane is a relatively inexpensive electron donor. This mini-review summarizes the peculiar microbiology of M. oxyfera and discusses the potential ecological importance and engineering application of the n-damo process. PMID:22905032

The role of graphene oxide and graphene oxide-based nanomaterials in the removal of pharmaceuticals from aqueous media: a review.

PubMed

Khan, Ayub; Wang, Jian; Li, Jun; Wang, Xiangxue; Chen, Zhongshan; Alsaedi, Ahmed; Hayat, Tasawar; Chen, Yuantao; Wang, Xiangke

2017-03-01

In this review paper, the ill effects of pharmaceuticals (PhAs) on the environment and their adsorption on graphene oxide (GO) and graphene oxide-based (GO-based) nanomaterials have been summarised and discussed. The adsorption of prominent PhAs discussed herein includes beta-blockers (atenolol and propranolol), antibiotics (tetracycline, ciprofloxacin and sulfamethoxazole), pharmaceutically active compounds (carbamazepine) and analgesics such as diclofenac. The adsorption of PhAs strictly depends upon the experimental conditions such as pH, adsorbent and adsorbate concentrations, temperature, ionic strength, etc. To understand the adsorption mechanism and feasibility of the adsorption process, the adsorption isotherms, thermodynamics and kinetic studies were also considered. Except for some cases, GO and its derivatives show excellent adsorption capacities for PhAs, which is crucial for their applications in the environmental pollution cleanup.

Corrosion study of the graphene oxide and reduced graphene oxide-based epoxy coatings

NASA Astrophysics Data System (ADS)

Ghauri, Faizan Ali; Raza, Mohsin Ali; Saad Baig, Muhammad; Ibrahim, Shoaib

2017-12-01

This work aims to determine the effect of graphene oxide (GO) and reduced graphene oxide (rGO) incorporation as filler on the corrosion protection ability of epoxy coatings in saline media. GO was derived from graphite powder following modified Hummers’ method, whereas rGO was obtained after reduction of GO with hydrazine solution. About 1 wt.% of GO or rGO were incorporated in epoxy resin by solution mixing process followed by ball milling. GO and rGO-based epoxy composite coatings were coated on mild steel substrates using film coater. The coated samples were characterized by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests after 1 and 24 h immersion in 3.5% NaCl. The results suggested that GO-based epoxy composite coatings showed high impedance and low corrosion rate.

VANADIA CATALYZED VAPOR PHASE OXIDATION OF METHANOL IN THE PRESENCE OF OZONE

EPA Science Inventory

Catalytic oxidation of methanol was carried out in the presence of ozone using vanadia based catalysts. The process can be used to selectively convert alcohols to aldehydes or ketones. It can also be used to control emissions of volatile organic compounds from Kraft mill and ot...

Opportunities for functional oxides in yttrium oxide-titanium oxide-zirconium oxide system: Applications for novel thermal barrier coatings

NASA Astrophysics Data System (ADS)

Francillon, Wesley

This dissertation is an investigation of materials and processed under consideration for next generation thermal structural oxides with potential applications as thermal barrier coatings; wherein, high temperature stability and mechanical properties affect durability. Two notable next generation materials systems under investigation are pyrochlore and co-doped zirconia oxides. The motivation for this work is based on current limitations of the currently used thermal barrier material of yttria stabilized zirconia (YSZ) deposited by the plasma spray processes. The rapid quenching associated with the plasma spray process, results in a metastable structure that is a non-transformable tetragonal structure in the yttria partially stabilized zirconia system rather than the equilibrium anticipated two phase mixture of cubic and monoclinic phases. It has been shown that this metastable structure offers enhanced toughness and thus durability during thermomechanical cycling from the operating temperatures in excess of 1000C to ambient. However, the metastable oxides are susceptible to partitioning at temperatures greater than 1200C, thus resulting in a transformation of the tetragonal phase oxides. Transformations of the tetragonal prime phase into the parent cubic and tetragonal prime phase result in coating degradation. Several of the emerging oxides are based on rare earth additions to zirconia. However, there is limited information of the high temperature stability of these oxide coatings and more notably these compositions exhibit limited toughness for durable performance. A potential ternary composition based on the YSZ system that offers the ability to tailor the phase structure is based YO1.5-TiO2 -ZrO2. The ternary of YO1.5-TiO2-ZrO 2 has the current TBC composition of seven molar percent yttria stabilized zirconia, pyrochlore phase oxide and zirconia doped with yttria and titania additions (Ti-YSZ). The Ti-YSZ phase field is of interest because at equilibrium it is a single tetragonal phase. Thus, compositions are of single phase tetragonal phase, theoretically, should not undergo high temperature partitioning. Single Tetragonal phase oxides of Ti-YSZ also offer the possibility of enhanced toughness and higher temperature stability akin to those observed in yttria partially stabilized zirconia. Many pyrochlore oxides are under review because they have shown to have lower thermal conductivity than YSZ oxides. This study focused on chemically synthesizing homogeneous starting material compositions in a metastable state (preferably amorphous), following its evolution according to the phase hierarchy under conditions of kinetic constraints. The current equilibrium diagram of YO1.5-TiO2-ZrO 2 is based on theoretical calculations. One of the contributions of this work is the redefined phase fields in YO1.5-TiO2-ZrO 2 based on our experimental results. Investigated compositions were based on tie lines of Y2-xTi2ZrxO7+x/2 and Y2Ti2-yZryO7 representing substitution of Zr4+ for Y3+ and Zr4+ for Ti4+ respectively. More notably, we observed extended metastable phases in pyrochlore and fluorite oxides at low temperature. The significance of this result is that it offers a larger compositional range for investing pyrochlore oxides with associated high temperature phase stability for TBC applications. In tetragonal oxides, our results showed that Ti-YSZ results have slower partitioning kinetics in comparison to YSZ at high temperature. This study also emphasized the deposition of advanced ceramic coatings by plasma spray for tetragonal and pyrochlore systems, compositionally complex functional oxides that may potentially have lower thermal conductivity values compared to current YSZ oxides. Next generation thermal barrier coatings require powders with high chemical purity, chemical homogeneity, controlled particle size/shape and pertinent phase state. Thermal spray offers an avenue to create novel materials and deposits directly from the precursor and compositionally controlled powder feedstock. This study contributed to investigating an unexplored field that offers a variety of opportunities in materials synthesis that would not be possible by conventional methods. Understanding processing-microstructure-property correlations is of considerable importance in thermal spray of functional oxide materials. This thesis demonstrated by radio-frequency thermal spray that the complex pyrochlore oxide Y 2Ti2O7 could be deposited by directly injecting molecularly mixed precursors to form oxide coatings. Structural analysis revealed the metastable fluorite phase; however, with thermal treatments at relatively low temperature of 700°C the pyrochlore phase was obtained. For Ti-YSZ coatings, the tetragonal phase oxides were obtained with unique microstructures, however, the tetragonal prime destabilized at 1200°C. This dissertation explored novel oxide compositions through detailed structural analysis. The approach presented a comprehensive and integrated investigation as it pertains to phase evolution of oxides in powder feedstock to coating characteristics (phase/properties).

Superoxide radical and UV irradiation in ultrasound assisted oxidative desulfurization (UAOD): A potential alternative for greener fuels

NASA Astrophysics Data System (ADS)

Chan, Ngo Yeung

This study is aimed at improving the current ultrasound assisted oxidative desulfurization (UAOD) process by utilizing superoxide radical as oxidant. Research was also conducted to investigate the feasibility of ultraviolet (UV) irradiation-assisted desulfurization. These modifications can enhance the process with the following achievements: (1) Meet the upcoming sulfur standards on various fuels including diesel fuel oils and residual oils; (2) More efficient oxidant with significantly lower consumption in accordance with stoichiometry; (3) Energy saving by 90%; (4) Greater selectivity in petroleum composition. Currently, the UAOD process and subsequent modifications developed in University of Southern California by Professor Yen's research group have demonstrated high desulfurization efficiencies towards various fuels with the application of 30% wt. hydrogen peroxide as oxidant. The UAOD process has demonstrated more than 50% desulfurization of refractory organic sulfur compounds with the use of Venturella type catalysts. Application of quaternary ammonium fluoride as phase transfer catalyst has significantly improved the desulfurization efficiency to 95%. Recent modifications incorporating ionic liquids have shown that the modified UAOD process can produce ultra-low sulfur, or near-zero sulfur diesels under mild conditions with 70°C and atmospheric pressure. Nevertheless, the UAOD process is considered not to be particularly efficient with respect to oxidant and energy consumption. Batch studies have demonstrated that the UAOD process requires 100 fold more oxidant than the stoichiometic requirement to achieve high desulfurization yield. The expected high costs of purchasing, shipping and storage of the oxidant would reduce the practicability of the process. The excess use of oxidant is not economically desirable, and it also causes environmental and safety issues. Post treatments would be necessary to stabilize the unspent oxidant residual to prevent the waste stream from becoming reactive or even explosive. High energy consumption is another drawback in the UAOD process. A typical 10 minutes ultrasonication applied in the UAOD process to achieve 95% desulfurization for 20g of diesel requires 450 kJ of energy, which is equivalent to approximately 50% of the energy that can be provided by the treated diesel. This great expenditure of energy is impractical for industries to adopt. In this study, modifications of the UAOD process, including the application of superoxide and selection of catalysts, were applied to lower the oxidant dosage and to improve the applicability towards heavy-distillates such as residual oil. The results demonstrated that the new system required 80% less oxidant as compared to previous generations of UAOD process without the loss of desulfurization efficiency. The new system demonstrated its suitability towards desulfurizing commercial mid-distillates including jet fuels, marine gas oil and sour diesel. This process also demonstrated a new method to desulfurize residual oil with high desulfurization yields. The new process development has been supported by Eco Energy Solutions Inc., Reno, Nevada and Intelligent Energy Inc., Long Beach, California. A feasibility study on UV assisted desulfurization by replacing ultrasound with UV irradiation was also conducted. The study demonstrated that the UV assisted desulfurization process consumes 90% less energy than the comparable process using ultrasonication. These process modifications demonstrated over 98% desulfurization efficiency on diesel oils and more than 75% on residual oils with significantly less oxidant and energy consumption. Also the feasibility to desulfurize commercial sour heavy oil was demonstrated. Based on the UAOD process and the commercialized modifications by Wan and Cheng, the feasible applications of superoxide and UV irradiation in the UAOD process could provide deep-desulfurization on various fuels with practical cost.

Resonant tunnelling in a quantum oxide superlattice

DOE PAGES

Choi, Woo Seok; Lee, Sang A.; You, Jeong Ho; ...

2015-06-24

Resonant tunneling is a quantum mechanical process that has long been attracting both scientific and technological attention owing to its intriguing underlying physics and unique applications for high-speed electronics. The materials system exhibiting resonant tunneling, however, has been largely limited to the conventional semiconductors, partially due to their excellent crystalline quality. Here we show that a deliberately designed transition metal oxide superlattice exhibits a resonant tunneling behaviour with a clear negative differential resistance. The tunneling occurred through an atomically thin, lanthanum δ- doped SrTiO 3 layer, and the negative differential resistance was realized on top of the bi-polar resistance switchingmore » typically observed for perovskite oxide junctions. This combined process resulted in an extremely large resistance ratio (~10 5) between the high and low resistance states. Lastly, the unprecedentedly large control found in atomically thin δ-doped oxide superlattices can open a door to novel oxide-based high-frequency logic devices.« less

Effects of plasma electrolytic oxidation process on the mechanical properties of additively manufactured porous biomaterials.

PubMed

Gorgin Karaji, Zahra; Hedayati, Reza; Pouran, Behdad; Apachitei, Iulian; Zadpoor, Amir A

2017-07-01

Metallic porous biomaterials are recently attracting more attention thanks to the additive manufacturing techniques which help produce more complex structures as compared to conventional techniques. On the other hand, bio-functional surfaces on metallic biomaterials such as titanium and its alloys are necessary to enhance the biological interactions with the host tissue. This study discusses the effect of plasma electrolytic oxidation (PEO), as a surface modification technique to produce bio-functional layers, on the mechanical properties of additively manufactured Ti6Al4V scaffolds based on the cubic unit cell. For this purpose, the PEO process with two different oxidation times was applied on scaffolds with four different values of relative density. The effects of the PEO process were studied by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), optical microscopy as well as static and dynamic (fatigue) mechanical testing under compression. SEM results indicated pore formation on the surface of the scaffolds after oxidation with a thickness of 4.85±0.36μm of the oxide layer after 2min and 9.04±2.27μm after 5min oxidation (based on optical images). The static test results showed the high effect of relative density of porous structure on its mechanical properties. However, oxidation did not influence most of the mechanical properties such as maximum stress, yield stress, plateau stress, and energy absorption, although its effect on the elastic modulus was considerable. Under fatigue loading, none of the scaffolds failed even after 10 6 loading cycles at 70% of their yield stress. Copyright © 2017 Elsevier B.V. All rights reserved.

Integrated aerobic biological-chemical treatment of winery wastewater diluted with urban wastewater. LED-based photocatalysis in the presence of monoperoxysulfate.

PubMed

Solís, Rafael R; Rivas, Francisco Javier; Ferreira, Leonor C; Pirra, Antonio; Peres, José A

2018-01-28

The oxidation of Winery Wastewater (WW) by conventional aerobic biological treatment usually leads to inefficient results due to the presence of organic substances, which are recalcitrant or toxic in conventional procedures. This study explores the combination of biological and chemical processes in order to complete the oxidation of biodegradable and non-biodegradable compounds in two sequential steps. Thus, a biological oxidation of a diluted WW is carried out by using the activated sludge process. Activated sludge was gradually acclimated to the Diluted Winery Wastewater (DWW). Some aspects concerning the biological process were evaluated (kinetics of the oxidation and sedimentation of the sludge produced). The biological treatment of the DWW led to a 40-50% of Chemical Oxygen Demand (COD) removal in 8 h, being necessary the application of an additional process. Different chemical processes combining UVA-LEDs radiation, monoperoxysulfate (MPS) and photocatalysts were applied in order to complete the COD depletion and efficient removal of polyphenols content, poorly oxidized in the previous biological step. From the options tested, the combination of UVA, MPS and a novel LaCoO 3 -TiO 2 composite, with double route of MPS decomposition through heterogeneous catalysis and photocatalysis, led to the best results (95% of polyphenol degradation, and additional 60% of COD removal). Initial MPS concentration and pH effect in this process were assessed.

Operating mechanisms of electrolytes in magnesium ion batteries: chemical equilibrium, magnesium deposition, and electrolyte oxidation.

PubMed

Kim, Dong Young; Lim, Younhee; Roy, Basab; Ryu, Young-Gyoon; Lee, Seok-Soo

2014-12-21

Since the early nineties there have been a number of reports on the experimental development of Mg electrolytes based on organo/amide-magnesium chlorides and their transmetalations. However, there are no theoretical papers describing the underlying operating mechanisms of Mg electrolytes, and there is no clear understanding of these mechanisms. We have therefore attempted to clarify the operating mechanisms of Mg electrolytes by studying the characteristics of Mg complexes, solvation, chemical equilibrium, Mg-deposition processes, electrolyte-oxidation processes, and oxidative degradation mechanism of RMgCl-based electrolytes, using ab initio calculations. The formation and solvation energies of Mg complexes highly depend on the characteristics of R groups. Thus, changes in R groups of RMgCl lead to changes in the equilibrium position and the electrochemical reduction and oxidation pathways and energies. We first provide a methodological scheme for calculating Mg reduction potential values in non-aqueous electrolytes and electrochemical windows. We also describe a strategy for designing Mg electrolytes to maximize the electrochemical windows and oxidative stabilities. These results will be useful not only for designing improved Mg electrolytes, but also for developing new electrolytes in the future.

Combustion synthesized indium-tin-oxide (ITO) thin film for source/drain electrodes in all solution-processed oxide thin-film transistors

NASA Astrophysics Data System (ADS)

Tue, Phan Trong; Inoue, Satoshi; Takamura, Yuzuru; Shimoda, Tatsuya

2016-06-01

We report combustion solution synthesized (SCS) indium-tin-oxide (ITO) thin film, which is a well-known transparent conductive oxide, for source/drain (S/D) electrodes in solution-processed amorphous zirconium-indium-zinc-oxide TFT. A redox-based combustion synthetic approach is applied to ITO thin film using acetylacetone as a fuel and metal nitrate as oxidizer. The structural and electrical properties of SCS-ITO precursor solution and thin films were systematically investigated with changes in tin concentration, indium metal precursors, and annealing conditions such as temperature, time, and ambient. It was found that at optimal conditions the SCS-ITO thin film exhibited high crystalline quality, atomically smooth surface (RMS ~ 4.1 Å), and low electrical resistivity (4.2 × 10-4 Ω cm). The TFT using SCS-ITO film as the S/D electrodes showed excellent electrical properties with negligible hysteresis. The obtained "on/off" current ratio, subthreshold swing factor, subthreshold voltage, and field-effect mobility were 5 × 107, 0.43 V/decade, 0.7 V, and 2.1 cm2/V s, respectively. The performance and stability of the SCS-ITO TFT are comparable to those of the sputtered-ITO TFT, emphasizing that the SCS-ITO film is a promising candidate for totally solution-processed oxide TFTs.

Zeolite-based Impedimetric Gas Sensor Device in Low-cost Technology for Hydrocarbon Gas Detection

PubMed Central

Reiß, Sebastian; Hagen, Gunter; Moos, Ralf

2008-01-01

Due to increasing environmental concerns the need for inexpensive selective gas sensors is increasing. This work deals with transferring a novel zeolite-based impedimetric hydrocarbon gas sensor principle, which has been originally manufactured in a costly combination of photolithography, thin-film processes, and thick-film processes to a low-cost technology comprising only thick-film processes and one electroplating step. The sensing effect is based on a thin chromium oxide layer between the interdigital electrodes and a Pt-loaded ZSM-5 zeolite film. When hydrocarbons are present in the sensor ambient, the electrical sensor impedance increases strongly and selectively. In the present work, the chromium oxide film is electroplated on Au screen-printed interdigital electrodes and then oxidized to Cr2O3. The electrode area is covered with the screen-printed zeolite. The sensor device is self-heated utilizing a planar platinum heater on the backside. The best sensor performance is obtained at a frequency of 3 Hz at around 350 °C. The good selectivity of the original sensor setup could be confirmed, but a strong cross-sensitivity to ammonia occurs, which might prohibit its original intention for use in automotive exhausts. PMID:27873966

Ceramic coating system or water oxidation environments

DOEpatents

Hong, Glenn T.

1996-01-01

A process for water oxidation of combustible materials in which during at least a part of the oxidation corrosive material is present and makes contact with at least a portion of the apparatus over a contact area on the apparatus. At least a portion of the contact surface area comprises titanium dioxide coated onto a titanium metal substrate. Such ceramic composites have been found to be highly resistant to environments encountered in the process of supercritical water oxidation. Such environments typically contain greater than 50 mole percent water, together with oxygen, carbon dioxide, and a wide range of acids, bases, and salts. Pressures are typically about 27.5 to about 1000 bar while temperatures range as high as 700.degree. C. The ceramic composites are also resistant to degradation mechanisms caused by thermal stresses.

Sliding durability of two carbide-oxide candidate high temperature fiber seal materials in air to 900 C

NASA Technical Reports Server (NTRS)

Dellacorte, Christopher; Steinetz, Bruce M.

1992-01-01

A test program to determine the friction and wear properties of two complex carbide oxide ceramic fibers for high temperature sliding seal applications is described. The fibers are based on Si, C, O, and Ti or Si, C, N, and O ceramic systems. Pin on disk tests using ceramic fiber covered pins and Inconel 718 disks, were conducted in air from 25 to 900 C to evaluate potential seal materials. This testing procedure was used in a previous study of oxide ceramic fibers which were found to exhibit wear behavior based predominantly on their mechanical properties. Like the oxide fibers tested previously, these carbide oxide ceramic fibers, show an increase in friction and wear with increased test temperature. At room temperature, the wear behavior seems to be based upon mechanical properties, namely tensile strength. At 500 and especially 900 C, the fibers wear by both mechanical fracture and by oxidative type wear. Based upon post test microscopic and x ray analyses, interaction between the fiber constituents and elements transferred from the counterface, namely Ni and Cr, may have occurred enhancing the tribochemical wear process. These results are interpreted.

Synthesis of Carboxylated-Graphenes by the Kolbe-Schmitt Process.

PubMed

Eng, Alex Yong Sheng; Sofer, Zdeněk; Sedmidubský, David; Pumera, Martin

2017-02-28

Graphene oxide is an oxidized form of graphene containing a large variety of oxygen groups. Although past models have suggested carboxylic acids to be present in significant amounts, recent evidence has shown otherwise. Toward the production of carboxyl-graphene, a synthetic method is presented herein based on the Kolbe-Schmitt process. A modified procedure of heating graphite oxide in the presence of a KOH/CaO mixture results in up to 11 atom % of carboxylic groups. The graphite oxide starting material and reaction temperature were investigated as two important factors, where a crumpled morphology of graphite oxide flakes and a lower 220 °C temperature preferentially led to greater carboxyl functionalization. Successful carboxylation caused a band gap opening of ∼2.5 eV in the smallest carboxyl-graphene particles, which also demonstrated a yellow fluorescence under UV light unseen in its counterpart produced at 500 °C. These results are in good agreement with theoretical calculations showing band gap opening and spin polarization of impurity states. This demonstrates the current synthetic process as yet another approach toward tuning the physical properties of graphene.

Molecular basis of intramolecular electron transfer in proteins during radical-mediated oxidations: Computer simulation studies in model tyrosine-cysteine peptides in solution

PubMed Central

Petruk, Ariel A.; Bartesaghi, Silvina; Trujillo, Madia; Estrin, Darío A.; Murgida, Daniel; Kalyanaraman, Balaraman; Marti, Marcelo A.; Radi, Rafael

2012-01-01

Experimental studies in hemeproteins and model Tyr/Cys-containing peptides exposed to oxidizing and nitrating species suggest that intramolecular electron transfer (IET) between tyrosyl radicals (Tyr-O●) and Cys residues controls oxidative modification yields. The molecular basis of this IET process is not sufficiently understood with structural atomic detail. Herein, we analyzed using molecular dynamics and quantum mechanics-based computational calculations, mechanistic possibilities for the radical transfer reaction in Tyr/Cys-containing peptides in solution and correlated them with existing experimental data. Our results support that Tyr-O● to Cys radical transfer is mediated by an acid/base equilibrium that involves deprotonation of Cys to form the thiolate, followed by a likely rate-limiting transfer process to yield cysteinyl radical and a Tyr phenolate; proton uptake by Tyr completes the reaction. Both, the pKa values of the Tyr phenol and Cys thiol groups and the energetic and kinetics of the reversible IET are revealed as key physico-chemical factors. The proposed mechanism constitutes a case of sequential, acid/base equilibrium-dependent and solvent-mediated, proton-coupled electron transfer and explains the dependency of oxidative yields in Tyr/Cys peptides as a function of the number of alanine spacers. These findings contribute to explain oxidative modifications in proteins that contain sequence and/or spatially close Tyr-Cys residues. PMID:22640642

Rapid oxidation/stabilization technique for carbon foams, carbon fibers and C/C composites

DOEpatents

Tan, Seng; Tan, Cher-Dip

2004-05-11

An enhanced method for the post processing, i.e. oxidation or stabilization, of carbon materials including, but not limited to, carbon foams, carbon fibers, dense carbon-carbon composites, carbon/ceramic and carbon/metal composites, which method requires relatively very short and more effective such processing steps. The introduction of an "oxygen spill over catalyst" into the carbon precursor by blending with the carbon starting material or exposure of the carbon precursor to such a material supplies required oxygen at the atomic level and permits oxidation/stabilization of carbon materials in a fraction of the time and with a fraction of the energy normally required to accomplish such carbon processing steps. Carbon based foams, solids, composites and fiber products made utilizing this method are also described.

A Theoretical Study of Methanol Oxidation on RuO 2(110): Bridging the Pressure Gap

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

Latimer, Allegra A.; Abild-Pedersen, Frank; Norskov, Jens K.

Partial oxidation catalysis is often fraught with selectivity problems, largely because there is a tendency of oxidation products to be more reactive than the starting material. One industrial process that has successfully overcome this problem is partial oxidation of methanol to formaldehyde. This process has become a global success, with an annual production of 30 million tons. Although ruthenium catalysts have not shown activity as high as the current molybdena or silver-based industrial standards, the study of ruthenium systems has the potential to elucidate which catalyst properties facilitate the desired partial oxidation reaction as opposed to deep combustion due tomore » a pressure-dependent selectivity “switch” that has been observed in ruthenium-based catalysts. In this work, we find that we are able to successfully rationalize this “pressure gap” using near-ab initio steady-state microkinetic modeling on RuO 2(110). We obtain molecular desorption prefactors from experiment and determine all other energetics using density functional theory. We show that, under ambient pressure conditions, formaldehyde production is favored on RuO 2(110), whereas under ultrahigh vacuum pressure conditions, full combustion to CO 2 takes place. We glean from our model several insights regarding how coverage effects, oxygen activity, and rate-determining steps influence selectivity and activity. As a result, we believe the understanding gained in this work might advise and inspire the greater partial oxidation community and be applied to other catalytic processes which have not yet found industrial success.« less

A Theoretical Study of Methanol Oxidation on RuO 2(110): Bridging the Pressure Gap

DOE PAGES

Latimer, Allegra A.; Abild-Pedersen, Frank; Norskov, Jens K.

2017-05-26

Partial oxidation catalysis is often fraught with selectivity problems, largely because there is a tendency of oxidation products to be more reactive than the starting material. One industrial process that has successfully overcome this problem is partial oxidation of methanol to formaldehyde. This process has become a global success, with an annual production of 30 million tons. Although ruthenium catalysts have not shown activity as high as the current molybdena or silver-based industrial standards, the study of ruthenium systems has the potential to elucidate which catalyst properties facilitate the desired partial oxidation reaction as opposed to deep combustion due tomore » a pressure-dependent selectivity “switch” that has been observed in ruthenium-based catalysts. In this work, we find that we are able to successfully rationalize this “pressure gap” using near-ab initio steady-state microkinetic modeling on RuO 2(110). We obtain molecular desorption prefactors from experiment and determine all other energetics using density functional theory. We show that, under ambient pressure conditions, formaldehyde production is favored on RuO 2(110), whereas under ultrahigh vacuum pressure conditions, full combustion to CO 2 takes place. We glean from our model several insights regarding how coverage effects, oxygen activity, and rate-determining steps influence selectivity and activity. As a result, we believe the understanding gained in this work might advise and inspire the greater partial oxidation community and be applied to other catalytic processes which have not yet found industrial success.« less

Novel Carbon Dioxide Microsensor Based on Tin Oxide Nanomaterial Doped With Copper Oxide

NASA Technical Reports Server (NTRS)

Xu, Jennifer C.; Hunter, Gary W.; Lukco, Dorothy; Liu, Chung-Chiun; Ward, Benjamin J.

2008-01-01

Carbon dioxide (CO2) is one of the major indicators of fire and therefore its measurement is very important for low-false-alarm fire detection and emissions monitoring. However, only a limited number of CO2 sensing materials exist due to the high chemical stability of CO2. In this work, a novel CO2 microsensor based on nanocrystalline tin oxide (SnO2) doped with copper oxide (CuO) has been successfully demonstrated. The CuO-SnO2 based CO2 microsensors are fabricated by means of microelectromechanical systems (MEMS) technology and sol-gel nanomaterial-synthesis processes. At a doping level of CuO: SnO2 = 1:8 (molar ratio), the resistance of the sensor has a linear response to CO2 concentrations for the range of 1 to 4 percent CO2 in air at 450 C. This approach has demonstrated the use of SnO2, typically used for the detection of reducing gases, in the detection of an oxidizing gas.

Photoinduced Cross-Linking of Dynamic Poly(disulfide) Films via Thiol Oxidative Coupling.

PubMed

Feillée, Noémi; Chemtob, Abraham; Ley, Christian; Croutxé-Barghorn, Céline; Allonas, Xavier; Ponche, Arnaud; Le Nouen, Didier; Majjad, Hicham; Jacomine, Léandro

2016-01-01

Initially developed as an elastomer with an excellent record of barrier and chemical resistance properties, poly(disulfide) has experienced a revival linked to the dynamic nature of the S-S covalent bond. A novel photobase-catalyzed oxidative polymerization of multifunctional thiols to poly(disulfide) network is reported. Based solely on air oxidation, the single-step process is triggered by the photodecarboxylation of a xanthone acetic acid liberating a strong bicyclic guanidine base. Starting with a 1 μm thick film based on trithiol poly(ethylene oxide) oligomer, the UV-mediated oxidation of thiols to disulfides occurs in a matter of minutes both selectively, i.e., without overoxidation, and quantitatively as assessed by a range of spectroscopic techniques. Thiolate formation and film thickness determine the reaction rates and yield. Spatial control of the photopolymerization serves to generate robust micropatterns, while the reductive cleavage of S-S bridges allows the recycling of 40% of the initial thiol groups. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Physical Morphology and Quantitative Characterization of Chemical Changes of Weathered PVC/Pine Composites

DTIC Science & Technology

2009-12-22

occurred by oxidation process. Also, oxidation and lignin (from the wood) degradation influenced the color (light- ness) of PVC based WPC upon weathering...and lignin (from the wood) degradation influenced the color (lightness) of PVC based WPC upon weathering. 15. SUBJECT TERMS 16. SECURITY...with DEab. More importantly, previous report showed that color change in wood during weathering was due to the lignin degradation [33]. Infrared spectra

Solvent free chemical oxidative polymerization as a universal method for the synthesis of ultra high molecular weight conjugated polymers based on 3,4-propylenedioxythiophenes.

PubMed

Kumar, Anshu; Singh, Rekha; Gopinathan, Sreelekha P; Kumar, Anil

2012-05-18

In this communication, we report on a solvent free chemical oxidative polymerization route for the monomers based on 3,4-propylenedioxythiophenes wherein the process is applicable to both solid as well as liquid monomers and results in the bulk synthesis of ultra high molecular weight polymers. This journal is © The Royal Society of Chemistry 2012

Optimization of combined in-vessel composting process and chemical oxidation for remediation of bottom sludge of crude oil storage tanks.

PubMed

Koolivand, Ali; Naddafi, Kazem; Nabizadeh, Ramin; Saeedi, Reza

2017-07-31

In this research, removal of petroleum hydrocarbons from oily sludge of crude oil storage tanks was investigated under the optimized conditions of in-vessel composting process and chemical oxidation with H 2 O 2 and Fenton. After determining the optimum conditions, the sludge was pre-treated with the optimum state of the oxidation process. Then, the determined optimum ratios of the sludge to immature compost were composted at a C:N:P ratio of 100:5:1 and moisture content of 55% for a period of 10 weeks. Finally, both pre-treated and composted mixtures were again oxidized with the optimum conditions of the oxidants. Results showed that total petroleum hydrocarbons (TPH) removal of the 1:8 and 1:10 composting reactors which were pre-treated with H 2 O 2 were 88.34% and 90.4%, respectively. In addition, reduction of TPH in 1:8 and 1:10 composting reactors which were pre-treated with Fenton were 83.90% and 84.40%, respectively. Without applying the pre-treatment step, the composting reactors had a removal rate of about 80%. Therefore, pre-treatment of the reactors increased the TPH removal. However, post-oxidation of both pre-treated and composted mixtures reduced only 13-16% of TPH. Based on the results, remarkable overall removal of TPH (about 99%) was achieved by using chemical oxidation and subsequent composting process. The study showed that chemical oxidation with H 2 O 2 followed by in-vessel composting is a viable choice for the remediation of the sludge.

Advanced Polymer Systems for Defence Applications: Power Generation, Protection and Sensing

DTIC Science & Technology

2014-05-01

oxide nanoparticles synthesized via non-sol-gel methods, e.g., via a flame process; and, (d) Amine sensors based on silver nanoparticle- doped ...Hongmin Chen, Guodong Chen, Xiaohong Gu, James L. Lee, E. E. Abdel-Hady, Y. C. Jean. Free Volumes, Glass Transitions, and Cross-Links in Zinc Oxide ...properties in a system of zinc oxide (ZnO) nanoparticles (20 nm) dispersed in waterborne polyurethane (WBPU) were measured using positron annihilation

Removal of mercury from coal via a microbial pretreatment process

DOEpatents

Borole, Abhijeet P [Knoxville, TN; Hamilton, Choo Y [Knoxville, TN

2011-08-16

A process for the removal of mercury from coal prior to combustion is disclosed. The process is based on use of microorganisms to oxidize iron, sulfur and other species binding mercury within the coal, followed by volatilization of mercury by the microorganisms. The microorganisms are from a class of iron and/or sulfur oxidizing bacteria. The process involves contacting coal with the bacteria in a batch or continuous manner. The mercury is first solubilized from the coal, followed by microbial reduction to elemental mercury, which is stripped off by sparging gas and captured by a mercury recovery unit, giving mercury-free coal. The mercury can be recovered in pure form from the sorbents via additional processing.

Fully transparent thin film transistors based on zinc oxide channel layer and molybdenum doped indium oxide electrodes

NASA Astrophysics Data System (ADS)

MÄ dzik, Mateusz; Elamurugu, Elangovan; Viegas, Jaime

2016-03-01

In this work we report the fabrication of thin film transistors (TFT) with zinc oxide channel and molybdenum doped indium oxide (IMO) electrodes, achieved by room temperature sputtering. A set of devices was fabricated, with varying channel width and length from 5μm to 300μm. Output and transfer characteristics were then extracted to study the performance of thin film transistors, namely threshold voltage and saturation current, enabling to determine optimal fabrication process parameters. Optical transmission in the UV-VIS-IR are also reported.

Ion-enhanced oxidation of aluminum as a fundamental surface process during target poisoning in reactive magnetron sputtering

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

Kuschel, Thomas; Keudell, Achim von

2010-05-15

Plasma deposition of aluminum oxide by reactive magnetron sputtering (RMS) using an aluminum target and argon and oxygen as working gases is an important technological process. The undesired oxidation of the target itself, however, causes the so-called target poisoning, which leads to strong hysteresis effects during RMS operation. The oxidation occurs by chemisorption of oxygen atoms and molecules with a simultaneous ion bombardment being present. This heterogenous surface reaction is studied in a quantified particle beam experiment employing beams of oxygen molecules and argon ions impinging onto an aluminum-coated quartz microbalance. The oxidation and/or sputtering rates are measured with thismore » microbalance and the resulting oxide layers are analyzed by x-ray photoelectron spectroscopy. The sticking coefficient of oxygen molecules is determined to 0.015 in the zero coverage limit. The sputtering yields of pure aluminum by argon ions are determined to 0.4, 0.62, and 0.8 at 200, 300, and 400 eV. The variation in the effective sticking coefficient and sputtering yield during the combined impact of argon ions and oxygen molecules is modeled with a set of rate equations. A good agreement is achieved if one postulates an ion-induced surface activation process, which facilitates oxygen chemisorption. This process may be identified with knock-on implantation of surface-bonded oxygen, with an electric-field-driven in-diffusion of oxygen or with an ion-enhanced surface activation process. Based on these fundamental processes, a robust set of balance equations is proposed to describe target poisoning effects in RMS.« less

JOWOG 22/2 - Actinide Chemical Technology (July 9-13, 2012)

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

Jackson, Jay M.; Lopez, Jacquelyn C.; Wayne, David M.

2012-07-05

The Plutonium Science and Manufacturing Directorate provides world-class, safe, secure, and reliable special nuclear material research, process development, technology demonstration, and manufacturing capabilities that support the nation's defense, energy, and environmental needs. We safely and efficiently process plutonium, uranium, and other actinide materials to meet national program requirements, while expanding the scientific and engineering basis of nuclear weapons-based manufacturing, and while producing the next generation of nuclear engineers and scientists. Actinide Process Chemistry (NCO-2) safely and efficiently processes plutonium and other actinide compounds to meet the nation's nuclear defense program needs. All of our processing activities are done in amore » world class and highly regulated nuclear facility. NCO-2's plutonium processing activities consist of direct oxide reduction, metal chlorination, americium extraction, and electrorefining. In addition, NCO-2 uses hydrochloric and nitric acid dissolutions for both plutonium processing and reduction of hazardous components in the waste streams. Finally, NCO-2 is a key team member in the processing of plutonium oxide from disassembled pits and the subsequent stabilization of plutonium oxide for safe and stable long-term storage.« less

Functionalization of Ti99.2 substrates surface by hybrid treatment investigated with spectroscopic methods

NASA Astrophysics Data System (ADS)

Jasinski, Jaroslaw Jan; Lubas, Malgorzata; Kurpaska, Lukasz; Napadlek, Wojciech; Sitarz, Maciej

2018-07-01

The article presents spectroscopic investigation of Ti 99.2 based functional substrates formed by hybrid oxidation process. Surface treatments were performed by combining methods of fluidized bed atmospheric diffusion treatment (FADT) with physical vapor deposition (PVD) - magnetron sputtering and laser surface texturing (LST) treatments. The processes were implemented to form a titanium diffusive layer saturated with oxygen in the substrate and a tight homogeneous oxide coating on Ti surface deposited with magnetron sputtering or laser texturing technique. The hybrid treatment was realized in Al2O3 fluidized bed reactor with air atmosphere, at 640 °C for 8 h and 12 h. At the same time, magnetron sputtering with the use of TiO2 target at a pressure of 3 × 102 mbar and laser surface texturing treatment with Nd:YAG λ = 1064 nm was performed. In order to investigate the effects of hybrid oxidation, microscopic (AFM, CLSM, SEM/SEM-EDX), spectroscopic (RS) and X-ray investigations (GID-XRD) were performed. Applied hybrid technique made possible to combine the effects of the generated layers and to reduce the stresses in the area of the PVD coating/oxidized Ti substrate interface. Furthermore, Raman spectroscopy results obtained at oxide layers manufactured with different variants of oxidation allowed detailed analysis of the created oxides. The coatings have shown structure with a Tiα(O) diffusion zone, a TiO2 rutile and anatase oxide zone deposited and textured on the substrate. Phase composition and morphology of these oxides is essential for the osseointegration process i.e. intensity of hydroxyapatite growing on the implant surface. Performed processes influenced the surface roughness parameter and cause the increase of substrate functional properties, which are important for biomedical applications.

The mechanisms of pyrite oxidation and leaching: A fundamental perspective

NASA Astrophysics Data System (ADS)

Chandra, A. P.; Gerson, A. R.

2010-09-01

Pyrite is the earth's most abundant sulfide mineral. Its frequent undesirable association with minerals of economic value such as sphalerite, chalcopyrite and galena, and precious metals such as gold necessitates costly separation processes such as leaching and flotation. Additionally pyrite oxidation is a major contributor to the environmental problem of acid rock drainage. The surface oxidation reactions of pyrite are therefore important both economically and environmentally. Significant variations in electrical properties resulting from lattice substitution of minor and trace elements into the lattice structure exist between pyrite from different geographical locations. Furthermore the presence of low coordination surface sites as a result of conchoidal fracture causes a reduction in the band gap at the surface compared to the bulk thus adding further electrochemical variability. Given the now general acceptance after decades of research that electrochemistry dominates the oxidation process, the geographical location, elemental composition and semi-conductor type (n or p) of pyrite are important considerations. Aqueous pyrite oxidation results in the production of sulfate and ferrous iron. However other products such as elemental sulfur, polysulfides, hydrogen sulfide, ferric hydroxide, iron oxide and iron(III) oxyhydroxide may also form. Intermediate species such as thiosulfate, sulfite and polythionates are also proposed to occur. Oxidation and leach rates are generally influenced by solution Eh, pH, oxidant type and concentration, hydrodynamics, grain size and surface area in relation to solution volume, temperature and pressure. Of these, solution Eh is most critical as expected for an electrochemically controlled process, and directly correlates with surface area normalised rates. Studies using mixed mineral systems further indicate the importance of electrochemical processes during the oxidation process. Spatially resolved surface characterisation of fresh and reacted pyrite surfaces is needed to identify site specific chemical processes. Scanning photoelectron microscopy (SPEM) and photoemission electron microscopy (PEEM) are two synchrotron based surface spectromicroscopic and microspectroscopic techniques that use XPS- and XANES-imaging to correlate chemistry with topography at a submicron scale. Recent data collected with these two techniques suggests that species are heterogeneously distributed on the surface and oxidation to be highly site specific.

Effective recycling of manganese oxide cathodes for lithium based batteries

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

Poyraz, Altug S.; Huang, Jianping; Cheng, Shaobo

Rechargeable lithium ion batteries (LIBs) occupy a prominent consumer presence due to their high cell potential and gravimetric energy density, there are also limited opportunities for electrode recycling. Currently used or proposed cathode recycling processes are multistep procedures which involve sequences of mechanical, thermal, and chemical leaching, where only the base material is recovered and significant processing is required to generate a recycled electrode structure. Another significant issue facing lithium based batteries is capacity fade due to structural degradation of the electroactive material upon extending cycling. Herein, inspired by heterogeneous catalyst thermal regeneration strategies, we present a new facile cathodemore » recycling process, where previously used cathodes are removed from a cell, heat treated, and then inserted into a new cell restoring the delivered capacity and cycle life. An environmentally sustainable manganese based material is employed, where binder-free self-supporting (BFSS) electrodes are prepared using a fibrous, high aspect ratio manganese oxide active material. After 200 discharge–charge cycles, the recycled BFSS electrodes display restored crystallinity and oxidation state of the manganese centers with the resulting electrochemistry (capacity and coulombic efficiency) reminiscent of freshly prepared BFSS cathodes. Of note, the BFSS electrode structure is robust with no degradation during the cell disassembly, electrode recovery, washing, and heat treatment steps; thus no post-processing is required for the recycled electrode. Furthermore, this work shows for the first time that a thermal regeneration method previously employed in catalyst systems can fully restore battery electrochemical performance, demonstrating a novel electrode recycling process which could open up new possibilities for energy storage devices with extended electrode lifecycles.« less

Effective recycling of manganese oxide cathodes for lithium based batteries

DOE PAGES

Poyraz, Altug S.; Huang, Jianping; Cheng, Shaobo; ...

2016-02-29

Rechargeable lithium ion batteries (LIBs) occupy a prominent consumer presence due to their high cell potential and gravimetric energy density, there are also limited opportunities for electrode recycling. Currently used or proposed cathode recycling processes are multistep procedures which involve sequences of mechanical, thermal, and chemical leaching, where only the base material is recovered and significant processing is required to generate a recycled electrode structure. Another significant issue facing lithium based batteries is capacity fade due to structural degradation of the electroactive material upon extending cycling. Herein, inspired by heterogeneous catalyst thermal regeneration strategies, we present a new facile cathodemore » recycling process, where previously used cathodes are removed from a cell, heat treated, and then inserted into a new cell restoring the delivered capacity and cycle life. An environmentally sustainable manganese based material is employed, where binder-free self-supporting (BFSS) electrodes are prepared using a fibrous, high aspect ratio manganese oxide active material. After 200 discharge–charge cycles, the recycled BFSS electrodes display restored crystallinity and oxidation state of the manganese centers with the resulting electrochemistry (capacity and coulombic efficiency) reminiscent of freshly prepared BFSS cathodes. Of note, the BFSS electrode structure is robust with no degradation during the cell disassembly, electrode recovery, washing, and heat treatment steps; thus no post-processing is required for the recycled electrode. Furthermore, this work shows for the first time that a thermal regeneration method previously employed in catalyst systems can fully restore battery electrochemical performance, demonstrating a novel electrode recycling process which could open up new possibilities for energy storage devices with extended electrode lifecycles.« less

Effect of processing conditions on microstructural features in Mn–Si sintered steels

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

Oro, Raquel, E-mail: raqueld@chalmers.se; Hryha, Eduard, E-mail: hryha@chalmers.se; Campos, Mónica, E-mail: campos@ing.uc3m.es

2014-09-15

Sintering of steels containing oxidation sensitive elements is possible if such elements are alloyed with others which present lower affinity for oxygen. In this work, a master alloy powder containing Fe–Mn–Si–C, specifically designed to create a liquid phase during sintering, has been used for such purpose. The effect of processing conditions such as sintering temperature and atmosphere was studied with the aim of describing the microstructural evolution as well as the morphology and distribution of oxides in the sintered material, evaluating the potential detrimental effect of such oxides on mechanical properties. Chemical analyses, metallography and fractography studies combined with X-raymore » photoelectron spectroscopy analyses on the fracture surfaces were used to reveal the main mechanism of fracture and their correlation with the chemical composition of the different fracture surfaces. The results indicate that the main mechanism of failure in these steels is brittle fracture in the surrounding of the original master alloy particles due to degradation of grain boundaries by the presence of oxide inclusions. Mn–Si oxide inclusions were observed on intergranular decohesive facets. The use of reducing atmospheres and high sintering temperatures reduces the amount and size of such oxide inclusions. Besides, high heating and cooling rates reduce significantly the final oxygen content in the sintered material. A model for microstructure development and oxide evolution during different stages of sintering is proposed, considering the fact that when the master alloy melts, the liquid formed can dissolve some of the oxides as well as the surface of the surrounding iron base particles. - Highlights: • Oxide distribution in steels containing oxidation-sensitive elements • Mn, Si introduced in a master alloy powder, mixed with a base iron powder • Selective oxidation of Mn and Si on iron grain boundaries • Decohesive fracture caused by degradation of grain boundaries by oxide inclusions • Reducing agents efficient at low temperatures critical for avoiding oxide inclusions.« less

Comparative study for degradation of industrial dyes by electrochemical advanced oxidation processes with BDD anode in a laboratory stirred tank reactor.

PubMed

Alcocer, Salvador; Picos, Alain; Uribe, Agustín R; Pérez, Tzayam; Peralta-Hernández, Juan M

2018-08-01

Comparative degradation of the industrial dyes Blue BR, Violet SBL and Brown MF 50 mg L -1 has been studied by the electrochemical oxidation (EOx), electro-Fenton (EF), photoelectro-Fenton (PEF) process based on BDD electrode. Each dye was tested in 0.05 mM Na 2 SO 4 with 0.5 mM Fe 2+ at pH 3.0, and electrolyzed in a stirred tank reactor under galvanostatic conditions with 2.0, 5.0, 7.0, 11.0 and 18.0 mA cm -2 . Dyes were oxidized via hydroxyl radicals (OH) formed at the BDD anode from water oxidation coupled with Fenton's reaction cathodically produced hydrogen peroxide (H 2 O 2 ). Under Na 2 SO 4 medium close to 100% the decolorization was achieved. Through the color abatement rate the dyes behavior was analyzed at the beginning of the oxidation process. Dissolved Organic Carbon (DOC) was tested to evaluate the degradation. From DOC removal, it was established an increasing relative oxidation power of the EOx < EF < PEF, according with their decolorization trend. This study highlights the potential of the electrochemical/BDD process for the degradation of industrial dyes found in wastewaters under appropriate experimental conditions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Formation and processing of DNA damage substrates for the hNEIL enzymes.

PubMed

Fleming, Aaron M; Burrows, Cynthia J

2017-06-01

Reactive oxygen species (ROS) are harnessed by the cell for signaling at the same time as being detrimental to cellular components such as DNA. The genome and transcriptome contain instructions that can alter cellular processes when oxidized. The guanine (G) heterocycle in the nucleotide pool, DNA, or RNA is the base most prone to oxidation. The oxidatively-derived products of G consistently observed in high yields from hydroxyl radical, carbonate radical, or singlet oxygen oxidations under conditions modeling the cellular reducing environment are discussed. The major G base oxidation products are 8-oxo-7,8-dihydroguanine (OG), 5-carboxamido-5-formamido-2-iminohydantoin (2Ih), spiroiminodihydantoin (Sp), and 5-guanidinohydantoin (Gh). The yields of these products show dependency on the oxidant and the reaction context that includes nucleoside, single-stranded DNA (ssDNA), double-stranded DNA (dsDNA), and G-quadruplex DNA (G4-DNA) structures. Upon formation of these products in cells, they are recognized by the DNA glycosylases in the base excision repair (BER) pathway. This review focuses on initiation of BER by the mammalian Nei-like1-3 (NEIL1-3) glycosylases for removal of 2Ih, Sp, and Gh. The unique ability of the human NEILs to initiate removal of the hydantoins in ssDNA, bulge-DNA, bubble-DNA, dsDNA, and G4-DNA is outlined. Additionally, when Gh exists in a G4 DNA found in a gene promoter, NEIL-mediated repair is modulated by the plasticity of the G4-DNA structure provided by additional G-runs flanking the sequence. On the basis of these observations and cellular studies from the literature, the interplay between DNA oxidation and BER to alter gene expression is discussed. Copyright © 2017 Elsevier Inc. All rights reserved.

Thermal Catalytic Oxidation of Airborne Contaminants by a Reactor Using Ultra-Short Channel Length, Monolithic Catalyst Substrates

NASA Technical Reports Server (NTRS)

Perry, J. L.; Tomes, K. M.; Tatara, J. D.

2005-01-01

Contaminated air, whether in a crewed spacecraft cabin or terrestrial work and living spaces, is a pervasive problem affecting human health, performance, and well being. The need for highly effective, economical air quality processes spans a wide range of terrestrial and space flight applications. Typically, air quality control processes rely on absorption-based processes. Most industrial packed-bed adsorption processes use activated carbon. Once saturated, the carbon is either dumped or regenerated. In either case, the dumped carbon and concentrated waste streams constitute a hazardous waste that must be handled safely while minimizing environmental impact. Thermal catalytic oxidation processes designed to address waste handling issues are moving to the forefront of cleaner air quality control and process gas decontamination processes. Careful consideration in designing the catalyst substrate and reactor can lead to more complete contaminant destruction and poisoning resistance. Maintenance improvements leading to reduced waste handling and process downtime can also be realized. Performance of a prototype thermal catalytic reaction based on ultra-short waste channel, monolith catalyst substrate design, under a variety of process flow and contaminant loading conditions, is discussed.

Processing of uranium oxide and silicon carbide based fuel using polymer infiltration and pyrolysis

NASA Astrophysics Data System (ADS)

Singh, Abhishek K.; Zunjarrao, Suraj C.; Singh, Raman P.

2008-09-01

Ceramic composite pellets consisting of uranium oxide, UO 2, contained within a silicon carbide matrix, were fabricated using a novel processing technique based on polymer infiltration and pyrolysis (PIP). In this process, particles of depleted uranium oxide, in the form of U 3O 8, were dispersed in liquid allylhydridopolycarbosilane (AHPCS), and subjected to pyrolysis up to 900 °C under a continuous flow of ultra high purity argon. The pyrolysis of AHPCS, at these temperatures, produced near-stoichiometric amorphous silicon carbide ( a-SiC). Multiple polymer infiltration and pyrolysis (PIP) cycles were performed to minimize open porosity and densify the silicon carbide matrix. Analytical characterization was conducted to investigate chemical interaction between U 3O 8 and SiC. It was observed that U 3O 8 reacted with AHPCS during the very first pyrolysis cycle, and was converted to UO 2. As a result, final composition of the material consisted of UO 2 particles contained in an a-SiC matrix. The physical and mechanical properties were also quantified. It is shown that this processing scheme promotes uniform distribution of uranium fuel source along with a high ceramic yield of the parent matrix.

Integration of the Anammox process to the rejection water and main stream lines of WWTPs.

PubMed

Morales, Nicolás; Val Del Río, Ángeles; Vázquez-Padín, José Ramón; Méndez, Ramón; Mosquera-Corral, Anuska; Campos, José Luis

2015-12-01

Nowadays the application of Anammox based processes in the wastewater treatment plants has given a step forward. The new goal consists of removing the nitrogen present in the main stream of the WWTPs to improve their energetic efficiencies. This new approach aims to remove not only the nitrogen but also to provide a better use of the energy contained in the organic matter. The organic matter will be removed either by an anaerobic psychrophilic membrane reactor or an aerobic stage operated at low solids retention time followed by an anaerobic digestion of the generated sludge. Then ammonia coming from these units will be removed in an Anammox based process in a single unit system. The second strategy provides the best results in terms of operational costs and would allow reductions of about 28%. Recent research works performed on Anammox based processes and operated at relatively low temperatures and/or low ammonia concentrations were carried out in single-stage systems using biofilms, granules or a mixture of flocculent nitrifying and granular Anammox biomasses. These systems allowed the appropriated retention of Anammox and ammonia oxidizing bacteria but also the proliferation of nitrite oxidizing bacteria which seems to be the main drawback to achieve the required effluent quality for disposal. Therefore, prior to the implementation of the Anammox based processes at full scale to the water line, a reliable strategy to avoid nitrite oxidation should be defined in order to maintain the process stability and to obtain the desired effluent quality. If not, the application of a post-denitrification step should be necessary. Copyright © 2015 Elsevier Ltd. All rights reserved.

CMOS array design automation techniques. [metal oxide semiconductors

NASA Technical Reports Server (NTRS)

Ramondetta, P.; Feller, A.; Noto, R.; Lombardi, T.

1975-01-01

A low cost, quick turnaround technique for generating custom metal oxide semiconductor arrays using the standard cell approach was developed, implemented, tested and validated. Basic cell design topology and guidelines are defined based on an extensive analysis that includes circuit, layout, process, array topology and required performance considerations particularly high circuit speed.

77 FR 63827 - Request for Nominations of Experts for the Clean Air Scientific Advisory Committee (CASAC) Oxides...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-10-17

... health-based) air quality standards for oxides of nitrogen (NO X ). DATES: Nominations should be..., medicine, public health, biostatistics and risk assessment. Process and Deadline for Submitting Nominations... later than November 7, 2012. EPA values and welcomes diversity. In an effort to obtain nominations of...

Review of the Primary National Ambient Air Quality Standard for Sulfur Oxides: Risk and Exposure Assessment Planning Document

EPA Science Inventory

The U.S. Environmental Protection Agency (EPA) is conducting a review of the air quality criteria and the primary (health-based) national ambient air quality standards (NAAQS) for sulfur oxides (SOx). The major phases of the process for reviewing NAAQS include the following: (1) ...

The effect of hydrogen peroxide on uranium oxide films on 316L stainless steel

NASA Astrophysics Data System (ADS)

Wilbraham, Richard J.; Boxall, Colin; Goddard, David T.; Taylor, Robin J.; Woodbury, Simon E.

2015-09-01

For the first time the effect of hydrogen peroxide on the dissolution of electrodeposited uranium oxide films on 316L stainless steel planchets (acting as simulant uranium-contaminated metal surfaces) has been studied. Analysis of the H2O2-mediated film dissolution processes via open circuit potentiometry, alpha counting and SEM/EDX imaging has shown that in near-neutral solutions of pH 6.1 and at [H2O2] ⩽ 100 μmol dm-3 the electrodeposited uranium oxide layer is freely dissolving, the associated rate of film dissolution being significantly increased over leaching of similar films in pH 6.1 peroxide-free water. At H2O2 concentrations between 1 mmol dm-3 and 0.1 mol dm-3, formation of an insoluble studtite product layer occurs at the surface of the uranium oxide film. In analogy to corrosion processes on common metal substrates such as steel, the studtite layer effectively passivates the underlying uranium oxide layer against subsequent dissolution. Finally, at [H2O2] > 0.1 mol dm-3 the uranium oxide film, again in analogy to common corrosion processes, behaves as if in a transpassive state and begins to dissolve. This transition from passive to transpassive behaviour in the effect of peroxide concentration on UO2 films has not hitherto been observed or explored, either in terms of corrosion processes or otherwise. Through consideration of thermodynamic solubility product and complex formation constant data, we attribute the transition to the formation of soluble uranyl-peroxide complexes under mildly alkaline, high [H2O2] conditions - a conclusion that has implications for the design of both acid minimal, metal ion oxidant-free decontamination strategies with low secondary waste arisings, and single step processes for spent nuclear fuel dissolution such as the Carbonate-based Oxidative Leaching (COL) process.

Processing of fused silicide coatings for carbon-based materials

NASA Technical Reports Server (NTRS)

Smialek, J. L.

1983-01-01

The processing and oxidation resistance of fused Al-Si and Ni-Si slurry coatings on ATJ graphite was studied. Ni-Si coatings in the 70 to 90 percent Si range were successfully processed to melt, wet, and bond to the graphite. The molten coatings also infiltrated the porosity in graphite and reacted with it to form SiC in the coating. Cyclic oxidation at 1200 C showed that these coatings were not totally protective because of local attack of the substrate, due to the extreme thinness of the coatings in combination with coating cracks. Previously announced in STAR as N83-27019

Abasic and oxidized ribonucleotides embedded in DNA are processed by human APE1 and not by RNase H2

PubMed Central

Malfatti, Matilde Clarissa; Balachander, Sathya; Antoniali, Giulia; Koh, Kyung Duk; Saint-Pierre, Christine; Gasparutto, Didier; Chon, Hyongi; Crouch, Robert J.

2017-01-01

Abstract Ribonucleoside 5′-monophosphates (rNMPs) are the most common non-standard nucleotides found in DNA of eukaryotic cells, with over 100 million rNMPs transiently incorporated in the mammalian genome per cell cycle. Human ribonuclease (RNase) H2 is the principal enzyme able to cleave rNMPs in DNA. Whether RNase H2 may process abasic or oxidized rNMPs incorporated in DNA is unknown. The base excision repair (BER) pathway is mainly responsible for repairing oxidized and abasic sites into DNA. Here we show that human RNase H2 is unable to process an abasic rNMP (rAP site) or a ribose 8oxoG (r8oxoG) site embedded in DNA. On the contrary, we found that recombinant purified human apurinic/apyrimidinic endonuclease-1 (APE1) and APE1 from human cell extracts efficiently process an rAP site in DNA and have weak endoribonuclease and 3′-exonuclease activities on r8oxoG substrate. Using biochemical assays, our results provide evidence of a human enzyme able to recognize and process abasic and oxidized ribonucleotides embedded in DNA. PMID:28977421

The effect of heat treatment simulating porcelain firing processes on titanium corrosion resistance.

PubMed

Sokołowski, Grzegorz; Rylska, Dorota; Sokołowski, Jerzy

2016-01-01

Corrosion resistance of titanium used in metal-ceramic restorations in manufacturing is based on the presence of oxide layer on the metal surface. The procedures used during combining metallic material with porcelain may affect the changes in oxide layers structure, and thus anticorrosive properties of metallic material. The aim of the study was an evaluation of potential changes in the structure and selected corrosion properties of titanium after sandblasting and thermal treatment applicable to the processes of ceramics fusion. Milled titanium elements were subjected to a few variants of the processes typical of ceramics fusion and studied in terms of resistance to electrochemical corrosion. The study included the OCP changes over time, measurements of Icorr, Ecorr and Rp as well as potentiodynamic examinations. Surface microstructure and chemical composition were analyzed using SEM and EDS methods. The results obtained allow us to conclude that the processes corresponding to ceramic oxidation and fusion on titanium in the variants used in the study do not cause deterioration of its anticorrosive properties, and partially enhance the resistance. This depends on the quality of oxide layers structure. Titanium elements treated by porcelain firing processes do not lose their corrosion resistance.

Thermo-luminescence and neutron absorption cross section evaluations of compounds of Lithium based oxide ceramic breeders in Li-Zr-O system

NASA Astrophysics Data System (ADS)

Mukherjee, Sumanta; Naik, Yeshwant

2018-04-01

Lithium-zirconium based oxides were prepared by combustion route. Thermal analysis (TG and DTA) was used to study the combustion process. The nucleation and growth stages were identified and their activation energies were predicted. The suitability of these oxide breeders was evaluated based on their radiation stability, variation in thermal behavior upon γ irradiation, neutron absorption and tritium breeding characteristics. Nuclear properties of these oxide ceramics were evaluated with a view to use them as efficient neutron absorbers and simultaneously breed tritium. Total neutron absorption cross sections were evaluated as a function of neutron energy in the range of 0 to 20 MeV. Resonant absorption is predicted for the neutron of energy 2.3 keV manly due to contribution from neutron induced nuclear reactions of 7Li in this energy range.

A metallic metal oxide (Ti5O9)-metal oxide (TiO2) nanocomposite as the heterojunction to enhance visible-light photocatalytic activity

NASA Astrophysics Data System (ADS)

Li, L. H.; Deng, Z. X.; Xiao, J. X.; Yang, G. W.

2015-06-01

Coupling titanium dioxide (TiO2) with other semiconductors is a popular method to extend the optical response range of TiO2 and improve its photon quantum efficiency, as coupled semiconductors can increase the separation rate of photoinduced charge carriers in photocatalysts. Differing from normal semiconductors, metallic oxides have no energy gap separating occupied and unoccupied levels, but they can excite electrons between bands to create a high carrier mobility to facilitate kinetic charge separation. Here, we propose the first metallic metal oxide-metal oxide (Ti5O9-TiO2) nanocomposite as a heterojunction for enhancing the visible-light photocatalytic activity of TiO2 nanoparticles and we demonstrate that this hybridized TiO2-Ti5O9 nanostructure possesses an excellent visible-light photocatalytic performance in the process of photodegrading dyes. The TiO2-Ti5O9 nanocomposites are synthesized in one step using laser ablation in liquid under ambient conditions. The as-synthesized nanocomposites show strong visible-light absorption in the range of 300-800 nm and high visible-light photocatalytic activity in the oxidation of rhodamine B. They also exhibit excellent cycling stability in the photodegrading process. A working mechanism for the metallic metal oxide-metal oxide nanocomposite in the visible-light photocatalytic process is proposed based on first-principle calculations of Ti5O9. This study suggests that metallic metal oxides can be regarded as partners for metal oxide photocatalysts in the construction of heterojunctions to improve photocatalytic activity.

A metallic metal oxide (Ti5O9)-metal oxide (TiO2) nanocomposite as the heterojunction to enhance visible-light photocatalytic activity.

PubMed

Li, L H; Deng, Z X; Xiao, J X; Yang, G W

2015-01-26

Coupling titanium dioxide (TiO2) with other semiconductors is a popular method to extend the optical response range of TiO2 and improve its photon quantum efficiency, as coupled semiconductors can increase the separation rate of photoinduced charge carriers in photocatalysts. Differing from normal semiconductors, metallic oxides have no energy gap separating occupied and unoccupied levels, but they can excite electrons between bands to create a high carrier mobility to facilitate kinetic charge separation. Here, we propose the first metallic metal oxide-metal oxide (Ti5O9-TiO2) nanocomposite as a heterojunction for enhancing the visible-light photocatalytic activity of TiO2 nanoparticles and we demonstrate that this hybridized TiO2-Ti5O9 nanostructure possesses an excellent visible-light photocatalytic performance in the process of photodegrading dyes. The TiO2-Ti5O9 nanocomposites are synthesized in one step using laser ablation in liquid under ambient conditions. The as-synthesized nanocomposites show strong visible-light absorption in the range of 300-800 nm and high visible-light photocatalytic activity in the oxidation of rhodamine B. They also exhibit excellent cycling stability in the photodegrading process. A working mechanism for the metallic metal oxide-metal oxide nanocomposite in the visible-light photocatalytic process is proposed based on first-principle calculations of Ti5O9. This study suggests that metallic metal oxides can be regarded as partners for metal oxide photocatalysts in the construction of heterojunctions to improve photocatalytic activity.

Removal of refractory contaminants in municipal landfill leachate by hydrogen, oxygen and palladium: a novel approach of hydroxyl radical production.

PubMed

Yu, Yingjian; Chen, Zhulei; Guo, Zhiyuan; Liao, Zhuwei; Yang, Lie; Wang, Jia; Chen, Zhuqi

2015-04-28

Municipal solid waste (MSW) leachate contains various refractory pollutants that pose potential threats to both surface water and groundwater. This paper established a novel catalytic oxidation process for leachate treatment, in which OH is generated in situ by pumping both H2 and O2 in the presence of Pd catalyst and Fe(2+). Volatile fatty acids in the leachate were removed almost completely by aeration and/or mechanical mixing. In this approach, a maximum COD removal of 56.7% can be achieved after 4h when 200mg/L Fe(2+) and 1250mg/L Pd/Al2O3 (pH 3.0) are used as catalysts. After oxidation, the BOD/COD ratio in the proposed process increased from 0.03 to 0.25, indicating that the biodegradability of the leachate was improved. By comparing the efficiency on COD removal and economical aspect of the proposed Pd-based in-situ process with traditional Fenton, electro-Fenton and UV-Fenton for leachate treatments, the proposed Pd-based in-situ process has potential economic advantages over other advanced oxidation processes while the COD removal efficiency was maintained. Copyright © 2015 Elsevier B.V. All rights reserved.

In-depth investigation of spin-on doped solar cells with thermally grown oxide passivation

NASA Astrophysics Data System (ADS)

Ahmad, Samir Mahmmod; Cheow, Siu Leong; Ludin, Norasikin A.; Sopian, K.; Zaidi, Saleem H.

Solar cell industrial manufacturing, based largely on proven semiconductor processing technologies supported by significant advancements in automation, has reached a plateau in terms of cost and efficiency. However, solar cell manufacturing cost (dollar/watt) is still substantially higher than fossil fuels. The route to lowering cost may not lie with continuing automation and economies of scale. Alternate fabrication processes with lower cost and environmental-sustainability coupled with self-reliance, simplicity, and affordability may lead to price compatibility with carbon-based fuels. In this paper, a custom-designed formulation of phosphoric acid has been investigated, for n-type doping in p-type substrates, as a function of concentration and drive-in temperature. For post-diffusion surface passivation and anti-reflection, thermally-grown oxide films in 50-150-nm thickness were grown. These fabrication methods facilitate process simplicity, reduced costs, and environmental sustainability by elimination of poisonous chemicals and toxic gases (POCl3, SiH4, NH3). Simultaneous fire-through contact formation process based on screen-printed front surface Ag and back surface through thermally grown oxide films was optimized as a function of the peak temperature in conveyor belt furnace. Highest efficiency solar cells fabricated exhibited efficiency of ∼13%. Analysis of results based on internal quantum efficiency and minority carried measurements reveals three contributing factors: high front surface recombination, low minority carrier lifetime, and higher reflection. Solar cell simulations based on PC1D showed that, with improved passivation, lower reflection, and high lifetimes, efficiency can be enhanced to match with commercially-produced PECVD SiN-coated solar cells.

Oxidation of ammonium sulfite by a multi-needle-to-plate gas phase pulsed corona discharge reactor

NASA Astrophysics Data System (ADS)

Ren, Hua; Lu, Na; Shang, Kefeng; Li, Jie; Wu, Yan

2013-03-01

The oxidation of ammonium sulfite in the ammonia-based flue gas desulfurization (FGD) process was investigated in a multi-needle-to-plate gas phase pulsed corona discharge reactor in this paper. The effect of several parameters, including capacitance and peak pulse voltage of discharge system, electrode gap and bubbling gas flow rate on the oxidation rate of ammonium sulfite was reviewed. The oxidation rate of ammonium sulfite could reach 47.2% at the capacitance, the peak pulse voltage, electrode gap and bubbling gas flow rate equal to 2 nF, -24.6 k V, 35 mm and 4 L min-1 within treatment time of 40 min The experimental results indicate that the gas phase pulsed discharge system with a multi-needle-to-plate electrode can oxide the ammonium sulfite. The oxidation rate increased with the applied capacitance and peak pulse voltage and decreased with the electrode gap. As the bubbling gas flow rate increased, the oxidation rate increased first and then tended to reach a stationary value. These results would be important for the process optimization of the (NH4)2SO3 to (NH4)2SO4 oxidation.

The oxidation of carbon monoxide using tin oxide based catalysts

NASA Technical Reports Server (NTRS)

Sampson, Christopher F.; Jorgensen, Norman

1990-01-01

The preparation conditions for precious metal/tin oxide catalysts were optimized for maximum carbon monoxide/oxygen recombination efficiency. This was achieved by controlling the tin digestion, the peptization to form the sol, the calcination process and the method of adding the precious metals. Extensive studies of the tin oxide structure were carried out over the temperature range 20 to 500 C in air or hydrogen environments using Raman scattering and X ray diffraction. Adsorbed species on tin oxide, generated in an environment containing carbon monoxide, gave rise to a Raman band at about 1600 cm(exp -1) which was assigned to carbonaceous groups, possible carbonate.

Effects of Graphene Oxide Addition on Mechanical and Thermal Properties of Evoh Films

NASA Astrophysics Data System (ADS)

González-Ruiz, Jesús; Yataco-Lazaro, Lourde; Virginio, Sueli; das Graças da Silva-Valenzuela, Maria; Moura, Esperidiana; Valenzuela-Díaz, Francisco

Currently, ethylene vinyl alcohol (EVOH) is one of the oxygen barrier materials most used for food packaging. The addition of graphene oxide nanosheets to the EVOH matrix is employed to improve their mechanic al and barrier properties. In this work, films of EVOH-based composites reinforced with graphene oxide were prepared by melt extrusion, using a twin screw extruder machine and blown extrusion process. The graphene oxide was prepared via chemical oxidation of natural graphite and then was exfoliated into nanosheets using the sonochemical method. The composite films samples were characterized using FTIR and DSC analysis. In addition, their mechanical properties were also determined.

Removal of ammonia from urine vapor by a dual-catalyst system

NASA Technical Reports Server (NTRS)

Budininkas, P.

1977-01-01

The feasibility of removing ammonia from urine vapor by a low-temperature dual-catalyst system has been demonstrated. The process is based on the catalytic oxidation of ammonia to a mixture of nitrogen, nitrous oxide, and water, followed by a catalytic decomposition of the nitrous oxide into its elements. Potential ammonia oxidation and nitrous oxide decomposition catalysts were first screened with artificial gas mixtures, then tested with the actual urine vapor produced by boiling untreated urine. A suitable dual-catalyst bed arrangement was found that achieved the removal of ammonia and also organic carbon, and recovered water of good quality from urine vapor.

Oxide semiconductor thin-film transistors: a review of recent advances.

PubMed

Fortunato, E; Barquinha, P; Martins, R

2012-06-12

Transparent electronics is today one of the most advanced topics for a wide range of device applications. The key components are wide bandgap semiconductors, where oxides of different origins play an important role, not only as passive component but also as active component, similar to what is observed in conventional semiconductors like silicon. Transparent electronics has gained special attention during the last few years and is today established as one of the most promising technologies for leading the next generation of flat panel display due to its excellent electronic performance. In this paper the recent progress in n- and p-type oxide based thin-film transistors (TFT) is reviewed, with special emphasis on solution-processed and p-type, and the major milestones already achieved with this emerging and very promising technology are summarizeed. After a short introduction where the main advantages of these semiconductors are presented, as well as the industry expectations, the beautiful history of TFTs is revisited, including the main landmarks in the last 80 years, finishing by referring to some papers that have played an important role in shaping transparent electronics. Then, an overview is presented of state of the art n-type TFTs processed by physical vapour deposition methods, and finally one of the most exciting, promising, and low cost but powerful technologies is discussed: solution-processed oxide TFTs. Moreover, a more detailed focus analysis will be given concerning p-type oxide TFTs, mainly centred on two of the most promising semiconductor candidates: copper oxide and tin oxide. The most recent data related to the production of complementary metal oxide semiconductor (CMOS) devices based on n- and p-type oxide TFT is also be presented. The last topic of this review is devoted to some emerging applications, finalizing with the main conclusions. Related work that originated at CENIMAT|I3N during the last six years is included in more detail, which has led to the fabrication of high performance n- and p-type oxide transistors as well as the fabrication of CMOS devices with and on paper. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Distributive Processing by the Iron(II)/α-Ketoglutarate-Dependent Catalytic Domains of the TET Enzymes Is Consistent with Epigenetic Roles for Oxidized 5-Methylcytosine Bases.

PubMed

Tamanaha, Esta; Guan, Shengxi; Marks, Katherine; Saleh, Lana

2016-08-03

The ten-eleven translocation (TET) proteins catalyze oxidation of 5-methylcytosine ((5m)C) residues in nucleic acids to 5-hydroxymethylcytosine ((5hm)C), 5-formylcytosine ((5f)C), and 5-carboxycytosine ((5ca)C). These nucleotide bases have been implicated as intermediates on the path to active demethylation, but recent reports have suggested that they might have specific regulatory roles in their own right. In this study, we present kinetic evidence showing that the catalytic domains (CDs) of TET2 and TET1 from mouse and their homologue from Naegleria gruberi, the full-length protein NgTET1, are distributive in both chemical and physical senses, as they carry out successive oxidations of a single (5m)C and multiple (5m)C residues along a polymethylated DNA substrate. We present data showing that the enzyme neither retains (5hm)C/(5f)C intermediates of preceding oxidations nor slides along a DNA substrate (without releasing it) to process an adjacent (5m)C residue. These findings contradict a recent report by Crawford et al. ( J. Am. Chem. Soc. 2016 , 138 , 730 ) claiming that oxidation of (5m)C by CD of mouse TET2 is chemically processive (iterative). We further elaborate that this distributive mechanism is maintained for TETs in two evolutionarily distant homologues and posit that this mode of function allows the introduction of (5m)C forms as epigenetic markers along the DNA.

Treatment of statin compounds by advanced oxidation processes: Kinetic considerations and destruction mechanisms

NASA Astrophysics Data System (ADS)

Razavi, Behnaz; Song, Weihua; Santoke, Hanoz; Cooper, William J.

2011-03-01

This study examined the use of advanced oxidation/reduction processes (AO/RPs) for the destruction of cholesterol lowering statin pharmaceuticals. AO/RPs which utilize the oxidizing hydroxyl radical ( rad OH) and reducing aqueous electron (e -aq), to degrade chemical contaminants are alternatives to traditional water treatment methods, and are alternatives as water reuse becomes more generally implemented. Four major statin pharmaceuticals, fluvastatin, lovastatin, pravastatin and simvastatin, were studied, and the absolute bimolecular reaction rate constants with rad OH determined, (6.96±0.16)×10 9, (2.92±0.06)×10 9, (4.16±0.13)×10 9, and (3.13±0.15)×10 9 M -1 s -1, and for e -aq (2.31±0.06)×10 9, (0.45±0.01)×10 9, (1.26±0.01)×10 9, and (0.69±0.02)×10 9 M -1 s -1, respectively. To provide additional information on the radicals formed upon oxidation, transient spectra were measured and the overall reaction efficiency determined. Radical-based destruction mechanisms for destruction of the statins are proposed based on the LC-MS determination of the stable reaction by-products formed using 137Cs γ-irradiation of statin solutions. Knowing the reaction rates, reaction efficiencies and destruction mechanisms of these compounds is essential for the consideration of the use of advanced oxidation/reduction processes for the destruction of statins in aqueous systems.

Hydrometallurgical process for the recovery of high value metals from spent lithium nickel cobalt aluminum oxide based lithium-ion batteries

NASA Astrophysics Data System (ADS)

Joulié, M.; Laucournet, R.; Billy, E.

2014-02-01

A hydrometallurgical process is developed to recover valuable metals of the lithium nickel cobalt aluminum oxide (NCA) cathodes from spent lithium-ion batteries (LIBs). Effect of parameters such as type of acid (H2SO4, HNO3 and HCl), acid concentration (1-4 mol L-1), leaching time (3-18 h) and leaching temperature (25-90 °C) with a solid to liquid ratio fixed at 5% (w/v) are investigated to determine the most efficient conditions of dissolution. The preliminary results indicate that HCl provides higher leaching efficiency. In optimum conditions, a complete dissolution is performed for Li, Ni, Co and Al. In the nickel and cobalt recovery process, at first the Co(II) in the leaching liquor is selectively oxidized in Co(III) with NaClO reagent to recover Co2O3, 3H2O by a selective precipitation at pH = 3. Then, the nickel hydroxide is precipitated by a base addition at pH = 11. The recovery efficiency of cobalt and nickel are respectively 100% and 99.99%.

Inheritance of Crystallographic Orientation during Lithiation/Delithiation Processes of Single-Crystal α-Fe2O3 Nanocubes in Lithium-Ion Batteries.

PubMed

Ma, Xiaowei; Zhang, Manyu; Liang, Chongyun; Li, Yuesheng; Wu, Jingjing; Che, Renchao

2015-11-04

Iron oxides are very promising anode materials based on conversion reactions for lithium-ion batteries (LIBs). During conversion processes, the crystal structure and composition of the electrode material are drastically changed. Surprisingly, in our study, inheritance of a crystallographic orientation was found during lithiation/delithiation processes of single-crystal α-Fe2O3 nanocubes by ex situ transmission electron microscopy. Single-crystal α-Fe2O3 was first transformed into numerous Fe nanograins embedded in a Li2O matrix, and then the conversion between Fe and FeO nanograins became the main reversible electrochemical reaction for energy storage. Interestingly, these Fe/FeO nanograins had almost the same crystallographic orientation, indicating that the lithiated/delithiated products can inherit the crystallographic orientation of single-crystal α-Fe2O3. This finding is important for understanding the detailed electrochemical conversion processes of iron oxides, and this feature may also exist during lithiation/delithiation processes of other transition-metal oxides.

Light-emitting diodes based on solution-processed nontoxic quantum dots: oxides as carrier-transport layers and introducing molybdenum oxide nanoparticles as a hole-inject layer.

PubMed

Bhaumik, Saikat; Pal, Amlan J

2014-07-23

We report fabrication and characterization of solution-processed quantum dot light-emitting diodes (QDLEDs) based on a layer of nontoxic and Earth-abundant zinc-diffused silver indium disulfide (AIZS) nanoparticles as an emitting material. In the QDLEDs fabricated on indium tin oxide (ITO)-coated glass substrates, we use layers of oxides, such as graphene oxide (GO) and zinc oxide (ZnO) nanoparticles as a hole- and electron-transport layer, respectively. In addition, we introduce a layer of MoO3 nanoparticles as a hole-inject one. We report a comparison of the characteristics of different device architectures. We show that an inverted device architecture, ITO/ZnO/AIZS/GO/MoO3/Al, yields a higher electroluminescence (EL) emission, compared to direct ones, for three reasons: (1) the GO/MoO3 layers introduce barriers for electrons to reach the Al electrode, and, similarly, the ZnO layers acts as a barrier for holes to travel to the ITO electrode; (2) the introduction of a layer of MoO3 nanoparticles as a hole-inject layer reduces the barrier height for holes and thereby balances charge injection in the inverted structure; and (3) the wide-bandgap zinc oxide next to the ITO electrode does not absorb the EL emission during its exit from the device. In the QDLEDs with oxides as carrier inject and transport layers, the EL spectrum resembles the photoluminescence emission of the emitting material (AIZS), implying that excitons are formed in the quaternary nanocrystals and decay radiatively.

Iron-based catalysts for photocatalytic ozonation of some emerging pollutants of wastewater.

PubMed

Espejo, Azahara; Beltrán, Fernando J; Rivas, Francisco J; García-Araya, Juan F; Gimeno, Olga

2015-01-01

A synthetic secondary effluent containing an aqueous mixture of emerging contaminants (ECs) has been treated by photocatalytic ozonation using Fe(3+) or Fe3O4 as catalysts and black light lamps as the radiation source. For comparative purposes, ECs have also been treated by ultraviolet radiation (UVA radiation, black light) and ozonation (pH 3 and 7). With the exception of UVA radiation, O3-based processes lead to the total removal of ECs in the mixture. The time taken to achieve complete degradation depends on the oxidation process applied. Ozonation at pH 3 is the most effective technique. The addition of iron based catalysts results in a slight inhibition of the parent compounds degradation rate. However, a positive effect is experienced when measuring the total organic carbon (TOC) and the chemical oxygen demand (COD) removals. Photocatalytic oxidation in the presence of Fe(3+) leads to 81% and 88% of TOC and COD elimination, respectively, compared to only 23% and 29% of TOC and COD removals achieved by single ozonation. The RCT concept has been used to predict the theoretical ECs profiles in the homogeneous photocatalytic oxidation process studied. Treated wastewater effluent was toxic to Daphnia magna when Fe(3+) was used in photocatalytic ozonation. In this case, toxicity was likely due to the ferryoxalate formed in the process. Single ozonation significantly reduced the toxicity of the treated wastewater.

Sulfur-oxidizing autotrophic and mixotrophic denitrification processes for drinking water treatment: elimination of excess sulfate production and alkalinity requirement.

PubMed

Sahinkaya, Erkan; Dursun, Nesrin

2012-09-01

This study evaluated the elimination of alkalinity need and excess sulfate generation of sulfur-based autotrophic denitrification process by stimulating simultaneous autotrophic and heterotrophic (mixotrophic) denitrification process in a column bioreactor by methanol supplementation. Also, denitrification performances of sulfur-based autotrophic and mixotrophic processes were compared. In autotrophic process, acidity produced by denitrifying sulfur-oxidizing bacteria was neutralized by the external NaHCO(3) supplementation. After stimulating mixotrophic denitrification process, the alkalinity need of the autotrophic process was satisfied by the alkalinity produced by heterotrophic denitrifiers. Decreasing and lastly eliminating the external alkalinity supplementation did not adversely affect the process performance. Complete denitrification of 75 mg L(-1) NO(3)-N under mixotrophic conditions at 4 h hydraulic retention time was achieved without external alkalinity supplementation and with effluent sulfate concentration lower than the drinking water guideline value of 250 mg L(-1). The denitrification rate of mixotrophic process (0.45 g NO(3)-N L(-1) d(-1)) was higher than that of autotrophic one (0.3 g NO(3)-N L(-1) d(-1)). Batch studies showed that the sulfur-based autotrophic nitrate reduction rate increased with increasing initial nitrate concentration and transient accumulation of nitrite was observed. Copyright © 2012 Elsevier Ltd. All rights reserved.

Composites based on PET and red mud residues as catalyst for organic removal from water.

PubMed

Bento, Natálya I; Santos, Patrícia S C; de Souza, Talita E; Oliveira, Luiz C A; Castro, Cínthia S

2016-08-15

In this study, we obtained a composite based on carbon/iron oxide from red mud and PET (poly(ethylene terephthalate)) wastes by mechanical mixture (10, 15 and 20wt.% of PET powder/red mud) followed by a controlled thermal treatment at 400°C under air. XRD analyses revealed that the α-Fe2O3 is the main phase formed from red mud. TPR analyses showed that the iron oxide present in the composites undergoes reduction at lower temperature to form Fe(2+) species present in Fe3O4, indicating that the iron oxide in the composite can exhibit greater reactivity in the catalytic processes compared to the original red mud. In fact, catalytic tests showed that the composites presented higher capacity to remove methylene blue dye (MB), presenting about 90% of removal after 24h of reaction. The MB removal was also monitored by mass spectrometer with ionization via electrospray (ESI-MS), which demonstrated the occurrence of the oxidation process, showing the formation of MB oxidation products. The stability of the composites was confirmed after four reuse cycles. The results seem to indicate that PET carbon deposited over the iron oxide from red mud promotes adsorption of the contaminant allowing its contact with the iron atoms and their consequent reaction. Copyright © 2016 Elsevier B.V. All rights reserved.

Materials science, integration, and performance characterization of high-dielectric constant thin film based devices

NASA Astrophysics Data System (ADS)

Fan, Wei

To overcome the oxidation and diffusion problems encountered during Copper integration with oxide thin film-based devices, TiAl/Cu/Ta heterostructure has been first developed in this study. Investigation on the oxidation and diffusion resistance of the laminate structure showed high electrical conductance and excellent thermal stability in oxygen environment. Two amorphous oxide layers that were formed on both sides of the TiAl barrier after heating in oxygen have been revealed as the structure that effectively prevents oxygen penetration and protects the integrity of underlying Cu layer. Polycrystalline (BaxSr1-x)TiO3 (BST) thin films were subsequently deposited on the Cu-based bottom electrode by RF magnetron sputtering to investigate the interaction between the oxide and Cu layers. The thickness of the interfacial layer and interface roughness play critical roles in the optimization of the electrical performance of the BST capacitors using Cu-based electrode. It was determined that BST deposition at moderate temperature followed by rapid thermal annealing in pure oxygen yields BST/Cu capacitors with good electrical properties for application to high frequency devices. The knowledge obtained on the study of barrier properties of TiAl inspired a continuous research on the materials science issues related to the application of the hybrid TiAlOx, as high-k gate dielectric in MOSFET devices. Novel fabrication process such as deposition of ultra-thin TiAl alloy layer followed by oxidation with atomic oxygen has been established in this study. Stoichiometric amorphous TiAlOx layers, exhibiting only Ti4+ and Al3+ states, were produced with a large variation of oxidation temperature (700°C to room temperature). The interfacial SiOx formation between TiAlOx and Si was substantially inhibited by the use of the low temperature oxidation process. Electrical characterization revealed a large permittivity of 30 and an improved band structure for the produced TiAlOx layers, compared with pure TiO2. A modified 3-element model was adopted to extract the true C-V behavior of the TiAlOx-based MOS capacitor. Extremely small equivalent oxide thickness (EOT) less than 0.5 nm with dielectric leakage 4˜5 magnitude lower than that for SiO2 has been achieved on TiAlOx layer as a result of its excellent dielectric properties.

Probing ground-state hole transfer between equivalent, electrochemically inaccessible states in multiporphyrin arrays using time-resolved optical spectroscopy.

PubMed

Song, Hee-eun; Taniguchi, Masahiko; Kirmaier, Christine; Bocian, David F; Lindsey, Jonathan S; Holten, Dewey

2009-01-01

A new strategy is described and implemented for determining the rates of hole-transfer between equivalent porphyrins in multiporphyrin architectures. The approach allows access to these rates between sites that are not the most easily oxidized components of the array. The specific architectures investigated with this new strategy are triads consisting of one zinc porphyrin (Zn) and two free base porphyrins (Fb). The triads employ a diphenylethyne linker (ZnFbFbU) and a phenylene linker (ZnFbFbPhi). The zinc porphyrin is selectively oxidized to produce Zn(+)FbFb, the free base porphyrins are excited to produce the excited-state mixture Zn(+)Fb*Fb and Zn(+)FbFb*, and the subsequent dynamics are monitored by ultrafast absorption spectroscopy. The system evolves by a combination of energy- and hole-transfer processes involving (adjacent and nonadjacent) zinc and free base porphyrin constituents that are complete within 100 ps of excitation; the rate constants of many of these processes are derived from prior studies of the oxidized forms of the benchmark dyads (ZnFbU and ZnFbPhi). One of the excited-state decay channels produces the metastable state ZnFbFb(+) that decays to a second metastable state ZnFb(+)Fb by the target hole-transfer process, followed by rapid hole transfer to produce the Zn(+)FbFb thermodynamic ground state of the system. The rate constant for hole transfer between the free base porphyrins in the oxidized ZnFbFb triads is found to be (0.5 ns)(-1) and (0.6 ns)(-1) across phenylene and diphenylethyne linkers, respectively. These rate constants are comparable to those recently measured, using a related but distinct strategy, for ground-state hole transfer between zinc porphyrins in oxidized ZnZnFb triads. The two complementary strategies provide unique approaches for probing hole transfer between equivalent sites in multiporphyrin arrays, with the choice of method being guided by the particular target process and the ease of synthesis of the necessary architectures.

Collector-up aluminum gallium arsenide/gallium arsenide heterojunction bipolar transistors using oxidized aluminum arsenide for current confinement

NASA Astrophysics Data System (ADS)

Massengale, Alan Ross

1998-12-01

The discovery in 1990 that the wet thermal oxidation of AlAs can create a stable native oxide has added a new constituent, AlAs-oxide, to the AlGaAs/GaAs materials system. Native oxides of high Al mole-fraction AlGaAs are being used to confine electrical and/or optical fields in many types of electronic and optoelectronic structures with very promising results. Among these devices are collector-up heterojunction bipolar transistors (HBTs). Collector-up HBTs offer a means to reduce base-collector capacitance relative to their emitter-up counterparts, and thus to improve device performance. A novel method for fabricating collector-up AlGaAs/GaAs HBTs where an AlAs layer is inserted into the emitter layer and is oxidized in water vapor at 450sp°C has been developed. The resulting AlAs-oxide serves as a current confining layer that constricts collector current flow to the intrinsic portion of the device. Compared to previous methods of fabricating these devices, the process of converting AlAs into an insulator requires only one growth, and does not suffer from implant damage in the base. Because the lateral oxidation of AlAs is a process that proceeds at rates of microns per minute, one of the major challenges facing its implementation is the ability to accurately control the oxidation rate over the wafer, and from one wafer to the next. In the course of work on the oxidation of AlAs, a method to lithographically form lateral oxidation stop layers has been achieved. This technique utilizes impurity induced layer disordering (IILD) in heavily Si-doped buried planes, combined with selective surface patterning and thermal annealing, to create a lateral variation in the Al mole-fraction of the layer to be oxidized.

Carbonate-activated hydrogen peroxide oxidation process for azo dye decolorization: Process, kinetics, and mechanisms.

PubMed

Li, Yang; Li, Lei; Chen, Zi-Xi; Zhang, Jie; Gong, Li; Wang, Yi-Xuan; Zhao, Han-Qing; Mu, Yang

2018-02-01

Advanced oxidation processes offer effective solutions in treating wastewater from various industries. This study is the first time to investigate the potential of carbonate-activated hydrogen peroxide (CAP) oxidation process for the removal of organic pollutant from highly alkaline wastewaters. Azo dye acid orange 7 (AO7) was selected as a model pollutant. The influences of various parameters on AO7 decolorization by the CAP oxidation were evaluated. Furthermore, the active species involved in AO7 degradation were explored using scavenger experiments and electron spin resonance analysis. Additionally, AO7 degradation products by the CAP oxidation were identified to elucidate possible transformation pathways. Results showed that the CAP oxidation had better AO7 decolorization performance compared to bicarbonate-activated hydrogen peroxide method. The AO7 decolorization efficiency augmented from 3.70 ± 0.76% to 54.27 ± 2.65% when carbonate concentration was increased from 0 to 50 mM at pH 13.0, and then changed slightly with further increasing carbonate concentration to 70 mM. It increased almost linearly from 5.95 ± 0.32% to 94.03 ± 0.39% as H 2 O 2 concentration was increased from 5 to 50 mM. Moreover, trace amount of Co(II) could facilitate AO7 decolorization by the CAP reaction. Superoxide and carbonate radicals might be the main reactive oxygen species involved in the CAP process. Finally, a possible degradation pathway of AO7 by the CAP oxidation was proposed based on the identified products. Copyright © 2017 Elsevier Ltd. All rights reserved.

Catalytic oxidative desulfurization of liquid hydrocarbon fuels using air

NASA Astrophysics Data System (ADS)

Sundararaman, Ramanathan

Conventional approaches to oxidative desulfurization of liquid hydrocarbons involve use of high-purity, expensive water soluble peroxide for oxidation of sulfur compounds followed by post-treatment for removal of oxidized sulfones by extraction. Both are associated with higher cost due to handling, storage of oxidants and yield loss with extraction and water separation, making the whole process more expensive. This thesis explores an oxidative desulfurization process using air as an oxidant followed by catalytic decomposition of sulfones thereby eliminating the aforementioned issues. Oxidation of sulfur compounds was realized by a two step process in which peroxides were first generated in-situ by catalytic air oxidation, followed by catalytic oxidation of S compounds using the peroxides generated in-situ completing the two step approach. By this technique it was feasible to oxidize over 90% of sulfur compounds present in real jet (520 ppmw S) and diesel (41 ppmw S) fuels. Screening of bulk and supported CuO based catalysts for peroxide generation using model aromatic compound representing diesel fuel showed that bulk CuO catalyst was more effective in producing peroxides with high yield and selectivity. Testing of three real diesel fuels obtained from different sources for air oxidation over bulk CuO catalyst showed different level of effectiveness for generating peroxides in-situ which was consistent with air oxidation of representative model aromatic compounds. Peroxides generated in-situ was then used as an oxidant to oxidize sulfur compounds present in the fuel over MoO3/SiO2 catalyst. 81% selectivity of peroxides for oxidation of sulfur compounds was observed on MoO3/SiO2 catalyst at 40 °C and under similar conditions MoO3/Al2O3 gave only 41% selectivity. This difference in selectivity might be related to the difference in the nature of active sites of MoO3 on SiO2 and Al2O 3 supports as suggested by H2-TPR and XRD analyses. Testing of supported and bulk MgO catalysts for decomposition of sulfones showed that these catalysts are effective in decomposing oxidized sulfur compounds such as dibenzothiophene sulfone and 3-methyl benzothiophene sulfone to biphenyl and isopropyl benzene respectively and SO2. Study of catalyst structure-activity relationship revealed that in the range of 40--140 nm of MgO, crystallite size plays a critical role on activity of the catalyst for sulfone decomposition. In testing other alkali oxides, it was demonstrated that CaO was effective as a reagent in decomposing oxidized sulfur compounds in a crude oil at a much lower temperature than used for MgO based catalyst. Preliminary data on potential regeneration scheme of spent CaO is also discussed.

Coexistence of Fe(II)- and Mn(II)-oxidizing bacteria govern the formation of deep sea umber deposits

NASA Astrophysics Data System (ADS)

Peng, Xiaotong; Ta, Kaiwen; Chen, Shun; Zhang, Lijuan; Xu, Hengchao

2015-11-01

The genesis of umber deposits has remained controversial for several decades. Recently, microbial Fe(II) oxidation associated with low-temperature diffuse venting has been identified as a key process for the formation of umber deposits, but the exact biogeochemical mechanisms involved to the precipitation of Mn oxides in umber deposits still remain unknown. Here, we used nano secondary ion mass spectrometer, synchrotron-based X-ray absorption spectroscopy, electron microscopy, and molecular techniques to demonstrate the coexistence of two types of metal-oxidizing bacteria within deep-sea hydrothermal umber deposits at the South Mid-Atlantic Ridge, where we found unique spheroids composed of biogenic Fe oxyhydroxides and Mn oxides in the deposits. Our data show that Fe oxyhydroxides and Mn oxides are metabolic by-products of lithotrophic Fe(II)-oxidizing bacteria and heterotrophic Mn(II)-oxidizing bacteria, respectively. The hydrothermal vents fuel lithotrophic microorganisms, which constitute a trophic base that might support the activities of heterogenic Mn(II)-oxidizing bacteria. The biological origin of umber deposits shed light on the importance of geomicrobiological interaction in triggering the formation of metalliferous deposits, with important implications for the generation of submarine Mn deposits and crusts.

Study of catalytic reaction processes on the {gamma}-Al{sub 2}O{sub 3} chemiluminescence-based gas sensors

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

Utsunomiya, K.; Nakagawa, M.; Nishiyama, K.

The authors have investigated a new chemiluminescence (CL)-based gas sensor made of aluminum oxide ({gamma}-Al{sub 2}O{sub 3}) which emits CL during the catalytic oxidation of combustible vapors in air. The CL intensity is proportional to the concentration in the wide region from 1 to 1000 ppm of ethanol, butanol and acetone in air. However, it has a tendency to saturate in concentrations above 1000 ppm. For the detection of vapors in the environmental atmosphere, improvements of the sensitivity and the linear characteristics of the sensor are necessary. Catalytic reaction processes on the sensor were studied for this purpose.

Chemiluminescence and reactivity of the composites based on blends of polypropylene and polyamide

NASA Astrophysics Data System (ADS)

Vorontsov, N. V.; Popov, A. A.; Margolin, A. L.

2017-12-01

The effect of the composition of blends based on isotactic polypropylene (PP) and aliphatic polyamide 6/66-4 (PA) on the rate of photo-oxidation of their mixtures in air at room temperature has been studied. The decay of photoinduced chemiluminescence was studied to determine the kinetics of peroxyl radical termination in composites and the rate constants of this process depending on the composition of the mixtures. In the presence of PA, the rate of photo-oxidation of mixtures is much higher than the rates of photo-oxidation of separately taken components, PP and PA. Thus, the kinetics of photo-oxidation of mixtures differs from the simple sum of photo-oxidation kinetics of PP and PA, which should be expected in the absence of chemical and physical interaction of the components of the mixture. A decrease in the rate constants due to PA additives indicates a decrease in the mobility of molecules in the composites and explains the observed increase in photo-oxidation of mixtures.

First-principles calculations of orientation dependence of Si thermal oxidation based on Si emission model

NASA Astrophysics Data System (ADS)

Nagura, Takuya; Kawachi, Shingo; Chokawa, Kenta; Shirakawa, Hiroki; Araidai, Masaaki; Kageshima, Hiroyuki; Endoh, Tetsuo; Shiraishi, Kenji

2018-04-01

It is expected that the off-state leakage current of MOSFETs can be reduced by employing vertical body channel MOSFETs (V-MOSFETs). However, in fabricating these devices, the structure of the Si pillars sometimes cannot be maintained during oxidation, since Si atoms sometimes disappear from the Si/oxide interface (Si missing). Thus, in this study, we used first-principles calculations based on the density functional theory, and investigated the Si emission behavior at the various interfaces on the basis of the Si emission model including its atomistic structure and dependence on Si crystal orientation. The results show that the order in which Si atoms are more likely to be emitted during thermal oxidation is (111) > (110) > (310) > (100). Moreover, the emission of Si atoms is enhanced as the compressive strain increases. Therefore, the emission of Si atoms occurs more easily in V-MOSFETs than in planar MOSFETs. To reduce Si missing in V-MOSFETs, oxidation processes that induce less strain, such as wet or pyrogenic oxidation, are necessary.

Hydrogen Annealing Of Single-Crystal Superalloys

NASA Technical Reports Server (NTRS)

Smialek, James L.; Schaeffer, John C.; Murphy, Wendy

1995-01-01

Annealing at temperature equal to or greater than 2,200 degrees F in atmosphere of hydrogen found to increase ability of single-crystal superalloys to resist oxidation when subsequently exposed to oxidizing atmospheres at temperatures almost as high. Supperalloys in question are principal constituents of hot-stage airfoils (blades) in aircraft and ground-based turbine engines; also used in other high-temperature applications like chemical-processing plants, coal-gasification plants, petrochemical refineries, and boilers. Hydrogen anneal provides resistance to oxidation without decreasing fatigue strength and without need for coating or reactive sulfur-gettering constituents. In comparison with coating, hydrogen annealing costs less. Benefits extend to stainless steels, nickel/chromium, and nickel-base alloys, subject to same scale-adhesion and oxidation-resistance considerations, except that scale is chromia instead of alumina.

Fabrication of oxide layer on zirconium by micro-arc oxidation: Structural and antimicrobial characteristics.

PubMed

Fidan, S; Muhaffel, F; Riool, M; Cempura, G; de Boer, L; Zaat, S A J; Filemonowicz, A Czyrska-; Cimenoglu, H

2017-02-01

The aim of this study was to cover the surfaces of zirconium (Zr) with an antimicrobial layer for biomedical applications. For this purpose, the micro-arc oxidation (MAO) process was employed in a sodium silicate and sodium hydroxide containing base electrolyte with and without addition of silver acetate (AgC 2 H 3 O 2 ). In general, synthesized MAO layers were composed of zirconium oxide (ZrO 2 ) and zircon (ZrSiO 4 ). Addition of AgC 2 H 3 O 2 into the base electrolyte caused homogenous precipitation of silver-containing particles in the MAO layer, which exhibited excellent antibacterial efficiency against methicillin-resistant Staphylococcus aureus (MRSA) as compared to the untreated and MAO-treated Zr. Copyright © 2016 Elsevier B.V. All rights reserved.

Solid oxide membrane-assisted controllable electrolytic fabrication of metal carbides in molten salt.

PubMed

Zou, Xingli; Zheng, Kai; Lu, Xionggang; Xu, Qian; Zhou, Zhongfu

2016-08-15

Silicon carbide (SiC), titanium carbide (TiC), zirconium carbide (ZrC), and tantalum carbide (TaC) have been electrochemically produced directly from their corresponding stoichiometric metal oxides/carbon (MOx/C) precursors by electrodeoxidation in molten calcium chloride (CaCl2). An assembled yttria stabilized zirconia solid oxide membrane (SOM)-based anode was employed to control the electrodeoxidation process. The SOM-assisted controllable electrochemical process was carried out in molten CaCl2 at 1000 °C with a potential of 3.5 to 4.0 V. The reaction mechanism of the electrochemical production process and the characteristics of these produced metal carbides (MCs) were systematically investigated. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses clearly identify that SiC, TiC, ZrC, and TaC carbides can be facilely fabricated. SiC carbide can be controlled to form a homogeneous nanowire structure, while the morphologies of TiC, ZrC, and TaC carbides exhibit porous nodular structures with micro/nanoscale particles. The complex chemical/electrochemical reaction processes including the compounding, electrodeoxidation, dissolution-electrodeposition, and in situ carbonization processes in molten CaCl2 are also discussed. The present results preliminarily demonstrate that the molten salt-based SOM-assisted electrodeoxidation process has the potential to be used for the facile and controllable electrodeoxidation of MOx/C precursors to micro/nanostructured MCs, which can potentially be used for various applications.

Improved Stability and Performance of Visible Photoelectrochemical Water Splitting on Solution-Processed Organic Semiconductor Thin Films by Ultrathin Metal Oxide Passivation

DOE PAGES

Wang, Lei; Yan, Danhua; Shaffer, David W.; ...

2017-12-27

Solution-processable organic semiconductors have potentials as visible photoelectrochemical (PEC) water splitting photoelectrodes due to their tunable small band gap and electronic energy levels, but they are typically limited by poor stability and photocatalytic activity. In this study, we demonstrate the direct visible PEC water oxidation on solution-processed organic semiconductor thin films with improved stability and performance by ultrathin metal oxide passivation layers. N-type fullerene-derivative thin films passivated by sub-2 nm ZnO via atomic layer deposition enabled the visible PEC water oxidation at wavelengths longer than 600 nm in harsh alkaline electrolyte environments with up to 30 μA/cm 2 photocurrents atmore » the thermodynamic water-oxidation equilibrium potential and the photoanode half-lifetime extended to ~1000 s. The systematic investigation reveals the enhanced water oxidation catalytic activity afforded by ZnO passivation and the charge tunneling governing the hole transfer through passivation layers. Further enhanced PEC performances were realized by improving the bottom ohmic contact to the organic semiconductor, achieving ~60 μA/cm 2 water oxidation photocurrent at the equilibrium potential, the highest values reported for organic semiconductor thin films to our knowledge. The improved stability and performance of passivated organic photoelectrodes and discovered design rationales provide useful guidelines for realizing the stable visible solar PEC water splitting based on organic semiconductor thin films.« less

Improved Stability and Performance of Visible Photoelectrochemical Water Splitting on Solution-Processed Organic Semiconductor Thin Films by Ultrathin Metal Oxide Passivation

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

Wang, Lei; Yan, Danhua; Shaffer, David W.

Solution-processable organic semiconductors have potentials as visible photoelectrochemical (PEC) water splitting photoelectrodes due to their tunable small band gap and electronic energy levels, but they are typically limited by poor stability and photocatalytic activity. In this study, we demonstrate the direct visible PEC water oxidation on solution-processed organic semiconductor thin films with improved stability and performance by ultrathin metal oxide passivation layers. N-type fullerene-derivative thin films passivated by sub-2 nm ZnO via atomic layer deposition enabled the visible PEC water oxidation at wavelengths longer than 600 nm in harsh alkaline electrolyte environments with up to 30 μA/cm 2 photocurrents atmore » the thermodynamic water-oxidation equilibrium potential and the photoanode half-lifetime extended to ~1000 s. The systematic investigation reveals the enhanced water oxidation catalytic activity afforded by ZnO passivation and the charge tunneling governing the hole transfer through passivation layers. Further enhanced PEC performances were realized by improving the bottom ohmic contact to the organic semiconductor, achieving ~60 μA/cm 2 water oxidation photocurrent at the equilibrium potential, the highest values reported for organic semiconductor thin films to our knowledge. The improved stability and performance of passivated organic photoelectrodes and discovered design rationales provide useful guidelines for realizing the stable visible solar PEC water splitting based on organic semiconductor thin films.« less

An Environmentally Friendly Process Involving Refining and Membrane-Based Electrolysis for Magnesium Recovery from Partially Oxidized Scrap Alloy

NASA Astrophysics Data System (ADS)

Guan, Xiaofei; Pal, Uday B.; Powell, Adam C.

2013-10-01

Magnesium is recovered from partially oxidized scrap alloy by combining refining and solid oxide membrane (SOM) electrolysis. In this combined process, a molten salt eutectic flux (45 wt.% MgF2-55 wt.% CaF2) containing 10 wt.% MgO and 2 wt.% YF3 was used as the medium for magnesium recovery. During refining, magnesium and its oxide are dissolved from the scrap into the molten flux. Forming gas is bubbled through the flux and the dissolved magnesium is removed via the gas phase and condensed in a separate condenser at a lower temperature. The molten flux has a finite solubility for magnesium and acts as a selective medium for magnesium dissolution, but not aluminum or iron, and therefore the magnesium recovered has high purity. After refining, SOM electrolysis is performed in the same reactor to enable electrolysis of the dissolved magnesium oxide in the molten flux producing magnesium at the cathode and oxygen at the SOM anode. During SOM electrolysis, it is necessary to decrease the concentration of the dissolved magnesium in the flux to improve the faradaic current efficiency and prevent degradation of the SOM. Thus, for both refining and SOM electrolysis, it is very important to measure and control the magnesium solubility in the molten flux. High magnesium solubility facilitates refining whereas lower solubility benefits the SOM electrolysis process. Computational fluid dynamics modeling was employed to simulate the flow behavior of the flux stirred by the forming gas. Based on the modeling results, an optimized design of the stirring tubes and its placement in the flux are determined for efficiently removing the dissolved magnesium and also increasing the efficiency of the SOM electrolysis process.

Subunit mass analysis for monitoring antibody oxidation.

PubMed

Sokolowska, Izabela; Mo, Jingjie; Dong, Jia; Lewis, Michael J; Hu, Ping

2017-04-01

Methionine oxidation is a common posttranslational modification (PTM) of monoclonal antibodies (mAbs). Oxidation can reduce the in-vivo half-life, efficacy and stability of the product. Peptide mapping is commonly used to monitor the levels of oxidation, but this is a relatively time-consuming method. A high-throughput, automated subunit mass analysis method was developed to monitor antibody methionine oxidation. In this method, samples were treated with IdeS, EndoS and dithiothreitol to generate three individual IgG subunits (light chain, Fd' and single chain Fc). These subunits were analyzed by reversed phase-ultra performance liquid chromatography coupled with an online quadrupole time-of-flight mass spectrometer and the levels of oxidation on each subunit were quantitated based on the deconvoluted mass spectra using the UNIFI software. The oxidation results obtained by subunit mass analysis correlated well with the results obtained by peptide mapping. Method qualification demonstrated that this subunit method had excellent repeatability and intermediate precision. In addition, UNIFI software used in this application allows automated data acquisition and processing, which makes this method suitable for high-throughput process monitoring and product characterization. Finally, subunit mass analysis revealed the different patterns of Fc methionine oxidation induced by chemical and photo stress, which makes it attractive for investigating the root cause of oxidation.

Mediated electrochemical oxidation (MEO) process: a study on nonylphenol ethoxylates (NPE) oxidation in batch mode using cerium (IV) oxidant

NASA Astrophysics Data System (ADS)

Setiyanto, H.; Adyatmika, I. M.; Syaifullah, M. M.; Zulfikar, M. A.; Buchari

2018-05-01

Nonylphenol ethoxylate (NPE-10) is one type of non-ionic surfactants from the class of alkylphenol ethoxylate (APE). This compound is already tightened their use in European Union countries. However, these surfactants are still used widely in Indonesia because the price is relatively cheap. Consequently, these compounds can accumulate in aquatic environments. NPE-10 can disrupt aquatic ecosystems. This study aimed to describe the electro-oxidation process of NPE-10 based on the parameters of a potential difference, concentration of NPE-10, concentration of Ce (III), and oxidation time. The result of oxidation NPE-10 was measured by the amount of current generated from voltammetry technique. Studies of cyclic voltammetry using carbon paste electrodes illustrates the potential value of the oxidation of Ce (III) / Ce (IV) of 1.25 V and the reduction potential value of Ce (IV) / Ce (III) of 1.192 V. NPE-10 are electroactive irreversible because it only provides the potential value of oxidation at 1.44 V. Percent of total degradation of 84.96% was obtained at electro-oxidation of 500 ppm NPE-10 by the addition of 0.015 M Ce (III) for 90 minutes at 0.2 M H2SO4and the use of potential of 6 V.

Using digital flow cytometry to assess the degradation of three cyanobacteria species after oxidation processes.

PubMed

Wert, Eric C; Dong, Mei Mei; Rosario-Ortiz, Fernando L

2013-07-01

Depending on drinking water treatment conditions, oxidation processes may result in the degradation of cyanobacteria cells causing the release of toxic metabolites (microcystin), odorous metabolites (MIB, geosmin), or disinfection byproduct precursors. In this study, a digital flow cytometer (FlowCAM(®)) in combination with chlorophyll-a analysis was used to evaluate the ability of ozone, chlorine, chlorine dioxide, and chloramine to damage or lyse cyanobacteria cells added to Colorado River water. Microcystis aeruginosa (MA), Oscillatoria sp. (OSC) and Lyngbya sp. (LYN) were selected for the study due to their occurrence in surface water supplies, metabolite production, and morphology. Results showed that cell damage was observed without complete lysis or fragmentation of the cell membrane under many of the conditions tested. During ozone and chlorine experiments, the unicellular MA was more susceptible to oxidation than the filamentous OSC and LYN. Rate constants were developed based on the loss of chlorophyll-a and oxidant exposure, which showed the oxidants degraded MA, OSC, and LYN according to the order of ozone > chlorine ~ chlorine dioxide > chloramine. Digital and binary images taken by the digital flow cytometer provided qualitative insight regarding cell damage. When applying this information, drinking water utilities can better understand the risk of cell damage or lysis during oxidation processes. Copyright © 2013 Elsevier Ltd. All rights reserved.

Pulsed Electron Beam Water Radiolysis for Sub-Microsecond Hydroxyl Radical Protein Footprinting

PubMed Central

Watson, Caroline; Janik, Ireneusz; Zhuang, Tiandi; Charvátová, Olga; Woods, Robert J.; Sharp, Joshua S.

2009-01-01

Hydroxyl radical footprinting is a valuable technique for studying protein structure, but care must be taken to ensure that the protein does not unfold during the labeling process due to oxidative damage. Footprinting methods based on sub-microsecond laser photolysis of peroxide that complete the labeling process faster than the protein can unfold have been recently described; however, the mere presence of large amounts of hydrogen peroxide can also cause uncontrolled oxidation and minor conformational changes. We have developed a novel method for sub-microsecond hydroxyl radical protein footprinting using a pulsed electron beam from a 2 MeV Van de Graaff electron accelerator to generate a high concentration of hydroxyl radicals by radiolysis of water. The amount of oxidation can be controlled by buffer composition, pulsewidth, dose, and dissolved nitrous oxide gas in the sample. Our results with ubiquitin and β-lactoglobulin A demonstrate that one sub-microsecond electron beam pulse produces extensive protein surface modifications. Highly reactive residues that are buried within the protein structure are not oxidized, indicating that the protein retains its folded structure during the labeling process. Time-resolved spectroscopy indicates that the major part of protein oxidation is complete in a timescale shorter than that of large scale protein motions. PMID:19265387

Catalyst evaluation for high-purity H2 production by sorption-enhanced steam-methane reforming coupled to a Ca/Cu process

NASA Astrophysics Data System (ADS)

Navarro, M. V.; López, J. M.; García, T.; Grasa, G.; Murillo, R.

2017-09-01

The operational limits of a commercial nickel-based catalyst under the conditions of a sorption-enhanced steam-methane reforming process coupled to a Ca/Cu chemical loop are investigated for high-purity H2 production in a cyclic operation. The performance of the reforming catalyst is tested by means of a high number of oxidation-reduction-reforming cycles. After 100 oxidation-reduction cycles, this catalyst retains its exceptional reforming activity. The methane conversion values are close to the thermodynamic equilibrium under very demanding conditions: temperature between 500 °C - 700 °C and mass hourly space velocity of 8.8 kgCH4 h-1 kgcat-1. After 200 cycles, the sample shows reduction in its reforming activity in line with a lower dispersion of the Ni species. Sintering of Ni nanocrystals is evidenced during the oxidation-reduction multi-cycles. The performance of the catalyst after 200 oxidation-reduction cycles mixed with a CaO-based CO2 sorbent is studied under optimal conditions calculated for the sorption-enhanced reforming process coupled to a Ca/Cu cycle (temperature of 650 °C, steam/methane ratio of 4, sorbent/catalyst ratio of 4 and space velocity of 0.75 kgCH4 h-1 kgcat-1). Remarkably, an equilibrium value over 92 vol.% H2 concentration is achieved, highlighting this catalyst as a promising candidate for the next steps of the process development.

In vivo degradation in modern orthopaedic UHMWPE bearings and structural characterization of a novel alternative UHMWPE material

NASA Astrophysics Data System (ADS)

Reinitz, Steven D.

Ultra-high molecular weight polyethylene (UHMWPE) remains the most common bearing material for total joint arthroplasty. Advances in radiation cross-linking and other post-consolidation treatments have led to a rapid differentiation of polyethylene products on the market, with more than twenty unique materials currently being sold by the five largest orthopaedic manufacturers alone. Through oxidation, cross-link density, and free radical measurements, this work demonstrates for the first time that in vivo material degradation is occurring in cross-linked UHMWPE materials. Based on the rate of the reaction in certain materials, it is concluded that oxidative degradation may compromise the mechanical properties of the bearings in as few as ten years, potentially leading to early clinical failure of the devices. Using the knowledge gained from this work as well as previously published observations about UHMWPE oxidation, a two-mechanism model of oxidation is proposed that offers an explanation for the observed in vivo changes. From this model it is concluded that oxidative degradation is in part the result of in vivo chemical species. The two-mechanism model of oxidation suggests that different processing techniques for UHMWPE may reduce the risk of oxidative degradation. It is concluded that by avoiding any radiation cross-linking step, Equal Channel Angular Processing (ECAP) can produce UHMWPE materials with a reduced risk for in vivo oxidation while at the same time offering superior mechanical properties compared to commercially available UHMWPE materials, as well as similar wear behavior. Using dynamic mechanical analysis, the entanglement density in ECAP materials is quantified, and is related back to the ECAP processing parameters. The relationship between entanglement density and resultant material properties is established. The results will allow informed processing parameter selection for producing optimized materials for orthopaedics and other applications.

Graphene oxide for acid catalyzed-reactions: Effect of drying process

NASA Astrophysics Data System (ADS)

Gong, H. P.; Hua, W. M.; Yue, Y. H.; Gao, Z.

2017-03-01

Graphene oxides (GOs) were prepared by Hummers method through various drying processes, and characterized by XRD, SEM, FTIR, XPS and N2 adsorption. Their acidities were measured using potentiometric titration and acid-base titration. The catalytic properties were investigated in the alkylation of anisole with benzyl alcohol and transesterification of triacetin with methanol. GOs are active catalysts for both reaction, whose activity is greatly affected by their drying processes. Vacuum drying GO exhibits the best performance in transesterification while freezing drying GO is most active for alkylation. The excellent catalytic behavior comes from abundant surface acid sites as well as proper surface functional groups, which can be obtained by selecting appropriate drying process.

Effect of photocatalytic oxidation technology on GaN CMP

NASA Astrophysics Data System (ADS)

Wang, Jie; Wang, Tongqing; Pan, Guoshun; Lu, Xinchun

2016-01-01

GaN is so hard and so chemically inert that it is difficult to obtain a high material removal rate (MRR) in the chemical mechanical polishing (CMP) process. This paper discusses the application of photocatalytic oxidation technology in GaN planarization. Three N-type semiconductor particles (TiO2, SnO2, and Fe2O3) are used as catalysts and added to the H2O2-SiO2-based slurry. By optical excitation, highly reactive photoinduced holes are produced on the surface of the particles, which can oxidize OH- and H2O absorbed on the surface of the catalysts; therefore, more OH* will be generated. As a result, GaN MRRs in an H2O2-SiO2-based polishing system combined with catalysts are improved significantly, especially when using TiO2, the MRR of which is 122 nm/h. The X-ray photoelectron spectroscopy (XPS) analysis shows the variation trend of chemical composition on the GaN surface after polishing, revealing the planarization process. Besides, the effect of pH on photocatalytic oxidation combined with TiO2 is analyzed deeply. Furthermore, the physical model of GaN CMP combined with photocatalytic oxidation technology is proposed to describe the removal mechanism of GaN.

Oxidation behavior and electrical property of ferritic stainless steel interconnects with a Cr-La alloying layer by high-energy micro-arc alloying process

NASA Astrophysics Data System (ADS)

Feng, Z. J.; Zeng, C. L.

Chromium volatility, poisoning of the cathode material and rapidly decreasing electrical conductivity are the major problems associated with the application of ferritic stainless steel interconnects of solid oxide fuel cells operated at intermediate temperatures. Recently, a novel and simple high-energy micro-arc alloying (HEMAA) process is proposed to prepare LaCrO 3-based coatings for the type 430 stainless steel interconnects using a LaCrO 3-Ni rod as deposition electrode. In this work, a Cr-La alloying layer is firstly obtained on the alloy surface by HEMAA using Cr and La as deposition electrode, respectively, followed by oxidation treatment at 850 °C in air to form a thermally grown LaCrO 3 coating. With the formation of a protective scale composed of a thick LaCrO 3 outer layer incorporated with small amounts of Cr-rich oxides and a thin Cr 2O 3-rich sub-layer, the oxidation rate of the coated steel is reduced remarkably. A low and stable electrical contact resistance is achieved with the application of LaCrO 3-based coatings, with a value less than 40 mΩ cm 2 during exposure at 850 °C in air for up to 500 h.

Infiltrated La0.4Sr0.4Fe0.03Ni0.03Ti0.94O3 based anodes for all ceramic and metal supported solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Nielsen, Jimmi; Persson, Åsa H.; Sudireddy, Bhaskar R.; Irvine, John T. S.; Thydén, Karl

2017-12-01

For improved robustness, durability and to avoid severe processing challenges alternatives to the Ni:YSZ composite electrode is highly desirable. The Ni:YSZ composite electrode is conventionally used for solid oxide fuel cell and solid oxide electrolysis cell. In the present study we report on high performing nanostructured Ni:CGO electrocatalyst coated A site deficient Lanthanum doped Strontium Titanate (La0.4Sr0.4Fe0.03Ni0.03Ti0.94O3) based anodes. The anodes were incorporated into the co-sintered DTU metal supported solid oxide fuel cell design and large sized 12 cm × 12 cm cells were fabricated. The titanate material showed good processing characteristics and surface wetting properties towards the Ni:CGO electrocatalyst coating. The cell performances were evaluated on single cell level (active area 16 cm2) and a power density at 0.7 V and 700 °C of 0.650 Wcm-2 with a fuel utilization of 31% was achieved. Taking the temperature into account the performances of the studied anodes are among the best reported for redox stable and corrosion resistant alternatives to the conventional Ni:YSZ composite solid oxide cell electrode.

Interfacial Redox Reactions Associated Ionic Transport in Oxide-Based Memories.

PubMed

Younis, Adnan; Chu, Dewei; Shah, Abdul Hadi; Du, Haiwei; Li, Sean

2017-01-18

As an alternative to transistor-based flash memories, redox reactions mediated resistive switches are considered as the most promising next-generation nonvolatile memories that combine the advantages of a simple metal/solid electrolyte (insulator)/metal structure, high scalability, low power consumption, and fast processing. For cation-based memories, the unavailability of in-built mobile cations in many solid electrolytes/insulators (e.g., Ta 2 O 5 , SiO 2 , etc.) instigates the essential role of absorbed water in films to keep electroneutrality for redox reactions at counter electrodes. Herein, we demonstrate electrochemical characteristics (oxidation/reduction reactions) of active electrodes (Ag and Cu) at the electrode/electrolyte interface and their subsequent ions transportation in Fe 3 O 4 film by means of cyclic voltammetry measurements. By posing positive potentials on Ag/Cu active electrodes, Ag preferentially oxidized to Ag + , while Cu prefers to oxidize into Cu 2+ first, followed by Cu/Cu + oxidation. By sweeping the reverse potential, the oxidized ions can be subsequently reduced at the counter electrode. The results presented here provide a detailed understanding of the resistive switching phenomenon in Fe 3 O 4 -based memory cells. The results were further discussed on the basis of electrochemically assisted cations diffusions in the presence of absorbed surface water molecules in the film.

EFFECTS OF AQUATIC HUMIC SUBSTANCES ON ANALYSIS FOR HYDROGEN PEROXIDE USING PEROXIDASE-CATALYZED OXIDATIONS OF TRIARYLMETHANES OR P-HYDROXYPENYLACETIC ACID (JOURNAL VERSION)

EPA Science Inventory

A sensitive procedure is described for trace analysis of hydrogen peroxide in water. The process involves the peroxide-catalyzed oxidation of the leuco forms of two dyes, crystal violet and malachite green. The sensitivity of this procedure, as well as of another procedure based ...

Nitride Fuel Development Using Cryo-process Technique

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

O'Brien, Brandi M; Windes, William E

A new cryo-process technique has been developed for the fabrication of advanced fuel for nuclear systems. The process uses a new cryo-processing technique whereby small, porous microspheres (<2000 µm) are formed from sub-micron oxide powder. A simple aqueous particle slurry of oxide powder is pumped through a microsphere generator consisting of a vibrating needle with controlled amplitude and frequency. As the water-based droplets are formed and pass through the microsphere generator they are frozen in a bath of liquid nitrogen and promptly vacuum freeze-dried to remove the water. The resulting porous microspheres consist of half micron sized oxide particles heldmore » together by electrostatic forces and mechanical interlocking of the particles. Oxide powder microspheres ranging from 750 µm to 2000 µm are then converted into a nitride form using a high temperature fluidized particle bed. Carbon black can be added to the oxide powder before microsphere formation to augment the carbothermic reaction during conversion to a nitride. Also, the addition of ethyl alcohol to the aqueous slurry reduces the surface tension energy of the droplets resulting in even smaller droplets forming in the microsphere generator. Initial results from this new process indicate a lower impurity contamination in the final nitrides due to the single feed stream of particles, material handling and conversion are greatly simplified, a minimum of waste and personnel exposure are anticipated, and finally the conversion kinetics may be greatly increased because of the small oxide powder size (sub-micron) forming the porous microsphere. Thus far the fabrication process has been successful in demonstrating all of these improvements with surrogate ZrO2 powder. Further tests will be conducted in the future using the technique on UO2 powders.« less

SELF ALIGNED TIP DEINSULATION OF ATOMIC LAYER DEPOSITED AL2O3 AND PARYLENE C COATED UTAH ELECTRODE ARRAY BASED NEURAL INTERFACES

PubMed Central

Xie, Xianzong; Rieth, Loren; Negi, Sandeep; Bhandari, Rajmohan; Caldwell, Ryan; Sharma, Rohit; Tathireddy, Prashant; Solzbacher, Florian

2014-01-01

The recently developed alumina and Parylene C bi-layer encapsulation improved the lifetime of neural interfaces. Tip deinsulation of Utah electrode array based neural interfaces is challenging due to the complex 3D geometries and high aspect ratios of the devices. A three-step self-aligned process was developed for tip deinsulation of bilayer encapsulated arrays. The deinsulation process utilizes laser ablation to remove Parylene C, O2 reactive ion etching to remove carbon and Parylene residues, and buffered oxide etch to remove alumina deposited by atomic layer deposition, and expose the IrOx tip metallization. The deinsulated iridium oxide area was characterized by scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy to determine the morphology, surface morphology, composition, and electrical properties of the deposited layers and deinsulated tips. The alumina layer was found to prevent the formation of micro cracks on iridium oxide during the laser ablation process, which has been previously reported as a challenge for laser deinsulation of Parylene films. The charge injection capacity, charge storage capacity, and impedance of deinsulated iridium oxide were characterized to determine the deinsulation efficacy compared to Parylene-only insulation. Deinsulated iridium oxide with bilayer encapsulation had higher charge injection capacity (240 vs 320 nC) and similar electrochemical impedance (2.5 vs 2.5 kΩ) compared to deinsulated iridium oxide with only Parylene coating for an area of 2 × 10−4 cm2. Tip impedances were in the ranges of 20 to 50 kΩ, with median of 32 KΩ and standard deviation of 30 kΩ, showing the effectiveness of the self-aligned deinsulation process for alumina and Parylene C bi-layer encapsulation. The relatively uniform tip impedance values demonstrated the consistency of tip exposures. PMID:24771981

Microstructure and growth mechanism of Al{sub 2}O{sub 3}/Al ceramic matrix composite made by directed oxidation of Al alloys

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

Qin, C.D.; Lai, M.O.; Cotterell, B.

Since the Lanxide process was advanced for forming of Al{sub 2}O{sub 3} ceramic composite by directed oxidation of Al alloys, much work has been done with various mechanisms being proposed. The mechanisms have claimed that only certain dopants are essential to the growth process. Nevertheless, no united consensus has yet been reached. In the present work, Al alloy containing 5% Mg was oxidized in air for 12 hours at 1,150 C with or without surface dopants of MgO or Pd. The resultant composites showed very different microstructures. Without any surface doping, the alloy did not develop any portion of compositemore » as the initial intimate oxide film stops further oxidation. This intimate oxide film can either be broken off by mechanical means or penetrated by reaction with surface dopants, so that the composite can grow and develop. The results show that the previously reported incubation time is not only related to reaction processes but also to the initial mechanical disturbances. Doping with Pd made the composite darker in color as the grains of the alumina ceramic matrix and inclusions of Al metal are finer. This shows that Pd may make the top oxide layer less intimate, and more nucleation sites are therefore available for oxidation. A new model is presented for oxide sustained growth based on the existence of oxygen active top surface layer and the capillary flow of molten metal around ceramic phase.« less

Metal Oxide Gas Sensors: Sensitivity and Influencing Factors

PubMed Central

Wang, Chengxiang; Yin, Longwei; Zhang, Luyuan; Xiang, Dong; Gao, Rui

2010-01-01

Conductometric semiconducting metal oxide gas sensors have been widely used and investigated in the detection of gases. Investigations have indicated that the gas sensing process is strongly related to surface reactions, so one of the important parameters of gas sensors, the sensitivity of the metal oxide based materials, will change with the factors influencing the surface reactions, such as chemical components, surface-modification and microstructures of sensing layers, temperature and humidity. In this brief review, attention will be focused on changes of sensitivity of conductometric semiconducting metal oxide gas sensors due to the five factors mentioned above. PMID:22294916

Oxidation Potentials in Matte Smelting of Copper and Nickel

NASA Astrophysics Data System (ADS)

Matousek, Jan W.

2014-09-01

The oxidation potential, given as the base-ten logarithm of the oxygen partial pressure in bars and the temperature [log pO2/ T, °C], defines the state of oxidation of pyrometallurgical extraction and refining processes. This property varies from copper making, [-6/1150]; to lead/zinc smelting, [-10/1200]; to iron smelting, [-13/1600]. The current article extends the analysis to the smelting of copper and nickel/copper sulfide concentrates to produce mattes of the type Cu(Ni)FeS(O) and iron silicate slags, FeOxSiO2—with oxidation potentials of [-7.5/1250].

Electrical properties of solution-deposited ZnO thin-film transistors by low-temperature annealing.

PubMed

Lim, Chul; Oh, Ji Young; Koo, Jae Bon; Park, Chan Woo; Jung, Soon-Won; Na, Bock Soon; Chu, Hye Yong

2014-11-01

Flexible oxide thin-film transistors (Oxide-TFTs) have emerged as next generation transistors because of their applicability in electronic device. In particular, the major driving force behind solution-processed zinc oxide film research is its prospective use in printing for electronics. A low-temperature process to improve the performance of solution-processed n-channel ZnO thin-film transistors (TFTs) fabricated via spin-coating and inkjet-printing is introduced here. ZnO nanoparticles were synthesized using a facile sonochemical method that was slightly modified based on a previously reported method. The influence of the annealing atmosphere on both nanoparticle-based TFT devices fabricated via spin-coating and those created via inkjet printing was investigated. For the inkjet-printed TFTs, the characteristics were improved significantly at an annealing temperature of 150 degrees C. The field effect mobility, V(th), and the on/off current ratios were 3.03 cm2/Vs, -3.3 V, and 10(4), respectively. These results indicate that annealing at 150 degrees C 1 h is sufficient to obtain a mobility (μ(sat)) as high as 3.03 cm2/Vs. Also, the active layer of the solution-based ZnO nanoparticles allowed the production of high-performance TFTs for low-cost, large-area electronics and flexible devices.

Electrochemical and ab initio investigations to design a new phenothiazine based organic redox polymeric material for metal-ion battery cathodes.

PubMed

Godet-Bar, T; Leprêtre, J-C; Le Bacq, O; Sanchez, J-Y; Deronzier, A; Pasturel, A

2015-10-14

Different N-substituted phenothiazines have been synthesized and their electrochemical behavior has been investigated in CH3CN in order to design the best polyphenothiazine based cathodic material candidate for lithium batteries. These compounds exhibit two successive reversible one-electron oxidation processes. Ab initio calculations demonstrate that the potential of the first process is a result of both the hybridization effects between the substituent and the phenothiazine unit as well as the change of conformation of the phenothiazine heterocycle during the oxidation process. More specifically, we show that an asymmetric molecular orbital spreading throughout an external cycle of the phenothiazine unit and the alkyl fragment is formed only if the alkyl fragment is long enough (from the methyl moiety onwards) and is at the origin of the bent conformation for N-substituted phenothiazines during oxidation. Electrochemical investigations supported by ab initio calculations allow the selection of a phenothiazinyl unit which is then polymerized by a Suzuki coupling strategy to avoid the common solubilization issue in carbonate-based liquid electrolytes of lithium cells. The first electrochemical measurements performed show that phenothiazine derivatives pave the way for a promising family of redox polymers intended to be used as organic positives for lithium batteries.

Health Effects of Dietary Oxidized Tyrosine and Dityrosine Administration in Mice with Nutrimetabolomic Strategies.

PubMed

Yang, Yuhui; Zhang, Hui; Yan, Biao; Zhang, Tianyu; Gao, Ying; Shi, Yonghui; Le, Guowei

2017-08-16

This study aims to investigate the health effects of long-term dietary oxidized tyrosine (O-Tyr) and its main product (dityrosine) administration on mice metabolism. Mice received daily intragastric administration of either O-Tyr (320 μg/kg body weight), dityrosine (Dityr, 320 μg/kg body weight), or saline for consecutive 6 weeks. Urine and plasma samples were analyzed by NMR-based metabolomics strategies. Body weight, clinical chemistry, oxidative damage indexes, and histopathological data were obtained as complementary information. O-Tyr and Dityr exposure changed many systemic metabolic processes, including reduced choline bioavailability, led to fat accumulation in liver, induced hepatic injury, and renal dysfunction, resulted in changes in gut microbiota functions, elevated risk factor for cardiovascular disease, altered amino acid metabolism, induced oxidative stress responses, and inhibited energy metabolism. These findings implied that it is absolutely essential to reduce the generation of oxidation protein products in food system through improving modern food processing methods.

Superhydrophobic surfaces by electrochemical processes.

PubMed

Darmanin, Thierry; Taffin de Givenchy, Elisabeth; Amigoni, Sonia; Guittard, Frederic

2013-03-13

This review is an exhaustive representation of the electrochemical processes reported in the literature to produce superhydrophobic surfaces. Due to the intensive demand in the elaboration of superhydrophobic materials using low-cost, reproducible and fast methods, the use of strategies based on electrochemical processes have exponentially grown these last five years. These strategies are separated in two parts: the oxidation processes, such as oxidation of metals in solution, the anodization of metals or the electrodeposition of conducting polymers, and the reduction processed such as the electrodeposition of metals or the galvanic deposition. One of the main advantages of the electrochemical processes is the relative easiness to produce various surface morphologies and a precise control of the structures at a micro- or a nanoscale. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for continuous synthesis of metal oxide powders

DOEpatents

Berry, David A.; Haynes, Daniel J.; Shekhawat, Dushyant; Smith, Mark W.

2015-09-08

A method for the rapid and continuous production of crystalline mixed-metal oxides from a precursor solution comprised of a polymerizing agent, chelated metal ions, and a solvent. The method discharges solution droplets of less than 500 .mu.m diameter using an atomizing or spray-type process into a reactor having multiple temperature zones. Rapid evaporation occurs in a first zone, followed by mixed-metal organic foam formation in a second zone, followed by amorphous and partially crystalline oxide precursor formation in a third zone, followed by formation of the substantially crystalline mixed-metal oxide in a fourth zone. The method operates in a continuous rather than batch manner and the use of small droplets as the starting material for the temperature-based process allows relatively high temperature processing. In a particular embodiment, the first zone operates at 100-300.degree. C., the second zone operates at 300-700.degree. C., and the third operates at 700-1000.degree. C., and fourth zone operates at at least 700.degree. C. The resulting crystalline mixed-metal oxides display a high degree of crystallinity and sphericity with typical diameters on the order of 50 .mu.m or less.

Monte Carlo simulations of safeguards neutron counter for oxide reduction process feed material

NASA Astrophysics Data System (ADS)

Seo, Hee; Lee, Chaehun; Oh, Jong-Myeong; An, Su Jung; Ahn, Seong-Kyu; Park, Se-Hwan; Ku, Jeong-Hoe

2016-10-01

One of the options for spent-fuel management in Korea is pyroprocessing whose main process flow is the head-end process followed by oxide reduction, electrorefining, and electrowining. In the present study, a well-type passive neutron coincidence counter, namely, the ACP (Advanced spent fuel Conditioning Process) safeguards neutron counter (ASNC), was redesigned for safeguards of a hot-cell facility related to the oxide reduction process. To this end, first, the isotopic composition, gamma/neutron emission yield and energy spectrum of the feed material ( i.e., the UO2 porous pellet) were calculated using the OrigenARP code. Then, the proper thickness of the gammaray shield was determined, both by irradiation testing at a standard dosimetry laboratory and by MCNP6 simulations using the parameters obtained from the OrigenARP calculation. Finally, the neutron coincidence counter's calibration curve for 100- to 1000-g porous pellets, in consideration of the process batch size, was determined through simulations. Based on these simulation results, the neutron counter currently is under construction. In the near future, it will be installed in a hot cell and tested with spent fuel materials.

Contrast image formation based on thermodynamic approach and surface laser oxidation process for optoelectronic read-out system

NASA Astrophysics Data System (ADS)

Scherbak, Aleksandr; Yulmetova, Olga

2018-05-01

A pulsed fiber laser with the wavelength 1.06 μm was used to treat titanium nitride film deposited on beryllium substrates in the air with intensities below an ablation threshold to provide oxide formation. Laser oxidation results were predicted by the chemical thermodynamic method and confirmed by experimental techniques (X-ray diffraction). The developed technology of contrast image formation is intended to be used for optoelectronic read-out system.

The oxidative stability of carbon fibre reinforced glass-matrix composites

NASA Technical Reports Server (NTRS)

Prewo, K. M.; Batt, J. A.

1988-01-01

The environmental stability of carbon fibre reinforced glass-matrix composites is assessed. Loss of composite strength due to oxidative exposure at elevated temperatures under no load, static load and cyclic fatigue as well as due to thermal cycling are all examined. It is determined that strength loss is gradual and predictable based on the oxidation of carbon fibres. The glass matrix was not found to prevent this degradation but simply to limit it to a gradual process progressing from the composite surfaces inward.

Pt and Pd catalyzed oxidation of Li 2O 2 and DMSO during Li–O 2 battery charging

DOE PAGES

Gittleson, Forrest S.; Ryu, Won-Hee; Schwab, Mark; ...

2016-01-01

Rechargeable Li-O 2 and Li-air batteries require electrode and electrolyte materials that synergistcally promote long-term cell operation. We investigate the role of noble metals Pt and Pd as catalysts for the Li-O 2 oxidation process and their compatibility with a dimethyl sulfoxide (DMSO) based electrolyte. Lastly, we identify a basis for low potential Li 2O 2 evolution followed by oxidative decomposition of the electrolyte to form carbonate side products.

Optimization Recovery of Yttrium Oxide in Precipitation, Extraction, and Stripping Process

NASA Astrophysics Data System (ADS)

Perwira, N. I.; Basuki, K. T.; Biyantoro, D.; Effendy, N.

2018-04-01

Yttrium oxide can be used as a dopant control rod of nuclear reactors in YSH material and superconductors. Yttrium oxide is obtained in the Xenotime mineral derived from byproduct of tin mining PT Timah Bangka which contain rare earth elements (REE) dominant Y, Dy, and Gd whose content respectively about 29.53%, 7.76%, and 2.58%. Both usage in the field of nuclear and non-nuclear science and technology is need to pure from the impurities. The presence of impurities in the yttrium oxide may affect the characteristic of the material and the efficiency of its use. Thus it needs to be separated by precipitation and extraction-stripping and calcination in the making of the oxide. However, to obtain higher levels of Yttrium oxide, it is necessary to determine the optimum conditions for its separation. The purpose of this research was to determine the optimum pH of precipitation, determine acid media and concentration optimum in extraction and stripping process and determine the efficiency of the separation of Y from REE concentrate. This research was conducted with pH variation in the precipitation process that pHs were 4 - 8, the difference of acid media for the extraction process, i.e., HNO3, HCl and H2SO4 with each concentration of 0,5 M; 1 M; 1,5 M; and 2 M and for stripping process were HNO3, HCl, and H2SO4 with each concentration of 1 M; 2M; and 3 M. Based on the result, the optimum pH of precipitation process was 6,5, the optimumacid media was HNO3 0,5 M, and for stripping process media was HNO3 3 M. The efficiency of precipitation process at pH 6,5 was 69,53 %, extraction process was 96.39% and stripping process was 4,50%. The separation process from precipitation to extraction had increased the purity and the highest efficiency recovery of Y was in the extraction process and obtained Y2O3 purer compared to the feed with the Y2O3 content of 92.87%.

The effect of upper gastrointestinal system endoscopy process on serum oxidative stress levels.

PubMed

Turan, Mehmet Nuri; Aslan, Mehmet; Bolukbas, Filiz Fusun; Bolukbas, Cengiz; Selek, Sahbettin; Sabuncu, Tevfik

2016-12-01

Some authors have investigated the effects of oxidative stress in some process such as undergoing laparoscopic. However, the effect of upper gastrointestinal system endoscopy process on oxidative stress is unclear. We evaluated the short-term effect of upper gastrointestinal system endoscopy process on oxidative stress. Thirty patients who underwent endoscopy process and 20 healthy controls were enrolled in the prospective study. Serum total antioxidant capacity and total oxidant status measurements were measured before and after endoscopy process. The ratio percentage of total oxidant status to total antioxidant capacity was regarded as oxidative stress index. Before endoscopy process, serum total antioxidant capacity levels were higher, while serum total oxidant status levels and oxidative stress index values were lower in patients than controls, but this difference was not statistically significant (all, p > 0.05). After endoscopy process, serum total antioxidant capacity and total oxidant status levels were significantly higher in patients than before endoscopy process (both, p < 0.05). However, oxidative stress index values were slight higher in patients but this difference was not statistically significant (p > 0.05). We observed that serum TAC and TOS levels were increased in patients who underwent endoscopy process after endoscopy process. However, short-time upper gastrointestinal system endoscopy process did not cause an important change in the oxidative stress index. Further studies enrolling a larger number of patients are required to clarify the results obtained here.

Insight into the Mechanism of Graphene Oxide Degradation via the Photo-Fenton Reaction

PubMed Central

2015-01-01

Graphene represents an attractive two-dimensional carbon-based nanomaterial that holds great promise for applications such as electronics, batteries, sensors, and composite materials. Recent work has demonstrated that carbon-based nanomaterials are degradable/biodegradable, but little work has been expended to identify products formed during the degradation process. As these products may have toxicological implications that could leach into the environment or the human body, insight into the mechanism and structural elucidation remain important as carbon-based nanomaterials become commercialized. We provide insight into a potential mechanism of graphene oxide degradation via the photo-Fenton reaction. We have determined that after 1 day of treatment intermediate oxidation products (with MW 150–1000 Da) were generated. Upon longer reaction times (i.e., days 2 and 3), these products were no longer present in high abundance, and the system was dominated by graphene quantum dots (GQDs). On the basis of FTIR, MS, and NMR data, potential structures for these oxidation products, which consist of oxidized polycyclic aromatic hydrocarbons, are proposed. PMID:24860637

Lateral photovoltaic effect in flexible free-standing reduced graphene oxide film for self-powered position-sensitive detection

PubMed Central

Moon, In Kyu; Ki, Bugeun; Yoon, Seonno; Oh, Jungwoo

2016-01-01

Lightweight, simple and flexible self-powered photodetectors are urgently required for the development and application of advanced optical systems for the future of wearable electronic technology. Here, using a low-temperature reduction process, we report a chemical approach for producing freestanding monolithic reduced graphene oxide papers with different gradients of the carbon/oxygen concentration ratio. We also demonstrate a novel type of freestanding monolithic reduced graphene oxide self-powered photodetector based on a symmetrical metal–semiconductor–metal structure. Upon illumination by a 633-nm continuous wave laser, the lateral photovoltage is observed to vary linfearly with the laser position between two electrodes on the reduced graphene oxide surface. This result may suggest that the lateral photovoltaic effect in the reduced graphene oxide film originates from the built-in electric field by the combination of both the photothermal electric effect and the gradient of the oxygen-to-carbon composition. These results represent substantial progress toward novel, chemically synthesized graphene-based photosensors and suggest one-step integration of graphene-based optoelectronics in the future. PMID:27634110

Charge pump-based MOSFET-only 1.5-bit pipelined ADC stage in digital CMOS technology

NASA Astrophysics Data System (ADS)

Singh, Anil; Agarwal, Alpana

2016-10-01

A simple low-power and low-area metal-oxide-semiconductor field-effect transistor-only fully differential 1.5-bit pipelined analog-to-digital converter stage is proposed and designed in Taiwan Semiconductor Manufacturing Company 0.18 μm-technology using BSIM3v3 parameters with supply voltage of 1.8 V in inexpensive digital complementary metal-oxide semiconductor (CMOS) technology. It is based on charge pump technique to achieve the desired voltage gain of 2, independent of capacitor mismatch and avoiding the need of power hungry operational amplifier-based architecture to reduce the power, Si area and cost. Various capacitances are implemented by metal-oxide semiconductor capacitors, offering compatibility with cheaper digital CMOS process in order to reduce the much required manufacturing cost.

Work function characterization of solution-processed cobalt silicide

DOE PAGES

Ullah, Syed Shihab; Robinson, Matt; Hoey, Justin; ...

2012-05-08

Cobalt silicide thin films were prepared by spin-coating Si6H12-based inks onto various substrates followed by a thermal treatment. The work function of the solution processed Co-Si was determined by both capacitance-voltage (C-V) measurements of metal-oxide-semiconductor (MOS) structures as well as by ultraviolet photoelectron spectroscopy (UPS). The UPS-derived work function was 4.80 eV for a Co-Si film on Si (100) while C-V of MOS structures yielded a work function of 4.36 eV where the metal was solution-processed Co-Si, the oxide was SiO2 and the semiconductor was a B-doped Si wafer.

Selective Internal Oxidation and Severe Plastic Deformation of Multiphase Fe-Y Alloys

NASA Astrophysics Data System (ADS)

Kachur, Stephen J.

Oxide dispersion strengthened (ODS) alloys are known for their desirable mechanical properties and unique microstructures. These alloys are characterized by an even dispersion of oxide phase throughout a metallic matrix, and exhibit high strength and enhanced creep properties at elevated temperatures. This makes them ideal candidate materials for use in many structural applications, such as coal-fired power plants or in next generation nuclear reactors. Currently most often produced by mechanical alloying, a powder metallurgy based process that utilizes high energy ball milling, these alloys are difficult and costly to produce. One proposed method for forming ODS alloys without high-energy ball milling is to internally oxidize a bulk alloy before subjecting it to severe plastic deformation to induce an even oxide distribution. This work examines such a processing scheme with a focus on the internal oxidation behavior. Internal oxidation has been shown to occur orders of magnitude faster than expected in multi-phase alloys where a highly reactive oxidizable solute has negligible solubility and diffusivity in other, more-noble, phases. Commonly referred to as in situ oxidation, this accelerated oxidation process has potential for use in a processing scheme for ODS alloys. While in situ oxidation has been observed in many different alloy systems, a comprehensive study of alloy composition and microstructure has not been performed to describe the unusual oxidation rates. This work used Fe-Y binary alloys as model system to study effects of composition and microstructure. These alloys have been shown to exhibit in situ oxidation, and additionally, Y is typically introduced during mechanical alloying to form Y-rich oxides in Fe-based ODS alloys. Alloys with Y content between 1.5 and 15 wt% were prepared using a laboratory scale arc-melting furnace. These alloys were two phase mixtures of Fe and Fe17Y2. First, samples were oxidized between 600 and 800 °C for 2 to 72 hours, using a Rhines pack to maintain low oxygen partial pressures so that in situ oxidation could occur. Oxidation rates were accelerated when compared to traditional theory, and were not well described by a single parabolic rate constant throughout the duration of the experiment. While results agreed with Wagner theory that increased Y content should lead to decreased oxidation rates, this was attributed to a depletion of oxygen supply from the Rhines pack over time. Samples were also subjected to plastic deformation to observe how changes in microstructure influenced kinetics. Connectivity of the oxidizable phase was found to be critical to promoting the fastest rates of oxidation. Oxidation studies where then carried out using thermogravimetric analysis. A gaseous mixture of Ar-H2 was passed through a dew point control unit to vary oxidant partial pressure between 10-25 and 10-20 atm. Flow rate of the gas parallel to the sample surface was also altered. Canonical correlation analysis was then used to analyze and simplify the relationships between input and output variables. This analysis pointed to the importance of quantifying the relationship between the size of formed oxides and changes in oxidation kinetics over time. Where sustained parabolic kinetics were observed, oxides were small throughout the depth of internal oxidation. The effects of oxide size on penetration depth were then numerically modeled and incorporated into existing oxidation theory to show that the observed kinetics could be qualitatively described. After oxidation experiments, severe plastic deformation was applied to both oxidized and unoxidized microstructures using equal channel angular pressing. By manipulating pressing temperature and the number of passes, microstructures were altered to varying degrees of success. No oxide refinement was observed, but increasing temperatures and number of passes allowed for even dispersion of both oxides and Fe17Y2 intermetallic.

Electrospinning of ceramic nanofibers

NASA Astrophysics Data System (ADS)

Eick, Benjamin M.

Silicon Carbide (SiC) nanofibers of diameters as low as 20 nm are fabricated. The fibers were produced through the electrostatic spinning of the preceramic poly(carbomethylsilane) with pyrolysis to ceramic. A new technique was used where the preceramic was blended with polystyrene (PS) and, subsequent to electrospinning, was exposed to UV to crosslink the PS and prevent fibers flowing during pyrolysis. Electrospun SiC fibers were characterized by FTIR, TGA-DTA, SEM, TEM, XRD, and SAED. Fibers were shown to be polycrystalline and nanograined with alpha-SiC 15R polytype being dominant, where commercial fiber production methods form beta-SiC 3C. Pyrolysis of the bulk polymer blend to SiC produced alpha-SiC 15R as the dominant polytype with larger grains showing that electrospinning nanofibers affects resultant crystallinity. Fibers produced were shown to have a core-shell structure of an oxide scale that was variable by pyrolysis conditions. Metal oxide powders (chromium oxide, cobalt oxide, iron oxide, silicon oxide, tantalum oxide, titanium oxide, tungsten oxide, vanadium oxide, and zirconium oxide), were converted to metal carbide powders and metal nitride powders by the process of carbothermal reduction (CTR). Synthetic pitch was explored as an alternative to graphite which is a common carbon source for CTR. It was shown via characterization with XRD that pitch performs as well and in some cases better than graphite and is therefore a viable alternative in CTR. Conversion of metal oxide powders with pitch led to conversion of sol-gel based metal oxide nanofibers produced by electrospinning. Pitch was soluble in the solutions xv that were electrospun allowing for intimate contact between the sol-gel and the carbon source for CTR. This method became a two step processing method to produce metal carbide and nitride nanofibers: first electrospin sol-gel based metal oxide nanofibers and subsequently pyrolize them in the manner of CTR to transform them. Results indicate that this method was capable of transforming hafnium, niobium, tantalum, titanium, vanadium, and zirconium sol-gel nanofibers to metal carbides and nitrides.

Process for combined control of mercury and nitric oxide.

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

Livengood, C. D.; Mendelsohn, M. H.

Continuing concern about the effects of mercury in the environment may lead to requirements for the control of mercury emissions from coal-fired power plants. If such controls are mandated, the use of existing flue-gas cleanup systems, such as wet scrubbers currently employed for flue-gas desulfurization, would be desirable, Such scrubbers have been shown to be effective for capturing oxidized forms of mercury, but cannot capture the very insoluble elemental mercury (Hg{sup 0}) that can form a significant fraction of the total emissions. At Argonne National Laboratory, we have proposed and tested a concept for enhancing removal of Hg{sup 0}, as well as nitric oxide, through introduction of an oxidizing agent into the flue gas upstream of a scrubber, which readily absorbs the soluble reaction products. Recently, we developed a new method for introducing the oxidizing agent into the flue-gas stream that dramatically improved reactant utilization. The oxidizing agent employed was NOXSORB{trademark}, which is a commercial product containing chloric acid and sodium chlorate. When a dilute solution of this agent was introduced into a gas stream containing Hg{sup 0} and other typical flue-gas species at 300 F, we found that about 100% of the mercury was removed from the gas phase and recovered in process liquids. At the same time, approximately 80% of the nitric oxide was removed. The effect of sulfur dioxide on this process was also investigated and the results showed that it slightly decreased the amount of Hg{sup 0} oxidized while appearing to increase the removal of nitric oxide from the gas phase. We are currently testing the effects of variations in NOXSORB{trademark} concentration, sulfur dioxide concentration, nitric oxide concentration, and reaction time (residence time). Preliminary economic projections based on the results to date indicate that the chemical cost for nitric oxide oxidation could be less thanmore » $$5,000/ton removed, while for Hg{sup 0} oxidation it would be about $$20,000/lb removed.« less

Physical and chemical mechanism underlying ultrasonically enhanced hydrochloric acid leaching of non-oxidative roasting of bastnaesite.

PubMed

Zhang, Dongliang; Li, Mei; Gao, Kai; Li, Jianfei; Yan, Yujun; Liu, Xingyu

2017-11-01

In this study, we investigated an alternative to the conventional hydrochloric acid leaching of roasted bastnaesite. The studies suggested that the rare earth oxyfluorides in non-oxidatively roasted bastnaesite can be selectively leached only at elevated temperatures Further, the Ce(IV) in oxidatively roasted bastnaesite does not leach readily at low temperatures, and it is difficult to induce it to form a complex with F - ions in order to increase the leaching efficiency. Moreover, it is inevitably reduced to Ce(III) at elevated temperatures. Thus, the ultrasonically-assisted hydrochloric acid leaching of non-oxidatively roasted bastnaesite was studied in detail, including, the effects of several process factors and the, physical and chemical mechanisms underlying the leaching process. The results show that the leaching rate for the ultrasonically assisted process at 55°C (65% rare earth oxides) is almost the same as that for the conventional leaching process at 85°C. Based on the obtained results, it is concluded that ultrasonic cavitation plays a key role in the proposed process, resulting not only in a high shear stress, which damages the solid surface, but also in the formation of hydroxyl radicals (OH) and hydrogen peroxide (H 2 O 2 ). Standard electrode potential analysis and experimental results indicate that Ce(III) isoxidized by the hydroxyl radicals to Ce(IV), which can be leached with F - ions in the form of a complex, and that the Ce(IV) can subsequently be reduced to Ce(III) by the H 2 O 2. This prevents the Cl - ions in the solution from being oxidized to form chlorine. These results imply that the ultrasonically-assisted process can be used for the leaching of non-oxidatively roasted bastnaesite at low temperatures in the absence of a reductant. Copyright © 2017 Elsevier B.V. All rights reserved.

Application of N-Doped Three-Dimensional Reduced Graphene Oxide Aerogel to Thin Film Loudspeaker.

PubMed

Kim, Choong Sun; Lee, Kyung Eun; Lee, Jung-Min; Kim, Sang Ouk; Cho, Byung Jin; Choi, Jung-Woo

2016-08-31

We built a thermoacoustic loudspeaker employing N-doped three-dimensional reduced graphene oxide aerogel (N-rGOA) based on a simple template-free fabrication method. A two-step fabrication process, which includes freeze-drying and reduction/doping, was used to realize a three-dimensional, freestanding, and porous graphene-based loudspeaker, whose macroscopic structure can be easily modulated. The simplified fabrication process also allows the control of structural properties of the N-rGOAs, including density and area. Taking advantage of the facile fabrication process, we fabricated and analyzed thermoacoustic loudspeakers with different structural properties. The anlayses showed that a N-rGOA with lower density and larger area can produce a higher sound pressure level (SPL). Furthermore, the resistance of the proposed loudspeaker can be easily controlled through heteroatom doping, thereby helping to generate higher SPL per unit driving voltage. Our success in constructing an array of optimized N-rGOAs able to withstand input power as high as 40 W demonstrates that a practical thermoacoustic loudspeaker can be fabricated using the proposed mass-producible solution-based process.

Complex capacitance spectroscopy as a probe for oxidation process of AlO{sub x}-based magnetic tunnel junctions

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

Huang, J.C.A.; Hsu, C.Y.; Taiwan SPIN Research Center, National Chung Cheng University, Chiayi, Taiwan

2004-12-13

Proper as well as under- and over-oxided CoFe-AlO{sub x}-CoFe magnetic tunnel junctions (MTJs) have been systematically investigated in a frequency range from 10{sup 2} to 10{sup 8} Hz by complex capacitance spectroscopy. The dielectric relaxation behavior of the MTJs remarkably disobeys the typical Cole-Cole arc law probably due to the existence of imperfectly blocked Schottky barrier in the metal-insulator interface. The dielectric relaxation response can be successfully modeled on the basis of Debye relaxation by incorporating an interfacial dielectric contribution. In addition, complex capacitance spectroscopy demonstrates significant sensitivity to the oxidation process of metallic Al layers, i.e., almost a fingerprintmore » of under, proper, and over oxidation. This technique provides a fast and simple method to inspect the AlO{sub x} barrier quality of MTJs.« less

Modified Graphene Oxide for Long Cycle Sodium-Ion Batteries

NASA Astrophysics Data System (ADS)

Shareef, Muhamed; Gunn, Harrison; Voigt, Victoria; Singh, Gurpreet

Hummer's process was modified to produce gram levels of 2-dimensional nanosheets of graphene oxide (GO) with varying degree of exfoliation and chemical functionalization. This was achieved by varying the weight ratios and reaction times of oxidizing agents used in the process. Based on Raman and Fourier transform infra red spectroscopy we show that potassium permanganate (KMnO4) is the key oxidizing agent while sodium nitrate (NaNO3) and sulfuric acid (H2SO4) play minor role during the exfoliation of graphite. Tested as working electrode in sodium-ion half-cell, the GO nanosheets produced using this optimized approach showed high rate capability and exceptionally high energy density of ~500 mAh/g for up to at least 100 cycles, which is among the highest reported for sodium/graphite electrodes. The average Coulombic efficiency was approximately 99 %. NSF Grant No. 1454151.

Free radicals, reactive oxygen species, oxidative stress and its classification.

PubMed

Lushchak, Volodymyr I

2014-12-05

Reactive oxygen species (ROS) initially considered as only damaging agents in living organisms further were found to play positive roles also. This paper describes ROS homeostasis, principles of their investigation and technical approaches to investigate ROS-related processes. Especial attention is paid to complications related to experimental documentation of these processes, their diversity, spatiotemporal distribution, relationships with physiological state of the organisms. Imbalance between ROS generation and elimination in favor of the first with certain consequences for cell physiology has been called "oxidative stress". Although almost 30years passed since the first definition of oxidative stress was introduced by Helmut Sies, to date we have no accepted classification of oxidative stress. In order to fill up this gape here classification of oxidative stress based on its intensity is proposed. Due to that oxidative stress may be classified as basal oxidative stress (BOS), low intensity oxidative stress (LOS), intermediate intensity oxidative stress (IOS), and high intensity oxidative stress (HOS). Another classification of potential interest may differentiate three categories such as mild oxidative stress (MOS), temperate oxidative stress (TOS), and finally severe (strong) oxidative stress (SOS). Perspective directions of investigations in the field include development of sophisticated classification of oxidative stresses, accurate identification of cellular ROS targets and their arranged responses to ROS influence, real in situ functions and operation of so-called "antioxidants", intracellular spatiotemporal distribution and effects of ROS, deciphering of molecular mechanisms responsible for cellular response to ROS attacks, and ROS involvement in realization of normal cellular functions in cellular homeostasis. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Development of oxide dispersion strengthened turbine blade alloy by mechanical alloying

NASA Technical Reports Server (NTRS)

Merrick, H. F.; Curwick, L. R. R.; Kim, Y. G.

1977-01-01

There were three nickel-base alloys containing up to 18 wt. % of refractory metal examined initially for oxide dispersion strengthening. To provide greater processing freedom, however, a leaner alloy was finally selected. This base alloy, alloy D, contained 0.05C/15Cr / 2Mo/4W/2Ta/4.5Al/2.Ti/015Zr/0.01-B/Bal. Ni. Following alloy selection, the effect of extrusion, heat treatment, and oxide volume fraction and size on microstructure and properties were examined. The optimum structure was achieved in zone annealed alloy D which contained 2.5 vol. % of 35 mm Y2O3 and which was extruded 16:1 at 1038 C.

Method of preparing and utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream

DOEpatents

Berry, David A; Shekhawat, Dushyant; Smith, Mark; Haynes, Daniel

2013-07-16

The disclosure relates to a method of utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream with a mitigation of carbon accumulation. The system is comprised of a catalytically active phase deposited onto an oxygen conducting phase, with or without supplemental support. The catalytically active phase has a specified crystal structure where at least one catalytically active metal is a cation within the crystal structure and coordinated with oxygen atoms within the crystal structure. The catalyst system employs an optimum coverage ratio for a given set of oxidation conditions, based on a specified hydrocarbon conversion and a carbon deposition limit. Specific embodiments of the catalyst system are disclosed.

Oxidation Resistant, Cr Retaining, Electrically Conductive Coatings on Metallic Alloys for SOFC Interconnects

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

Vladimir Gorokhovsky

2008-03-31

This report describes significant results from an on-going, collaborative effort to enable the use of inexpensive metallic alloys as interconnects in planar solid oxide fuel cells (SOFCs) through the use of advanced coating technologies. Arcomac Surface Engineering, LLC, under the leadership of Dr. Vladimir Gorokhovsky, is investigating filtered-arc and filtered-arc plasma-assisted hybrid coating deposition technologies to promote oxidation resistance, eliminate Cr volatility, and stabilize the electrical conductivity of both standard and specialty steel alloys of interest for SOFC metallic interconnect (IC) applications. Arcomac has successfully developed technologies and processes to deposit coatings with excellent adhesion, which have demonstrated a substantialmore » increase in high temperature oxidation resistance, stabilization of low Area Specific Resistance values and significantly decrease Cr volatility. An extensive matrix of deposition processes, coating compositions and architectures was evaluated. Technical performance of coated and uncoated sample coupons during exposures to SOFC interconnect-relevant conditions is discussed, and promising future directions are considered. Cost analyses have been prepared based on assessment of plasma processing parameters, which demonstrate the feasibility of the proposed surface engineering process for SOFC metallic IC applications.« less

Improvement of bias-stability in amorphous-indium-gallium-zinc-oxide thin-film transistors by using solution-processed Y{sub 2}O{sub 3} passivation

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

An, Sungjin; Mativenga, Mallory; Kim, Youngoo

2014-08-04

We demonstrate back channel improvement of back-channel-etch amorphous-indium-gallium-zinc-oxide (a-IGZO) thin-film transistors by using solution-processed yttrium oxide (Y{sub 2}O{sub 3}) passivation. Two different solvents, which are acetonitrile (35%) + ethylene glycol (65%), solvent A and deionized water, solvent B are investigated for the spin-on process of the Y{sub 2}O{sub 3} passivation—performed after patterning source/drain (S/D) Mo electrodes by a conventional HNO{sub 3}-based wet-etch process. Both solvents yield devices with good performance but those passivated by using solvent B exhibit better light and bias stability. Presence of yttrium at the a-IGZO back interface, where it occupies metal vacancy sites, is confirmed by X-ray photoelectronmore » spectroscopy. The passivation effect of yttrium is more significant when solvent A is used because of the existence of more metal vacancies, given that the alcohol (65% ethylene glycol) in solvent A may dissolve the metal oxide (a-IGZO) through the formation of alkoxides and water.« less

Formation of aqueous-phase sulfate during the haze period in China: Kinetics and atmospheric implications

NASA Astrophysics Data System (ADS)

Zhang, Haijie; Chen, Shilu; Zhong, Jie; Zhang, Shaowen; Zhang, Yunhong; Zhang, Xiuhui; Li, Zesheng; Zeng, Xiao Cheng

2018-03-01

Sulfate is one of the most important components in the aerosol due to its key role in air pollution and global climate change. Recent work has suggested that reactive nitrogen chemistry in aqueous water can explain the missing source of sulfate in the aqueous water. Herein, we have mapped out the energy profile of the oxidization process of SO2 leading from NO2 and two feasible three-step mechanisms have been proposed. For the oxidation of HOSO2- and HSO3- by the dissolved NO2 in weakly acidic and neutral aerosol (pH ≤ 7), the main contribution to the missing sulfate production comes from the oxidation of HOSO2-. The whole process is a self-sustaining process. For the oxidation of SO32- in alkaline aerosol (pH > 7), the third step - decomposition step of H2O or hydrolysis of SO3 step which are two parallel processes are the rate-limiting steps. The present results are of avail to better understand the missing source of sulfate in the aerosol and hence may lead to better science-based solutions for resolving the severe haze problems in China.

Degradation of chlorophenols and alkylphenol ethoxylates, two representative textile chemicals, in water by advanced oxidation processes: the state of the art on transformation products and toxicity.

PubMed

Karci, Akin

2014-03-01

Advanced oxidation processes based on the generation of reactive species including hydroxyl radicals are viable options in eliminating a wide array of refractory organic contaminants in industrial effluents. The assessment of transformation products and toxicity should be, however, the critical point that would allow the overall efficiency of advanced oxidation processes to be better understood and evaluated since some transformation products could have an inhibitory effect on certain organisms. This article reviews the most recent studies on transformation products and toxicity for evaluating advanced oxidation processes in eliminating classes of compounds described as "textile chemicals" from aqueous matrices and poses questions in need of further investigation. The scope of this paper is limited to the scientific studies with two classes of textile chemicals, namely chlorophenols and alkylphenol ethoxylates, whose use in textile industry is a matter of debate due to health risks to humans and harm to the environment. The article also raises the critical question: What is the state of the art knowledge on relationships between transformation products and toxicity? Copyright © 2013 Elsevier Ltd. All rights reserved.

Alternative photocatalysts to TiO2 for the photocatalytic reduction of CO2

NASA Astrophysics Data System (ADS)

Nikokavoura, Aspasia; Trapalis, Christos

2017-01-01

The increased concentration of CO2 in the atmosphere, originating from the burning of fossil fuels in stationary and mobile sources, is referred as the "Anthropogenic Greenhouse Effect" and constitutes a major environmental concern. The scientific community is highly concerned about the resulting enhancement of the mean atmospheric temperature, so a vast diversity of methods has been applied. Thermochemical, electrochemical, photocatalytic, photoelectrochemical processes, as well as combination of solar electricity generation and water splitting processes have been performed in order to lower the CO2 atmospheric levels. Photocatalytic methods are environmental friendly and succeed in reducing the atmospheric CO2 concentration and producing fuels or/and useful organic compounds at the same time. The most common photocatalysts for the CO2 reduction are the inorganic, the carbon based semiconductors and the hybrids based on semiconductors, which combine stability, low cost and appropriate structure in order to accomplish redox reactions. In this review, inorganic semiconductors such as single-metal oxide, mixed-metal oxides, metal oxide composites, layered double hydroxides (LDHs), salt composites, carbon based semiconductors such as graphene based composites, CNT composites, g-C3N4 composites and hybrid organic-inorganic materials (ZIFs) were studied. TiO2 and Ti based photocatalysts are extensively studied and therefore in this review they are not mentioned.

Preparation and Characterization of TiO2-Based Photocatalysts by Chemical Vapour Deposition

NASA Astrophysics Data System (ADS)

Nacevski, Goran; Marinkovski, Mirko; Tomovska, Radmila; Fajgar, Radek

In the present work, a novel technique for the preparation of TiO2-based photocatalysts modified with SiO2 is presented, using a pulsed ArF laser to induce a chemical vapor deposition process. The irradiated gas mixture was composed of TiCl4/SiCl4 precursors in excess of oxygen. Laser irradiation at 193 nm with a repetition frequency of 10 Hz induced the deposition of thin nano-sized mixed oxide films. In order to improve the photocatalytic activity of the catalysts and to expand the activity from the UV to the visible part of the spectrum, doping of the catalysts with chromium oxides was performed. For that aim, the same technique of catalyst preparation was used, irradiating the same gas mixture with the addition of chromyl chloride as Cr precursor. The thin films prepared were annealed up to 500°C in order to remove crystal defects, which could be responsible for poor photocatalytic activity. The dependence of structure and properties on reaction process and irradiation conditions (laser energy and fluence, precursors pressure) were examined. The main aim was to find the best conditions for the production of highly photoactive catalysts and to decrease deactivation processes during the photo-oxidation. The composition, structure and morphology of the oxide catalysts prepared were studied by various spectroscopies, electron microscopy and diffraction techniques.

Carbon nanotube-based three-dimensional monolithic optoelectronic integrated system

NASA Astrophysics Data System (ADS)

Liu, Yang; Wang, Sheng; Liu, Huaping; Peng, Lian-Mao

2017-06-01

Single material-based monolithic optoelectronic integration with complementary metal oxide semiconductor-compatible signal processing circuits is one of the most pursued approaches in the post-Moore era to realize rapid data communication and functional diversification in a limited three-dimensional space. Here, we report an electrically driven carbon nanotube-based on-chip three-dimensional optoelectronic integrated circuit. We demonstrate that photovoltaic receivers, electrically driven transmitters and on-chip electronic circuits can all be fabricated using carbon nanotubes via a complementary metal oxide semiconductor-compatible low-temperature process, providing a seamless integration platform for realizing monolithic three-dimensional optoelectronic integrated circuits with diversified functionality such as the heterogeneous AND gates. These circuits can be vertically scaled down to sub-30 nm and operates in photovoltaic mode at room temperature. Parallel optical communication between functional layers, for example, bottom-layer digital circuits and top-layer memory, has been demonstrated by mapping data using a 2 × 2 transmitter/receiver array, which could be extended as the next generation energy-efficient signal processing paradigm.

Hybrid reactor based on combined cavitation and ozonation: from concept to practical reality.

PubMed

Gogate, P R; Mededovic-Thagard, S; McGuire, D; Chapas, G; Blackmon, J; Cathey, R

2014-03-01

The present work gives an in depth discussion related to the development of a hybrid advanced oxidation reactor, which can be effectively used for the treatment of various types of water. The reactor is based on the principle of intensifying degradation/disinfection using a combination of hydrodynamic cavitation, acoustic cavitation, ozone injection and electrochemical oxidation/precipitation. Theoretical studies have been presented to highlight the uniform distribution of the cavitational activity and enhanced generation of hydroxyl radicals in the cavitation zone, as well as higher turbulence in the main reactor zone. The combination of these different oxidation technologies have been shown to result in enhanced water treatment ability, which can be attributed to the enhanced generation of hydroxyl radicals, enhanced contact of ozone and contaminants, and the elimination of mass transfer resistances during electrochemical oxidation/precipitation. Compared to the use of individual approaches, the hybrid reactor is expected to intensify the treatment process by 5-20 times, depending on the application in question, which can be confirmed based on the literature illustrations. Also, the use of Ozonix® has been successfully proven while processing recycled fluids at commercial sites on over 750 oil and natural gas wells during hydraulic operations around the United States. The superiority of the hybrid process over conventional chemical treatments in terms of bacteria and scale reduction as well as increased water flowability and better chemical compatibility, which is a key requirement for oil and gas applications, has been established. Copyright © 2013 Elsevier B.V. All rights reserved.

Abasic and oxidized ribonucleotides embedded in DNA are processed by human APE1 and not by RNase H2.

PubMed

Malfatti, Matilde Clarissa; Balachander, Sathya; Antoniali, Giulia; Koh, Kyung Duk; Saint-Pierre, Christine; Gasparutto, Didier; Chon, Hyongi; Crouch, Robert J; Storici, Francesca; Tell, Gianluca

2017-11-02

Ribonucleoside 5'-monophosphates (rNMPs) are the most common non-standard nucleotides found in DNA of eukaryotic cells, with over 100 million rNMPs transiently incorporated in the mammalian genome per cell cycle. Human ribonuclease (RNase) H2 is the principal enzyme able to cleave rNMPs in DNA. Whether RNase H2 may process abasic or oxidized rNMPs incorporated in DNA is unknown. The base excision repair (BER) pathway is mainly responsible for repairing oxidized and abasic sites into DNA. Here we show that human RNase H2 is unable to process an abasic rNMP (rAP site) or a ribose 8oxoG (r8oxoG) site embedded in DNA. On the contrary, we found that recombinant purified human apurinic/apyrimidinic endonuclease-1 (APE1) and APE1 from human cell extracts efficiently process an rAP site in DNA and have weak endoribonuclease and 3'-exonuclease activities on r8oxoG substrate. Using biochemical assays, our results provide evidence of a human enzyme able to recognize and process abasic and oxidized ribonucleotides embedded in DNA. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

Composite anode La0.8Sr0.2MnO3 impregnated with cobalt oxide for steam electrolysis

NASA Astrophysics Data System (ADS)

Li, Shisong; Cheng, Jigui; Xie, Kui; Li, Peipei; Wu, Yucheng

2013-12-01

Oxygen-ion conducting solid oxide electrolyzer (SOE) has attracted a great deal of interest because it converts electrical energy into chemical energy directly. The oxygen evolution reaction (OER) is occurred at the anode of solid oxide electrolyzer as the O2- being oxidized and form O2 gas, which is considered as one of the major cause of overpotentials in steam electrolyzers. This paper investigates the electrolysis of steam based on cobalt oxide impregnated La0.8Sr0.2MnO3 (LSM) composite anode in an oxide-ion-conducting solid oxide electrolyzer. The conductivity of LSM is studied versus temperature and oxygen partial pressure and correlated to the electrochemical properties of the composite electrodes in symmetric cells at 800 °C. Different contents of Co3O4 (wt.1%, 2%, 4%, 6%, 8%, 10%) were impregnated into LSM electrode and it was found that the polarization resistance (Rp) of symmetric cells gradually improved from 1.16 Ω•cm2 (LSM) to 0.24 Ω•cm2 (wt.10%Co3O4-LSM). Steam electrolysis based on LSM and wt.6%Co3O4-LSM anode electrolyzers are tested at 800°C and the AC impedance spectroscopy results indicated that the Rp of high frequency process significantly decreased from1.1 Ω•cm2 (LSM) to 0.5 Ω•cm2 (wt.6%Co3O4-LSM) under 1.8V electrolysis voltage and the Rp of low frequency process decreased from 14.9 Ω•cm2 to 5.7 Ω•cm2. Electrochemical catalyst Co3O4 can efficiently improve the electrode and enhance the performance of high temperature solid oxide electrolyzer.

Inhibitory Effect of Dissolved Silica on the H2O2 Decomposition by Iron(III) and Manganese(IV) Oxides: Implications for H2O2-based In Situ Chemical Oxidation

PubMed Central

Pham, Anh Le-Tuan; Doyle, Fiona M.; Sedlak, David L.

2011-01-01

The decomposition of H2O2 on iron minerals can generate •OH, a strong oxidant that can transform a wide range of contaminants. This reaction is critical to In Situ Chemical Oxidation (ISCO) processes used for soil and groundwater remediation, as well as advanced oxidation processes employed in waste treatment systems. The presence of dissolved silica at concentrations comparable to those encountered in natural waters decreases the reactivity of iron minerals toward H2O2, because silica adsorbs onto the surface of iron minerals and alters catalytic sites. At circumneutral pH values, goethite, amorphous iron oxide, hematite, iron-coated sand and montmorillonite that were pre-equilibrated with 0.05 – 1.5 mM SiO2 were significantly less reactive toward H2O2 decomposition than their original counterparts, with the H2O2 loss rates inversely proportional to the SiO2 concentration. In the goethite/H2O2 system, the overall •OH yield, defined as the percentage of decomposed H2O2 producing •OH, was almost halved in the presence of 1.5 mM SiO2. Dissolved SiO2 also slows the H2O2 decomposition on manganese(IV) oxide. The presence of dissolved SiO2 results in greater persistence of H2O2 in groundwater, lower H2O2 utilization efficiency and should be considered in the design of H2O2-based treatment systems. PMID:22129132

Porous metal oxide microspheres from ion exchange resin

NASA Astrophysics Data System (ADS)

Picart, S.; Parant, P.; Caisso, M.; Remy, E.; Mokhtari, H.; Jobelin, I.; Bayle, J. P.; Martin, C. L.; Blanchart, P.; Ayral, A.; Delahaye, T.

2015-07-01

This study is devoted to the synthesis and the characterization of porous metal oxide microsphere from metal loaded ion exchange resin. Their application concerns the fabrication of uranium-americium oxide pellets using the powder-free process called Calcined Resin Microsphere Pelletization (CRMP). Those mixed oxide ceramics are one of the materials envisaged for americium transmutation in sodium fast neutron reactors. The advantage of such microsphere precursor compared to classical oxide powder is the diminution of the risk of fine dissemination which can be critical for the handling of highly radioactive powders such as americium based oxides and the improvement of flowability for the filling of compaction chamber. Those millimetric oxide microspheres incorporating uranium and americium were synthesized and characterizations showed a very porous microstructure very brittle in nature which occurred to be adapted to shaping by compaction. Studies allowed to determine an optimal heat treatment with calcination temperature comprised between 700-800 °C and temperature rate lower than 2 °C/min. Oxide Precursors were die-pressed into pellets and then sintered under air to form regular ceramic pellets of 95% of theoretical density (TD) and of homogeneous microstructure. This study validated thus the scientific feasibility of the CRMP process to prepare bearing americium target in a powder free manner.

Chemical Modification of Polysaccharides

PubMed Central

Cumpstey, Ian

2013-01-01

This review covers methods for modifying the structures of polysaccharides. The introduction of hydrophobic, acidic, basic, or other functionality into polysaccharide structures can alter the properties of materials based on these substances. The development of chemical methods to achieve this aim is an ongoing area of research that is expected to become more important as the emphasis on using renewable starting materials and sustainable processes increases in the future. The methods covered in this review include ester and ether formation using saccharide oxygen nucleophiles, including enzymatic reactions and aspects of regioselectivity; the introduction of heteroatomic nucleophiles into polysaccharide chains; the oxidation of polysaccharides, including oxidative glycol cleavage, chemical oxidation of primary alcohols to carboxylic acids, and enzymatic oxidation of primary alcohols to aldehydes; reactions of uronic-acid-based polysaccharides; nucleophilic reactions of the amines of chitosan; and the formation of unsaturated polysaccharide derivatives. PMID:24151557

Activation of Hydrogen Peroxide by Iron-Containing Minerals and Catalysts in Circumneutral pH Solutions: Implications for ex situ and in situ Treatment of Contaminated Water and Soil

NASA Astrophysics Data System (ADS)

Pham, Anh Le Tuan

The decomposition of hydrogen peroxide (H2O2) on iron minerals can generate hydroxyl radical (•OH), a strong oxidant capable of transforming a wide range of contaminants. This reaction is critical to ex situ advanced oxidation processes employed in waste treatment systems, as well as in situ chemical oxidation processes used for soil and groundwater remediation. Unfortunately, the process in the ex situ treatment systems is relatively inefficient at circumneutral pH values. In this research, the development of iron-containing catalysts with improved efficiency was investigated. In addition, little is known about the factors that control the performance of in situ treatment systems. Another aim of this dissertation was to elucidate those factors to provide a basis for improving the efficiency of the remediation method. Two types of silica- and alumina-containing iron (hydr)oxide catalysts were synthesized by sol-gel processing techniques (Chapter 2). Relative to iron oxides, such as hematite and goethite, these catalysts were 10 to 80 times more effective in catalyzing the production of •OH from H2O2 under circumneutral conditions. The higher efficiency makes these catalysts promising candidates for ex situ advanced oxidation processes. Moreover, because alumina and silica alter the reactivity of the iron oxides with H2O2, understanding the activity of iron associated with natural aluminosilicates and silica-containing minerals in the subsurface is crucial to explaining the variability of •OH production observed in in situ treatment systems. In addition to the sol-gel technique used in Chapter 2, silica-containing iron (hydr)oxide catalysts were synthesized by immobilizing iron oxide onto mesoporous silica supports, such as SBA-15 (Chapter 5). The iron-containing SBA-15 was 10 times more effective than iron oxides in catalyzing the production of •OH from H2O2. Moreover, this catalyst could be employed for selective oxidation of small organic contaminants based on size exclusion. However, a major drawback of the mesoporous silica-based catalysts is their instability under circumneutral conditions (Chapter 6). The dissolution of mesoporous silica materials raises questions about their use for water treatment, because silica dissolution might compromise the behavior of the material. To gain insight into factors that control H2O2 persistence and •OH yield in in situ processes, the decomposition of H2O2 and transformation of contaminants were investigated in the presence of iron-containing minerals and aquifer materials (Chapter 3). Consistent with the observation described in Chapter 2, iron-containing aluminosilicates were more effective than iron oxides in converting H2O2 into •OH. In both iron-containing mineral and aquifer material systems, the yield of •OH was inversely correlated with the rate of H 2O2 decomposition. In the aquifer material systems, the yield also inversely correlated with the Mn content, consistent with the fact that the decomposition of H2O2 on manganese oxides does not produce •OH. The inverse correlation between Mn content and H2O2 loss rate and •OH yield suggests that the amount of Mn in aquifer materials could serve as a proxy for predicting H2O2 decomposition rates and contaminant oxidation efficiency. In addition to the surface and structure properties of iron solids, the presence of solutes, such as dissolved silica, also affected the decomposition of H2O2 (Chapter 4). The adsorption of dissolved silica onto mineral surfaces altered the catalytic sites, thereby decreasing the reactivity of iron- and manganese-containing minerals with H2O 2. Therefore, the presence of dissolved SiO2 could lead to greater persistence of H2O2 in groundwater, which should be considered in the design of in situ H2O 2-based treatment systems. In addition to in situ treatment, dissolved silica also can affect the reactivity of iron-containing catalysts used in ex situ processes. Therefore, its presence in contaminated industrial wastewater should be considered when ex situ treatment systems are designed.

A grey box model of glucose fermentation and syntrophic oxidation in microbial fuel cells.

PubMed

de Los Ángeles Fernandez, Maria; de Los Ángeles Sanromán, Maria; Marks, Stanislaw; Makinia, Jacek; Gonzalez Del Campo, Araceli; Rodrigo, Manuel; Fernandez, Francisco Jesus

2016-01-01

In this work, the fermentative and oxidative processes taking place in a microbial fuel cell (MFC) fed with glucose were studied and modeled. The model accounting for the bioelectrochemical processes was based on ordinary, Monod-type differential equations. The model parameters were estimated using experimental results obtained from three H-type MFCs operated at open or closed circuits and fed with glucose or ethanol. The experimental results demonstrate that similar fermentation processes were carried out under open and closed circuit operation, with the most important fermentation products being ethanol (with a yield of 1.81molmol(-1) glucose) and lactic acid (with a yield of 1.36molmol(-1) glucose). A peak in the electricity generation was obtained when glucose and fermentation products coexisted in the liquid bulk. However, almost 90% of the electricity produced came from the oxidation of ethanol. Copyright © 2015 Elsevier Ltd. All rights reserved.

Single-step treatment of 2,4-dinitrotoluene via zero-valent metal reduction and chemical oxidation.

PubMed

Thomas, J Mathew; Hernandez, Rafael; Kuo, Chiang-Hai

2008-06-30

Many nitroaromatic compounds (NACs) are considered toxic and potential carcinogens. The purpose of this study was to develop an integrated reductive/oxidative process for treating NACs contaminated waters. The process consists of the combination of zero-valent iron and an ozonation based treatment technique. Corrosion promoters are added to the contaminated water to minimize passivation of the metallic species. Water contaminated with 2,4-dinitrotoluene (DNT) was treated with the integrated process using a recirculated batch reactor. It was demonstrated that addition of corrosion promoters to the contaminated water enhances the reduction of 2,4-DNT with zero-valent iron. The addition of corrosion promoters resulted in 62% decrease in 2,4-DNT concentration to 2,4-diaminotoluene. The data shows that iron reduced the 2,4-DNT and ozone oxidized these products resulting in a 73% removal of TOC and a 96% decrease in 2,4-DNT concentration.

Fuel processing for PEM fuel cells: transport and kinetic issues of system design

NASA Astrophysics Data System (ADS)

Zalc, J. M.; Löffler, D. G.

In light of the distribution and storage issues associated with hydrogen, efficient on-board fuel processing will be a significant factor in the implementation of PEM fuel cells for automotive applications. Here, we apply basic chemical engineering principles to gain insight into the factors that limit performance in each component of a fuel processor. A system consisting of a plate reactor steam reformer, water-gas shift unit, and preferential oxidation reactor is used as a case study. It is found that for a steam reformer based on catalyst-coated foils, mass transfer from the bulk gas to the catalyst surface is the limiting process. The water-gas shift reactor is expected to be the largest component of the fuel processor and is limited by intrinsic catalyst activity, while a successful preferential oxidation unit depends on strict temperature control in order to minimize parasitic hydrogen oxidation. This stepwise approach of sequentially eliminating rate-limiting processes can be used to identify possible means of performance enhancement in a broad range of applications.

Investigation of solid organic waste processing by oxidative pyrolysis

NASA Astrophysics Data System (ADS)

Kolibaba, O. B.; Sokolsky, A. I.; Gabitov, R. N.

2017-11-01

A thermal analysis of a mixture of municipal solid waste (MSW) of the average morphological composition and its individual components was carried out in order to develop ways to improve the efficiency of its utilization for energy production in thermal reactors. Experimental studies were performed on a synchronous thermal analyzer NETZSCH STA 449 F3 Jupiter combined with a quadrupole mass spectrometer QMC 403. Based on the results of the experiments, the temperature ranges of the pyrolysis process were determined as well as the rate of decrease of the mass of the sample of solid waste during the drying and oxidative pyrolysis processes, the thermal effects accompanying these processes, as well as the composition and volumes of gases produced during oxidative pyrolysis of solid waste and its components in an atmosphere with oxygen content of 1%, 5%, and 10%. On the basis of experimental data the dependences of the yield of gas on the moisture content of MSW were obtained under different pyrolysis conditions under which a gas of various calorific values was produced.

Thermodynamic Analysis for the Refining Ability of Salt Flux for Aluminum Recycling

PubMed Central

Hiraki, Takehito; Miki, Takahiro; Nakajima, Kenichi; Matsubae, Kazuyo; Nakamura, Shinichiro; Nagasaka, Tetsuya

2014-01-01

The removability of impurities during the aluminum remelting process by oxidation was previously investigated by our research group. In the present work, alternative impurity removal with chlorination has been evaluated by thermodynamic analysis. For 43 different elements, equilibrium distribution ratios among metal, chloride flux and oxide slag phases in the aluminum remelting process were calculated by assuming the binary systems of aluminum and an impurity element. It was found that the removability of impurities isn’t significantly affected by process parameters such as chloride partial pressure, temperature and flux composition. It was shown that Ho, Dy, Li, La, Mg, Gd, Ce, Yb, Ca and Sr can be potentially eliminated into flux by chlorination from the remelted aluminum. Chlorination and oxidation are not effective to remove other impurities from the melting aluminum, due to the limited parameters which can be controlled during the remelting process. It follows that a proper management of aluminum scrap such as sorting based on the composition of the products is important for sustainable aluminum recycling. PMID:28788144

Parameters affecting the photocatalytic degradation of dyes using TiO2: a review

NASA Astrophysics Data System (ADS)

Reza, Khan Mamun; Kurny, ASW; Gulshan, Fahmida

2017-07-01

Traditional chemical, physical and biological processes for treating wastewater containing textile dye have such disadvantages as high cost, high energy requirement and generation of secondary pollution during treatment process. The advanced oxidation processes technology has been attracting growing attention for the decomposition of organic dyes. Such processes are based on the light-enhanced generation of highly reactive hydroxyl radicals, which oxidize the organic matter in solution and convert it completely into water, CO2 and inorganic compounds. In this presentation, the photocatalytic degradation of dyes in aqueous solution using TiO2 as photocatalyst under solar and UV irradiation has been reviewed. It is observed that the degradation of dyes depends on several parameters such as pH, catalyst concentration, substrate concentration and the presence of oxidants. Reaction temperature and the intensity of light also affect the degradation of dyes. Particle size, BET-surface area and different mineral forms of TiO2 also have influence on the degradation rate.

Effect of key parameters on the selective acid leach of nickel from mixed nickel-cobalt hydroxide

NASA Astrophysics Data System (ADS)

Byrne, Kelly; Hawker, William; Vaughan, James

2017-01-01

Mixed nickel-cobalt hydroxide precipitate (MHP) is a relatively recent intermediate product in primary nickel production. The material is now being produced on a large scale (approximately 60,000 t/y Ni as MHP) at facilities in Australia (Ravensthorpe, First Quantum Minerals) and Papua New Guinea (Ramu, MCC/Highlands Pacific). The University of Queensland Hydrometallurgy research group developed a new processing technology to refine MHP based on a selective acid leach. This process provides a streamlined route to obtaining a high purity nickel product compared with conventional leaching / solvent extraction processes. The selective leaching of nickel from MHP involves stabilising manganese and cobalt into the solid phase using an oxidant. This paper describes a batch reactor study investigating the timing of acid and oxidant addition on the rate and extent of nickel, cobalt, manganese leached from industrial MHP. For the conditions studied, it is concluded that the simultaneous addition of acid and oxidant provide the best process outcomes.

Influence of kinetics on the determination of the surface reactivity of oxide suspensions by acid-base titration.

PubMed

Duc, M; Adekola, F; Lefèvre, G; Fédoroff, M

2006-11-01

The effect of acid-base titration protocol and speed on pH measurement and surface charge calculation was studied on suspensions of gamma-alumina, hematite, goethite, and silica, whose size and porosity have been well characterized. The titration protocol has an important effect on surface charge calculation as well as on acid-base constants obtained by fitting of the titration curves. Variations of pH versus time after addition of acid or base to the suspension were interpreted as diffusion processes. Resulting apparent diffusion coefficients depend on the nature of the oxide and on its porosity.

Sunlight-induced Transformations of Graphene-based Nanomaterials in Aquatic Environments

EPA Science Inventory

Graphene-based nanomaterials and other related carbon nanomaterials (CNMs) can be released from products during their life cycles. Upon entry into aquatic environments, they are potentially transformed by photochemical reactions, oxidation reactions and biological processes, all ...

Nanostructure-directed chemical sensing: The IHSAB principle and the dynamics of acid/base-interface interaction

PubMed Central

Laminack, William

2013-01-01

Summary Nanostructure-decorated n-type semiconductor interfaces are studied in order to develop chemical sensing with nanostructured materials. We couple the tenets of acid/base chemistry with the majority charge carriers of an extrinsic semiconductor. Nanostructured islands are deposited in a process that does not require self-assembly in order to direct a dominant electron-transduction process that forms the basis for reversible chemical sensing in the absence of chemical-bond formation. Gaseous analyte interactions on a metal-oxide-decorated n-type porous silicon interface show a dynamic electron transduction to and from the interface depending upon the relative strength of the gas and metal oxides. The dynamic interaction of NO with TiO2, SnO2, NiO, CuxO, and AuxO (x >> 1), in order of decreasing acidity, demonstrates this effect. Interactions with the metal-oxide-decorated interface can be modified by the in situ nitridation of the oxide nanoparticles, enhancing the basicity of the decorated interface. This process changes the interaction of the interface with the analyte. The observed change to the more basic oxinitrides does not represent a simple increase in surface basicity but appears to involve a change in molecular electronic structure, which is well explained by using the recently developed IHSAB model. The optical pumping of a TiO2 and TiO2− xNx decorated interface demonstrates a significant enhancement in the ability to sense NH3 and NO2. Comparisons to traditional metal-oxide sensors are also discussed. PMID:23400337

Suppression of interfacial voids formation during silane (SiH4)-based silicon oxide bonding with a thin silicon nitride capping layer

NASA Astrophysics Data System (ADS)

Lee, Kwang Hong; Bao, Shuyu; Wang, Yue; Fitzgerald, Eugene A.; Seng Tan, Chuan

2018-01-01

The material properties and bonding behavior of silane-based silicon oxide layers deposited by plasma-enhanced chemical vapor deposition were investigated. Fourier transform infrared spectroscopy was employed to determine the chemical composition of the silicon oxide films. The incorporation of hydroxyl (-OH) groups and moisture absorption demonstrates a strong correlation with the storage duration for both as-deposited and annealed silicon oxide films. It is observed that moisture absorption is prevalent in the silane-based silicon oxide film due to its porous nature. The incorporation of -OH groups and moisture absorption in the silicon oxide films increase with the storage time (even in clean-room environments) for both as-deposited and annealed silicon oxide films. Due to silanol condensation and silicon oxidation reactions that take place at the bonding interface and in the bulk silicon, hydrogen (a byproduct of these reactions) is released and diffused towards the bonding interface. The trapped hydrogen forms voids over time. Additionally, the absorbed moisture could evaporate during the post-bond annealing of the bonded wafer pair. As a consequence, defects, such as voids, form at the bonding interface. To address the problem, a thin silicon nitride capping film was deposited on the silicon oxide layer before bonding to serve as a diffusion barrier to prevent moisture absorption and incorporation of -OH groups from the ambient. This process results in defect-free bonded wafers.

Purification and preparation of graphite oxide from natural graphite

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

Panatarani, C., E-mail: c.panatarani@phys.unpad.ac.id; Muthahhari, N.; Joni, I. Made

2016-03-11

Graphite oxide has attracted much interest as a possible route for preparation of natural graphite in the large-scale production and manipulation of graphene as a material with extraordinary electronic properties. Graphite oxide was prepared by modified Hummers method from purified natural graphite sample from West Kalimantan. We demonstrated that natural graphite is well-purified by acid leaching method. The purified graphite was proceed for intercalating process by modifying Hummers method. The modification is on the reaction time and temperature of the intercalation process. The materials used in the intercalating process are H{sub 2}SO{sub 4} and KMNO{sub 4}. The purified natural graphitemore » is analyzed by carbon content based on Loss on Ignition test. The thermo gravimetricanalysis and the Fouriertransform infrared spectroscopy are performed to investigate the oxidation results of the obtained GO which is indicated by the existence of functional groups. In addition, the X-ray diffraction and energy dispersive X-ray spectroscopy are also applied to characterize respectively for the crystal structure and elemental analysis. The results confirmed that natural graphite samples with 68% carbon content was purified into 97.68 % carbon content. While the intercalation process formed a formation of functional groups in the obtained GO. The results show that the temperature and reaction times have improved the efficiency of the oxidation process. It is concluded that these method could be considered as an important route for large-scale production of graphene.« less

Comprehensive process for the recovery of value and critical materials from electronic waste

DOE PAGES

Diaz, Luis A.; Lister, Tedd E.; Parkman, Jacob A.; ...

2016-04-08

The development of technologies that contribute to the proper disposal and treatment of electronic waste is not just an environmental need, but an opportunity for the recovery and recycle of valuable metals and critical materials. Value elements in electronic waste include gold, palladium, silver, copper, nickel, and rare earth elements (RE). Here, we present the development of a process that enables efficient recycling of metals from scrap mobile electronics. An electro recycling (ER) process, based on the regeneration of Fe 3+ as a weak oxidizer, is studied for the selective recovery of base metals while leaving precious metals for separatemore » extraction at reduced chemical demand. A separate process recovers rare earth oxides from magnets in electronics. Furthermore, recovery and extraction efficiencies ca. 90 % were obtained for the extraction of base metals from the non-ferromagnetic fraction in the two different solution matrices tested (H 2SO 4, and HCl). The effect of the pre-extraction of base metals in the increase of precious metals extraction efficiency was verified. On the other hand, the extraction of rare earths from the ferromagnetic fraction, performed by means of anaerobic extraction in acid media, was assessed for the selective recovery of rare earths. We developed a comprehensive flow sheet to process electronic waste to value products.« less

Development and characterization of reduced graphene oxide films for transient electronics

NASA Astrophysics Data System (ADS)

Sheikh, Rasel; Bhatkar, Omkar; Smith, David; Rizvi, Reza

2018-03-01

Emerging interests in hardware security as well as environmental concerns have given rise to the field of transient or temporary electronics, which can be decommissioned by an external stimulus with minimal impact to the surrounding environment. In this study, an all graphene based film is produced by a one-step deposition process. The conversion of graphene oxide (GO) to reduced graphene oxide (rGO) depends on an interfacial reduction reaction. Control of processing conditions such as the underlying substrate, pH of GO and the film drying environment results in an ability to tailor the internal architecture of the films and their electronic properties. Furthermore, the ability to create masks for selective reduction of GO during deposition was also demonstrated, which was used to create intricate yet well-defined patterns and connections required in electronic circuits and devices. All graphene based freestanding films with selectively reduced GO were used in transient electronics application as circuitry and RFID tag patterns.

Oxidation mechanism of T91 steel in liquid lead-bismuth eutectic: with consideration of internal oxidation

PubMed Central

Ye, Zhongfei; Wang, Pei; Dong, Hong; Li, Dianzhong; Zhang, Yutuo; Li, Yiyi

2016-01-01

Clarification of the microscopic events that occur during oxidation is of great importance for understanding and consequently controlling the oxidation process. In this study the oxidation product formed on T91 ferritic/martensitic steel in oxygen saturated liquid lead-bismuth eutectic (LBE) at 823 K was characterized at the nanoscale using focused-ion beam and transmission electron microscope. An internal oxidation zone (IOZ) under the duplex oxide scale has been confirmed and characterized systematically. Through the microscopic characterization of the IOZ and the inner oxide layer, the micron-scale and nano-scale diffusion of Cr during the oxidation in LBE has been determined for the first time. The micron-scale diffusion of Cr ensures the continuous advancement of IOZ and inner oxide layer, and nano-scale diffusion of Cr gives rise to the typical appearance of the IOZ. Finally, a refined oxidation mechanism including the internal oxidation and the transformation of IOZ to inner oxide layer is proposed based on the discussion. The proposed oxidation mechanism succeeds in bridging the gap between the existing models and experimental observations. PMID:27734928

Local Anodic Oxidation of Thin GeO Films and Formation of Nanostructures Based on Them

NASA Astrophysics Data System (ADS)

Astankova, K. N.; Kozhukhov, A. S.; Azarov, I. A.; Gorokhov, E. B.; Sheglov, D. V.; Latyshev, A. V.

2018-04-01

The process of local anodic oxidation of thin GeO films has been studied using an atomic force microscope. The electron-probe microanalysis showed that oxidized areas of a GeO film were germanium dioxide. The effect of the voltage pulse duration applied to the probe-substrate system and the atmospheric humidity on the height of the oxide structures has been studied. The kinetics of the local anodic oxidation (LAO) in a semi-contact mode obeys the Cabrera-Mott model for large times. The initial growth rate of the oxide ( R 0) significantly increases and the time of starting the oxidation ( t 0) decreases as the atmospheric humidity increases by 20%, which is related to an increase in the concentration of oxygen-containing ions at the surface of the oxidized GeO film. It was shown that nanostructures in thin GeO layers can be formed by the LAO method.

Controllable Preparation of Ultrathin Sandwich-Like Membrane with Porous Organic Framework and Graphene Oxide for Molecular Filtration

NASA Astrophysics Data System (ADS)

Zhu, Yuanzhi; Xu, Danyun; Zhao, Qingshan; Li, Yang; Peng, Wenchao; Zhang, Guoliang; Zhang, Fengbao; Fan, Xiaobin

2015-10-01

Porous organic frameworks (POFs) based membranes have potential applications in molecular filtration, despite the lack of a corresponding study. This study reports an interesting strategy to get processable POFs dispersion and a novel ultrathin sandwich-like membrane design. It was accidentally found that the hydrophobic N-rich Schiff based POFs agglomerates could react with lithium-ethylamine and formed stable dispersion in water. By successively filtrating the obtained POFs dispersion and graphene oxide (GO), we successfully prepared ultrathin sandwich-like hybrid membranes with layered structure, which showed significantly improved separation efficiency in molecular filtration of organic dyes. This study may provide a universal way to the preparation of processable POFs and their hybrid membranes with GO.

Solution-processed high-mobility neodymium-substituted indium oxide thin-film transistors formed by facile patterning based on aqueous precursors

NASA Astrophysics Data System (ADS)

Lin, Zhenguo; Lan, Linfeng; Sun, Sheng; Li, Yuzhi; Song, Wei; Gao, Peixiong; Song, Erlong; Zhang, Peng; Li, Meiling; Wang, Lei; Peng, Junbiao

2017-03-01

Solution-processed neodymium-substituted indium oxide (InNdO) thin-film transistors (TFTs) based on gel-like aqueous precursors were fabricated with a surface-selective deposition technique associated with ultraviolet irradiation. The Nd concentration can be easily tuned by changing the ratio of Nd2O3 to In2O3 precursors. It was found that Nd played roles of suppressing grain growth, suppressing oxygen vacancy formation, and increasing the electrical stability of TFTs. The InNdO TFT with a Nd:In ratio of 0.02:1 exhibited a mobility of as high as 15.6 cm2 V-1 s-1 with improved stability under gate-bias stress.

Investigation of Redox Metal Oxides for Carbonaceous Fuel Conversion and CO2 Capture

NASA Astrophysics Data System (ADS)

Galinsky, Nathan Lee

The chemical looping combustion (CLC) process uses metal oxides, also referred to as oxygen carriers, in a redox scheme for conversion of carbonaceous fuels into a concentrated stream of CO2 and steam while also producing heat and electricity. The unique redox scheme of CLC allows CO2 capture with minimal energy penalty. The CLC process performance greatly depends on the oxygen carrier that is chosen. To date, more than 1000 oxygen carriers have been developed for chemical-looping processes using metal oxides containing first-row transition metals. Oxygen carriers are typically mixed with an inert ceramic support to improve their overall mechanical stability and recyclability. This study focuses on design of (i) iron oxide oxygen carriers for conversion of gaseous carbonaceous fuels and (ii) development of perovskite CaMnO 3-d with improved stability and redox properties for conversion of solid fuels. Iron oxide is cheap and environmentally benign. However, it suffers from low activity with carbonaceous fuels due partially to the low ionic conductivity of iron oxides. In order to address the low activity of iron-oxide-based oxygen carriers, support addition has been shown to lower the energy barrier of oxygen anion transport within the oxygen carrier. This work adds a mixed-ionic-and-electronic-conductor (MIEC) support to iron oxide to help facilitate O2- transport inside the lattice of iron oxide. The MIEC-supported iron oxide is compared to commonly used supports including TiO2 and Al2O 3 and the pure ionic conductor support yttria-stabilized zirconia (YSZ) for conversion of different carbonaceous fuels and hydrogen. Results show that the MIEC-supported iron oxide exhibits up to 70 times higher activity than non-MIEC-supported iron oxides for methane conversion. The MIEC supported iron oxide also shows good recyclability with only minor agglomeration and carbon formation observed. The effect of support-iron oxide synergies is further investigated to understand other physical and chemical properties that lead to highly active and recyclable oxygen carriers. Perovskite and fluorite-structured MIEC supports are tested for conversion of methane. The perovskite supported iron oxides exhibit higher activity and stability resulting from the high mixed conductivity of the support. Fluorite-structured CeO2 oxygen carriers deactivated by 75% after 10 redox cycles. This deactivation was attributed to agglomeration of iron oxide. The agglomeration was determined to occur due to Fe x+ transport during the oxidation step leading to high content of Fe on the surface of the oxygen carrier. Besides the MIEC supports, inert MgAl2O4 supported iron oxide is observed to activate in methane. The activation is attributed to carbon formation causing physical degradation of the oxygen carrier and leading to higher surface area and porosity. To achieve high activity with solid fuels, chemical looping with oxygen uncoupling (CLOU) is commonly used. This process uses oxygen carriers with high PO2 that allows the oxygen carrier to release a portion of their lattice oxygen as gaseous oxygen. In turn, the gaseous oxygen can react with solid fuel particles at a higher rate than the lattice oxygen. CaMnO 3 perovskite oxygen carriers offer high potential for CLOU. However, pure CaMnO3 suffers from long-term recyclability and sulfur poisoning. Addition of A-site (Ba and Sr) and B-site (Fe, Ni, Co, Al, and V) dopants are used to improve the performance of the base CaMnO3 oxygen carrier. Sr (A-site) and Fe (B-site) exhibit high compatibility with the base perovskite structure. Both dopants observe oxygen uncoupling properties up to 200°C below that of pure CaMnO3. Additionally, the doped structures also exhibit higher stability at high temperatures (>1000°C) and during redox cycles. The doped oxygen carriers also demonstrate significantly improved activity for coal char conversion.

Formation of Deep Sea Umber Deposits Linked to Microbial Metal Oxidation at the South Atlantic Ridge

NASA Astrophysics Data System (ADS)

Peng, Xiaotong; Ta, Kaiwen; Chen, Shun; Zhang, Lijuan; Xu, Hengchao

2015-04-01

Umber deposits are important metalliferous deposits, which occur in off-axis half-graben structures at ancient and modern ocean floor. The genesis of umber deposits has remained controversial for several decades. Recently, microbial Fe(II) oxidation associated with low-temperature diffuse venting has been identified as a key process for the formation of umber deposits, but the exact biochemical mechanisms involved to the precipitation of Mn oxides and co-precipitation of Fe oxyhydroxides and Mn oxides in umber deposits still remain unknown. Here, we used nano secondary ion mass spectrometer, synchrotron-based X-ray absorption spectroscopy, electron microscopy, and molecular techniques to demonstrate the coexistence of two types of metal-oxidizing bacteria within deep-sea hydrothermal umber deposits at the South Atlantic Ridge, where we found unique spheroids composed of biogenic Fe oxyhydroxides and Mn oxides in the deposits. Our data suggest that Fe oxyhydroxides and Mn oxides are metabolic by-products of lithotrophic Fe(II)-oxidizing bacteria and heterotrophic Mn(II)-oxidizing bacteria, respectively. The hydrothermal vents fuel lithotrophic Fe(II)-oxidizing bacteria, which constitute a trophic base that may support the activities of heterotrophic Mn(II)-oxidizing bacteria. The biological origin of umber deposits underscore the importance of geomicrobiologcial interaction in triggering the formation of deep-sea deposits, with important implications for the generation of submarine Mn deposits and crusts.

H2S adsorption and decomposition on the gradually reduced α-Fe2O3(001) surface: A DFT study

NASA Astrophysics Data System (ADS)

Lin, Changfeng; Qin, Wu; Dong, Changqing

2016-11-01

Reduction of iron based desulfurizer occurs during hot gas desulfurization process, which will affect the interaction between H2S and the desulfurizer surface. In this work, a detailed adsorption behavior and dissociation mechanism of H2S on the perfect and reduced α-Fe2O3(001) surfaces, as well as the correlation between the interaction characteristic and reduction degree of iron oxide, have been studied by using periodic density functional theory (DFT) calculations. Results demonstrate that H2S firstly chemisorbs on surface at relatively higher oxidation state (reduction degree χ < 33%), then dissociative adsorption occurs and becomes the main adsorption type after χ > 33%. Reduction of iron oxide benefits the H2S adsorption. Further, dissociation processes of H2S via molecular and dissociative adsorption were investigated. Results show that after reduction of Fe2O3 into the oxidation state around FeO and Fe, the reduced surface exhibits very strong catalytic capacity for H2S decomposition into S species. Meanwhile, the overall dissociation process on all surfaces is exothermic. These results provide a fundamental understanding of reduction effect of iron oxide on the interaction mechanism between H2S and desulfurizer surface, and indicate that rational control of reduction degree of desulfurizer is essential for optimizing the hot gas desulfurization process.

Rapid cycling of reactive nitrogen in the marine boundary layer.

PubMed

Ye, Chunxiang; Zhou, Xianliang; Pu, Dennis; Stutz, Jochen; Festa, James; Spolaor, Max; Tsai, Catalina; Cantrell, Christopher; Mauldin, Roy L; Campos, Teresa; Weinheimer, Andrew; Hornbrook, Rebecca S; Apel, Eric C; Guenther, Alex; Kaser, Lisa; Yuan, Bin; Karl, Thomas; Haggerty, Julie; Hall, Samuel; Ullmann, Kirk; Smith, James N; Ortega, John; Knote, Christoph

2016-04-28

Nitrogen oxides are essential for the formation of secondary atmospheric aerosols and of atmospheric oxidants such as ozone and the hydroxyl radical, which controls the self-cleansing capacity of the atmosphere. Nitric acid, a major oxidation product of nitrogen oxides, has traditionally been considered to be a permanent sink of nitrogen oxides. However, model studies predict higher ratios of nitric acid to nitrogen oxides in the troposphere than are observed. A 'renoxification' process that recycles nitric acid into nitrogen oxides has been proposed to reconcile observations with model studies, but the mechanisms responsible for this process remain uncertain. Here we present data from an aircraft measurement campaign over the North Atlantic Ocean and find evidence for rapid recycling of nitric acid to nitrous acid and nitrogen oxides in the clean marine boundary layer via particulate nitrate photolysis. Laboratory experiments further demonstrate the photolysis of particulate nitrate collected on filters at a rate more than two orders of magnitude greater than that of gaseous nitric acid, with nitrous acid as the main product. Box model calculations based on the Master Chemical Mechanism suggest that particulate nitrate photolysis mainly sustains the observed levels of nitrous acid and nitrogen oxides at midday under typical marine boundary layer conditions. Given that oceans account for more than 70 per cent of Earth's surface, we propose that particulate nitrate photolysis could be a substantial tropospheric nitrogen oxide source. Recycling of nitrogen oxides in remote oceanic regions with minimal direct nitrogen oxide emissions could increase the formation of tropospheric oxidants and secondary atmospheric aerosols on a global scale.

Solar Fenton and solar TiO2 catalytic treatment of ofloxacin in secondary treated effluents: evaluation of operational and kinetic parameters.

PubMed

Michael, I; Hapeshi, E; Michael, C; Fatta-Kassinos, D

2010-10-01

Two different technical approaches based on advanced oxidation processes (AOPs), solar Fenton homogeneous photocatalysis (hv/Fe(2+)/H(2)O(2)) and heterogeneous photocatalysis with titanium dioxide (TiO(2)) suspensions were studied for the chemical degradation of the fluoroquinolone ofloxacin in secondary treated effluents. A bench-scale solar simulator in combination with an appropriate photochemical batch reactor was used to evaluate and select the optimal oxidation conditions of ofloxacin spiked in secondary treated domestic effluents. The concentration profile of the examined substrate during degradation was determined by UV/Vis spectrophotometry. Mineralization was monitored by measuring the dissolved organic carbon (DOC). The concentrations of Fe(2+) and H(2)O(2) were the key factors for the solar Fenton process, while the most important parameter of the heterogeneous photocatalysis was proved to be the catalyst loading. Kinetic analyses indicated that the photodegradation of ofloxacin can be described by a pseudo-first-order reaction. The rate constant (k) for the solar Fenton process was determined at different Fe(2+) and H(2)O(2) concentrations whereas the Langmuir-Hinshelwood (LH) kinetic expression was used to assess the kinetics of the heterogeneous photocatalytic process. The conversion of ofloxacin depends on several parameters based on the various experimental conditions, which were investigated. A Daphnia magna bioassay was used to evaluate the potential toxicity of the parent compound and its photo-oxidation by-products in different stages of oxidation. In the present study solar Fenton has been demonstrated to be more effective than the solar TiO(2) process, yielding complete degradation of the examined substrate and DOC reduction of about 50% in 30 min of the photocatalytic treatment. Copyright © 2010 Elsevier Ltd. All rights reserved.

Advanced oxidation processes for the removal of natural organic matter from drinking water sources: A comprehensive review.

PubMed

Sillanpää, Mika; Ncibi, Mohamed Chaker; Matilainen, Anu

2018-02-15

Natural organic matter (NOM), a key component in aquatic environments, is a complex matrix of organic substances characterized by its fluctuating amounts in water and variable molecular and chemical properties, leading to various interaction schemes with the biogeosphere and hydrologic cycle. These factors, along with the increasing amounts of NOM in surface and ground waters, make the effort of removing naturally-occurring organics from drinking water supplies, and also from municipal wastewater effluents, a challenging task requiring the development of highly efficient and versatile water treatment technologies. Advanced oxidation processes (AOPs) received an increasing amount of attention from researchers around the world, especially during the last decade. The related processes were frequently reported to be among the most suitable water treatment technologies to remove NOM from drinking water supplies and mitigate the formation of disinfection by products (DBPs). Thus, the present work overviews recent research and development studies conducted on the application of AOPs to degrade NOM including UV and/or ozone-based applications, different Fenton processes and various heterogeneous catalytic and photocatalytic oxidative processes. Other non-conventional AOPs such as ultrasonication, ionizing radiation and plasma technologies were also reported. Furthermore, since AOPs are unlikely to achieve complete oxidation of NOM, integration schemes with other water treatment technologies were presented including membrane filtration, adsorption and others processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Efficient photocatalytic oxidation of arsenite from contaminated water by Fe2O3-Mn2O3 nanocomposite under UVA radiation and process optimization with experimental design.

PubMed

Eslami, Hadi; Ehrampoush, Mohammad Hassan; Esmaeili, Abbas; Ebrahimi, Ali Asghar; Salmani, Mohammad Hossein; Ghaneian, Mohammad Taghi; Falahzadeh, Hossein

2018-09-01

The efficiency of photocatalytic oxidation process in arsenite (As(III)) removal from contaminated water by a new Fe 2 O 3 -Mn 2 O 3 nanocomposite under UV A radiation was investigated. The effect of nanocomposite dosage, pH and initial As(III) concentration on the photocatalytic oxidation of As(III) were studied by experimental design. The synthesized nanocomposite had a uniform and spherical morphological structure and contained 49.83% of Fe 2 O 3 and 29.36% of Mn 2 O 3 . Based on the experimental design model, in photocatalytic oxidation process, the effect of pH was higher than other parameters. At nanocomposite concentrations of more than 12 mg L -1 , pH 4 to 6 and oxidation time of 30 min, photocatalytic oxidation efficiency was more than 95% for initial As(III) concentration of less than 500 μg L -1 . By decreasing pH and increasing the nanocomposite concentration, the photocatalytic oxidation efficiency was increased. Furthermore, by increasing the oxidation time from 10 to 240 min, in addition to oxidation of As(III) to arsenate (As(V)), the residual As(V) was adsorbed on the Fe 2 O 3 -Mn 2 O 3 nanocomposite and total As concentration was decreased. Therefore, Fe 2 O 3 -Mn 2 O 3 nanocomposite as a bimetal oxide, at low doses and short time, can enhance and improve the efficiency of the photocatalytic oxidation and adsorption of As(III) from contaminated water resources. Furthermore, the energy and material costs of the UV A /Fe 2 O 3 -Mn 2 O 3 system for photocatalytic oxidation of 1  mg L -1 As(III) in the 1 L laboratory scale reactor was 0.0051 €. Copyright © 2018 Elsevier Ltd. All rights reserved.

Efficient peroxydisulfate activation process not relying on sulfate radical generation for water pollutant degradation.

PubMed

Zhang, Tao; Chen, Yin; Wang, Yuru; Le Roux, Julien; Yang, Yang; Croué, Jean-Philippe

2014-05-20

Peroxydisulfate (PDS) is an appealing oxidant for contaminated groundwater and toxic industrial wastewaters. Activation of PDS is necessary for application because of its low reactivity. Present activation processes always generate sulfate radicals as actual oxidants which unselectively oxidize organics and halide anions reducing oxidation capacity of PDS and producing toxic halogenated products. Here we report that copper oxide (CuO) can efficiently activate PDS under mild conditions without producing sulfate radicals. The PDS/CuO coupled process is most efficient at neutral pH for decomposing a model compound, 2,4-dichlorophenol (2,4-DCP). In a continuous-flow reaction with an empty-bed contact time of 0.55 min, over 90% of 2,4-DCP (initially 20 μM) and 90% of adsorbable organic chlorine (AOCl) can be removed at the PDS/2,4-DCP molar ratio of 1 and 4, respectively. Based on kinetic study and surface characterization, PDS is proposed to be first activated by CuO through outer-sphere interaction, the rate-limiting step, followed by a rapid reaction with 2,4-DCP present in the solution. In the presence of ubiquitous chloride ions in groundwater/industrial wastewater, the PDS/CuO oxidation shows significant advantages over sulfate radical oxidation by achieving much higher 2,4-DCP degradation capacity and avoiding the formation of highly chlorinated degradation products. This work provides a new way of PDS activation for contaminant removal.

Click chemistry approach to conventional vegetable tanning process: accelerated method with improved organoleptic properties.

PubMed

Krishnamoorthy, Ganesan; Ramamurthy, Govindaswamy; Sadulla, Sayeed; Sastry, Thotapalli Parvathaleswara; Mandal, Asit Baran

2014-09-01

Click chemistry approaches are tailored to generate molecular building blocks quickly and reliably by joining small units together selectively and covalently, stably and irreversibly. The vegetable tannins such as hydrolyzable and condensed tannins are capable to produce rather stable radicals or inhibit the progress of radicals and are prone to oxidations such as photo and auto-oxidation, and their anti-oxidant nature is well known. A lot remains to be done to understand the extent of the variation of leather stability, color variation (lightening and darkening reaction of leather), and poor resistance to water uptake for prolonged periods. In the present study, we have reported click chemistry approaches to accelerated vegetable tanning processes based on periodates catalyzed formation of oxidized hydrolysable and condensed tannins for high exhaustion with improved properties. The distribution of oxidized vegetable tannin, the thermal stability such as shrinkage temperature (T s) and denaturation temperature (T d), resistance to collagenolytic activities, and organoleptic properties of tanned leather as well as the evaluations of eco-friendly characteristics were investigated. Scanning electron microscopic analysis indicates the cross section of tightness of the leather. Differential scanning calorimetric analysis shows that the T d of leather is more than that of vegetable tanned or equal to aldehyde tanned one. The leathers exhibited fullness, softness, good color, and general appearance when compared to non-oxidized vegetable tannin. The developed process benefits from significant reduction in total solids and better biodegradability in the effluent, compared to non-oxidized vegetable tannins.

An Investigation Of The Effect Of Particle Size On Oxidation Of Pyrites In Coal.

NASA Astrophysics Data System (ADS)

Chan, Paul K.; Frost, David C.

1986-08-01

We have used X-ray photoelectron spectroscopy (XPS) to study the variation of surface pyrite density with coal particle size (53 4m - 250 4μm). We also detect and monitor pyrite oxidation to sulfate, an important process influencing the surface-dependency of coal-cleansing methods such as flotation. It is very likely that as coal is crushed as part of the processes employed to rid it of prospective pollutants one eventually reaches a pyrite size which may be called "characteristic". It is this parameter that we examine here. Good correlations are established between (i) the liberation of pyrite and particle size, (ii) surface pyrite/sulfate ratio, and (iii) oxidized and non-oxidized sulfur in a typical Canadian coal. For "non-oxidized", or "fresh" coal, the dispersion of pyrite on the coal surface is inversely proportional to coal particle radius, and the tangents of this curve intersect at a particular particle size (106±5 4μm). Although, for the oxidized coal, the appearance of the curves depend on oxidation time intervals at low temperature with humid air, there is an "optimum" particle size which exhibits maximum surface pyrite. Notably, this "optimum" size corresponds to the tangent's intersection for the non-oxidized coal, and hence the "characteristic" size of constituent pyrite. This should allow prediction of pyrite occurrence, a parameter of paramount interest in coal processing and cleaning technology. Coal surface characterization obtained by XPS after various conditioning steps and during flotation, allow both a functional analysis via the study of chemical shifts and a semi-quantitative analysis based on relative intensity measurements.

Direct observation of the oxidation of DNA bases by phosphate radicals formed under radiation: a model of the backbone-to-base hole transfer.

PubMed

Ma, Jun; Marignier, Jean-Louis; Pernot, Pascal; Houée-Levin, Chantal; Kumar, Anil; Sevilla, Michael D; Adhikary, Amitava; Mostafavi, Mehran

2018-05-30

In irradiated DNA, by the base-to-base and backbone-to-base hole transfer processes, the hole (i.e., the unpaired spin) localizes on the most electropositive base, guanine. Phosphate radicals formed via ionization events in the DNA-backbone must play an important role in the backbone-to-base hole transfer process. However, earlier studies on irradiated hydrated DNA, on irradiated DNA-models in frozen aqueous solution and in neat dimethyl phosphate showed the formation of carbon-centered radicals and not phosphate radicals. Therefore, to model the backbone-to-base hole transfer process, we report picosecond pulse radiolysis studies of the reactions between H2PO4˙ with the DNA bases - G, A, T, and C in 6 M H3PO4 at 22 °C. The time-resolved observations show that in 6 M H3PO4, H2PO4˙ causes the one-electron oxidation of adenine, guanine and thymine, by forming the cation radicals via a single electron transfer (SET) process; however, the rate constant of the reaction of H2PO4˙ with cytosine is too low (<107 L mol-1 s-1) to be measured. The rates of these reactions are influenced by the protonation states and the reorganization energies of the base radicals and of the phosphate radical in 6 M H3PO4.

In situ chemical degradation of DNAPLS in contaminated soils and sediments

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

Gates, D.D.; Korte, N.E.; Siegrist, R.L.

1996-08-01

An emerging approach to in situ treatment of organic contaminants is chemical degradation. The specific processes discussed in this chapter are in situ chemical oxidation using either hydrogen peroxide (H{sub 2}O{sub 2}) or potassium permanganate (KMnO{sub 4}) and in situ dechlorination of halogenated hydrocarbons using zero-valence base metals such as iron. These technologies are primarily chemical treatment processes, where the treatment goal is to manipulate the chemistry of the subsurface environment in such a manner that the contaminants of interest are destroyed and/or rendered non-toxic. Chemical properties that can be altered include pH, ionic strength, oxidation and reduction potential, andmore » chemical equilibria. In situ contaminant destruction processes alter or destroy contaminants in place and are typically applied to compounds that can be either converted to innocuous species such as CO{sub 2} and water, or can be degraded to species that are non-toxic or amenable to other in situ processes (i.e., bioremediation). With in situ chemical oxidation, the delivery and distribution of chemical reagents are critical to process effectiveness. In contrast, published approaches for the use of zero valence base metals suggest passive approaches in which the metals are used in a permeable reaction wall installed in situ in the saturated zone. Both types of processes are receiving increasing attention and are being applied both in technology demonstration and as final solutions to subsurface contaminant problems. 43 refs., 9 figs., 1 tab.« less

Study on emission characteristics and reduction strategy of nitrous oxide during wastewater treatment by different processes.

PubMed

Sun, Shichang; Bao, Zhiyuan; Sun, Dezhi

2015-03-01

Given the inexorable increase in global wastewater treatment, increasing amounts of nitrous oxide are expected to be emitted from wastewater treatment plants and released to the atmosphere. It has become imperative to study the emission and control of nitrous oxide in the various wastewater treatment processes currently in use. In the present investigation, the emission characteristics and the factors affecting the release of nitrous oxide were studied via full- and pilot-scale experiments in anoxic-oxic, sequencing batch reactor and oxidation ditch processes. We propose an optimal treatment process and relative strategy for nitrous oxide reduction. Our results show that both the bio-nitrifying and bio-denitrifying treatment units in wastewater treatment plants are the predominant sites for nitrous oxide production in each process, while the aerated treatment units are the critical sources for nitrous oxide emission. Compared with the emission of nitrous oxide from the anoxic-oxic (1.37% of N-influent) and sequencing batch reactor (2.69% of N-influent) processes, much less nitrous oxide (0.25% of N-influent) is emitted from the oxidation ditch process, which we determined as the optimal wastewater treatment process for nitrous oxide reduction, given the current technologies. Nitrous oxide emissions differed with various operating parameters. Controlling the dissolved oxygen concentration at a proper level during nitrification and denitrification and enhancing the utilization rate of organic carbon in the influent for denitrification are the two critical methods for nitrous oxide reduction in the various processes considered.

Nanoscale electrochemical patterning reveals the active sites for catechol oxidation at graphite surfaces.

PubMed

Patel, Anisha N; McKelvey, Kim; Unwin, Patrick R

2012-12-19

Graphite-based electrodes (graphite, graphene, and nanotubes) are used widely in electrochemistry, and there is a long-standing view that graphite step edges are needed to catalyze many reactions, with the basal surface considered to be inert. In the present work, this model was tested directly for the first time using scanning electrochemical cell microscopy reactive patterning and shown to be incorrect. For the electro-oxidation of dopamine as a model process, the reaction rate was measured at high spatial resolution across a surface of highly oriented pyrolytic graphite. Oxidation products left behind in a pattern defined by the scanned electrochemical cell served as surface-site markers, allowing the electrochemical activity to be correlated directly with the graphite structure on the nanoscale. This process produced tens of thousands of electrochemical measurements at different locations across the basal surface, unambiguously revealing it to be highly electrochemically active, with step edges providing no enhanced activity. This new model of graphite electrodes has significant implications for the design of carbon-based biosensors, and the results are additionally important for understanding electrochemical processes on related sp(2)-hybridized materials such as pristine graphene and nanotubes.

The fate of MtBE during Fenton-like treatments through laboratory scale column tests.

PubMed

Piscitelli, Daniela; Zingaretti, Daniela; Verginelli, Iason; Gavasci, Renato; Baciocchi, Renato

2015-12-01

In Situ Chemical Oxidation (ISCO) based on the Fenton's process is a proven technology for the treatment of groundwater contaminated by organic compounds. Nevertheless, the application of this treatment process to methyl tert-butyl ether (MtBE) is questioned, as there are concerns about its capacity to achieve complete mineralization. Many existing studies have focused on water contaminated by MtBE and are thus not representative of in situ treatments since they do not consider the presence of soil. In this work, the effectiveness of a Fenton-like process for MtBE treatment was proven in soil column tests performed at operating conditions (i.e., oxidant and contaminant concentration and flow rates) resembling those typically used for in situ applications. No MtBE by-products were detected in any of the tested conditions, thus suggesting that the tert-butyl group of MtBE was completely degraded. A mass balance based on the CO2 produced was used as evidence that most of the MtBE removed was actually mineralized. Finally, the obtained results show that preconditioning of soil with a chelating agent (EDTA) significantly enhanced MtBE oxidation. Copyright © 2015 Elsevier B.V. All rights reserved.

Preparation of ceramic coating on Ti substrate by Plasma electrolytic oxidation in different electrolytes and evaluation of its corrosion resistance

NASA Astrophysics Data System (ADS)

Shokouhfar, M.; Dehghanian, C.; Baradaran, A.

2011-01-01

Ceramic oxide coatings (titania) were produced on Ti by micro-arc oxidation in different aluminate and carbonate based electrolytes. This process was conducted under constant pulsed DC voltage condition. The effect of KOH and NaF in aluminate based solution was also studied. The surface morphology, growth and phase composition of coatings were investigated using scanning electron microscope and X-ray diffraction. Corrosion behavior of the coatings was also examined by potentiodynamic polarization and electrochemical impedance spectroscopy. It was found that the sparking initiation voltage (spark voltage) had a significant effect on the form and properties of coatings. Coatings obtained from potassium aluminate based solution had a lower spark voltage, higher surface homogeneity and a better corrosion resistance than the carbonate based solution. Addition of NaF instead of KOH had improper effects on the homogeneity and adhesion of coatings which in turn caused a poor corrosion protection behavior of the oxide layer. AC impedance curves showed two time constants which is an indication of the coatings with an outer porous layer and an inner compact layer.

Plasma and catalyst for the oxidation of NOx

NASA Astrophysics Data System (ADS)

Jõgi, Indrek; Erme, Kalev; Levoll, Erik; Raud, Jüri; Stamate, Eugen

2018-03-01

Efficient exhaust gas cleaning from NO x (NO and NO2) by absorption and adsorption based methods requires the oxidation of NO. The application of non-thermal plasma is considered as a promising oxidation method but the oxidation of NO by direct plasma remains limited due to the back-reaction of NO2 to NO mediated by O radicals in plasma. Indirect NO oxidation by plasma produced ozone allows to circumvent the back-reaction and further oxidize NO2 to N2O5 but the slow reaction rate for the latter process limits the efficiency of this process. Present paper gives an overview of the role of metal-oxide catalysts in the improvement of oxidation efficiency for both direct and indirect plasma oxidation of NO x . The plasma produced active oxygen species (O, O3) were shown to play an important role in the reactions taking place on the catalyst surfaces while the exact mechanism and extent of the effect were different for direct and indirect oxidation. In the case of direct plasma oxidation, both short and long lifetime oxygen species could reach the catalyst and participate in the oxidation of NO to NO2. The back-reaction in the plasma phase remained still important factor and limited the effect of catalyst. In the case of indirect oxidation, only ozone could reach the catalyst surface and improve the oxidation of NO2 to N2O5. The effect of catalyst at different experimental conditions was quantitatively described with the aid of simple global chemical kinetic models derived for the NO x oxidation either by plasma or ozone. The models allowed to compare the effect of different catalysts and to analyze the limitations for the efficiency improvement by catalyst.

Aerobic biodegradation of amphoteric amine-oxide-based surfactants: Effect of molecular structure, initial surfactant concentration and pH.

PubMed

Ríos, Francisco; Lechuga, Manuela; Fernández-Serrano, Mercedes; Fernández-Arteaga, Alejandro

2017-03-01

The present study was designed to provide information regarding the effect of the molecular structure of amphoteric amine-oxide-based surfactants and the initial surfactant concentration on their ultimate biodegradation. Moreover, given this parameter's pH-dependence, the effect of pH was also investigated. Three amine-oxide-based surfactants with structural differences in their hydrophobic alkyl chain were tested: Lauramine oxide (AO-R 12 ), Myristamine oxide (AO-R 14 ) and Cocamidopropylamine oxide (AO-Cocoamido). We studied the ultimate biodegradation using the Modified OECD Screening Test at initial surfactant concentrations ranged from 5 to 75 mg L -1 and at pH levels from 5 to 7.4. The results demonstrate that at pH 7.4, amine-oxide-based surfactants are readily biodegradable. In this study, we concluded that ω-oxidation can be assumed to be the main biodegradation pathway of amine-oxides and that differences in the biodegradability between them can be explained by the presence of an amide group in the alkyl chain of AO-Cocoamido; the CN fission of the amide group slows down their mineralization process. In addition, the increase in the concentration of the surfactant from 5 to 75 mg L -1 resulted in an increase in the final biodegradation of AO-R 12 and AO-R 14 . However, in the case of AO-Cocoamido, a clear relationship between the concentration and biodegradation cannot be stated. Conversely, the biodegradability of AO-R 12 and AO-R 14 was considerably lower in an acid condition than at a pH of 7.4, whereas AO-Cocoamido reached similar percentages in acid conditions and at a neutral pH. However, microorganisms required more time to acclimate. Copyright © 2016 Elsevier Ltd. All rights reserved.

Recapturing Graphite-Based Fuel Element Technology for Nuclear Thermal Propulsion

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

Trammell, Michael P; Jolly, Brian C; Miller, James Henry

ORNL is currently recapturing graphite based fuel forms for Nuclear Thermal Propulsion (NTP). This effort involves research and development on materials selection, extrusion, and coating processes to produce fuel elements representative of historical ROVER and NERVA fuel. Initially, lab scale specimens were fabricated using surrogate oxides to develop processing parameters that could be applied to full length NTP fuel elements. Progress toward understanding the effect of these processing parameters on surrogate fuel microstructure is presented.

DEVELOPMENT OF SULFATE RADICAL-BASED CHEMICAL OXIDATION PROCESSES FOR TREATMENT OF PCBS

EPA Science Inventory

This study investigates transition metal based activation of peroxymonosulfate for generation of highly reactive sulfate radicals to degrade Polychlorinated Biphenyls (PCBs) in contaminated aqueous and sediment systems. Environmental friendly transition metal iron (Fe (II), Fe (I...

Efficient conversion of dimethylarsinate into arsenic and its simultaneous adsorption removal over FeCx/N-doped carbon fiber composite in an electro-Fenton process.

PubMed

Lan, Huachun; Li, Jianfei; Sun, Meng; An, Xiaoqiang; Hu, Chengzhi; Liu, Ruiping; Liu, Huijuan; Qu, Jiuhui

2016-09-01

In this study, a FeCx/N-doped carbon fiber composite (FeCx/NCNFs) was developed via an electrospinning method. According to the characterization results of XRD, TEM and XPS, FeCx (a mixture of Fe7C3 and Fe3C) was either embedded in or attached to the NCNFs. It was used for the first time as a catalyst for dimethylarsinate (DMA) degradation and as an absorbent for inorganic arsenic (As (V)), with degradation and adsorption occurring simultaneously, in an electro-Fenton process. The effects of catalyst dosage, initial DMA concentration, solution pH, and applied current on the treatment efficiency and the corresponding H2O2 generation were systematically investigated. The results showed that DMA could be efficiently oxidized into As(V). 96% of DMA was degraded after reaction time of 360 min and the residual As(V) concentration in solution was below the allowable limit of 0.01 mg/L under the optimum treatment conditions. Based on an ESR and radical scavenger experiment, OH was proven to be the sole reactive oxygen species involved in the degradation process of DMA. DMA was oxidized to MMA as the primary oxidation product, which was subsequently oxidized to inorganic arsenic, As (V). TOC was also efficiently removed at the same time. The DMA removal mechanism for simultaneous degradation of dimethylarsinate and adsorption of arsenic over FeCx/NCNFs in the electro-Fenton process was also proposed based on the experimental results. Copyright © 2016. Published by Elsevier Ltd.

Modeling and experimental evaluation of the diffusion bonding of the oxide dispersion strengthened steel PM2000

NASA Astrophysics Data System (ADS)

Sittel, Wiebke; Basuki, Widodo W.; Aktaa, Jarir

2015-10-01

A modeling based optimization process of the solid state diffusion bonding is presented for joining ferritic oxide dispersion strengthened steels PM2000. An optimization study employing varying bonding temperatures and pressures results in almost the same strength and toughness of the bonded compared to the as received material. TEM investigations of diffusion bonded samples show a homogeneous distribution of oxide particles at the bonding seam similar to that in the bulk. Hence, no loss in strength or creep resistance due to oxide particle agglomeration is found, as verified by the mechanical properties observed for the joint.

CAV-OX CAVITATION OXIDIATION PROCESS - MAGNUM WATER TECHNOLOGY, INC. - APPLICATIONS ANALYSIS REPORT

EPA Science Inventory

This report evaluates the ability of the CAV-OX cavitation oxidation process to remove volatile organic compounds (VOC) present in aqueous wastes. This report also presents economic data based on the Superfund Innovative Technology Evaluation (SITE) Program demonstration and nine...

Nitrogen-doped partially reduced graphene oxide rewritable nonvolatile memory.

PubMed

Seo, Sohyeon; Yoon, Yeoheung; Lee, Junghyun; Park, Younghun; Lee, Hyoyoung

2013-04-23

As memory materials, two-dimensional (2D) carbon materials such as graphene oxide (GO)-based materials have attracted attention due to a variety of advantageous attributes, including their solution-processability and their potential for highly scalable device fabrication for transistor-based memory and cross-bar memory arrays. In spite of this, the use of GO-based materials has been limited, primarily due to uncontrollable oxygen functional groups. To induce the stable memory effect by ionic charges of a negatively charged carboxylic acid group of partially reduced graphene oxide (PrGO), a positively charged pyridinium N that served as a counterion to the negatively charged carboxylic acid was carefully introduced on the PrGO framework. Partially reduced N-doped graphene oxide (PrGODMF) in dimethylformamide (DMF) behaved as a semiconducting nonvolatile memory material. Its optical energy band gap was 1.7-2.1 eV and contained a sp2 C═C framework with 45-50% oxygen-functionalized carbon density and 3% doped nitrogen atoms. In particular, rewritable nonvolatile memory characteristics were dependent on the proportion of pyridinum N, and as the proportion of pyridinium N atom decreased, the PrGODMF film lost memory behavior. Polarization of charged PrGODMF containing pyridinium N and carboxylic acid under an electric field produced N-doped PrGODMF memory effects that followed voltage-driven rewrite-read-erase-read processes.

Pyroprocessing of oxidized sodium-bonded fast reactor fuel - An experimental study of treatment options for degraded EBR-II fuel

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

Hermann, S.D.; Gese, N.J.; Wurth, L.A.

An experimental study was conducted to assess pyrochemical treatment options for degraded EBR-II fuel. As oxidized material, the degraded fuel would need to be converted back to metal to enable electrorefining within an existing electro-metallurgical treatment process. A lithium-based electrolytic reduction process was studied to assess the efficacy of converting oxide materials to metal with a particular focus on the impact of zirconium oxide and sodium oxide on this process. Bench-scale electrolytic reduction experiments were performed in LiCl-Li{sub 2}O at 650 C. degrees with combinations of manganese oxide (used as a surrogate for uranium oxide), zirconium oxide, and sodium oxide.more » In the absence of zirconium or sodium oxide, the electrolytic reduction of MnO showed nearly complete conversion to metal. The electrolytic reduction of a blend of MnO-ZrO{sub 2} in LiCl - 1 wt% Li{sub 2}O showed substantial reduction of manganese, but only 8.5% of the zirconium was found in the metal phase. The electrolytic reduction of the same blend of MnO-ZrO{sub 2} in LiCl - 1 wt% Li{sub 2}O - 6.2 wt% Na{sub 2}O showed substantial reduction of manganese, but zirconium reduction was even less at 2.4%. This study concluded that ZrO{sub 2} cannot be substantially reduced to metal in an electrolytic reduction system with LiCl - 1 wt% Li{sub 2}O at 650 C. degrees due to the perceived preferential formation of lithium zirconate. This study also identified a possible interference that sodium oxide may have on the same system by introducing a parasitic and cyclic reaction of dissolved sodium metal between oxidation at the anode and reduction at the cathode. When applied to oxidized sodium-bonded EBR-II fuel (e.g., U-10Zr), the prescribed electrolytic reduction system would not be expected to substantially reduce zirconium oxide, and the accumulation of sodium in the electrolyte could interfere with the reduction of uranium oxide, or at least render it less efficient.« less

Metal-oxide-based energetic materials and synthesis thereof

DOEpatents

Tillotson, Thomas M. , Simpson; Randall, L [Livermore, CA; Hrubesh, Lawrence W [Pleasanton, CA

2006-01-17

A method of preparing energetic metal-oxide-based energetic materials using sol-gel chemistry has been invented. The wet chemical sol-gel processing provides an improvement in both safety and performance. Essentially, a metal-oxide oxidizer skeletal structure is prepared from hydrolyzable metals (metal salts or metal alkoxides) with fuel added to the sol prior to gelation or synthesized within the porosity metal-oxide gel matrix. With metal salt precursors a proton scavenger is used to destabilize the sol and induce gelation. With metal alkoxide precursors standard well-known sol-gel hydrolysis and condensation reactions are used. Drying is done by standard sol-gel practices, either by a slow evaporation of the liquid residing within the pores to produce a high density solid nanocomposite, or by supercritical extraction to produce a lower density, high porous nanocomposite. Other ingredients may be added to this basic nanostructure to change physical and chemical properties, which include organic constituents for binders or gas generators during reactions, burn rate modifiers, or spectral emitters.

Integrative Advanced Oxidation and Biofiltration for Treating Pharmaceuticals in Wastewater.

PubMed

Lester, Yaal; Aga, Diana S; Love, Nancy G; Singh, Randolph R; Morrissey, Ian; Linden, Karl G

2016-11-01

  Advanced oxidation of active pharmaceutical ingredients (APIs) in wastewater produces transformation products (TPs) that are often more biodegradable than the parent compounds. Secondary effluent from a wastewater treatment plant was treated using UV-based advanced oxidation (LPUV/H2O2 and MPUV/NO3) followed by biological aerated filtration (BAF), and different APIs and their transformation products were monitored. The advanced oxidation processes degraded the APIs by 55-87% (LPUV/H2O2) and 58-95% (MPUV/NO3), while minor loss of APIs was achieved in the downstream BAF system. Eleven TPs were detected following oxidation of carbamazepine (5) and iopromide (6); three key TPs were biodegraded in the BAF system. The other TPs remained relatively constant in the BAF. The decrease in UV absorbance (UVA254) of the effluent in the BAF system was linearly correlated to the degradation of the APIs (for the MPUV/NO3-BAF), and can be applied to monitor the biotransformation of APIs in biological-based systems.

Formation of lysine-derived oxidation products and loss of tryptophan during processing of porcine patties with added avocado byproducts.

PubMed

Utrera, Mariana; Rodríguez-Carpena, Javier-Germán; Morcuende, David; Estévez, Mario

2012-04-18

The effects of the addition of avocado oil and a phenolic-rich avocado peel extract on protein oxidation were studied in porcine patties subjected to cooking and chilled storage. Protein oxidation was assessed by means of tryptophan loss and the formation of specific lysine oxidation products, such as α-aminoadipic semialdehyde (AAS), α-aminoadipic acid (AAA), and Schiff bases. In the present paper, quantitative data of AAA are reported for the first time on a food matrix. The addition of the avocado extract inhibited the formation of AAS, AAA, and Schiff bases in patties during cooking and subsequent chilled storage. The antioxidant effect may respond to the protecting effect of phenolic compounds, mainly procyanidins, found on the avocado extract. Apparently, the combination of both strategies (back-fat replacement and addition of avocado extract) does not lead to an enhanced advantage on the oxidative stability of the product. The novel methodologies used in the present study enable a better comprehension of the mechanisms and consequences of protein oxidation in food systems.

Different effects of water molecules on CO oxidation with different reaction mechanisms.

PubMed

Liu, Shan Ping; Zhao, Ming; Sun, Guo En; Gao, Wang; Jiang, Qing

2018-03-28

The effects of water molecules (promotion/prohibition) on CO oxidation remain debated. Herein, using density functional theory calculations, we demonstrate that water molecules can facilitate the CO + O/O 2 oxidation process, but prohibit the CO + OH oxidation process, which is consistent with the experimental finding that water molecules have two distinct effects on CO oxidation. For the CO + O/O 2 oxidation mechanisms, we find that the reactants were pushed towards each other due to the steric effect of the water molecules, which decreases the reaction barriers and promotes the CO + O/O 2 oxidation process. For the CO + OH oxidation mechanisms, water molecules increase the stability of the COOH* intermeditae by H-bonds and van der Waals forces, which increase the barriers of the COOH* transformation process and the COOH*-tra dissociation process, and prohibit the CO + OH oxidation process. These results clarify the different effects of water molecules on CO oxidation and shed light on catalyst usage in the CO oxidation industry.

Learning-based controller for biotechnology processing, and method of using

DOEpatents

Johnson, John A.; Stoner, Daphne L.; Larsen, Eric D.; Miller, Karen S.; Tolle, Charles R.

2004-09-14

The present invention relates to process control where some of the controllable parameters are difficult or impossible to characterize. The present invention relates to process control in biotechnology of such systems, but not limited to. Additionally, the present invention relates to process control in biotechnology minerals processing. In the inventive method, an application of the present invention manipulates a minerals bioprocess to find local exterma (maxima or minima) for selected output variables/process goals by using a learning-based controller for bioprocess oxidation of minerals during hydrometallurgical processing. The learning-based controller operates with or without human supervision and works to find processor optima without previously defined optima due to the non-characterized nature of the process being manipulated.

Effects of Material Degradation on the Structural Integrity of Composite Materials: Experimental Investigation and Modeling of High Temperature Degradation Mechanisms

NASA Technical Reports Server (NTRS)

Cunningham, Ronan A.; McManus, Hugh L.

1996-01-01

It has previously been demonstrated that simple coupled reaction-diffusion models can approximate the aging behavior of PMR-15 resin subjected to different oxidative environments. Based on empirically observed phenomena, a model coupling chemical reactions, both thermal and oxidative, with diffusion of oxygen into the material bulk should allow simulation of the aging process. Through preliminary modeling techniques such as this it has become apparent that accurate analytical models cannot be created until the phenomena which cause the aging of these materials are quantified. An experimental program is currently underway to quantify all of the reaction/diffusion related mechanisms involved. The following contains a summary of the experimental data which has been collected through thermogravimetric analyses of neat PMR-15 resin, along with analytical predictions from models based on the empirical data. Thermogravimetric analyses were carried out in a number of different environments - nitrogen, air and oxygen. The nitrogen provides data for the purely thermal degradation mechanisms while those in air provide data for the coupled oxidative-thermal process. The intent here is to effectively subtract the nitrogen atmosphere data (assumed to represent only thermal reactions) from the air and oxygen atmosphere data to back-figure the purely oxidative reactions. Once purely oxidative (concentration dependent) reactions have been quantified it should then be possible to quantify the diffusion of oxygen into the material bulk.

Stable and null current hysteresis perovskite solar cells based nitrogen doped graphene oxide nanoribbons hole transport layer

PubMed Central

Kim, Jeongmo; Mat Teridi, Mohd Asri; Mohd Yusoff, Abd. Rashid bin; Jang, Jin

2016-01-01

Perovskite solar cells are becoming one of the leading technologies to reduce our dependency on traditional power sources. However, the frequently used component poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) has several shortcomings, such as an easily corroded indium-tin-oxide (ITO) interface at elevated temperatures and induced electrical inhomogeneity. Herein, we propose solution-processed nitrogen-doped graphene oxide nanoribbons (NGONRs) as a hole transport layer (HTL) in perovskite solar cells, replacing the conducting polymer PEDOT:PSS. The conversion efficiency of NGONR-based perovskite solar cells has outperformed a control device constructed using PEDOT:PSS. Moreover, our proposed NGONR-based devices also demonstrate a negligible current hysteresis along with improved stability. This work provides an effective route for substituting PEDOT:PSS as the effective HTL. PMID:27277388

Automated Calibration of Atmospheric Oxidized Mercury Measurements.

PubMed

Lyman, Seth; Jones, Colleen; O'Neil, Trevor; Allen, Tanner; Miller, Matthieu; Gustin, Mae Sexauer; Pierce, Ashley M; Luke, Winston; Ren, Xinrong; Kelley, Paul

2016-12-06

The atmosphere is an important reservoir for mercury pollution, and understanding of oxidation processes is essential to elucidating the fate of atmospheric mercury. Several recent studies have shown that a low bias exists in a widely applied method for atmospheric oxidized mercury measurements. We developed an automated, permeation tube-based calibrator for elemental and oxidized mercury, and we integrated this calibrator with atmospheric mercury instrumentation (Tekran 2537/1130/1135 speciation systems) in Reno, Nevada and at Mauna Loa Observatory, Hawaii, U.S.A. While the calibrator has limitations, it was able to routinely inject stable amounts of HgCl 2 and HgBr 2 into atmospheric mercury measurement systems over periods of several months. In Reno, recovery of injected mercury compounds as gaseous oxidized mercury (as opposed to elemental mercury) decreased with increasing specific humidity, as has been shown in other studies, although this trend was not observed at Mauna Loa, likely due to differences in atmospheric chemistry at the two locations. Recovery of injected mercury compounds as oxidized mercury was greater in Mauna Loa than in Reno, and greater still for a cation-exchange membrane-based measurement system. These results show that routine calibration of atmospheric oxidized mercury measurements is both feasible and necessary.

Photochemical charge separation in zeolites: Electron transfer dynamics, nanocrystals and zeolitic membranes. Final technical report

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

Dutta, Prabir K.

2001-09-30

Aluminosilicate zeolites provide an excellent host for photochemical charge separation. Because of the constraints provided by the zeolite, the back electron transfer from the reduced acceptor to the oxidized sensitizer is slowed down. This provides the opportunity to separate the charge and use it in a subsequent reaction for water oxidation and reduction. Zeolite-based ruthenium oxide catalysts have been found to be efficient for the water splitting process. This project has demonstrated the usefulness of zeolite hosts for photolytic splitting of water.

IMPACTS OF ANTIFOAM ADDITIONS AND ARGON BUBBLING ON DEFENSE WASTE PROCESSING FACILITY REDUCTION/OXIDATION

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

Jantzen, C.; Johnson, F.

2012-06-05

During melting of HLW glass, the REDOX of the melt pool cannot be measured. Therefore, the Fe{sup +2}/{Sigma}Fe ratio in the glass poured from the melter must be related to melter feed organic and oxidant concentrations to ensure production of a high quality glass without impacting production rate (e.g., foaming) or melter life (e.g., metal formation and accumulation). A production facility such as the Defense Waste Processing Facility (DWPF) cannot wait until the melt or waste glass has been made to assess its acceptability, since by then no further changes to the glass composition and acceptability are possible. therefore, themore » acceptability decision is made on the upstream process, rather than on the downstream melt or glass product. That is, it is based on 'feed foward' statistical process control (SPC) rather than statistical quality control (SQC). In SPC, the feed composition to the melter is controlled prior to vitrification. Use of the DWPF REDOX model has controlled the balanjce of feed reductants and oxidants in the Sludge Receipt and Adjustment Tank (SRAT). Once the alkali/alkaline earth salts (both reduced and oxidized) are formed during reflux in the SRAT, the REDOX can only change if (1) additional reductants or oxidants are added to the SRAT, the Slurry Mix Evaporator (SME), or the Melter Feed Tank (MFT) or (2) if the melt pool is bubble dwith an oxidizing gas or sparging gas that imposes a different REDOX target than the chemical balance set during reflux in the SRAT.« less

Effect of interface reaction and diffusion on stress-oxidation coupling at high temperature

NASA Astrophysics Data System (ADS)

Yue, Mengkun; Dong, Xuelin; Fang, Xufei; Feng, Xue

2018-04-01

High-temperature structural materials undergo oxidation during the service, and stress would generate in the oxide film. Understanding the coupling effect between stress and oxidation contributes to the understanding of material degradation and failure during the oxidation process. Here, we propose a model to investigative the coupling effect of stress and oxidation at high temperature by considering the three-stage oxidation process, where both the interface reaction and the diffusion process are present. The governing equations including the oxidation kinetics and stress equilibrium for isothermal oxidation under stress-oxidation coupling effect have been derived. The theory is validated by comparing with the experimental results of SiO2 grown on Si substrate. Results show that the coupling of stress and oxidation influences the growth of the oxide film by affecting all three stages of the oxidation process.

Extraction of trace metals from fly ash

DOEpatents

Blander, M.; Wai, C.M.; Nagy, Z.

1983-08-15

A process is described for recovering silver, gallium and/or other trace metals from a fine grained industrial fly ash associated with a process for producing phosphorous. The fly ash has a silicate base and contains surface deposits of the trace metals as oxides, chlorides or the like. The process is carried out by contacting the fly ash with AlCl/sub 3/ in an alkali halide melt to react the trace metals with the AlCl/sub 3/ to form compositions soluble in the melt and a residue containing the silicate and aluminum oxide or other aluminum precipitate, and separating the desired trace metal or metals from the melt by electrolysis or other separation techniques.

Extraction of trace metals from fly ash

DOEpatents

Blander, Milton; Wai, Chien M.; Nagy, Zoltan

1984-01-01

A process for recovering silver, gallium and/or other trace metals from a fine grained industrial fly ash associated with a process for producing phosphorous, the fly ash having a silicate base and containing surface deposits of the trace metals as oxides, chlorides or the like, with the process being carried out by contacting the fly ash with AlCl.sub.3 in an alkali halide melt to react the trace metals with the AlCl.sub.3 to form compositions soluble in the melt and a residue containing the silicate and aluminum oxide or other aluminum precipitate, and separating the desired trace metal or metals from the melt by electrolysis or other separation techniques.

Electronic Devices Based on Oxide Thin Films Fabricated by Fiber-to-Film Process.

PubMed

Meng, You; Liu, Ao; Guo, Zidong; Liu, Guoxia; Shin, Byoungchul; Noh, Yong-Young; Fortunato, Elvira; Martins, Rodrigo; Shan, Fukai

2018-05-30

Technical development for thin-film fabrication is essential for emerging metal-oxide (MO) electronics. Although impressive progress has been achieved in fabricating MO thin films, the challenges still remain. Here, we report a versatile and general thermal-induced nanomelting technique for fabricating MO thin films from the fiber networks, briefly called fiber-to-film (FTF) process. The high quality of the FTF-processed MO thin films was confirmed by various investigations. The FTF process is generally applicable to numerous technologically relevant MO thin films, including semiconducting thin films (e.g., In 2 O 3 , InZnO, and InZrZnO), conducting thin films (e.g., InSnO), and insulating thin films (e.g., AlO x ). By optimizing the fabrication process, In 2 O 3 /AlO x thin-film transistors (TFTs) were successfully integrated by fully FTF processes. High-performance TFT was achieved with an average mobility of ∼25 cm 2 /(Vs), an on/off current ratio of ∼10 7 , a threshold voltage of ∼1 V, and a device yield of 100%. As a proof of concept, one-transistor-driven pixel circuit was constructed, which exhibited high controllability over the light-emitting diodes. Logic gates based on fully FTF-processed In 2 O 3 /AlO x TFTs were further realized, which exhibited good dynamic logic responses and voltage amplification by a factor of ∼4. The FTF technique presented here offers great potential in large-area and low-cost manufacturing for flexible oxide electronics.

Solid Oxide Membrane (SOM) Process for Facile Electrosynthesis of Metal Carbides and Composites

NASA Astrophysics Data System (ADS)

Zou, Xingli; Chen, Chaoyi; Lu, Xionggang; Li, Shangshu; Xu, Qian; Zhou, Zhongfu; Ding, Weizhong

2017-02-01

Metal carbides (MCs) and composites including TiC, SiC, TaC, ZrC, NbC, Ti5Si3/TiC, and Nb/Nb5Si3 have been directly electrosynthesized from their stoichiometric metal oxides/carbon (MOs/C) mixture precursors by an innovative solid oxide membrane (SOM)-assisted electrochemical process. MOs/C mixture powders including TiO2/C, SiO2/C, Ta2O5/C, ZrO2/C, Nb2O5/C, TiO2/SiO2/C, Nb2O5/SiO2 were pressed to form porous pellets and then served as cathode precursors. A SOM-based anode, made from yttria-stabilized zirconia (YSZ)-based membrane, was used to control the electroreduction process. The SOM electrochemical process was performed at 1273 K (1000 °C) and 3.5 to 4.0 V in molten CaCl2. The oxygen component contained in the MOs/C precursors was gradually removed during electroreduction process, and thus, MOs/C can be directly converted into MCs and composites at the cathode. The reaction mechanism of the electroreduction process and the characteristics of the obtained MCs and composites products were systematically investigated. The results show that the electrosynthesis process typically involves compounding, electroreduction, dissolution-electrodeposition, and in situ carbonization processes. The products can be predesigned and controlled to form micro/nanostructured MCs and composites. Multicomponent multilayer composites (MMCs) have also been tried to electrosynthesize in this work. It is suggested that the SOM-assisted electroreduction process has great potential to be used for the facile and green synthesis of various MCs and composites.

CeO2-Y2O3-ZrO2 Membrane with Enhanced Molten Salt Corrosion Resistance for Solid Oxide Membrane (SOM) Electrolysis Process

NASA Astrophysics Data System (ADS)

Zou, Xingli; Li, Xin; Shen, Bin; Lu, Xionggang; Xu, Qian; Zhou, Zhongfu; Ding, Weizhong

2017-02-01

Innovative CeO2-Y2O3-ZrO2 membrane has been successfully developed and used in the solid oxide membrane (SOM) electrolysis process for green metallic materials production. The x mol pct ceria/(8- x) mol pct yttria-costabilized zirconia ( xCe(8- x)YSZ, x = 0, 1, 4, or 7) membranes have been fabricated and investigated as the membrane-based inert anodes to control the SOM electroreduction process in molten salt. The characteristics of these fabricated xCe(8- x)YSZ membranes including their corrosion resistances in molten salt and their degradation mechanisms have been systematically investigated and compared. The results show that the addition of ceria in the YSZ-based membrane can inhibit the depletion of yttrium during the SOM electrolysis, which thus makes the ceria-reinforced YSZ-based membranes possess enhanced corrosion resistances to molten salt. The ceria/yttria-costabilized zirconia membranes can also provide reasonable oxygen ion conductivity during electrolysis. Further investigation shows that the newly modified 4Ce4YSZ ceramic membrane has the potential to be used as novel inert SOM anode for the facile and sustainable production of metals/alloys/composites materials such as Si, Ti5Si3, TiC, and Ti5Si3/TiC from their metal oxides precursors in molten CaCl2.

US-UK Collaboration on Fossil Energy Advanced Materials: Task 1—Steam Oxidation

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

Holcomb, Gordon R.; Tylczak, Joseph; Carney, Casey

This presentation goes over the following from the US-UK collaboration on Fossil Energy Advanced Materials: Task 1, Steam Oxidation: US-led or co-led deliverables, Phase II products (US), 2011-present, Phase III products, Phase III Plan, an explanation of sCO 2 compared with sH 2O, an explanation of Ni-base Alloys, an explanation of 300 Series (18Cr-8Ni)/E-Brite, an explanation of the typical Microchannel HX Fabrication process, and an explanation of diffusion bonded Ni-base superalloys.

Flexible Electronics Powered by Mixed Metal Oxide Thin Film Transistors

NASA Astrophysics Data System (ADS)

Marrs, Michael

A low temperature amorphous oxide thin film transistor (TFT) and amorphous silicon PIN diode backplane technology for large area flexible digital x-ray detectors has been developed to create 7.9-in. diagonal backplanes. The critical steps in the evolution of the backplane process include the qualification and optimization of the low temperature (200 °C) metal oxide TFT and a-Si PIN photodiode process, the stability of the devices under forward and reverse bias stress, the transfer of the process to flexible plastic substrates, and the fabrication and assembly of the flexible detectors. Mixed oxide semiconductor TFTs on flexible plastic substrates suffer from performance and stability issues related to the maximum processing temperature limitation of the polymer. A novel device architecture based upon a dual active layer improves both the performance and stability. Devices are directly fabricated below 200 ºC on a polyethylene naphthalate (PEN) substrate using mixed metal oxides of either zinc indium oxide (ZIO) or indium gallium zinc oxide (IGZO) as the active semiconductor. The dual active layer architecture allows for adjustment to the saturation mobility and threshold voltage stability without the requirement of high temperature annealing, which is not compatible with flexible plastic substrates like PEN. The device performance and stability is strongly dependent upon the composition of the mixed metal oxide; this dependency provides a simple route to improving the threshold voltage stability and drive performance. By switching from a single to a dual active layer, the saturation mobility increases from 1.2 cm2/V-s to 18.0 cm2/V-s, while the rate of the threshold voltage shift decreases by an order of magnitude. This approach could assist in enabling the production of devices on flexible substrates using amorphous oxide semiconductors. Low temperature (200°C) processed amorphous silicon photodiodes were developed successfully by balancing the tradeoffs between low temperature and low stress (less than -70 MPa compressive) and device performance. Devices with a dark current of less than 1.0 pA/mm2 and a quantum efficiency of 68% have been demonstrated. Alternative processing techniques, such as pixelating the PIN diode and using organic photodiodes have also been explored for applications where extreme flexibility is desired.

Oxide Based Transistor for Flexible Displays

DTIC Science & Technology

2014-09-15

thin film transistors (TFTs) for next generation display technologies. A detailed and comprehensive study was carried out to ascertain the process...Box 12211 Research Triangle Park, NC 27709-2211 Thin film transistors , flexible electronics, RF sputtering, Transparent amorphous oxide semiconductors...NC A&T and RTI, International investigated In free GaSnZnO (GSZO) material system, as the active channel in thin film transistors (TFTs) for next

Controlling sludge settleability in the oxidation ditch process.

PubMed

Hartley, K J

2008-03-01

This paper describes an investigation aimed at developing an operating technique for controlling sludge settleability in the oxidation ditch form of the nitrification denitrification activated sludge process. It was hypothesized that specific sludge volume index (SSVI) is lowest at an optimum process anoxic fraction and increases at higher and lower fractions. Using effluent ammonia:nitrate ratio as a surrogate for anoxic fraction, it was found that a simple empirical model based on a three solids retention time moving average nitrogen ratio was able to replicate the long-term SSVI variations in two independent oxidation ditches at a full-scale plant. Operating data from a second oxidation ditch plant during periods when a prefermenter was on- or off-line showed that SSVI also varies with RBCOD, greater RBCOD giving lower SSVI. It was concluded that best settleability occurs at about the same anoxic fraction as lowest effluent total nitrogen concentration, with an ammonia:nitrate ratio of about 1. An operating rule of thumb is to use dissolved oxygen control to maintain effluent ammonia and nitrate nitrogen concentrations about equal. A third oxidation ditch plant deliberately operated in this manner achieved 15-month median operating values for SSVI of 60mL/g and for effluent ammonia, nitrate and total N, respectively, of 0.2, 0.3 and 2.0mgN/L.

Nano-SiC region formation in (100) Si-on-insulator substrate: Optimization of hot-C+-ion implantation process to improve photoluminescence intensity

NASA Astrophysics Data System (ADS)

Mizuno, Tomohisa; Omata, Yuhsuke; Kanazawa, Rikito; Iguchi, Yusuke; Nakada, Shinji; Aoki, Takashi; Sasaki, Tomokazu

2018-04-01

We experimentally studied the optimization of the hot-C+-ion implantation process for forming nano-SiC (silicon carbide) regions in a (100) Si-on-insulator substrate at various hot-C+-ion implantation temperatures and C+ ion doses to improve photoluminescence (PL) intensity for future Si-based photonic devices. We successfully optimized the process by hot-C+-ion implantation at a temperature of about 700 °C and a C+ ion dose of approximately 4 × 1016 cm-2 to realize a high intensity of PL emitted from an approximately 1.5-nm-thick C atom segregation layer near the surface-oxide/Si interface. Moreover, atom probe tomography showed that implanted C atoms cluster in the Si layer and near the oxide/Si interface; thus, the C content locally condenses even in the C atom segregation layer, which leads to SiC formation. Corrector-spherical aberration transmission electron microscopy also showed that both 4H-SiC and 3C-SiC nanoareas near both the surface-oxide/Si and buried-oxide/Si interfaces partially grow into the oxide layer, and the observed PL photons are mainly emitted from the surface SiC nano areas.

Bulk-heterojunction organic solar cells sandwiched by solution processed molybdenum oxide and titania nanosheet layers

NASA Astrophysics Data System (ADS)

Itoh, Eiji; Goto, Yoshinori; Fukuda, Katsutoshi

2014-02-01

The contributions of ultrathin titania nanosheet (TN) crystallites were studied in both an inverted bulk-heterojunction (BHJ) cell in an indium-tin oxide (ITO)/titania nanosheet (TN)/poly(3-hexylthiophene) (P3HT):phenyl-C61-butyric acid methylester (PCBM) active layer/MoOx/Ag multilayered photovoltaic device and a conventional BHJ cell in ITO/MoOx/P3HT:PCBM active layer/TN/Al multilayered photovoltaic device. The insertion of only one or two layers of poly(diallyldimethylammonium chloride) (PDDA) and TN multilayered film prepared by the layer-by-layer deposition technique effectively decreased the leakage current and increased the open circuit voltage (VOC), fill factor (FF), and power conversion efficiency (η). The conventional cell sandwiched between a solution-processed, partially crystallized molybdenum oxide hole-extracting buffer layer and a TN electron extracting buffer layer showed comparable cell performance to a device sandwiched between vacuum-deposited molybdenum oxide and TN layers, whereas the inverted cell with solution-processed molybdenum oxide showed a poorer performance probably owing to the increment in the leakage current across the film. The abnormal S-shaped curves observed in the inverted BHJ cell above VOC disappeared with the use of a polyfluorene-based cationic semiconducting polymer as a substitute for an insulating PDDA film, resulting in the improved cell performance.

Passively mode-locked fiber laser based on a hollow-core photonic crystal fiber filled with few-layered graphene oxide solution.

PubMed

Liu, Zhi-Bo; He, Xiaoying; Wang, D N

2011-08-15

We demonstrate a nanosecond-pulse erbium-doped fiber laser that is passively mode locked by a hollow-core photonic crystal fiber filled with few-layered graphene oxide solution. Owing to the good solution processing capability of few-layered graphene oxide, which can be filled into the core of a hollow-core photonic crystal fiber through a selective hole filling process, a graphene saturable absorber can be successfully fabricated. The output pulses obtained have a center wavelength, pulse width, and repetition rate of 1561.2 nm, 4.85 ns, and 7.68 MHz, respectively. This method provides a simple and efficient approach to integrate the graphene into the optical fiber system. © 2011 Optical Society of America

Electrodeposition for Electrochemical Energy Conversion and Storage Devices

NASA Astrophysics Data System (ADS)

Shaigan, Nima

Electrodeposition of metals, alloys, metal oxides, conductive polymers, and their composites plays a pivotal role in fabrication processes of some recently developed electrochemical energy devices, most particularly fuel cells, supercapacitors, and batteries. Unique nanoscale architectures of electrocatalysts for low temperature fuel cells, including proton exchange membrane fuel cell (PEMFC) and direct methanol fuel cell (DMFC), can only be obtained through electrodeposition processes. Promising, cost-effective conductive/protective coatings for stainless steel interconnects used in solid oxide fuel cells (SOFCs) have been achieved employing a variety of electrodeposition techniques. In supercapacitors, anodic deposition of metal oxides, conductive polymers, and their composites is a versatile technique for fabrication of electrodes with distinctive morphology and exceptional specific capacitance. Electrodeposition is also very recently employed for preparation of Sn-based anodes for lithium ion batteries.

Control of Ga-oxide interlayer growth and Ga diffusion in SiO2/GaN stacks for high-quality GaN-based metal-oxide-semiconductor devices with improved gate dielectric reliability

NASA Astrophysics Data System (ADS)

Yamada, Takahiro; Watanabe, Kenta; Nozaki, Mikito; Yamada, Hisashi; Takahashi, Tokio; Shimizu, Mitsuaki; Yoshigoe, Akitaka; Hosoi, Takuji; Shimura, Takayoshi; Watanabe, Heiji

2018-01-01

A simple and feasible method for fabricating high-quality and highly reliable GaN-based metal-oxide-semiconductor (MOS) devices was developed. The direct chemical vapor deposition of SiO2 films on GaN substrates forming Ga-oxide interlayers was carried out to fabricate SiO2/GaO x /GaN stacked structures. Although well-behaved hysteresis-free GaN-MOS capacitors with extremely low interface state densities below 1010 cm-2 eV-1 were obtained by postdeposition annealing, Ga diffusion into overlying SiO2 layers severely degraded the dielectric breakdown characteristics. However, this problem was found to be solved by rapid thermal processing, leading to the superior performance of the GaN-MOS devices in terms of interface quality, insulating property, and gate dielectric reliability.

Computational Modeling of Cobalt-Based Water Oxidation: Current Status and Future Challenges

PubMed Central

Schilling, Mauro; Luber, Sandra

2018-01-01

A lot of effort is nowadays put into the development of novel water oxidation catalysts. In this context, mechanistic studies are crucial in order to elucidate the reaction mechanisms governing this complex process, new design paradigms and strategies how to improve the stability and efficiency of those catalysts. This review is focused on recent theoretical mechanistic studies in the field of homogeneous cobalt-based water oxidation catalysts. In the first part, computational methodologies and protocols are summarized and evaluated on the basis of their applicability toward real catalytic or smaller model systems, whereby special emphasis is laid on the choice of an appropriate model system. In the second part, an overview of mechanistic studies is presented, from which conceptual guidelines are drawn on how to approach novel studies of catalysts and how to further develop the field of computational modeling of water oxidation reactions. PMID:29721491

High-Performance Flexible Perovskite Solar Cells on Ultrathin Glass: Implications of the TCO

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

Dou, Benjia; Miller, Elisa M.; Christians, Jeffrey A.

For halide perovskite solar cells (PSCs) to fulfill their vast potential for combining low-cost, high efficiency, and high throughput production they must be scaled using a truly transformative method, such as roll-to-roll processing. Bringing this reality closer to fruition, the present work demonstrates flexible perovskite solar cells with 18.1% power conversion efficiency on flexible Willow Glass substrates. Here, we highlight the importance of the transparent conductive oxide (TCO) layers on device performance by studying various TCOs. And while tin-doped indium oxide (ITO) and indium zinc oxide (IZO) based PSC devices demonstrate high photovoltaic performances, aluminum-doped zinc oxide (AZO) based devicesmore » underperformed in all device parameters. Analysis of X-ray photoemission spectroscopy data shows that the stoichiometry of the perovskite film surface changes dramatically when it is fabricated on AZO, demonstrating the importance of the substrate in perovskite film formation.« less

High-Performance Flexible Perovskite Solar Cells on Ultrathin Glass: Implications of the TCO

DOE PAGES

Dou, Benjia; Miller, Elisa M.; Christians, Jeffrey A.; ...

2017-09-27

For halide perovskite solar cells (PSCs) to fulfill their vast potential for combining low-cost, high efficiency, and high throughput production they must be scaled using a truly transformative method, such as roll-to-roll processing. Bringing this reality closer to fruition, the present work demonstrates flexible perovskite solar cells with 18.1% power conversion efficiency on flexible Willow Glass substrates. Here, we highlight the importance of the transparent conductive oxide (TCO) layers on device performance by studying various TCOs. And while tin-doped indium oxide (ITO) and indium zinc oxide (IZO) based PSC devices demonstrate high photovoltaic performances, aluminum-doped zinc oxide (AZO) based devicesmore » underperformed in all device parameters. Analysis of X-ray photoemission spectroscopy data shows that the stoichiometry of the perovskite film surface changes dramatically when it is fabricated on AZO, demonstrating the importance of the substrate in perovskite film formation.« less

Computational Modeling of Cobalt-based Water Oxidation: Current Status and Future Challenges

NASA Astrophysics Data System (ADS)

Schilling, Mauro; Luber, Sandra

2018-04-01

A lot of effort is nowadays put into the development of novel water oxidation catalysts. In this context mechanistic studies are crucial in order to elucidate the reaction mechanisms governing this complex process, new design paradigms and strategies how to improve the stability and efficiency of those catalysis. This review is focused on recent theoretical mechanistic studies in the field of homogeneous cobalt-based water oxidation catalysts. In the first part, computational methodologies and protocols are summarized and evaluated on the basis of their applicability towards real catalytic or smaller model systems, whereby special emphasis is laid on the choice of an appropriate model system. In the second part, an overview of mechanistic studies is presented, from which conceptual guidelines are drawn on how to approach novel studies of catalysts and how to further develop the field of computational modeling of water oxidation reactions.

Electrooxidation of organics in waste water

NASA Technical Reports Server (NTRS)

Hitchens, G. D.; Murphy, Oliver J.; Kaba, Lamine; Verostko, Charles E.

1990-01-01

Electrooxidation is a means of removing organic solutes directly from waste waters without the use of chemical expendables. Research sponsored by NASA is currently being pursued to demonstrate the feasibility of the concept for oxidation of organic impurities common to urine, shower waters and space-habitat humidity condensates. Electrooxidation of urine and waste water ersatz was experimentally demonstrated. This paper discusses the electrooxidation principle, reaction kinetics, efficiency, power, size, experimental test results and water-reclamation applications. Process operating potentials and the use of anodic oxidation potentials that are sufficiently low to avoid oxygen formation and chloride oxidation are described. The design of an electrochemical system that incorporates a membrane-based electrolyte based on parametric test data and current fuel-cell technology is presented.

Flexible Proton-Gated Oxide Synaptic Transistors on Si Membrane.

PubMed

Zhu, Li Qiang; Wan, Chang Jin; Gao, Ping Qi; Liu, Yang Hui; Xiao, Hui; Ye, Ji Chun; Wan, Qing

2016-08-24

Ion-conducting materials have received considerable attention for their applications in fuel cells, electrochemical devices, and sensors. Here, flexible indium zinc oxide (InZnO) synaptic transistors with multiple presynaptic inputs gated by proton-conducting phosphorosilicate glass-based electrolyte films are fabricated on ultrathin Si membranes. Transient characteristics of the proton gated InZnO synaptic transistors are investigated, indicating stable proton-gating behaviors. Short-term synaptic plasticities are mimicked on the proposed proton-gated synaptic transistors. Furthermore, synaptic integration regulations are mimicked on the proposed synaptic transistor networks. Spiking logic modulations are realized based on the transition between superlinear and sublinear synaptic integration. The multigates coupled flexible proton-gated oxide synaptic transistors may be interesting for neuroinspired platforms with sophisticated spatiotemporal information processing.

The Chemical Adventures of Sherlock Holmes: The Blackwater Escape.

ERIC Educational Resources Information Center

Waddell, Thomas G.; Rybolt, Thomas R.

2003-01-01

Presents a mystery based on the well-known characters, Sherlock Holmes and Dr. Watson. Emphasizes qualitative inorganic analysis, laboratory observations, and oxidation-reduction processes. (Author/YDS)

High performance Si nanowire field-effect-transistors based on a CMOS inverter with tunable threshold voltage.

PubMed

Van, Ngoc Huynh; Lee, Jae-Hyun; Sohn, Jung Inn; Cha, Seung Nam; Whang, Dongmok; Kim, Jong Min; Kang, Dae Joon

2014-05-21

We successfully fabricated nanowire-based complementary metal-oxide semiconductor (NWCMOS) inverter devices by utilizing n- and p-type Si nanowire field-effect-transistors (NWFETs) via a low-temperature fabrication processing technique. We demonstrate that NWCMOS inverter devices can be operated at less than 1 V, a significantly lower voltage than that of typical thin-film based complementary metal-oxide semiconductor (CMOS) inverter devices. This low-voltage operation was accomplished by controlling the threshold voltage of the n-type Si NWFETs through effective management of the nanowire (NW) doping concentration, while realizing high voltage gain (>10) and ultra-low static power dissipation (≤3 pW) for high-performance digital inverter devices. This result offers a viable means of fabricating high-performance, low-operation voltage, and high-density digital logic circuits using a low-temperature fabrication processing technique suitable for next-generation flexible electronics.

Structural characterization of nano-oxide layers in PtMn based specular spin valves

NASA Astrophysics Data System (ADS)

Zhou, Min; Chen, Lifan; Diao, Zhitao; Park, Chang-Man; Huai, Yiming

2005-05-01

A systematic structure characterization of nano-oxide layers (NOLs) and specular spin valves using x-ray diffraction and high-resolution transmission electron microscopy (HRTEM) has been studied. High-angle x-ray diffraction data show almost identical fcc textures for both natural and plasma NOL spin-valves. Low-angle x-ray reflectivity spectrum shows more deteriorated Kiessig fringes at high incident angles for natural oxide sample, indicating rougher interfaces in natural oxidation than in plasma oxidation. Oxygen exposure plays an important role in NOLs process. Fabricating NOLs without any crystal structure degradation is critical to obtain high MR ratio. HRTEM reveals that oxide clusters mixing with insufficiently oxidized CoFe layers prevailed in natural NOL, and the natural oxidation was inhomogeneous. In contrast, plasma NOL has a thinner, more homogeneously oxidized CoFe layers with sharp interfaces. In plasma NOLs, the structures still maintain CoFe crystal structure. The structures and magnetic correlation of the NOL specular spin valves are discussed.

The 1200 C cyclic oxidation behavior of two nickel-aluminum alloys (Ni3AL and NiAl) with additions of chromium, silicon, and titanium

NASA Technical Reports Server (NTRS)

Lowell, C. E.; Santoro, G. J.

1972-01-01

The alloys Ni3Al and NiAl with and without 1 and 3 atomic percent chromium, silicon, and titanium replacing the aluminum were cyclically oxidized at 1200 C for times to 200 hours, and the results were compared with those obtained with the alloy B-1900 subjected to the same oxidation process. The evaluation was based on metal recession, specific weight change, metallography, electron microprobe analysis, and X-ray diffraction. The oxidation resistance of Ni3Al was improved by Si, unaffected by Ti, and degraded by Cr. The oxidation resistance of NiAl was slightly improved by Ti, unaffected by Si, and degraded by Cr. The oxidation resistance of Ni3Al with 1 atomic percent Si was nearly equal to that of NiAl. Alloy B-1900 exhibited oxidation resistance comparable to that of Ni3Al + Cr compositions.

Solid-State Diffusional Behaviors of Functional Metal Oxides at Atomic Scale.

PubMed

Chen, Jui-Yuan; Huang, Chun-Wei; Wu, Wen-Wei

2018-02-01

Metal/metal oxides have attracted extensive research interest because of their combination of functional properties and compatibility with industry. Diffusion and thermal reliability have become essential issues that require detailed study to develop atomic-scaled functional devices. In this work, the diffusional reaction behavior that transforms piezoelectric ZnO into magnetic Fe 3 O 4 is investigated at the atomic scale. The growth kinetics of metal oxides are systematically studied through macro- and microanalyses. The growth rates are evaluated by morphology changes, which determine whether the growth behavior was a diffusion- or reaction-controlled process. Furthermore, atom attachment on the kink step is observed at the atomic scale, which has important implications for the thermodynamics of functional metal oxides. Faster growth planes simultaneously decrease, which result in the predominance of low surface energy planes. These results directly reveal the atomic formation process of metal oxide via solid-state diffusion. In addition, the nanofabricated method provides a novel approach to investigate metal oxide evolution and sheds light on diffusional reaction behavior. More importantly, the results and phenomena of this study provide considerable inspiration to enhance the material stability and reliability of metal/oxide-based devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemistry and spectroelectrochemistry of bioactive hydroxyquinolines: a mechanistic study.

PubMed

Sokolová, Romana; Nycz, Jacek E; Ramešová, Šárka; Fiedler, Jan; Degano, Ilaria; Szala, Marcin; Kolivoška, Viliam; Gál, Miroslav

2015-05-21

The oxidation mechanism of selected hydroxyquinoline carboxylic acids such as 8-hydroxyquinoline-7-carboxylic acid (1), the two positional isomers 2-methyl-8-hydroxyquinoline-7-carboxylic acid (3) and 2-methyl-5-hydroxyquinoline-6-carboxylic acid (4), as well as other hydroxyquinolines were studied in aprotic environment using cyclic voltammetry, controlled potential electrolysis, in situ UV-vis and IR spectroelectrochemistry, and HPLC-MS/MS techniques. IR spectroelectrochemistry showed that oxidation unexpectedly proceeds together with protonation of the starting compound. We proved that the nitrogen atom in the heterocycle of hydroxyquinolines is protonated during the apparent 0.7 electron oxidation process. This was rationalized by the autodeprotonation reaction by another two starting molecules of hydroxyquinoline, so that the overall oxidation mechanism involves two electrons and three starting molecules. Both the electrochemical and spectroelectrochemical results showed that the oxidation mechanism is not influenced by the presence of the carboxylic group in the chemical structure of hydroxyquinolines, as results from oxidation of 2,7-dimethyl-5-hydroxyquinoline (6). In the presence of a strong proton acceptor such as pyridine, the oxidation ECEC process involves two electrons and two protons per one molecule of the hydroxyquinoline derivative. The electron transfer efficiency of hydroxyquinolines in biosystems may be related to protonation of biocompounds containing nitrogen bases. Molecular orbital calculations support the experimental findings.

Growth and Etch Rate Study of Low Temperature Anodic Silicon Dioxide Thin Films

PubMed Central

Ashok, Akarapu; Pal, Prem

2014-01-01

Silicon dioxide (SiO2) thin films are most commonly used insulating films in the fabrication of silicon-based integrated circuits (ICs) and microelectromechanical systems (MEMS). Several techniques with different processing environments have been investigated to deposit silicon dioxide films at temperatures down to room temperature. Anodic oxidation of silicon is one of the low temperature processes to grow oxide films even below room temperature. In the present work, uniform silicon dioxide thin films are grown at room temperature by using anodic oxidation technique. Oxide films are synthesized in potentiostatic and potentiodynamic regimes at large applied voltages in order to investigate the effect of voltage, mechanical stirring of electrolyte, current density and the water percentage on growth rate, and the different properties of as-grown oxide films. Ellipsometry, FTIR, and SEM are employed to investigate various properties of the oxide films. A 5.25 Å/V growth rate is achieved in potentiostatic mode. In the case of potentiodynamic mode, 160 nm thickness is attained at 300 V. The oxide films developed in both modes are slightly silicon rich, uniform, and less porous. The present study is intended to inspect various properties which are considered for applications in MEMS and Microelectronics. PMID:24672287

Patterning and reduction of graphene oxide using femtosecond-laser irradiation

NASA Astrophysics Data System (ADS)

Kang, SeungYeon; Evans, Christopher C.; Shukla, Shobha; Reshef, Orad; Mazur, Eric

2018-07-01

Graphene has emerged as one of the most versatile materials ever discovered due to its extraordinary electronic, optical, thermal, and mechanical properties. However, device fabrication is a well-known challenge and requires novel fabrication methods to realize the complex integration of graphene-based devices. Here, we demonstrate direct laser writing of reduced graphene oxide using femtosecond-laser irradiation at λ = 795 nm. We perform a systematic study of the reduction process of graphene oxide to graphene by varying both the laser fluence and the pulse repetition rate. Our observations show that the reduction has both thermal and non-thermal features, and suggest that we can achieve better resolution and conductivity using kHz pulse trains than using MHz pulse trains or a continuous wave laser. Our reduced graphene oxide lines written at 10-kHz exhibit a 5 order-of-magnitude decrease in resistivity compared to a non-irradiated control sample. This study provides new insight into the reduction process of graphene oxide and opens doors to achieving a high degree of flexibility and control in the fabrication of graphene layers.

In-situ sequential laser transfer and laser reduction of graphene oxide films

NASA Astrophysics Data System (ADS)

Papazoglou, S.; Petridis, C.; Kymakis, E.; Kennou, S.; Raptis, Y. S.; Chatzandroulis, S.; Zergioti, I.

2018-04-01

Achieving high quality transfer of graphene on selected substrates is a priority in device fabrication, especially where drop-on-demand applications are involved. In this work, we report an in-situ, fast, simple, and one step process that resulted in the reduction, transfer, and fabrication of reduced graphene oxide-based humidity sensors, using picosecond laser pulses. By tuning the laser illumination parameters, we managed to implement the sequential printing and reduction of graphene oxide flakes. The overall process lasted only a few seconds compared to a few hours that our group has previously published. DC current measurements, X-Ray Photoelectron Spectroscopy, X-Ray Diffraction, and Raman Spectroscopy were employed in order to assess the efficiency of our approach. To demonstrate the applicability and the potential of the technique, laser printed reduced graphene oxide humidity sensors with a limit of detection of 1700 ppm are presented. The results demonstrated in this work provide a selective, rapid, and low-cost approach for sequential transfer and photochemical reduction of graphene oxide micro-patterns onto various substrates for flexible electronics and sensor applications.

Boehmite nanostructures preparation by hydrothermal method from anodic aluminium oxide membrane.

PubMed

Yang, X; Wang, J Y; Pan, H Y

2009-02-01

Boehmite nanostructures were successfully synthesized from porous anodic aluminium oxide (AAO) membrane by a simple and efficient hydro-thermal method. The experiment used high purity alumina as raw material, and the whole reaction process avoided superfluous impurities to be introduced. Thus, the purity of Boehmite products was ensured. The examinations of the morphology and structure were carried out by atomic force microscope (AFM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Composition of the specimens was analyzed using energy dispersive X-ray spectroscope (EDX) and X-ray diffraction (XRD). Based on these observations the growth process was analyzed.

Preparation and properties of polytetrafluoroethylene impregnated with rhenium oxides

NASA Technical Reports Server (NTRS)

Leibecki, H. F.; Easter, R. W.

1973-01-01

The results of tests carried out to determine the properties of polytetrafluorethylene (PTFE) impregnated with rhenium oxides are presented. The tests included measurement of physical properties of the impregnated material and investigation of the effects of preparation process variables. Based on the latter tests a mechanism to describe the permeation process is postulated which identifies the rate controlling step to be diffusion of ReF6 molecules into the solid during the initial ReF6 soak. Physical property tests indicated that the electronic conductance is increased by many orders of magnitude while the desirable properties of the PTFE remain virtually unchanged.

Enhancement of a-IGZO TFT Device Performance Using a Clean Interface Process via Etch-Stopper Nano-layers

NASA Astrophysics Data System (ADS)

Chung, Jae-Moon; Zhang, Xiaokun; Shang, Fei; Kim, Ji-Hoon; Wang, Xiao-Lin; Liu, Shuai; Yang, Baoguo; Xiang, Yong

2018-05-01

To overcome the technological and economic obstacles of amorphous indium-gallium-zinc-oxide (a-IGZO)-based display backplane for industrial production, a clean etch-stopper (CL-ES) process is developed to fabricate a-IGZO-based thin film transistor (TFT) with improved uniformity and reproducibility on 8.5th generation glass substrates (2200 mm × 2500 mm). Compared with a-IGZO-based TFT with back-channel-etched (BCE) structure, a newly formed ES nano-layer ( 100 nm) and a simultaneous etching of a-IGZO nano-layer (30 nm) and source-drain electrode layer are firstly introduced to a-IGZO-based TFT device with CL-ES structure to improve the uniformity and stability of device for large-area display. The saturation electron mobility of 8.05 cm2/V s and the V th uniformity of 0.72 V are realized on the a-IGZO-based TFT device with CL-ES structure. In the negative bias temperature illumination stress and positive bias thermal stress reliability testing under a ± 30 V bias for 3600 s, the measured V th shift of CL-ES-structured device significantly decreased to - 0.51 and + 1.94 V, which are much lower than that of BCE-structured device (- 3.88 V, + 5.58 V). The electrical performance of the a-IGZO-based TFT device with CL-ES structure implies that the economic transfer from a silicon-based TFT process to the metal oxide semiconductor-based process for LCD fabrication is highly feasible.

Chemical reaction of atomic oxygen with evaporated films of copper, part 4

NASA Technical Reports Server (NTRS)

Fromhold, A. T.; Williams, J. R.

1990-01-01

Evaporated copper films were exposed to an atomic oxygen flux of 1.4 x 10(exp 17) atoms/sq cm per sec at temperatures in the range 285 to 375 F (140 to 191 C) for time intervals between 2 and 50 minutes. Rutherford backscattering spectroscopy (RBS) was used to determine the thickness of the oxide layers formed and the ratio of the number of copper to oxygen atoms in the layers. Oxide film thicknesses ranged from 50 to 3000 A (0.005 to 0.3 microns, or equivalently, 5 x 10(exp -9) to 3 x 10(exp -7); it was determined that the primary oxide phase was Cu2O. The growth law was found to be parabolic (L(t) varies as t(exp 1/2)), in which the oxide thickness L(t) increases as the square root of the exposure time t. The analysis of the data is consistent with either of the two parabolic growth laws. (The thin-film parabolic growth law is based on the assumption that the process is diffusion controlled, with the space charge within the growing oxide layer being negligible. The thick-film parabolic growth law is also based on a diffusion controlled process, but space-charge neutrality prevails locally within very thick oxides.) In the absence of a voltage measurement across the growing oxide, a distinction between the two mechanisms cannot be made, nor can growth by the diffusion of neutral atomic oxygen be entirely ruled out. The activation energy for the reaction is on the order of 1.1 eV (1.76 x 10(exp -19) joule, or equivalently, 25.3 kcal/mole).

Process for the manufacture of an attrition resistant sorbent used for gas desulfurization

DOEpatents

Venkataramani, Venkat S.; Ayala, Raul E.

2003-09-16

This process produces a sorbent for use in desulfurization of coal gas. A zinc titanate compound and a metal oxide are mixed by milling the compounds in an aqueous medium, the resulting mixture is dried and then calcined, crushed, sleved and formed into pellets for use in a moving-bed reactor. Metal oxides suitable for use as an additive in this process include: magnesium oxide, magnesium oxide plus molybdenum oxide, calcium oxide, yttrium oxide, hafnium oxide, zirconium oxide, cupric oxide, and tin oxide. The resulting sorbent has a percentage of the original zinc or titanium ions substituted for the oxide metal of the chosen additive.

On the preparation of TiAl alloy by direct reduction of the oxide mixtures in calcium chloride melt

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

Prabhat K. Tripathy; Derek J. Fray

2011-11-01

In recent years, TiAl-based intermetallic alloys are being increasingly considered for application in areas such as (i) automobile/transport sector (passenger cars, trucks and ships) (ii) aerospace industry (jet engines and High Speed Civil Transport propulsion system) and (iii) industrial gas turbines. These materials offer excellent (i) high temperature properties (at higher than 6000C) (ii) mechanical strength and (iii) resistance to corrosion and as a result have raised renewed interest. The combination of these properties make them possible replacement materials for traditional nickel-based super-alloys, which are nearly as twice as dense (than TiAl based alloys). Since the microstructures of these intermetallicmore » alloys affect, to a significant extent, their ultimate performance, further improvements (by way of alteration/modification of these microstructures), have been the subject matter of intense research investigations. It has now been established that the presence of alloy additives, such as niobium, tantalum, manganese, boron, chromium, silicon, nickel and yttrium etc, in specific quantities, impart marked improvement to the properties, viz. fatigue strength, fracture toughness, oxidation resistance and room temperature ductility, of these alloys. From a number of possible alloy compositions, {gamma}-TiAl and Ti-Al-Nb-Cr have, of late, emerged as two promising engineering alloys/materials. . The conventional fabrication process of these alloys include steps such as melting, forging and heat treatment/annealing of the alloy compositions. However, an electrochemical process offers an attractive proposition to prepare these alloys, directly from the mixture of the respective oxides, in just one step. The experimental approach, in this new process, was, therefore, to try to electrochemically reduce the (mixed) oxide pellet to an alloy phase. The removal of oxygen, from the (mixed) oxide pellet, was effected by polarizing the oxide pellet against a graphite electrode in a pool of molten calcium chloride at a temperature of 9000C. The dominant mechanism of the oxygen removal was the ionization of oxygen followed by its subsequent discharge, as CO2/CO, at the anode surface. The removal of oxygen from the oxide mixture helped form the alloy in situ. The presentation shall cover the detailed experimental results pertaining to the preparation, evaluation and characterization of Ti-47Al-2Nb-2Cr (atom%) alloy.« less

Electrocatalytic Water Oxidation Promoted by 3 D Nanoarchitectured Turbostratic δ-MnOx on Carbon Nanotubes.

PubMed

Zhang, Biaobiao; Li, Yuanyuan; Valvo, Mario; Fan, Lizhou; Daniel, Quentin; Zhang, Peili; Wang, Linqin; Sun, Licheng

2017-11-23

The development of manganese-based water oxidation electrocatalysts is desirable for the production of solar fuels, as manganese is earth-abundant, inexpensive, non-toxic, and has been employed by the Photosystem II in nature for a billion years. Herein, we directly constructed a 3 D nanoarchitectured turbostratic δ-MnO x on carbon nanotube-modified nickel foam (MnO x /CNT/NF) by electrodeposition and a subsequent annealing process. The MnO x /CNT/NF electrode gives a benchmark catalytic current density (10 mA cm -2 ) at an overpotential (η) of 270 mV under alkaline conditions. A steady current density of 19 mA cm -2 is obtained during electrolysis at 1.53 V for 1.0 h. To the best of our knowledge, this work represents the most efficient manganese-oxide-based water oxidation electrode and demonstrates that manganese oxides, as a structural and functional model of oxygen-evolving complex (OEC) in Photosystem II, can also become comparable to those of most Ni- and Co-based catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of relative humidity and Cd/Zn stoichiometry in the photo-oxidation process of cadmium yellows (CdS/Cd1-xZnxS) in oil paintings.

PubMed

Monico, Letizia; Chieli, Annalisa; De Meyer, Steven; Cotte, Marine; de Nolf, Wout; Falkenberg, Gerald; Janssens, Koen; Romani, Aldo; Miliani, Costanza

2018-06-06

Cadmium yellows (CdYs) refer to a family of cadmium sulfide pigments which have been widely used by artists since the late 19th c. Despite being considered stable, they are suffering from discoloration in iconic paintings, such as Joy of Life by Matisse, Flowers in a blue vase by Van Gogh and the Scream by Munch, most likely due to the formation of CdSO₄·nH₂O. Questions about what the factors driving the CdYs degradation are and how they affect the overall process are still open. Here, we study a series of oil mock-up paints made of CdYs of different stoichiometry (CdS/Cd₀.₇₆Zn₀.₂₄S) and crystalline structure (hexagonal/cubic) before and after aging at variable relative humidity under exposure to light and in darkness. Synchrotron-based X-ray methods combined with UV-Visible and FTIR spectroscopies show that: (i) Cd₀.₇₆Zn₀.₂₄S is more susceptible to photo-oxidation than CdS; both compounds can act as photocatalysts for the oil oxidation. (ii) The photo-oxidation of CdS/Cd₀.₇₆Zn₀.₂₄S to CdSO₄·nH₂O is triggered by moisture. (iii) The nature of alteration products depends on the aging conditions and Cd/Zn stoichiometry. Based on our findings, we propose a scheme for the mechanism of the photocorrosion process and photocatalytic activity of CdY pigments in the oil binder. Overall, our results form a reliable basis for understanding the degradation of CdS-based paints of artworks and contribute towards developing better ways of preserving them for future generations. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unidirectional oxide hetero-interface thin-film diode

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

Park, Youngmin; Lee, Eungkyu; Lee, Jinwon

2015-10-05

The unidirectional thin-film diode based on oxide hetero-interface, which is well compatible with conventional thin-film fabrication process, is presented. With the metal anode/electron-transporting oxide (ETO)/electron-injecting oxide (EIO)/metal cathode structure, it exhibits that electrical currents ohmically flow at the ETO/EIO hetero-interfaces for only positive voltages showing current density (J)-rectifying ratio of ∼10{sup 5} at 5 V. The electrical properties (ex, current levels, and working device yields) of the thin-film diode (TFD) are systematically controlled by changing oxide layer thickness. Moreover, we show that the oxide hetero-interface TFD clearly rectifies an AC input within frequency (f) range of 10{sup 2} Hz < f < 10{sup 6} Hz, providing amore » high feasibility for practical applications.« less

Confirming Pseudomonas putida as a reliable bioassay for demonstrating biocompatibility enhancement by solar photo-oxidative processes of a biorecalcitrant effluent.

PubMed

García-Ripoll, A; Amat, A M; Arques, A; Vicente, R; Ballesteros Martín, M M; Pérez, J A Sánchez; Oller, I; Malato, S

2009-03-15

Experiments based on Vibrio fischeri, activated sludge and Pseudomonas putida have been employed to check variation in the biocompatibility of an aqueous solution of a commercial pesticide, along solar photo-oxidative process (TiO(2) and Fenton reagent). Activated sludge-based experiments have demonstrated a complete detoxification of the solution, although important toxicity is still detected according to the more sensitive V. fischeri assays. In parallel, the biodegradability of organic matter is strongly enhanced, with BOD(5)/COD ratio above 0.8. Bioassays run with P. putida have given similar trends, remarking the convenience of using P. putida culture as a reliable and reproducible method for assessing both toxicity and biodegradability, as a substitute to other more time consuming methods.

Association between shortage of energy supply and nuclear gene mutations leading to carcinomatous transformation.

PubMed

DU, Jianping

2016-01-01

Anaerobic bacteria use glycolysis, an oxygen-independent metabolic pathway, whereas energy metabolism in the evolved eukaryotic cell is performed via oxidative phosphorylation, with all eukaryotic cell activities depending upon high energy consumption. However, in cancer cells evolving from eukaryotic cells, the energy metabolism switches from oxidative phosphorylation to glycolysis. The shortage of energy supply induces cancer cells to acquire specific characteristics. Base pair renewal is the most energy-consuming process in the cell, and shortage of energy supply may lead to errors in this process; the more prominent the shortage in energy supply, the more errors are likely to occur in base pair renewal, resulting in gene mutations and expression of cancer cell characteristics. Thus, shortage of energy supply is associated with carcinomatous transformation.

Biological Superoxide In Manganese Oxide Formation

NASA Astrophysics Data System (ADS)

Hansel, C.; Learman, D.; Zeiner, C.; Santelli, C. M.

2011-12-01

Manganese (Mn) oxides are among the strongest sorbents and oxidants within the environment, controlling the fate and transport of numerous elements and the degradation of recalcitrant carbon. Both bacteria and fungi mediate the oxidation of Mn(II) to Mn(III/IV) oxides but the genetic and biochemical mechanisms responsible remain poorly understood. Furthermore, the physiological basis for microbial Mn(II) oxidation remains an enigma. We have recently reported that a common marine bacterium (Roseobacter sp. AzwK-3b) oxidizes Mn(II) via reaction with extracellular superoxide (O2-) produced during exponential growth. Here we expand this superoxide-mediated Mn(II) oxidation pathway to fungi, introducing a surprising homology between prokaryotic and eukaryotic metal redox processes. For instance, Stibella aciculosa, a common soil Ascomycete filamentous fungus, precipitates Mn oxides at the base of asexual reproductive structures (synnemata) used to support conidia (Figure 1). This distribution is a consequence of localized production of superoxide (and it's dismutation product hydrogen peroxide, H2O2), leading to abiotic oxidation of Mn(II) by superoxide. Disruption of NADPH oxidase activity using the oxidoreductase inhibitor DPI leads to diminished cell differentiation and subsequent Mn(II) oxidation inhibition. Addition of Cu(II) (an effective superoxide scavenger) leads to a concentration dependent decrease in Mn oxide formation. We predict that due to the widespread production of extracellular superoxide within the fungal and likely bacterial kingdoms, biological superoxide may be an important contributor to the cycling of Mn, as well as other metals (e.g., Hg, Fe). Current and future explorations of the genes and proteins involved in superoxide production and Mn(II) oxidation will ideally lend insight into the physiological and biochemical basis for these processes.

Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts

DOE PAGES

Sasaki, Kotaro; Marinkovic, Nebojsa; Isaacs, Hugh S.; ...

2015-11-17

Understanding oxidation/dissolution mechanisms of Pt is critical in designing durable catalysts for the oxygen reduction reaction (ORR), but exact mechanisms remain unclear. Our present work explores the oxidation/dissolution of Pt and Pt monolayer (ML) electrocatalysts over a wide range of applied potentials using cells that facilitate in situ measurements by combining X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) measurements. Furthermore, the X-ray absorption near edge structure (XANES) measurement demonstrated that Pt nanoparticle surfaces were oxidized from metallic Pt to α-PtO 2-type oxide during the potential sweep from 0.41 to 1.5 V, and the transition state of O or OHmore » adsorption on Pt and the onset of the place exchange process were revealed by the delta mu (Δμ) method. Only the top layers of Pt nanoparticles were oxidized, while the inner Pt atoms remained intact. At a higher potential over 1.9 V, α-PtO 2-type surface oxides dissolve due to local acidification caused by the oxygen evolution reaction and carbon corrosion. Pt oxidation of Pt ML on the Pd nanoparticle electrocatalyst is considerably hampered compared with the Pt/C catalyst, presumably because preferential Pd oxidation proceeds at the defects in Pt MLs up to 0.91 V and through O penetrated through the Pt MLs by the place exchange process above 1.11 V.« less

Microgravity Studies of Liquid-Liquid Phase Transitions in Alumina-Yttria Melts

NASA Technical Reports Server (NTRS)

Guynes, Buddy (Technical Monitor); Weber, Richard; Nordine, Paul

2004-01-01

The scientific objective of this research is to increase the fundamental knowledge base for liquid- phase processing of technologically important oxide materials. The experimental objective is to define conditions and hardware requirements for microgravity flight experiments to test and expand the experimental hypotheses that: 1. Liquid phase transitions can occur in undercooled melts by a diffusionless process. 2. Onset of the liquid phase transition is accompanied by a large change in the temperature dependence of melt viscosity. Experiments on undercooled YAG (Y3A15012)- and rare earth oxide aluminate composition liquids demonstrated a large departure from an Arrhenian temperature dependence of viscosity. Liquid YAG is nearly inviscid at its 2240 K melting point. Glass fibers were pulled from melts undercooled by ca. 600 K indicating that the viscosity is on the order of 100 Pans (1000 Poise) at 1600 K. This value of viscosity is 500 times greater than that obtained by extrapolation of data for temperatures above the melting point of YAG. These results show that the liquids are extremely fragile and that the onset of the highly non-Arrhenian viscosity-temperature relationship occurs at a temperature considerably below the equilibrium melting point of the solid phases. Further results on undercooled alumina-yttria melts containing 23-42 mole % yttrium oxide indicate that a congruent liquid-liquid phase transition occurs in the undercooled liquids. The rates of transition are inconsistent with a diffusion-limited process. This research is directed to investigation of the scientifically interesting phenomena of polyamorphism and fragility in undercooled rare earth oxide aluminum oxide liquids. The results bear on the technologically important problem of producing high value rare earth-based optical materials.

Pyrite oxidation in the presence of hematite and alumina: I. Batch leaching experiments and kinetic modeling calculations.

PubMed

Tabelin, Carlito Baltazar; Veerawattananun, Suchol; Ito, Mayumi; Hiroyoshi, Naoki; Igarashi, Toshifumi

2017-02-15

Pyrite is one of the most common and geochemically important sulfide minerals in nature because of its role in the redox recycling of iron (Fe). It is also the primary cause of acid mine drainage (AMD) that is considered as a serious and widespread problem facing the mining and mineral processing industries. In the environment, pyrite oxidation occurs in the presence of ubiquitous metal oxides, but the roles that they play in this process remain largely unknown. This study evaluates the effects of hematite (α-Fe 2 O 3 ) and alumina (α-Al 2 O 3 ) on pyrite oxidation by batch-reactor type experiments, surface-sensitive characterization of the oxidation layer and thermodynamic/kinetic modeling calculations. In the presence of hematite, dissolved sulfur (S) concentration dramatically decreased independent of the pH, and the formation of intermediate sulfoxy anionic species on the surface of pyrite was retarded. These results indicate that hematite minimized the overall extent of pyrite oxidation, but the kinetic model could not explain how this suppression occurred. In contrast, pyrite oxidation was enhanced in the alumina suspension as suggested by the higher dissolved S concentration and stronger infrared (IR) absorption bands of surface-bound oxidation products. Based on the kinetic model, alumina enhanced the oxidative dissolution of pyrite because of its strong acid buffering capacity, which increased the suspension pH. The higher pH values increased the oxidation of Fe 2+ to Fe 3+ by dissolved O 2 (DO) that enhanced the overall oxidative dissolution kinetics of pyrite. Copyright © 2016 Elsevier B.V. All rights reserved.

Stabilization of red fruit-based smoothies by high-pressure processing. Part A. Effects on microbial growth, enzyme activity, antioxidant capacity and physical stability.

PubMed

Hurtado, Adriana; Guàrdia, Maria Dolors; Picouet, Pierre; Jofré, Anna; Ros, José María; Bañón, Sancho

2017-02-01

Non-thermal pasteurization by high-pressure processing (HPP) is increasingly replacing thermal processing (TP) to maintain the properties of fresh fruit products. However, most of the research on HPP-fruit products only partially addresses fruit-pressure interaction, which limits its practical interest. The objective of this study was to assess the use of a mild HPP treatment to stabilize red fruit-based smoothies (microbial, enzymatic, oxidative and physical stability). HPP (350 MPa/10 °C/5 min) was slightly less effective than TP (85 °C/7 min) in inactivating microbes (mesophilic and psychrophilic bacteria, coliforms, yeasts and moulds) in smoothies kept at 4 °C for up to 28 days. The main limitation of using HPP was its low efficacy in inactivating oxidative (polyphenol oxidase and peroxidase) and hydrolytic (pectin methyl esterase) enzymes. Data on antioxidant status, colour parameters, browning index, transmittance, turbidity and viscosity confirmed that the HPP-smoothies have a greater tendency towards oxidation and clarification, which might lead to undesirable sensory and nutritional changes (see Part B). The microbial quality of smoothies was adequately controlled by mild HPP treatment without affecting their physical-chemical characteristics; however, oxidative and hydrolytic enzymes are highly pressure-resistant, which suggests that additional strategies should be used to stabilize smoothies. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

In Situ Chemical Modification of Schottky Barrier in Solution-Processed Zinc Tin Oxide Diode.

PubMed

Son, Youngbae; Li, Jiabo; Peterson, Rebecca L

2016-09-14

Here we present a novel in situ chemical modification process to form vertical Schottky diodes using palladium (Pd) rectifying bottom contacts, amorphous zinc tin oxide (Zn-Sn-O) semiconductor made via acetate-based solution process, and molybdenum top ohmic contacts. Using X-ray photoelectron spectroscopy depth profiling, we show that oxygen plasma treatment of Pd creates a PdOx interface layer, which is then reduced back to metallic Pd by in situ reactions during Zn-Sn-O film annealing. The plasma treatment ensures an oxygen-rich environment in the semiconductor near the Schottky barrier, reducing the level of oxygen-deficiency-related defects and improving the rectifying contact. Using this process, we achieve diodes with high forward current density exceeding 10(3)A cm(-2) at 1 V, rectification ratios of >10(2), and ideality factors of around 1.9. The measured diode current-voltage characteristics are compared to numerical simulations of thermionic field emission with sub-bandgap states in the semiconductor, which we attribute to spatial variations in metal stoichiometry of amorphous Zn-Sn-O. To the best of our knowledge, this is the first demonstration of vertical Schottky diodes using solution-processed amorphous metal oxide semiconductor. Furthermore, the in situ chemical modification method developed here can be adapted to tune interface properties in many other oxide devices.

Novel Combination of Efficient Perovskite Solar Cells with Low Temperature Processed Compact TiO2 Layer via Anodic Oxidation.

PubMed

Du, Yangyang; Cai, Hongkun; Wen, Hongbin; Wu, Yuxiang; Huang, Like; Ni, Jian; Li, Juan; Zhang, Jianjun

2016-05-25

In this work, a facile and low temperature processed anodic oxidation approach is proposed for fabricating compact and homogeneous titanium dioxide film (AO-TiO2). In order to realize morphology and thickness control of AO-TiO2, the theory concerning anodic oxidation (AO) is unveiled and the influence of relevant parameters during the process of AO such as electrolyte ingredient and oxidation voltage on AO-TiO2 formation is observed as well. Meanwhile, we demonstrate that the planar perovskite solar cells (p-PSCs) fabricated in ambient air and utilizing optimized AO-TiO2 as electron transport layer (ETL) can deliver repeatable power conversion efficiency (PCE) over 13%, which possess superior open-circuit voltage (Voc) and higher fill factor (FF) compared to its counterpart utilizing conventional high temperature processed compact TiO2 (c-TiO2) as ETL. Through a further comparative study, it is indicated that the improvement of device performance should be attributed to more effective electron collection from perovskite layer to AO-TiO2 and the decrease of device series resistance. Furthermore, hysteresis effect about current density-voltage (J-V) curves in TiO2-based p-PSCs is also unveiled.

Theoretical insight into reaction mechanisms of 2,4-dinitroanisole with hydroxyl radicals for advanced oxidation processes.

PubMed

Zhou, Yang; Liu, Xiaoqiang; Jiang, Weidong; Shu, Yuanjie

2018-01-24

The detailed degradation mechanism of an insensitive explosive, 2,4-dinitroanisole (DNAN), in advanced oxidation processes (AOPs) was investigated computationally at the M06-2X/6-311 + G(d,p)/SMD level of theory. Results obtained show that the addition-elimination reaction is the dominant mechanism. The phenol products formed can continue to be oxidized to benzoquinone radicals that are often detected by experiments and may be the initial reactants of ring-opening reactions. The H-abstraction reaction is an unavoidable competing mechanism; the intermediate generated can also undergo the process of addition-elimination reaction. The nitro departure reaction involves not only hydroxyl radical (•OH), but also other active substances (such as •H). More importantly, we found that AOP technology can easily degrade DNAN, similar to TNT and DNT. Thus, this method is worth trying in experiments. The conclusions of this work provide theoretical support for such experimental research. Graphical abstract Possible pathways of degradation by •OH radicals in advanced oxidation processes (AOPs) of the typical insensitive explosive 2,4-dinitroanisole (DNAN) were investigated by density functional theory (DFT) methods. Based on the Gibbs free energy barriers and intermediates, the dominant reaction mechanism was determined. The conclusions will be helpful in utilizing AOP technology to remove DNAN pollution.

The 2016 oxide electronic materials and oxide interfaces roadmap

NASA Astrophysics Data System (ADS)

Lorenz, M.; Ramachandra Rao, M. S.; Venkatesan, T.; Fortunato, E.; Barquinha, P.; Branquinho, R.; Salgueiro, D.; Martins, R.; Carlos, E.; Liu, A.; Shan, F. K.; Grundmann, M.; Boschker, H.; Mukherjee, J.; Priyadarshini, M.; DasGupta, N.; Rogers, D. J.; Teherani, F. H.; Sandana, E. V.; Bove, P.; Rietwyk, K.; Zaban, A.; Veziridis, A.; Weidenkaff, A.; Muralidhar, M.; Murakami, M.; Abel, S.; Fompeyrine, J.; Zuniga-Perez, J.; Ramesh, R.; Spaldin, N. A.; Ostanin, S.; Borisov, V.; Mertig, I.; Lazenka, V.; Srinivasan, G.; Prellier, W.; Uchida, M.; Kawasaki, M.; Pentcheva, R.; Gegenwart, P.; Miletto Granozio, F.; Fontcuberta, J.; Pryds, N.

2016-11-01

Oxide electronic materials provide a plethora of possible applications and offer ample opportunity for scientists to probe into some of the exciting and intriguing phenomena exhibited by oxide systems and oxide interfaces. In addition to the already diverse spectrum of properties, the nanoscale form of oxides provides a new dimension of hitherto unknown phenomena due to the increased surface-to-volume ratio. Oxide electronic materials are becoming increasingly important in a wide range of applications including transparent electronics, optoelectronics, magnetoelectronics, photonics, spintronics, thermoelectrics, piezoelectrics, power harvesting, hydrogen storage and environmental waste management. Synthesis and fabrication of these materials, as well as processing into particular device structures to suit a specific application is still a challenge. Further, characterization of these materials to understand the tunability of their properties and the novel properties that evolve due to their nanostructured nature is another facet of the challenge. The research related to the oxide electronic field is at an impressionable stage, and this has motivated us to contribute with a roadmap on ‘oxide electronic materials and oxide interfaces’. This roadmap envisages the potential applications of oxide materials in cutting edge technologies and focuses on the necessary advances required to implement these materials, including both conventional and novel techniques for the synthesis, characterization, processing and fabrication of nanostructured oxides and oxide-based devices. The contents of this roadmap will highlight the functional and correlated properties of oxides in bulk, nano, thin film, multilayer and heterostructure forms, as well as the theoretical considerations behind both present and future applications in many technologically important areas as pointed out by Venkatesan. The contributions in this roadmap span several thematic groups which are represented by the following authors: novel field effect transistors and bipolar devices by Fortunato, Grundmann, Boschker, Rao, and Rogers; energy conversion and saving by Zaban, Weidenkaff, and Murakami; new opportunities of photonics by Fompeyrine, and Zuniga-Perez; multiferroic materials including novel phenomena by Ramesh, Spaldin, Mertig, Lorenz, Srinivasan, and Prellier; and concepts for topological oxide electronics by Kawasaki, Pentcheva, and Gegenwart. Finally, Miletto Granozio presents the European action ‘towards oxide-based electronics’ which develops an oxide electronics roadmap with emphasis on future nonvolatile memories and the required technologies. In summary, we do hope that this oxide roadmap appears as an interesting up-to-date snapshot on one of the most exciting and active areas of solid state physics, materials science, and chemistry, which even after many years of very successful development shows in short intervals novel insights and achievements. Guest editors: M S Ramachandra Rao and Michael Lorenz

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system a review

NASA Astrophysics Data System (ADS)

Zahardis, J.; Petrucci, G. A.

2006-11-01

The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the primary products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. Anomalies in the relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide polymers. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei. The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, a series of atmospheric implications of oxidative processing of particulate containing fatty acids is presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semisolids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation. Other effects, including the potential role of aldehydic products of ozonolysis in increasing the oxidative capacity of the troposphere, are also discussed.

Predicting oxidation-limited lifetime of thin-walled components of NiCrW alloy 230

DOE PAGES

Duan, R.; Jalowicka, Aleksandra; Unocic, Kinga A.; ...

2016-10-18

Using alloy 230 as an example, a generalized oxidation lifetime model for chromia-forming Ni-base wrought alloys is proposed, which captures the most important damaging oxidation effects relevant for component design: wall thickness loss, scale spallation, and the occurrence of breakaway oxidation. For deriving input parameters and for verification of the model approach, alloy 230 specimens with different thicknesses were exposed for different times at temperatures in the range 950–1050 °C in static air. The studies focused on thin specimens (0.2–0.5 mm) to obtain data for critical subscale depletion processes resulting in breakaway oxidation within reasonably achievable test times up tomore » 3000 h. The oxidation kinetics and oxidation-induced subscale microstructural changes were determined by combining gravimetric data with results from scanning electron microscopy with energy dispersive X-ray spectroscopy. The modeling of the scale spallation and re-formation was based on the NASA cyclic oxidation spallation program, while a new model was developed to describe accelerated oxidation occurring after longer exposure times in the thinnest specimens. The calculated oxidation data were combined with the reservoir model equation, by means of which the relation between the consumption and the remaining concentration of Cr in the alloy was established as a function of temperature and specimen thickness. Based on this approach, a generalized lifetime diagram is proposed, in which wall thickness loss is plotted as a function of time, initial specimen thickness, and temperature. As a result, the time to reach a critical Cr level at the scale/alloy interface of 10 wt% is also indicated in the diagrams.« less

Predicting oxidation-limited lifetime of thin-walled components of NiCrW alloy 230

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

Duan, R.; Jalowicka, Aleksandra; Unocic, Kinga A.

Using alloy 230 as an example, a generalized oxidation lifetime model for chromia-forming Ni-base wrought alloys is proposed, which captures the most important damaging oxidation effects relevant for component design: wall thickness loss, scale spallation, and the occurrence of breakaway oxidation. For deriving input parameters and for verification of the model approach, alloy 230 specimens with different thicknesses were exposed for different times at temperatures in the range 950–1050 °C in static air. The studies focused on thin specimens (0.2–0.5 mm) to obtain data for critical subscale depletion processes resulting in breakaway oxidation within reasonably achievable test times up tomore » 3000 h. The oxidation kinetics and oxidation-induced subscale microstructural changes were determined by combining gravimetric data with results from scanning electron microscopy with energy dispersive X-ray spectroscopy. The modeling of the scale spallation and re-formation was based on the NASA cyclic oxidation spallation program, while a new model was developed to describe accelerated oxidation occurring after longer exposure times in the thinnest specimens. The calculated oxidation data were combined with the reservoir model equation, by means of which the relation between the consumption and the remaining concentration of Cr in the alloy was established as a function of temperature and specimen thickness. Based on this approach, a generalized lifetime diagram is proposed, in which wall thickness loss is plotted as a function of time, initial specimen thickness, and temperature. As a result, the time to reach a critical Cr level at the scale/alloy interface of 10 wt% is also indicated in the diagrams.« less

Nitrous oxide and methane emissions from different treatment processes in full-scale municipal wastewater treatment plants.

PubMed

Rena, Y G; Wang, J H; Li, H F; Zhang, J; Qi, P Y; Hu, Z

2013-01-01

Nitrous oxide (N2O) and methane (CH4) are two important greenhouse gases (GHG) emitted from biological nutrient removal (BNR) processes in municipal wastewater treatment plants (WWTP). In this study, three typical biological wastewater treatment processes were studied in WWTP of Northern China: pre-anaerobic carrousel oxidation ditch (A+OD) process, pre-anoxic anaerobic-anoxic-oxic (A-A/ A/O) process and reverse anaerobic-anoxic-oxic (r-A/ A/O) process. The N2O and CH4 emissions from these three different processes were measured in every processing unit of each WWTP. Results showed that N2O and CH4 were mainly discharged during the nitrification/denitrification process and the anaerobic/anoxic treatment process, respectively and the amounts of their formation and release were significantly influenced by different BNR processes implemented in these WWTP. The N2O conversion ratio of r-A/ A/O process was the lowest among the three WWTP, which were 10.9% and 18.6% lower than that of A-A/A/O process and A+OD process, respectively. Similarly, the CH4 conversion ratio of r-A/ A/O process was the lowest among the three WWTP, which were 89. I% and 80.8% lower than that of A-A/ A/O process and A+OD process, respectively. The factors influencing N2O and CH4 formation and emission in the three WWTP were investigated to explain the difference between these processes. The nitrite concentration and oxidation-reduction potential (ORP) value were found to be the dominant influencing factors affecting N2O and CH4 production, respectively. The flow-based emission factors of N2O and CH4 of the WWTP were figured out for better quantification of GHG emissions and further technical assessments of mitigation options.

Electrochemical advanced oxidation for cold incineration of the pharmaceutical ranitidine: mineralization pathway and toxicity evolution.

PubMed

Olvera-Vargas, Hugo; Oturan, Nihal; Brillas, Enric; Buisson, Didier; Esposito, Giovanni; Oturan, Mehmet A

2014-12-01

Ranitidine (RNTD) is a widely prescribed histamine H2-receptor antagonist whose unambiguous presence in water sources appointed it as an emerging pollutant. Here, the degradation of 0.1 mM of this drug in aqueous medium was studied by electrochemical advanced oxidation processes (EAOPs) like anodic oxidation with electrogenerated H2O2 and electro-Fenton using Pt/carbon-felt, BDD/carbon-felt and DSA-Ti/RuO2–IrO2/carbon-felt cells. The higher oxidation power of the electro-Fenton process using a BDD anode was demonstrated. The oxidative degradation of RNTD by the electrochemically generated OH radicals obeyed a pseudo-first order kinetics. The absolute rate constant for its hydroxylation reaction was 3.39 × 109 M−1 s−1 as determined by the competition kinetics method. Almost complete mineralization of the RNTN solution was reached by using a BDD anode in both anodic oxidation with electrogenerated H2O2 and electro-Fenton processes. Up to 11 cyclic intermediates with furan moiety were detected from the degradation of RNTD, which were afterwards oxidized to short-chain carboxylic acids before their mineralization to CO2 and inorganic ions such as NH4+, NO3− and SO42−. Based on identified products, a plausible reaction pathway was proposed for RNTD mineralization. Toxicity assessment by the Microtox® method revealed that some cyclic intermediates are more toxic than the parent molecule. Toxicity was quickly removed following the almost total mineralization of the treated solution. Overall results confirm the effectiveness of EAOPs for the efficient removal of RNTD and its oxidation by-products from water.

THERMOCHEMICAL HEAT STORAGE FOR CONCENTRATED SOLAR POWER

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

PROJECT STAFF

2011-10-31

Thermal energy storage (TES) is an integral part of a concentrated solar power (CSP) system. It enables plant operators to generate electricity beyond on sun hours and supply power to the grid to meet peak demand. Current CSP sensible heat storage systems employ molten salts as both the heat transfer fluid and the heat storage media. These systems have an upper operating temperature limit of around 400 C. Future TES systems are expected to operate at temperatures between 600 C to 1000 C for higher thermal efficiencies which should result in lower electricity cost. To meet future operating temperature andmore » electricity cost requirements, a TES concept utilizing thermochemical cycles (TCs) based on multivalent solid oxides was proposed. The system employs a pair of reduction and oxidation (REDOX) reactions to store and release heat. In the storage step, hot air from the solar receiver is used to reduce the oxidation state of an oxide cation, e.g. Fe3+ to Fe2+. Heat energy is thus stored as chemical bonds and the oxide is charged. To discharge the stored energy, the reduced oxide is re-oxidized in air and heat is released. Air is used as both the heat transfer fluid and reactant and no storage of fluid is needed. This project investigated the engineering and economic feasibility of this proposed TES concept. The DOE storage cost and LCOE targets are $15/kWh and $0.09/kWh respectively. Sixteen pure oxide cycles were identified through thermodynamic calculations and literature information. Data showed the kinetics of re-oxidation of the various oxides to be a key barrier to implementing the proposed concept. A down selection was carried out based on operating temperature, materials costs and preliminary laboratory measurements. Cobalt oxide, manganese oxide and barium oxide were selected for developmental studies to improve their REDOX reaction kinetics. A novel approach utilizing mixed oxides to improve the REDOX kinetics of the selected oxides was proposed. It partially replaces some of the primary oxide cations with selected secondary cations. This causes a lattice charge imbalance and increases the anion vacancy density. Such vacancies enhance the ionic mass transport and lead to faster re-oxidation. Reoxidation fractions of Mn3O4 to Mn2O3 and CoO to Co3O4 were improved by up to 16 fold through the addition of a secondary oxide. However, no improvement was obtained in barium based mixed oxides. In addition to enhancing the short term re-oxidation kinetics, it was found that the use of mixed oxides also help to stabilize or even improve the TES properties after long term thermal cycling. Part of this improvement could be attributed to a reduced grain size in the mixed oxides. Based on the measurement results, manganese-iron, cobalt-aluminum and cobalt iron mixed oxides have been proposed for future engineering scale demonstration. Using the cobalt and manganese mixed oxides, we were able to demonstrate charge and discharge of the TES media in both a bench top fixed bed and a rotary kiln-moving bed reactor. Operations of the fixed bed configuration are straight forward but require a large mass flow rate and higher fluid temperature for charging. The rotary kiln makes direct solar irradiation possible and provides significantly better heat transfer, but designs to transport the TES oxide in and out of the reactor will need to be defined. The final reactor and system design will have to be based on the economics of the CSP plant. A materials compatibility study was also conducted and it identified Inconel 625 as a suitable high temperature engineering material to construct a reactor holding either cobalt or manganese mixed oxides. To assess the economics of such a CSP plant, a packed bed reactor model was established as a baseline. Measured cobalt-aluminum oxide reaction kinetics were applied to the model and the influences of bed properties and process parameters on the overall system design were investigated. The optimal TES system design was found to be a network of eight fixed bed reactors at 18.75 MWth each with charge and discharge temperatures between 1200 C and 600 C, which provides a constant output temperature of 900 C. The charge and discharge time are 8 hours each respectively. This design was integrated into a process flowsheet of a CSP plant and the system's economics were determined using AspenPlus and NREL's Solar Advisory Model. Storage cost is very sensitive to materials cost and was calculated to be based around $40/kWh for cobalt based mixed oxide. It can potentially decrease to $10/kWh based on reduced materials cost on a bulk scale. The corresponding calculated LCOE was between $0.22 and 0.30/kW-h. The high LCOE is a result of the high charging temperature required in this first design and the cost of cobalt oxide. It is expected that a moving bed reactor using manganese oxide will significantly improve the economics of the proposed concept.« less

Off-line wafer level reliability control: unique measurement method to monitor the lifetime indicator of gate oxide validated within bipolar/CMOS/DMOS technology

NASA Astrophysics Data System (ADS)

Gagnard, Xavier; Bonnaud, Olivier

2000-08-01

We have recently published a paper on a new rapid method for the determination of the lifetime of the gate oxide involved in a Bipolar/CMOS/DMOS technology (BCD). Because this previous method was based on a current measurement with gate voltage as a parameter needing several stress voltages, it was applied only by lot sampling. Thus, we tried to find an indicator in order to monitor the gate oxide lifetime during the wafer level parametric test and involving only one measurement of the device on each wafer test cell. Using the Weibull law and Crook model, combined with our recent model, we have developed a new test method needing only one electrical measurement of MOS capacitor to monitor the quality of the gate oxide. Based also on a current measurement, the parameter is the lifetime indicator of the gate oxide. From the analysis of several wafers, we gave evidence of the possibility to detect a low performance wafer, which corresponds to the infantile failure on the Weibull plot. In order to insert this new method in the BCD parametric program, a parametric flowchart was established. This type of measurement is an important challenges, because the actual measurements, breakdown charge, Qbd, and breakdown electric field, Ebd, at parametric level and Ebd and interface states density, Dit during the process cannot guarantee the gate oxide lifetime all along fabrication process. This indicator measurement is the only one, which predicts the lifetime decrease.

Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments.

PubMed

Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M

2015-11-01

A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration--a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder.

Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments

PubMed Central

Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M

2015-01-01

A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration—a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder. PMID:25871933

Solution processed metal oxide thin film hole transport layers for high performance organic solar cells

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

Steirer, K. Xerxes; Berry, Joseph J.; Chesin, Jordan P.

2017-01-10

A method for the application of solution processed metal oxide hole transport layers in organic photovoltaic devices and related organic electronics devices is disclosed. The metal oxide may be derived from a metal-organic precursor enabling solution processing of an amorphous, p-type metal oxide. An organic photovoltaic device having solution processed, metal oxide, thin-film hole transport layer.

Comparison of Infectious Agents Susceptibility to Photocatalytic Effects of Nanosized Titanium and Zinc Oxides: A Practical Approach

NASA Astrophysics Data System (ADS)

Bogdan, Janusz; Zarzyńska, Joanna; Pławińska-Czarnak, Joanna

2015-08-01

Nanotechnology contributes towards a more effective eradication of pathogens that have emerged in hospitals, veterinary clinics, and food processing plants and that are resistant to traditional drugs or disinfectants. Since new methods of pathogens eradication must be invented and implemented, nanotechnology seems to have become the response to that acute need. A remarkable achievement in this field of science was the creation of self-disinfecting surfaces that base on advanced oxidation processes (AOPs). Thus, the phenomenon of photocatalysis was practically applied. Among the AOPs that have been most studied in respect of their ability to eradicate viruses, prions, bacteria, yeasts, and molds, there are the processes of TiO2/UV and ZnO/UV. Titanium dioxide (TiO2) and zinc oxide (ZnO) act as photocatalysts, after they have been powdered to nanoparticles. Ultraviolet (UV) radiation is an agent that determines their excitation. Methods using photocatalytic properties of nanosized TiO2 and ZnO prove to be highly efficient in inactivation of infectious agents. Therefore, they are being applied on a growing scale. AOP-based disinfection is regarded as a very promising tool that might help overcome problems in food hygiene and public health protection. The susceptibility of infectious agents to photocatalylic processes can be generally arranged in the following order: viruses > prions > Gram-negative bacteria > Gram-positive bacteria > yeasts > molds.

Bio-desulfurization and denitrification by anaerobic-anoxic process for the treatment of wastewater from flue gas washing.

PubMed

Song, Ziyu; Zhou, Xuemei; Li, Yuguang; Yang, Maohua; Xing, Jianmin

2013-01-01

For amine-based carbon dioxide capture, nitrogen oxides and sulfur oxides were the main pollutants that had a negative effect on the regeneration of solvent. Before carbon dioxide capture, the sulfur oxides in flue gas should be removed by the method of calcium salt, and then washed by alkaline solution to eliminate the residual nitrogen oxides and sulfur oxides. The washing wastewater containing sulfate and nitrate needs to be treated. In this study, a novel anaerobic-anoxic process was built up for the treatment of this washing wastewater. Nitrate was reduced to nitrogen by denitrifying bacteria. Sulfate was firstly reduced to sulfide by sulfate reducing bacteria, and then selectively oxidized to element sulfur by sulfide oxidizing bacteria. The treated liquid could be reused as absorption after the adjustment of pH value. The performances of this bioprocess were investigated under various pH values and S/N ratios. It was found that the optimal pH value of influent was 6.0, the percentages of denitrification and sulfate reducing could reach 90 and 89%, respectively. Seventy-six percent of sulfate was transformed into element sulfur. Nitrate significantly had a negative effect on sulfate reduction above 10 mM. As 20 mM nitrate, the sulfate reducing percentage would drop to 67%. These results showed that the anaerobic-anoxic process was feasible for the treatment of flue gas washing wastewater. It would be prospectively applied to other wastewater with the higher ratio of SO4(2-)/NO3(-).

The Obtaining of Nano Oxide Systems SiO2-REE with Alkoxide Technology

NASA Astrophysics Data System (ADS)

Amelina, Anna; Grinberg, Evgenii

A lot of oxides systems with REE as dopants are used in catalytic processes in organic synthesis. They are very perspectives as thermostable coating in aerospace technics. These systems are usually based on silicon or aluminium oxides and doped with rare-earth elements. This systems can be produced by different methods. One of the most perspective of them is “sol-gel”-method with silicium, aluminium and rare-earth alkoxides as a precursor of doped silica and alumina, or their derivatives. Thus the obtaining of composite SiO _{2} - REE oxide materials by the hydrolysis doped with rare-earth elements was suggested. Some of alcoholate derivatives such as El(OR)n were used in this processes. The SiO _{2}- REE oxides were precipitated during the sol-gel process, where tetraethoxysilane (TEOS) as used as SiO _{2} sources. Also it is known that alkoxides of alkali metals, including lithium alkoxides, are widely used in industry and synthetic chemistry, as well as a source of lithium in various mixed oxide compositions, such as lithium niobate, lithium tantalate or lithium silicate. Therefore, we attempted to obtain the lithium silicate, which is also doped with rare-earth elements. Lithium silicate was obtained by alkaline hydrolysis of tetraethoxysilane with lithium alkoxide. Lithium alkoxide were synthesized by dissolving at metal in the corresponding alcohol are examined. The dependence of the rate of dissolving of the metal on the method of mixing of the reaction mixture and the degree of metal dispersion was investigated. The mathematical model of the process was composed and also optimization of process was carried out. Some oxide SiO _{2}, Al _{2}O _{3} and rare-earth nanostructured systems were obtained by sol-gel-method. The size of particle was determined by electron and X-ray spectroscopy and was in the range of 5 - 15 nm. Purity of this oxide examples for contaminating of heavy metals consists n.(1E-4...1E-5) wt%. Sols obtained by this method may be used for producing of thin coats on ceramics and metallic surfaces.

Mesoporous metal oxides and processes for preparation thereof

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

Suib, Steven L.; Poyraz, Altug Suleyman

A process for preparing a mesoporous metal oxide, i.e., transition metal oxide. Lanthanide metal oxide, a post-transition metal oxide and metalloid oxide. The process comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to form the mesoporous metal oxide. A mesoporous metal oxide prepared by the above process. A method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides. The method comprises providing an acidic mixture comprising a metal precursor, an interface modifier,more » a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxides. Mesoporous metal oxides and a method of tuning structural properties of mesoporous metal oxides.« less

Quantifying the Global Nitrous Oxide Emissions Using a Trait-based Biogeochemistry Model

NASA Astrophysics Data System (ADS)

Zhuang, Q.; Yu, T.

2017-12-01

Nitrogen is an essential element for the global biogeochemical cycle. It is a key nutrient for organisms and N compounds including nitrous oxide significantly influence the global climate. The activities of bacteria and archaea are responsible for the nitrification and denitrification in a wide variety of environments, so microbes play an important role in the nitrogen cycle in soils. To date, most existing process-based models treated nitrification and denitrification as chemical reactions driven by soil physical variables including soil temperature and moisture. In general, the effect of microbes on N cycling has not been modeled in sufficient details. Soil organic carbon also affects the N cycle because it supplies energy to microbes. In my study, a trait-based biogeochemistry model quantifying N2O emissions from the terrestrial ecosystems is developed based on an extant process-based model TEM (Terrestrial Ecosystem Model). Specifically, the improvement to TEM includes: 1) Incorporating the N fixation process to account for the inflow of N from the atmosphere to biosphere; 2) Implementing the effects of microbial dynamics on nitrification process; 3) fully considering the effects of carbon cycling on N nitrogen cycling following the principles of stoichiometry of carbon and nitrogen in soils, plants, and microbes. The difference between simulations with and without the consideration of bacterial activity lies between 5% 25% based on climate conditions and vegetation types. The trait based module allows a more detailed estimation of global N2O emissions.

Laterally configured resistive switching device based on transition-metal nano-gap electrode on Gd oxide

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

Kawakita, Masatoshi; Okabe, Kyota; Kimura, Takashi

2016-01-11

We have developed a fabrication process for a laterally configured resistive switching device based on a Gd oxide. A nano-gap electrode connected by a Gd oxide with the ideal interfaces has been created by adapting the electro-migration method in a metal/GdO{sub x} bilayer system. Bipolar set and reset operations have been clearly observed in the Pt/GdO{sub x} system similarly in the vertical device based on GdO{sub x}. Interestingly, we were able to observe a clear bipolar switching also in a ferromagnetic CoFeB nano-gap electrode with better stability compared to the Pt/GdO{sub x} device. The superior performance of the CoFeB/GdO{sub x}more » device implies the importance of the spin on the resistive switching.« less

Indium-oxide nanoparticles for RRAM devices compatible with CMOS back-end-off-line

NASA Astrophysics Data System (ADS)

León Pérez, Edgar A. A.; Guenery, Pierre-Vincent; Abouzaid, Oumaïma; Ayadi, Khaled; Brottet, Solène; Moeyaert, Jérémy; Labau, Sébastien; Baron, Thierry; Blanchard, Nicholas; Baboux, Nicolas; Militaru, Liviu; Souifi, Abdelkader

2018-05-01

We report on the fabrication and characterization of Resistive Random Access Memory (RRAM) devices based on nanoparticles in MIM structures. Our approach is based on the use of indium oxide (In2O3) nanoparticles embedded in a dielectric matrix using CMOS-full-compatible fabrication processes in view of back-end-off-line integration for non-volatile memory (NVM) applications. A bipolar switching behavior has been observed using current-voltage measurements (I-V) for all devices. Very high ION/IOFF ratios have been obtained up to 108. Our results provide insights for further integration of In2O3 nanoparticles-based devices for NVM applications. He is currently a Postdoctoral Researcher in the Institute of Nanotechnologies of Lyon (INL), INSA de Lyon, France, in the Electronics Department. His current research include indium oxide nanoparticles for non-volatile memory applications, and the integrations of these devices in CMOS BEOL.

In Situ Chemical Oxidation for Groundwater Remediation: Site-Specific Engineering & Technology Application

DTIC Science & Technology

2010-10-01

PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) Colorado School of Mines,1500 Illinois St, Golden ,CO,80401 8. PERFORMING ORGANIZATION REPORT NUMBER 9...Protocol page 13 Overall ISCO Protocol Flow Diagram addition, laboratory studies may be used to select optimal chemistry parameters to maximize oxidant...Design Process 5. Because of the complexity of these oxidants’ chemistry and implementation, with much of the knowledge base residing with those

Chemiluminescent Diagnostics of Free-Radical Processes in an Abiotic System and in Liver Cells in the Presence of Nanoparticles Based on Rare-Earth Elements nReVO4:Eu3+ (Re = Gd, Y, La) and CeO2

NASA Astrophysics Data System (ADS)

Averchenko, E. A.; Kavok, N. S.; Klochkov, V. K.; Malyukin, Yu. V.

2014-11-01

We have used luminol-dependent chemiluminescence with Fenton's reagent to study the effect of nanoparticles based on rare-earth elements of different sizes and shapes on free-radical processes in abiotic and biotic cell-free systems, and also in isolated cells in vitro. We have estimated the effects of rare-earth orthovanadate nanoparticles of spherical (GdYVO4:Eu3+, 1-2 nm), spindle-shaped (GdVO4:Eu3+, 25 ×8 nm), and rod-shaped (LaVO4:Eu3+, 57 × (6-8) nm) nanoparticles and spherical CeO2 nanoparticles (sizes 1-2 nm and 8-10 nm). We have shown that in contrast to the abiotic system, in which all types of nanoparticles exhibit antiradical activity, in the presence of biological material, extra-small spherical (1-2 nm) nanoparticles of both types exhibit pro-oxidant activity, and also enhance pro-oxidant induced oxidative stress (for the pro-oxidants hydrogen peroxide and tert-butyl hydroperoxide). The effect of rare-earth orthovanadate spindle and rod shaped nanoparticles in this system was neutral; a moderate antioxidant effect was exhibited by 8-10 nm CeO2 nanoparticles.

Floating gate memory with charge storage dots array formed by Dps protein modified with site-specific binding peptides

NASA Astrophysics Data System (ADS)

Kamitake, Hiroki; Uenuma, Mutsunori; Okamoto, Naofumi; Horita, Masahiro; Ishikawa, Yasuaki; Yamashita, Ichro; Uraoka, Yukiharu

2015-05-01

We report a nanodot (ND) floating gate memory (NFGM) with a high-density ND array formed by a biological nano process. We utilized two kinds of cage-shaped proteins displaying SiO2 binding peptide (minTBP-1) on their outer surfaces: ferritin and Dps, which accommodate cobalt oxide NDs in their cavities. The diameters of the cobalt NDs were regulated by the cavity sizes of the proteins. Because minTBP-1 is strongly adsorbed on the SiO2 surface, high-density cobalt oxide ND arrays were obtained by a simple spin coating process. The densities of cobalt oxide ND arrays based on ferritin and Dps were 6.8 × 1011 dots cm-2 and 1.2 × 1012 dots cm-2, respectively. After selective protein elimination and embedding in a metal-oxide-semiconductor (MOS) capacitor, the charge capacities of both ND arrays were evaluated by measuring their C-V characteristics. The MOS capacitor embedded with the Dps ND array showed a wider memory window than the device embedded with the ferritin ND array. Finally, we fabricated an NFGM with a high-density ND array based on Dps, and confirmed its competent writing/erasing characteristics and long retention time.

Synergistic effects of water addition and step heating on the formation of solution-processed zinc tin oxide thin films: towards high-mobility polycrystalline transistors

NASA Astrophysics Data System (ADS)

Huang, Genmao; Duan, Lian; Zhao, Yunlong; Zhang, Yunge; Dong, Guifang; Zhang, Deqiang; Qiu, Yong

2016-11-01

Thin-film transistors (TFTs) with high mobility and good uniformity are attractive for next-generation flat panel displays. In this work, solution-processed polycrystalline zinc tin oxide (ZTO) thin film with well-ordered microstructure is prepared, thanks to the synergistic effect of water addition and step heating. The step heating treatment other than direct annealing induces crystallization, while adequate water added to precursor solution further facilitates alloying and densification process. The optimal polycrystalline ZTO film is free of hierarchical sublayers, and featured with an increased amount of ternary phases, as well as a decreased fraction of oxygen vacancies and hydroxides. TFT devices based on such an active layer exhibit a remarkable field-effect mobility of 52.5 cm2 V-1 s-1, a current on/off ratio of 2 × 105, a threshold voltage of 2.32 V, and a subthreshold swing of 0.36 V dec-1. Our work offers a facile method towards high-performance solution-processed polycrystalline metal oxide TFTs.

Investigation of reactions between trace gases and functional CuO nanospheres and octahedrons using NEXAFS-TXM imaging

PubMed Central

Henzler, Katja; Heilemann, Axel; Kneer, Janosch; Guttmann, Peter; Jia, He; Bartsch, Eckhard; Lu, Yan; Palzer, Stefan

2015-01-01

In order to take full advantage of novel functional materials in the next generation of sensorial devices scalable processes for their fabrication and utilization are of great importance. Also understanding the processes lending the properties to those materials is essential. Among the most sought-after sensor applications are low-cost, highly sensitive and selective metal oxide based gas sensors. Yet, the surface reactions responsible for provoking a change in the electrical behavior of gas sensitive layers are insufficiently comprehended. Here, we have used near-edge x-ray absorption fine structure spectroscopy in combination with x-ray microscopy (NEXAFS-TXM) for ex-situ measurements, in order to reveal the hydrogen sulfide induced processes at the surface of copper oxide nanoparticles, which are ultimately responsible for triggering a percolation phase transition. For the first time these measurements allow the imaging of trace gas induced reactions and the effect they have on the chemical composition of the metal oxide surface and bulk. This makes the new technique suitable for elucidating adsorption processes in-situ and under real operating conditions. PMID:26631608

A general melt-injection-decomposition route to oriented metal oxide nanowire arrays

NASA Astrophysics Data System (ADS)

Han, Dongqiang; Zhang, Xinwei; Hua, Zhenghe; Yang, Shaoguang

2016-12-01

In this manuscript, a general melt-injection-decomposition (MID) route has been proposed and realized for the fabrication of oriented metal oxide nanowire arrays. Nitrate was used as the starting materials, which was injected into the nanopores of the anodic aluminum oxide (AAO) membrane through the capillarity action in its liquid state. At higher temperature, the nitrate decomposed into corresponding metal oxide within the nanopores of the AAO membrane. Oriented metal oxide nanowire arrays were formed within the AAO membrane as a result of the confinement of the nanopores. Four kinds of metal oxide (CuO, Mn2O3, Co3O4 and Cr2O3) nanowire arrays are presented here as examples fabricated by this newly developed process. X-ray diffraction, scanning electron microscopy and transmission electron microscopy studies showed clear evidence of the formations of the oriented metal oxide nanowire arrays. Formation mechanism of the metal oxide nanowire arrays is discussed based on the Thermogravimetry and Differential Thermal Analysis measurement results.

Parameters for measurement of oxidative stress in diabetes mellitus: applicability of enzyme-linked immunosorbent assay for clinical evaluation.

PubMed

Noiri, Eisei; Tsukahara, Hirokazu

2005-05-01

Investigations of the mechanisms involved in the onset and progression of diabetes have recently confronted the role of reactive oxygen species (ROS) and oxidative stress. Prolonged exposure to hyperglycemic conditions induces nonenzymatic glycation of protein via the so-called Maillard reaction, resulting in Schiff-base products and Amadori products that engender ROS production. These processes initiate and exacerbate micro- and macrovascular complications in diabetes. Increased oxidative stress is induced by excessive ROS production and inadequate antioxidant defenses. Recently, oxidative stress status markers have been associated directly with the severity and prognosis of diabetes. To examine oxidative stress, reliable and high-throughput methods are needed to examine large numbers of clinical samples. The emerging availability of enzyme-linked immunosorbent assay (ELISA) for oxidative stress status markers allows its application to assessment of various pathophysiologic conditions, including diabetes. This review outlines the recent achievements of ELISA application for clinical studies elucidating oxidative stress. It introduces the potential applicability of ELISA for investigating oxidative stress in diabetes.

Coupling mechanism between wear and oxidation processes of 304 stainless steel in hydrogen peroxide environments.

PubMed

Dong, Conglin; Yuan, Chengqing; Bai, Xiuqin; Li, Jian; Qin, Honglin; Yan, Xinping

2017-05-24

Stainless steel is widely used in strongly oxidizing hydrogen peroxide (H 2 O 2 ) environments. It is crucial to study its wear behaviour and failure mode. The tribological properties and oxidation of 304 stainless steel were investigated using a MMW-1 tribo-tester with a three-electrode setup in H 2 O 2 solutions with different concentrations. Corrosion current densities (CCDs), coefficients of frictions (COFs), wear mass losses, wear surface topographies, and metal oxide films were analysed and compared. The results show that the wear process and oxidation process interacted significantly with each other. Increasing the concentration of H 2 O 2 or the oxidation time was useful to form a layer of integrated, homogeneous, compact and thick metal oxide film. The dense metal oxide films with higher mechanical strengths improved the wear process and also reduced the oxidation reaction. The wear process removed the metal oxide films to increase the oxidation reaction. Theoretical data is provided for the rational design and application of friction pairs in oxidation corrosion conditions.

Compound oxidized styrylphosphine. [flame resistant vinyl polymers

NASA Technical Reports Server (NTRS)

Paciorek, K. J. L. (Inventor)

1979-01-01

A process is described for preparing flame resistant, nontoxic vinyl polymers which contain phosphazene groups and which do not emit any toxic or corrosive products when they are oxidatively degraded. Homopolymers, copolymers, and terpolymers of a styrene based monomer are prepared by polymerizing at least one oxidized styrylphosphine monomer from a group of organic azides, or by polymerizing p-diphenylphosphinestyrene and then oxidizing that monomer with an organoazide from the group of (C6H5)2P(O)N3, (C6H5O)2P(O)N3, (C6H5)2C3N3(N3), and C6H5C3N3(N3)2. Copolymers can also be prepared by copolymerizing styrene with at least one oxidized styrylphosphine monomer.

Bioprocessing in space

NASA Technical Reports Server (NTRS)

Westgate, P.; Kohlmann, K.; Hendrickson, R.; Ladisch, M. R.; Mitchell, C. A. (Principal Investigator)

1992-01-01

Two approaches for biomass processing in Controlled Ecological Life Support Systems are compared in a literature survey. The approaches are based on (1) total oxidation of plant matter and (2) the potential of bioregenerative recovery.

Nonlinear electronic transport and enhanced catalytic behavior caused by native oxides on Cu nanowires

NASA Astrophysics Data System (ADS)

Hajimammadov, Rashad; Csendes, Zita; Ojakoski, Juha-Matti; Lorite, Gabriela Simone; Mohl, Melinda; Kordas, Krisztian

2017-09-01

Electrical transport properties of individual nanowires (both in axial and transversal directions) and their random networks suggest rapid oxidation when Cu is exposed to ambient conditions. The oxidation process is elucidated by thorough XRD, XPS and Raman analyzes conducted for a period of 30 days. Based on the obtained experimental data, we may conclude that first, cuprous oxide and copper hydroxide form that finally transform to cupric oxide. In electrical applications, oxidation of copper is not a true problem as long as thin films or bulk metal is concerned. However, as highlighted in our work, this is not the case for nanowires, since the oxidized surface plays quite important role in the contact formation and also in the conduction of percolated nanowire networks. On the other hand, by taking advantage of the mixed surface oxide states present on the nanowires along with their large specific surface area, we tested and found excellent catalytic activity of the oxidized nanowires in phenol oxidation, which suggests further applications of these materials in catalysis.

Enhancement of arsenite removal using manganese oxide coupled with iron (III) trimesic

NASA Astrophysics Data System (ADS)

Phanthasri, Jakkapop; Khamdahsag, Pummarin; Jutaporn, Panitan; Sorachoti, Kwannapat; Wantala, Kitirote; Tanboonchuy, Visanu

2018-01-01

A simultaneous removal of As(III) was investigated on a mixture of manganese oxide based octahedral molecular sieves (K-OMS2) and iron-benzenetricarboxylate (Fe-BTC). As(III) removal was stimulated by an oxidation cooperated with adsorption process. K-OMS2 and Fe-BTC were separately synthesized and characterized by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). K-OMS2 showed characters of pure cryptomelane phase, nanorod structure, and a mixed-valent manganese framework with the coexistence of Mn(IV) and Mn(III). As(III) was successfully oxidized to As(V) by K-OMS2 in a temperature range of 303-333 K. An intermediate adsorption of As(V) was carried out with Fe-BTC in the same batch. A maximum adsorption capacity, described by Langmuir isotherm model, was observed at 76.34 mg/g. With an As(III) initial concentration of 5 mg/L, when K-OMS2 and Fe-BTC were simultaneously introduced into the solution, the As(III) removal process was completed within 60 min. Thus, it shortened the process time compared to the case where K-OMS2 was added first, followed by the addition of Fe-BTC.

Synthesis of Diopside by Solution Combustion Process Using Glycine Fuel

NASA Astrophysics Data System (ADS)

Sherikar, Baburao N.; Umarji, A. M.

Nano ceramic Diopside (CaMgSi2O6) powders are synthesized by Solution Combustion Process(SCS) using Calcium nitrate, Magnesium nitrate as oxidizer and glycine as fuel, fumed silica as silica source. Ammonium nitrate (AN) is used as extra oxidizer. Effect of AN on Diopside phase formation is investigated. The adiabatic flame temperatures are calculated theoretically for varying amount of AN according to thermodynamic concept and correlated with the observed flame temperatures. A “Multi channel thermocouple setup connected to computer interfaced Keithley multi voltmeter 2700” is used to monitor the thermal events during the process. An interpretation based on maximum combustion temperature and the amount of gases produced during reaction for various AN compositions has been proposed for the nature of combustion and its correlation with the characteristics of as synthesized powder. These powders are characterized by XRD, SEM showing that the powders are composed of polycrystalline oxides with crystallite size of 58nm to 74nm.

Fischer-Tropsch Cobalt Catalyst Activation and Handling Through Wax Enclosure Methods

NASA Technical Reports Server (NTRS)

Klettlinger, Jennifer L. S.; Yen, Chia H.; Nakley, Leah M.; Surgenor, Angela D.

2016-01-01

Fischer-Tropsch (F-T) synthesis is considered a gas to liquid process which converts syn-gas, a gaseous mixture of hydrogen and carbon monoxide, into liquids of various hydrocarbon chain length and product distributions. Cobalt based catalysts are used in F-T synthesis and are the focus of this paper. One key concern with handling cobalt based catalysts is that the active form of catalyst is in a reduced state, metallic cobalt, which oxidizes readily in air. In laboratory experiments, the precursor cobalt oxide catalyst is activated in a fixed bed at 350 ?C then transferred into a continuous stirred tank reactor (CSTR) with inert gas. NASA has developed a process which involves the enclosure of active cobalt catalyst in a wax mold to prevent oxidation during storage and handling. This improved method allows for precise catalyst loading and delivery into a CSTR. Preliminary results indicate similar activity levels in the F-T reaction in comparison to the direct injection method. The work in this paper was supported by the NASA Fundamental Aeronautics Subsonics Fixed Wing Project.

Resistive switching memory devices composed of binary transition metal oxides using sol-gel chemistry.

PubMed

Lee, Chanwoo; Kim, Inpyo; Choi, Wonsup; Shin, Hyunjung; Cho, Jinhan

2009-04-21

We describe a novel and versatile approach for preparing resistive switching memory devices based on binary transition metal oxides (TMOs). Titanium isopropoxide (TIPP) was spin-coated onto platinum (Pt)-coated silicon substrates using a sol-gel process. The sol-gel-derived layer was converted into a TiO2 film by thermal annealing. A top electrode (Ag electrode) was then coated onto the TiO2 films to complete device fabrication. When an external bias was applied to the devices, a switching phenomenon independent of the voltage polarity (i.e., unipolar switching) was observed at low operating voltages (about 0.6 VRESET and 1.4 VSET). In addition, it was confirmed that the electrical properties (i.e., retention time, cycling test and switching speed) of the sol-gel-derived devices were comparable to those of vacuum deposited devices. This approach can be extended to a variety of binary TMOs such as niobium oxides. The reported approach offers new opportunities for preparing the binary TMO-based resistive switching memory devices allowing a facile solution processing.

Process-based reactive transport model to quantify arsenic mobility during aquifer storage and recovery of potable water.

PubMed

Wallis, Ilka; Prommer, Henning; Pichler, Thomas; Post, Vincent; Norton, Stuart B; Annable, Michael D; Simmons, Craig T

2011-08-15

Aquifer storage and recovery (ASR) is an aquifer recharge technique in which water is injected in an aquifer during periods of surplus and withdrawn from the same well during periods of deficit. It is a critical component of the long-term water supply plan in various regions, including Florida, USA. Here, the viability of ASR as a safe and cost-effective water resource is currently being tested at a number of sites due to elevated arsenic concentrations detected during groundwater recovery. In this study, we developed a process-based reactive transport model of the coupled physical and geochemical mechanisms controlling the fate of arsenic during ASR. We analyzed multicycle hydrochemical data from a well-documented affected southwest Floridan site and evaluated a conceptual/numerical model in which (i) arsenic is initially released during pyrite oxidation triggered by the injection of oxygenated water (ii) then largely complexes to neo-formed hydrous ferric oxides before (iii) being remobilized during recovery as a result of both dissolution of hydrous ferric oxides and displacement from sorption sites by competing anions.

Catalytic degradation of picric acid by heterogeneous Fenton-based processes.

PubMed

Dulova, Niina; Trapido, Marina; Dulov, Aleksandr

2011-01-01

The efficiency of goethite, magnetite and iron powder (Fe0) in catalysing the Fenton-based oxidation of picric acid (PA) in aqueous solution was studied. The effect of pH, hydrogen peroxide concentration, and catalyst type and dosage on treatment efficacy was investigated. The adsorption of PA from aqueous solution by heterogeneous catalysts was also examined. The results demonstrated negligible PA removal in H2O2/alpha-FeOOH and H2O2/Fe3O4 systems independent of process pH, and hydrogen peroxide and catalyst dosage. The PA adsorption effects of both iron oxides turned out to be insignificant for all studied pH values and catalyst dosages. The H2O2/Fe0 system proved efficient at degrading PA, but only under acidic conditions (pH 3). The results indicated that, due to rather fast leaching of ferrous ions from the iron powder surface, PA degradation was carried out mainly by the classic Fenton oxidation mechanism in the bulk solution. The adsorption of PA onto the iron powder surface may also contribute to the overall efficiency of PA degradation.

Efficacy of a Solution-Based Approach for Making Sodalite Waste Forms for an Oxide Reduction Salt Utilized in the Reprocessing of Used Uranium Oxide Fuel

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

Riley, Brian J.; Pierce, David A.; Frank, Steven M.

2015-04-01

This paper describes various approaches for making sodalite with a LiCl-Li2O oxide reduction salt used to recover uranium from used oxide fuel. The approaches include sol-gel and solution-based synthesis processes. As-made products were mixed with 5 and 10 mass% of a Na2O-B2O3-SiO2 glass binder and these, along with product without a binder, were heated using either a cold-press-and-sinter method or hot uniaxial pressing. The results demonstrate the limitation of sodalite yield due to the fast intermediate reactions between Na+ and Cl- to form halite in solution and Li2O and SiO2 to form lithium silicates (e.g., Li2SiO3 or Li2Si2O5) in themore » calcined and sintered pellets. The results show that pellets can be made with high sodalite fractions (~92 mass%) and low porosities using a solution-based approach and this LiCl-Li2O salt.« less

Effect of curing agents on the oxidative and nitrosative damage to meat proteins during processing of fermented sausages.

PubMed

Villaverde, A; Morcuende, D; Estévez, M

2014-07-01

The effect of increasing concentrations of curing agents, ascorbate (0, 250, and 500 ppm), and nitrite (0, 75, and 150 ppm), on the oxidative and nitrosative damage to proteins during processing of fermented sausages was studied. The potential influence of these reactions on color and texture of the fermented sausages was also addressed. Nitrite had a pro-oxidant effect on tryptophan depletion and promoted the formation of protein carbonyls and Schiff bases. The nitration degree in the fermented sausages was also dependent on nitrite concentration. On the other hand, ascorbate acted as an efficient inhibitor of the oxidative and nitrosative damage to meat proteins. As expected, nitrite clearly favored the formation of the cured red color and ascorbate acted as an enhancer of color formation. Nitrite content was positively correlated with hardness. The chemistry behind the action of nitrite and ascorbate on muscle proteins during meat fermentation is thoroughly discussed. The results suggest that ascorbate (500 ppm) may be required to compensate the pro-oxidant impact of nitrite on meat proteins. This study provides insight on the action of curing agents on meat proteins during processing of fermented sausages. This chemistry background provides understanding of the potential influence of the oxidative and nitrosative damage to proteins on the quality of processed muscle foods. The study provides novel information on the impact of the combination of nitrite and ascorbate on the chemical deterioration of proteins and the influence on particular quality traits of fermented sausages. These data may be of interest for the design of cured muscle foods of enhanced quality. © 2014 Institute of Food Technologists®

Steady-state voltammetry of hydroxide ion oxidation in aqueous solutions containing ammonia.

PubMed

Daniele, Salvatore; Baldo, M Antonietta; Bragato, Carlo; Abdelsalam, Mamdouh Elsayed; Denuault, Guy

2002-07-15

An oxidation process observed in dilute aqueous solutions of ammonia was investigated under steady-state conditions with gold microelectrodes with radii in the range 2.5-30 microm. Over the ammonia concentration range 0.1-10 mM, a well-defined voltammetric wave was observed at approximately 1.4 V versus Ag/AgCl. It was attributed to the oxidation of hydroxide ions that arise from the dissociation of the weak base. The steady-state limiting current was found to depend on the concentration of supporting electrolyte, and in solution with low electrolyte, it was enhanced by migration contribution, as expected for a negatively charged species that oxidizes on a positively charged electrode. In addition, the steady-state limiting current was proportional to both the ammonia concentration and the electrode radius. The overall electrode process was analyzed in terms of a CE mechanism (homogeneous chemical reaction preceding the heterogeneous electron transfer) with a fast chemical reaction when measurements were carried out in solutions containing NH3 at < or = 5 mM and with electrodes having a radius of > or = 5 microm. This was ascertained by comparing experimental and theoretical data obtained by simulation. The formation of the soluble complex species Au(NH3)2+ was also considered as a possible alternative to explain the presence of the oxidation wave. This process however was ruled out, as the experimental data did not fit theoretical predictions in any of the conditions employed in the investigation. Instead, the direct oxidation of NH3, probably to N2O, was invoked to explain the anomalous currents found when the CE process was strongly kinetically hindered. Throughout this study, a parallel was made between the CE mechanism investigated here and that known to occur during the hydrogen evolution reaction from weak acids.

Tungsten oxide--fly ash oxide composites in adsorption and photocatalysis.

PubMed

Visa, Maria; Bogatu, Cristina; Duta, Anca

2015-05-30

A novel composite based on tungsten oxide and fly ash was hydrothermally synthetized to be used as substrate in the advanced treatment of wastewaters with complex load resulted from the textile industry. The proposed treatment consists of one single step process combining photocatalysis and adsorption. The composite's crystalline structure was investigated by X-ray diffraction and FTIR, while atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to analyze the morphology. The adsorption capacity and photocatalytic properties of the material were tested on mono- and multi-pollutants systems containing two dyes (Bemacid Blau - BB and Bemacid Rot - BR) and one heavy metal ion-Cu(2+), and the optimized process conditions were identified. The results indicate better removal efficiencies using the novel composite material in the combined adsorption and photocatalysis, as compared to the separated processes. Dyes removal was significantly enhanced in the photocatalytic process by adding hydrogen peroxide and the mechanism was presented and discussed. The pseudo second order kinetics model best fitted the experimental data, both in the adsorption and in the combined processes. The kinetic parameters were calculated and correlated with the properties of the composite substrate. Copyright © 2015 Elsevier B.V. All rights reserved.

Optimization of mechanical performance of oxidative nano-particle electrode nitrile butadiene rubber conducting polymer actuator.

PubMed

Kim, Baek-Chul; Park, S J; Cho, M S; Lee, Y; Nam, J D; Choi, H R; Koo, J C

2009-12-01

Present work delivers a systematical evaluation of actuation efficiency of a nano-particle electrode conducting polymer actuator fabricated based on Nitrile Butadiene Rubber (NBR). Attempts are made for maximizing mechanical functionality of the nano-particle electrode conducting polymer actuator that can be driven in the air. As the conducting polymer polypyrrole of the actuator is to be fabricated through a chemical oxidation polymerization process that may impose certain limitations on both electrical and mechanical functionality of the actuator, a coordinated study for optimization process of the actuator is necessary for maximizing its performance. In this article actuation behaviors of the nano-particle electrode polypyrrole conducting polymer is studied and an optimization process for the mechanical performance maximization is performed.

MATERIAL AND PROCESS DEVELOPMENT LEADING TO ECONOMICAL HIGH-PERFORMANCE THIN-FILM SOLID OXIDE FUEL CELLS

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

Jie Guan; Atul Verma; Nguyen Minh

2003-04-01

This document summarizes the technical progress from September 2002 to March 2003 for the program, Material and Process Development Leading to Economical High-Performance Thin-Film Solid Oxide Fuel Cells, contract number DE-AC26-00NT40711. The causes have been identified for the unstable open circuit voltage (OCV) and low performance exhibited by the anode-supported lanthanum gallate based cells from the earlier development. Promising results have been obtained in the area of synthesis of electrolyte and cathode powders, which showed excellent sintering and densification at low temperatures. The fabrication of cells using tapecalendering process for anode-supported thin lanthanum gallate electrolyte cells and their performance optimizationmore » is in progress.« less

3D printing process of oxidized nanocellulose and gelatin scaffold.

PubMed

Xu, Xiaodong; Zhou, Jiping; Jiang, Yani; Zhang, Qi; Shi, Hongcan; Liu, Dongfang

2018-08-01

For tissue engineering applications tissue scaffolds need to have a porous structure to meet the needs of cell proliferation/differentiation, vascularisation and sufficient mechanical strength for the specific tissue. Here we report the results of a study of the 3D printing process for composite materials based on oxidized nanocellulose and gelatin, that was optimised through measuring rheological properties of different batches of materials after different crosslinking times, simulation of the pneumatic extrusion process and 3D scaffolds fabrication with Solidworks Flow Simulation, observation of its porous structure by SEM, measurement of pressure-pull performance, and experiments aimed at finding out the vitro cytotoxicity and cell morphology. The materials printed are highly porous scaffolds with good mechanical properties.

Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen

NASA Astrophysics Data System (ADS)

Luo, Si

Abstract of the Dissertation. Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen. by. Si Luo. Doctor of Philosophy. in. Chemistry. Stony Brook University. 2017. The environmental impacts of fossil fuel consumption and the resulting global warming have attracted increasing attention to technologies and fuels that are both sustainable and renewable in the 21st century. To date, hydrogen has been proposed as an encouraging candidate of the next generation of chemical fuels, which meets all demands for carbon free and efficient chemistries that could be produced from a variety of sources. However, despite tremendous efforts, there is a clear need to develop new catalysts for the production of hydrogen through catalytic processes that are sustainable, such as in the photocatalytic splitting of water (PCS: H2O → H2 + 0.5O2) and the water-gas shift process (WGS: CO + H2O → H2 + CO2). This thesis is primarily motivated by this challenge and has focused on the photochemical and thermal production of H2 by the employment of novel TiO2 based catalysts. TiO2 is one of the most widely studied photocatalysts in all history, due to its relatively high activity, robust stability, safety and low cost. In this thesis, several TiO2-based mixed metal oxide nano catalysts (CeOx-TiO2, Ru-TiO2, Ga-TiO2) have been synthesized with carefully controlled morphology/structure and with inclusion of co-catalysts (Pt). These novel materials were comprehensively characterized to better understand their morphology, crystal structure, and electronic properties in an attempt to unravel phenomena responsible for high catalytic performance for the production of H2 from H2O. We have discovered the importance of low-dimensional metal oxide and interfacial stabilized nano-scaled mixed metal oxides for H2 production, while learning how best to tune such structure to optimize both thermal and photochemical conversion. Optimized structure and/or composition have been identified for TiO2 modified in different ways by another metal oxide (CeOx) or with dopants (Ga, Ru). In addition, we have also studied the water gas shift reaction on several TiO2 supported catalysts, where similar concepts can be applied. Advanced In situ characterization enabled the investigation of the catalyst structure, surface chemical intermediates and active species under reaction conditions. The influence of metal-oxide, oxide-oxide interactions has been further revealed for both the water-gas shift and the photocatalytic splitting of water.

Effect of replacement of tin doped indium oxide (ITO) by ZnO: analysis of environmental impact categories

NASA Astrophysics Data System (ADS)

Ziemińska-Stolarska, Aleksandra; Barecka, Magda; Zbiciński, Ireneusz

2017-10-01

Abundant use of natural resources is doubtlessly one of the greatest challenges of sustainable development. Process alternatives, which enable sustainable manufacturing of valuable products from more accessible resources, are consequently required. One of examples of limited resources is Indium, currently broadly used for tin doped indium oxide (ITO) for production of transparent conductive films (TCO) in electronics industry. Therefore, candidates for Indium replacement, which would offer as good performance as the industrial state-of-the-art technology based on ITO are widely studied. However, the environmental impact of new layers remains unknown. Hence, this paper studies the environmental effect of ITO replacement by zinc oxide (ZnO) by means life cycle assessment (LCA) methodology. The analysis enables to quantify the environmental impact over the entire period of life cycle of products—during manufacturing, use phase and waste generation. The analysis was based on experimental data for deposition process. Further, analysis of different impact categories was performed in order to determine specific environmental effects related to technology change. What results from the analysis, is that ZnO is a robust alternative material for ITO replacement regarding environmental load and energy efficiency of deposition process which is also crucial for sustainable TCO layer production.

Development of Protective Coatings for Chromium-Base Alloys

NASA Technical Reports Server (NTRS)

English, J. J.; MacMillan, C. A.; Williams, D. N.; Bartlett, E. S.

1966-01-01

Chromium alloy sheet was clad with 5 to 10-mil-thick oxidation-resistant nickel-base alloy foils. Specimens also contained 1/2 to 1-mil-thick intermediate layers of platinum, tungsten, and/or W-25Re. Cladding was done by the isostatic hot gas-pressure bonding,.process. The clad chromium-alloy specimens were cyclic oxidation tested at 2100 F and 2300 F for up to 200 hours to determine the effectiveness of these metal claddings in protecting the chromium alloy Cr-5W from oxidation and contamination. Cladding systems consisting of 5-mil-thick Ni-20Cr-20W modified with 3 to 5 weight percent aluminum and containing a 1 /2-mil tungsten diffusion barrier demonstrated potential for long-time service at temperatures as high as 2300 F.

Functionalized graphene-based cathode for highly reversible lithium-sulfur batteries.

PubMed

Kim, Jin Won; Ocon, Joey D; Park, Dong-Won; Lee, Jaeyoung

2014-05-01

In this article, we highlight the salient issues in the development of lithium-sulfur battery (LSB) cathodes, present different points of view in solving them, and argue, why in the future, functionalized graphene or graphene oxide might be the ultimate solution towards LSB commercialization. As shown by previous studies and also in our recent work, functionalized graphene and graphene oxide enhance the reversibility of the charge-discharge process by trapping polysulfides in the oxygen functional groups on the graphene surface, thus minimizing polysulfide dissolution. This will be helpful for the rational design of new cathode structures based on graphene for LSBs with minimal capacity fading, low extra cost, and without the unnecessary weight increase caused by metal/metal oxide additives. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coaxial metal-oxide-semiconductor (MOS) Au/Ga2O3/GaN nanowires.

PubMed

Hsieh, Chin-Hua; Chang, Mu-Tung; Chien, Yu-Jen; Chou, Li-Jen; Chen, Lih-Juann; Chen, Chii-Dong

2008-10-01

Coaxial metal-oxide-semiconductor (MOS) Au-Ga2O3-GaN heterostructure nanowires were successfully fabricated by an in situ two-step process. The Au-Ga2O3 core-shell nanowires were first synthesized by the reaction of Ga powder, a mediated Au thin layer, and a SiO2 substrate at 800 degrees C. Subsequently, these core-shell nanowires were nitridized in ambient ammonia to form a GaN coating layer at 600 degrees C. The GaN shell is a single crystal, an atomic flat interface between the oxide and semiconductor that ensures that the high quality of the MOS device is achieved. These novel 1D nitride-based MOS nanowires may have promise as building blocks to the future nitride-based vertical nanodevices.

Multifunctional overcoats on vanadium dioxide thermochromic thin films with enhanced luminous transmission and solar modulation, hydrophobicity and anti-oxidation

NASA Astrophysics Data System (ADS)

Liu, Chang; Wang, Ning; Long, Yi

2013-10-01

Vanadium dioxide (VO2) has a great potential to be utilized as solar energy switching glazing, even though there exist some intrinsic problems of low luminous transmittance (Tlum) and poor oxidation resistance. Si-Al based anti-reflection (AR) sol-gel coatings processed at low temperature have been developed to tackle these issues assisted by adjusting ramping rate and annealing temperature. Si-Al based AR coating gives large relative enhancement on the transmittance (22% for Tlum, 14% for the whole solar spectrum Tsol,) and successfully maintains IR contrast at 2500 nm wavelength with 18% relative increase in solar modulation (ΔTsol). The optimized Si-Al based AR coating annealing conditions are recorded at 3 °C/min ramping rate and 100 °C annealing temperature. Fluorinated-Si based gel offers a new direction of multifunctional overcoat on thermochromic smart windows with hydrophobicity (contact angle 111°), averaged 14% relatively increased luminous transmittance and enhanced oxidation resistance.

How to make an efficient and robust molecular catalyst for water oxidation.

PubMed

Garrido-Barros, Pablo; Gimbert-Suriñach, Carolina; Matheu, Roc; Sala, Xavier; Llobet, Antoni

2017-10-16

Energy has been a central subject for human development from Homo erectus to date. The massive use of fossil fuels during the last 50 years has generated a large CO 2 concentration in the atmosphere that has led to the so-called global warming. It is very urgent to come up with C-neutral energy schemes to be able to preserve Planet Earth for future generations to come and still preserve our modern societies' life style. One of the potential solutions is water splitting with sunlight (hν-WS) that is also associated with "artificial photosynthesis", since its working mode consists of light capture followed by water oxidation and proton reduction processes. The hydrogen fuel generated in this way is named as "solar fuel". For this set of reactions, the catalytic oxidation of water to dioxygen is one of the crucial processes that need to be understood and mastered in order to build up potential devices based on hν-WS. This tutorial describes the different important aspects that need to be considered to come up with efficient and oxidatively robust molecular water oxidation catalysts (Mol-WOCs). It is based on our own previous work and completed with essential contributions from other active groups in the field. We mainly aim at describing how the ligands can influence the properties of the Mol-WOCs and showing a few key examples that overall provide a complete view of today's understanding in this field.

Oxidation kinetics of the combustible fraction of construction and demolition wastes.

PubMed

Chang, N B; Lin, K S; Sun, Y P; Wang, H P

2001-01-01

Proper disposal of construction and demolition wastes (CDW) has received wide attention recently due to significantly large quantities of waste streams collected from razed or retrofitted buildings in many metropolitan regions. Burning the combustible fractions of CDW (CCDW) and possibly recovering part of the heat content for economic uses could be valuable for energy conservation. This paper explores the oxidation kinetics of CCDW associated with its ash characterization. Kinetic parameters for the oxidation of CCDW were numerically calculated using thermal gravimetric analysis (TGA) and the resultant rate equations were therefore developed for illustrating the oxidation processes of CCDW simultaneously. Based on three designated heating rates, each of the oxidation processes can be featured distinctively with five different stages according to the rate of weight change at the temperature between 300 K and 923 K. In addition, Fourier transform infrared (FTIR) spectroscopy was employed, associated with a lab-scale fixed-bed incinerator for monitoring the composition of flue gas. Carbon dioxide (CO2) was found as a major component in the flue gas. The fuel analysis also included an ash composition analysis via the use of X-ray powder diffraction (XRD), atomic absorption (AA) spectroscopy, inductively coupled plasma-atomic emission spectroscopy (ICP-AES), and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDX). The ash streams were identified as nonhazardous materials based on the toxicity characteristic leaching procedure (TCLP). Overall, the scientific findings gained in this study will be helpful for supporting a sound engineering design of real-world CCDW incineration systems.

Self-Assembled Nano-energetic Gas Generators based on Bi2O3

NASA Astrophysics Data System (ADS)

Hobosyan, Mkhitar; Trevino, Tyler; Martirosyan, Karen

2012-10-01

Nanoenergetic Gas-Generators are formulations that rapidly release a large amount of gaseous products and generate a fast moving thermal wave. They are mainly based on thermite systems, which are pyrotechnic mixtures of metal powders (fuel- Al, Mg, etc.) and metal oxides (oxidizer, Bi2O3, Fe2O3, WO3, MoO3 etc.) that can generate an exothermic oxidation-reduction reaction referred to as a thermite reaction. A thermite reaction releases a large amount of energy and can generate rapidly extremely high temperatures. The intimate contact between the fuel and oxidizer can be enhanced by use of nano instead of micro particles. The contact area between oxidizer and metal particles depends from method of mixture preparation. In this work we utilize the self-assembly processes, which use the electrostatic forces to produce ordered and self-organized binary systems. In this process the intimate contact significantly enhances and gives the ability to build an energetic material in molecular level, which is crucial for thepressure discharge efficiency of nano-thermites. The DTA-TGA, Zeta-size analysis and FTIR technique were performed to characterize the Bi2O3 particles. The self-assembly of Aluminum and Bi2O3 was conducted in sonic bath with appropriate solvents and linkers. The resultant thermite pressure discharge values were tested in modified Parr reactor. In general, the self-assembled thermites give much higher-pressure discharge values than the thermites prepared with conventional roll-mixing technique.

Selective Oxidation of a 0.1C-6Mn-2Si Third Generation Advanced High-Strength Steel During Dew-Point Controlled Annealing

NASA Astrophysics Data System (ADS)

Pourmajidian, Maedeh; McDermid, Joseph R.

2018-03-01

The present study investigates the selective oxidation of a 0.1C-6Mn-2Si medium-Mn advanced high-strength steel during austenization annealing heat treatments as a function of process atmosphere oxygen partial pressure and annealing time. It was determined that the surface oxide growth kinetics followed a parabolic rate law with the minimum rate belonging to the lowest oxygen partial pressure atmosphere at a dew point of 223 K (- 50 °C). The chemistry of the surface and subsurface oxides was studied using STEM + EELS on the sample cross sections, and it was found that the surface oxides formed under the 223 K (- 50 °C) dew-point atmosphere consisted of a layered configuration of SiO2, MnSiO3, and MnO, while in the case of the higher pO2 process atmospheres, only MnO was detected at the surface. Consistent with the Wagner calculations, it was shown that the transition to internal oxidation for Mn occurred under the 243 K (- 30 °C) and 278 K (+ 5 °C) dew-point atmospheres. However, the predictions of the external to internal oxidation for Si using the Wagner model did not correlate well with the experimental findings nor did the predictions of the Mataigne et al. model for multi-element alloys. Investigations of the internal oxide network at the grain boundaries revealed a multilayer oxide structure composed of amorphous SiO2 and crystalline MnSiO3, respectively, at the oxide core and outer shell. A mechanism for the formation of the oxide morphologies observed, based on kinetic and thermodynamic factors, was proposed. It is expected that only the fine and nodule-like MnO oxides formed on the surface of the samples annealed under the 278 K (+ 5 °C) dew-point process atmosphere for 60 and 120 seconds are sufficiently thin and of the desired dispersed morphology to promote reactive wetting by the molten galvanizing bath.

Tailoring gadolinium-doped ceria-based solid oxide fuel cells to achieve 2 W cm(-2) at 550 °C.

PubMed

Lee, Jin Goo; Park, Jeong Ho; Shul, Yong Gun

2014-06-04

Low-temperature operation is necessary for next-generation solid oxide fuel cells due to the wide variety of their applications. However, significant increases in the fuel cell losses appear in the low-temperature solid oxide fuel cells, which reduce the cell performance. To overcome this problem, here we report Gd0.1Ce0.9O1.95-based low-temperature solid oxide fuel cells with nanocomposite anode functional layers, thin electrolytes and core/shell fibre-structured Ba0.5Sr0.5Co0.8Fe0.2O3-δ-Gd0.1Ce0.9O1.95 cathodes. In particular, the report describes the use of the advanced electrospinning and Pechini process in the preparation of the core/shell-fibre-structured cathodes. The fuel cells show a very high performance of 2 W cm(-2) at 550 °C in hydrogen, and are stable for 300 h even under the high current density of 1 A cm(-2). Hence, the results suggest that stable and high-performance solid oxide fuel cells at low temperatures can be achieved by modifying the microstructures of solid oxide fuel cell components.

TEMPO-oxidized cellulose nanofibers

NASA Astrophysics Data System (ADS)

Isogai, Akira; Saito, Tsuguyuki; Fukuzumi, Hayaka

2011-01-01

Native wood celluloses can be converted to individual nanofibers 3-4 nm wide that are at least several microns in length, i.e. with aspect ratios >100, by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation and successive mild disintegration in water. Preparation methods and fundamental characteristics of TEMPO-oxidized cellulose nanofibers (TOCN) are reviewed in this paper. Significant amounts of C6 carboxylate groups are selectively formed on each cellulose microfibril surface by TEMPO-mediated oxidation without any changes to the original crystallinity (~74%) or crystal width of wood celluloses. Electrostatic repulsion and/or osmotic effects working between anionically-charged cellulose microfibrils, the ζ-potentials of which are approximately -75 mV in water, cause the formation of completely individualized TOCN dispersed in water by gentle mechanical disintegration treatment of TEMPO-oxidized wood cellulose fibers. Self-standing TOCN films are transparent and flexible, with high tensile strengths of 200-300 MPa and elastic moduli of 6-7 GPa. Moreover, TOCN-coated poly(lactic acid) films have extremely low oxygen permeability. The new cellulose-based nanofibers formed by size reduction process of native cellulose fibers by TEMPO-mediated oxidation have potential application as environmentally friendly and new bio-based nanomaterials in high-tech fields.

Ionizing Organic Compound Based Nanocomposites for Efficient Gamma-Ray Sensor

NASA Technical Reports Server (NTRS)

Singh, N. B.; Dayal, Vishall; Su, Ching-Hua; Arnold, Bradley; Choa, Fow-Sen; Kabandana, Monia G. K.; House, David

2017-01-01

Thin film and nanocrystalline materials of oxides have been very attractive choice as low cost option for gamma-ray detection and have shown great promise. Our studies on pure oxide films indicated that thickness and microstructure have pronounced effect on sensitivity. Since the interaction of gamma-ray with composites involves all three interaction processes; photoelectric effect, Compton scattering, and pair production, composites containing ionic organics have better chance for enhancing sensitivity. In the composites of ionizing organics oxidation effect of unusual oxides changes much faster and hence increases the sensitivity of radiation. In this study, we have used nickel oxide and titanium oxide in ionic organics to develop composite materials for low energy gamma-ray sensing. We prepared composites containing ethylene carbonate and evaluated the effect of commercial Cs-137 radiation source by studying current-voltage relationship at several frequencies. Radiated samples showed higher resistivity compared to as prepared composites.

Oxidation-resisting technology of W-Re thermocouples and their industrial applications

NASA Astrophysics Data System (ADS)

Wang, K.; Dai, M.; Dong, J.; Wang, L.; Wang, T.

2013-09-01

We use DSC/TG, SEM and EPMA approaches to investigate the high temperature oxidation behaviors of the Type C W-Re thermocouple wires and W-Re powders which the wires were made from. To solve the oxidization of W-Re thermocouples the chemical method, other than the commonly used physical method, i.e. vacuum-pumping method, was developed. Several solid-packed techniques such as stuffing with inert material, chemical deoxidizing, gas-absorbing and sealing were employed to prevent the W-Re thermocouples from oxidizing. Based on comprehensive consideration of various parameters in process industries, a series of industrial W-Re thermocouples has been successfully used in oxidizing and reducing atmospheres, high temperature alkali and other harsh environments. The service life is 6 to 12 months in strong oxidizing atmosphere of Cr2O3-Al2O3 brick kiln and 2 to 3 months in high temperature alkali and in reducing atmosphere of CO.

Facile hydrothermal preparation of titanium dioxide decorated reduced graphene oxide nanocomposite

PubMed Central

Chang, Betty Yea Sze; Huang, Nay Ming; An’amt, Mohd Nor; Marlinda, Abdul Rahman; Norazriena, Yusoff; Muhamad, Muhamad Rasat; Harrison, Ian; Lim, Hong Ngee; Chia, Chin Hua

2012-01-01

A simple single-stage approach, based on the hydrothermal technique, has been introduced to synthesize reduced graphene oxide/titanium dioxide nanocomposites. The titanium dioxide nanoparticles are formed at the same time as the graphene oxide is reduced to graphene. The triethanolamine used in the process has two roles. It acts as a reducing agent for the graphene oxide as well as a capping agent, allowing the formation of titanium dioxide nanoparticles with a narrow size distribution (~20 nm). Transmission electron micrographs show that the nanoparticles are uniformly distributed on the reduced graphene oxide nanosheet. Thermogravimetric analysis shows the nanocomposites have an enhanced thermal stability over the original components. The potential applications for this technology were demonstrated by the use of a reduced graphene oxide/titanium dioxide nanocomposite-modified glassy carbon electrode, which enhanced the electrochemical performance compared to a conventional glassy carbon electrode when interacting with mercury(II) ions in potassium chloride electrolyte. PMID:22848166

Adaptability as the key to success for the ubiquitous marine nitrite oxidizer Nitrococcus

PubMed Central

Füssel, Jessika; Lücker, Sebastian; Yilmaz, Pelin; Nowka, Boris; van Kessel, Maartje A. H. J.; Bourceau, Patric; Hach, Philipp F.; Littmann, Sten; Berg, Jasmine; Spieck, Eva; Daims, Holger; Kuypers, Marcel M. M.; Lam, Phyllis

2017-01-01

Nitrite-oxidizing bacteria (NOB) have conventionally been regarded as a highly specialized functional group responsible for the production of nitrate in the environment. However, recent culture-based studies suggest that they have the capacity to lead alternative lifestyles, but direct environmental evidence for the contribution of marine nitrite oxidizers to other processes has been lacking to date. We report on the alternative biogeochemical functions, worldwide distribution, and sometimes high abundance of the marine NOB Nitrococcus. These largely overlooked bacteria are capable of not only oxidizing nitrite but also reducing nitrate and producing nitrous oxide, an ozone-depleting agent and greenhouse gas. Furthermore, Nitrococcus can aerobically oxidize sulfide, thereby also engaging in the sulfur cycle. In the currently fast-changing global oceans, these findings highlight the potential functional switches these ubiquitous bacteria can perform in various biogeochemical cycles, each with distinct or even contrasting consequences. PMID:29109973

Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis.

PubMed

Smith, Rodney D L; Prévot, Mathieu S; Fagan, Randal D; Zhang, Zhipan; Sedach, Pavel A; Siu, Man Kit Jack; Trudel, Simon; Berlinguette, Curtis P

2013-04-05

Large-scale electrolysis of water for hydrogen generation requires better catalysts to lower the kinetic barriers associated with the oxygen evolution reaction (OER). Although most OER catalysts are based on crystalline mixed-metal oxides, high activities can also be achieved with amorphous phases. Methods for producing amorphous materials, however, are not typically amenable to mixed-metal compositions. We demonstrate that a low-temperature process, photochemical metal-organic deposition, can produce amorphous (mixed) metal oxide films for OER catalysis. The films contain a homogeneous distribution of metals with compositions that can be accurately controlled. The catalytic properties of amorphous iron oxide prepared with this technique are superior to those of hematite, whereas the catalytic properties of a-Fe(100-y-z)Co(y)Ni(z)O(x) are comparable to those of noble metal oxide catalysts currently used in commercial electrolyzers.

Water exchange in manganese-based water-oxidizing catalysts in photosynthetic systems: from the water-oxidizing complex in photosystem II to nano-sized manganese oxides.

PubMed

Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Eaton-Rye, Julian J; Tomo, Tatsuya; Nishihara, Hiroshi; Satoh, Kimiyuki; Carpentier, Robert; Shen, Jian-Ren; Allakhverdiev, Suleyman I

2014-09-01

The water-oxidizing complex (WOC), also known as the oxygen-evolving complex (OEC), of photosystem II in oxygenic photosynthetic organisms efficiently catalyzes water oxidation. It is, therefore, responsible for the presence of oxygen in the Earth's atmosphere. The WOC is a manganese-calcium (Mn₄CaO₅(H₂O)₄) cluster housed in a protein complex. In this review, we focus on water exchange chemistry of metal hydrates and discuss the mechanisms and factors affecting this chemical process. Further, water exchange rates for both the biological cofactor and synthetic manganese water splitting are discussed. The importance of fully unveiling the water exchange mechanism to understand the chemistry of water oxidation is also emphasized here. This article is part of a special issue entitled: photosynthesis research for sustainability: keys to produce clean energy. Copyright © 2014 Elsevier B.V. All rights reserved.